Influence of genetic processes on geochemistry of fe-oxy-hydroxides in supergene Zn non-sulfide deposits

In supergene Zn non-sulfide deposits, the Fe-oxy-hydroxides (FeO/OH) are mainly concentrated in the residual zones (gossan) on top of the oxidized ore bodies, although they can also be found throughout the whole weathering profile coexisting with the primary and secondary ore assemblages. Fe-oxy-hydroxides are rarely pure as they form in systems where a wide range of metals, most of them of economic importance (e.g., Zn, Pb, Co, REE, Sc, Ga, Ge, V, etc.), freely circulate and can be “captured” under specific conditions. Although their occurrence can be widespread, and they have a potential to scavenge and accumulate critical metals, FeO/OH are considered gangue phases during the existing processing routes of Zn non-sulfide ores. Moreover, very little is known about the role of the deposit type on the geochemistry of FeO/OH formed in a specific association. Therefore, this paper provides a comprehensive assessment of the trace element footprint of FeO/OH from a number of Zn non-sulfide deposits, in order to define parameters controlling the metals’ enrichment process in the mineral phase. To achieve this, we selected FeO/OH-bearing mineralized samples from four supergene Zn non-sulfide ores in diverse settings, namely Hakkari (Turkey), Jabali (Yemen), Cristal (Peru) and Kabwe (Zambia). The petrography of FeO/OH was investigated by means of scanning electron microscope energy dispersive analysis (SEM-EDS), while the trace element composition was assessed using laser ablation-ICP-MS (LA-ICP-MS). Statistical analyses performed on LA-ICP-MS data defined several interelement associations, which can be ascribed to the different nature of the studied deposits, the dominant ore-formation process and subsequent evolution of the deposits and the environmental conditions under which FeO/OH phases were formed. Based on our results, the main new inferences are: (A) Zinc, Si, Pb, Ga and Ge enrichment in FeO/OH is favored in ores where the direct replacement of sulfides is the dominant process and/or where the pyrite is abundant (e.g., Cristal and Hakkari). (B) When the dissolution of the host-rock is a key process during the supergene ore formation (i.e., Jabali), the buffering toward basic pH of the solutions favors the uptake in FeO/OH of elements leached from the host carbonate rock (i.e., Mn), whilst restricting the uptake of elements derived from the dissolution of sulfides (i.e., Zn, Pb, Ga and Ge), as well as silica. (C) The input of exotic phases can produce significant enrichment in “unconventional” metals in FeO/OH (i.e., Cr and Co at Kabwe; Y at Cristal) depending on whether the optimal pH-Eh conditions are attained. (D) In the Kabwe deposit, FeO/OH records heterogeneous geochemical conditions within the system: where locally basic conditions prevailed during the alteration process, the V and U concentration in FeO/OH is favored; yet conversely, more acidic weathering produced Zn-and Si-bearing FeO/OH

Mineralogy and genesis of the kihabe Zn-Pb-V prospect, Aha Hills, Northwest Botswana

The Kihabe Zn-Pb-V > (Cu-Ag-Ge) prospect is located at the boundary between Namibia and Botswana (Aha Hills, Ngamiland District) in a strongly deformed Proterozoic fold belt, corresponding to the NE extension of the Namibian Damara Orogen. The Kihabe prospect contains Zn-Pb resources of 14.4 million tonnes at 2.84% zinc equivalent, Ag resources of 3.3 million ounces, and notable V-Ge amounts, still not evaluated at a resource level. The ores are represented by a mixed sulfide–nonsulfide mineralization. Sulfide minerals consist mainly of sphalerite, galena and pyrite in a metamorphic quartzwacke. Among the nonsulfide assemblage, two styles of mineralization occur in the investigated samples: A first one, characterized by hydrothermal willemite and baileychlore, and a second one consisting of supergene smithsonite, cerussite, hemimorphite, Pb-phosphates, arsenates and vanadates. Willemite is present in two generations, which postdate sulfide emplacement and may also form at their expenses. These characteristics are similar to those observed in the willemite occurrences of the nearby Otavi Mountainland, which formed through hydrothermal processes, during the final stages of the Damara Orogeny. The formation of the Kihabe willemite is likely coeval. Baileychlore is characterized by textures indicating direct precipitation from solutions and dissolution–crystallization mechanisms. Both processes are typical of hydrothermal systems, thus suggesting a hydrothermal genesis for the Kihabe Zn-chlorite as well. Baileychlore could represent an alteration halo possibly associated either with the sulfide or with willemite mineralization. The other nonsulfide minerals, smithsonite, cerussite, various Pb-phosphates and vanadates, are clearly genetically associated with late phases of supergene alteration, which overprinted both the sulfide and the willemite-and baileychlore-bearing mineralizations. Supergene alteration probably occurred in this part of Botswana from the Late Cretaceous to the Miocene

Vanadium ore resources of the African continent: State of the Art

As part of the critical metals group, vanadium is an essential commodity for the low- and zero-CO2 energy generation, storage and transport. This contribution aims to carry out a review of the known vanadium ore sources and mineralizations located in Africa, which are highly diversified in their geological and mineralogical characteristics, and can be classified in: 1. Vanadiferous (titano)magnetite deposits; 2. Sandstone-hosted (U)-vanadium deposits; 3. Calcrete-hosted (U)-vanadium deposits; 4. Vanadate deposits; 5. Graphite-associated vanadium deposits; 6. Vanadium occurrences associated with laterite, bauxite, and phosphate ores. The economically most significant vanadium sources in Africa are associated with titanomagnetite layers in mafic–ultramafic layered magmatic intrusions (e.g., the Bushveld Complex in South Africa and the Great Dyke in Zimbabwe). Vanadium has been historically mined also in vanadate deposits deriving from the supergene alteration of Pb-Zn-Cu sulfide ores in Namibia and Zambia. Several areas in these countries, where potentially re-processable old tailings and slags have been accumulated, still have economic potential. Vanadium mineralizations are associated with graphite bodies in the Mozambique Metamorphic Belt. Vanadium is also enriched in uranium ores occurring in the Upper Paleozoic-Mesozoic Karoo continental sediments: typical examples are found in Botswana, South Africa, and Zimbabwe. Significant uranium-vanadium concentrations (where carnotite prevails) occur in relatively recent (Tertiary-Quaternary) calcrete duricrusts in paleo-fluviatile beds, which are widespread throughout the African continent. These derive from the weathering of U-(V)-fertile source rocks, which under favorable paleoclimatic conditions resulted in the vanadium precipitation in the critical zone. Variable vanadium amounts have been also recorded in iron ore deposits, phosphorites, and laterites, even though the phosphate deposits seem to have the most favorable characteristics for potentially economic vanadium concentrations. On the whole, South Africa holds the most significant vanadium ore resources globally. However, also many other African countries, where this metal could be profitably extracted as a by-product from other economic ores, will probably be at the forefront of vanadium production in the near future

Critical elements in nonsulphide Zn deposits: A reanalysis of the Kabwe Zn-Pb ores (central Zambia)

The Kabwe Zn-Pb deposit (central Zambia) consists of a cluster of mixed sulfide and non-sulfide orebodies. The sulfide ores comprise sphalerite, galena, pyrite, chalcopyrite and accessory Ge-sulfides (±Ga and In). The non-sulfide ores comprise: (1) willemite-dominated zones encasing massive sulfide orebodies and (2) oxide-dominated alteration bands, overlying both the sulfide and Zn-silicate orebodies. This study focuses on the Ge, In and Ga distribution in the non-sulfide mineralization, and was carried out on a suite of Kabwe specimens, housed in the Natural History Museum Ore Collection (London). Petrography confirmed that the original sulfides were overprinted by at least two contrasting oxidation stages dominated by the formation of willemite (W1 and W2), and a further event characterized by weathering-related processes. Oxygen isotopic analyses have shown that W1 and W2 are unrelated genetically and furthermore not related to supergene Zn-Pb-carbonates in the oxide-dominated assemblage. The δ18O composition of 13.9-15.7‰ V-SMOW strongly supports a hydrothermal origin for W1. The δ18O composition of W2 (-3.5‰ to 0‰ V-SMOW) indicates that it precipitated from groundwaters of meteoric origin in either a supergene or a low-T hydrothermal environment. Gallium and Ge show a diversity of distribution among the range of Zn-bearing minerals. Gallium has been detected at the ppm level in W1, sphalerite, goethite and hematite. Germanium occurs at ppm levels in W1 and W2, and in scarcely detectable amounts in hemimorphite, goethite and hematite. Indium has low concentrations in goethite and hematite. These different deportments among the various phases are probably due to the different initial Ga, In and Ge abundances in the mineralization, to the different solubilities of the three elements at different temperatures and pH values, and finally to their variable affinities with the various minerals formed

Mapping hydrothermal and supergene alteration zones associated with carbonate-hosted Zn-Pb deposits by using PRISMA satellite imagery supported by field-based hyperspectral data, mineralogical and geochemical analysis

Delineating hydrothermal alteration and supergene caps is fundamental for mineral exploration of sulfide ores. The aim of this study is to apply a multi-scale workflow based on hyperspectral remote and proximal sensing data in order to delineate hydrothermal dolomitization and supergene alteration associated with the Mississippi Valley-Type Zn-Pb(-Ag) deposit of Jabali (Western Yemen). The area was investigated through hyperspectral images derived from the new launched Italian Space Agency's PRISMA satellite, which has a higher spectral resolution compared to multispectral sensors and covers the mineral-diagnostic wavelength regions (such as the 2100 nm to 2300 nm range) with a Signal to Noise Ratio (SNR) ≥ 100. Spectral mineral maps were produced through the band ratios method using specific feature extraction indices applied to the hyperspectral satellite data. The results were validated by using Visible Near InfraRed (VNIR) to Short Wave InfraRed (SWIR) reflectance spectra, mineralogical (XRPD) and geochemical (ICP-ES/MS) analyses on rock samples collected in the Jabali area. The dolomites footprint was mapped using a PRISMA Level 2C image, by enhancing the spectral differences between limestones and dolomites in the SWIR-2 region (major features centered at 2340 nm and 2320 nm, respectively). Gossans were detected due to the Fe3+ absorption band in the VNIR region at 900 nm. The Zn-Pb mineralized area, extended for approximately 25 km2, was thus identified by recognizing gossan occurrences in dolomites. The study demonstrates that the PRISMA satellite is effective in identifying Zn-Pb mineralized outcrops in sedimentary basins

New investigations on Zn-clays from Skorpion (Namibia)

Zn-bearing clay minerals occur in several nonsulfide zinc ores, which consist of concentrations of Zn-oxidized minerals such as smithsonite, hydrozincite, hemimorphite, sauconite, and willemite [1,2]. These deposits can be genetically related to both supergene and hypogene processes [1]. Zn-clays are worldwide associated with several supergene nonsulfide ores, where they can represent an important metal source [2,3,4]. The best example is the world-class Skorpion mineralization in Namibia, which is considered so far the largest supergene nonsulfide zinc deposit in the world (original reserves of 24.6 Mt ore at 10.6% Zn). The Skorpion deposit is hosted in Neoproterozoic rocks that are part of a volcano-sedimentary sequence within the Gariep Belt in the southern part of the country. In this deposit the trioctahedral Zn-bearing smectite, named sauconite (0.5Ca,Na)0.3Zn3[AlSi3O10](OH)2·4(H2O), predominates over the other Zn-oxidized minerals, mainly represented by smithsonite, hemimorphite and Zn-bearing phosphates [5,6]. Sauconite mainly occurs here in metasiliciclastic rocks, as coatings/impregnations in intergranular spaces and voids. It is considered to have been formed through the breakdown or dissolution of detrital feldspar and mica, or also by replacement of earlier deposited hemimorphite and smithsonite [6]. Petrographic and chemical analyses (energy and wavelength dispersive X-ray spectroscopy, EDS and WDS) show that the smectite-bearing samples collected for this study consist of an association of sauconite, quartz, smithsonite, K-feldspar and micas (Figure 1). Sauconite shows variable contents of Al and Zn, as well as Fe, Mg and Mn. The interlayer cations are represented by Ca and K in variable amounts. Plots of Zn/Altot vs. Si/Altot show a positive correlation; a positive trend is also observed for the correlations Zn/Altot vs. Ca/K ratios, which is consistent with charge compensation between the layers. TEM-HRTEM investigations carried out on selected samples have allowed to determine the chemistry and the texture of the Zn-clays and related minerals, revealing new and complex mineral assemblages. References: [1] Hitzman MW et al. (2003) Econ Geol 98: 685-714 [2] Boni M and Mondillo N (2015) Ore Geology Reviews 67: 208-233 [3] Boni M et al. (2008) Econ Geol 104: 267-89 [4] Mondillo M et al. (2016) Am Min 100: 2484-96 [5] Borg G et al. (2003) Econ Geol 98: 749-771 [6] Kärner K (2005) PhD thesis 252

Curcumin effects on Leydig cell functions and potential therapeutic uses

Curcumin has been ascribed with countless therapeutic effects, but its impact on testicular function has been scarcely researched. Leydig cells comprise the androgen-secreting population of the testis and may give rise to Leydig cell tumours (LCTs). Due to their steroid-secreting nature, LCTs entail endocrine, reproductive, and psychological disorders. Approximately 10% are malignant and do not respond to chemotherapy and radiotherapy. The aim of this study was to assess curcumin’s impact on Leydig cells’ functions and its potential effect on LCT growth. In vitro assays on MA-10 Leydig cells showed that curcumin (20–80 μmol/L) stimulates acute steroidogenesis, both in the presence and absence of db-cAMP. This effect is accompanied by an increase in StAR expression. Regarding curcumin’s in vitro cytostatic capacity, we show that 40–80 μmol/L curcumin reduces MA-10 Leydig cells’ proliferative capacity, which could be explained by the arrest in G2/M and the reduced viability due to the activation of the apoptotic pathway. Finally, CB6F1 mice were inoculated with MA-10 cells to generate ectopic LCT in both flanks. They received i.p. injections of 20 mg/kg curcumin or vehicle every other day for 15 days. We unveiled curcumin’s capacity to inhibit LCT growth as evidenced by reduced tumour volume, weight, and area under the growth curves. No detrimental effects on general health parameters or testicular integrity were observed. These results provide novel evidence of curcumin’s effects on the endocrine cell population of the testis and propose this natural compound as a therapeutic agent for LCT

Novel echocardiographic techniques to assess left atrial size, anatomy and function

Three-dimensional echocardiography (3DE) and speckle tracking echocardiography (STE) have recently applied as imaging techniques to accurately evaluate left atrial (LA) size, anatomy and function. 3DE and off-line quantification softwares, have allowed, in comparison to magnetic resonance imaging, the most time-efficient and accurate method of LA volume quantification. STE provides a non-Doppler, angle-independent and objective quantification of LA myocardial deformation. Data regarding feasibility, accuracy and clinical applications of LA analysis by 3DE and STE are rapidly gathering. This review describes the fundamental concepts of LA 3DE and STE, illustrates how to obtain respective measurements and discuss their recognized and emerging clinical applications