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

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

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

GC-MS analysis of soil faecal biomarkers uncovers mammalian species and the economic management of the archeological site "Le Colombare di Negrar"

: The identification of the mammalian species based on faecal sediments in modern and ancient environments is the aim of the research of archaeologists, forensic scientists and ecologists. Here, we set up and validated an optimized gas chromatography-mass spectrometry (GC-MS) method, characterized by a time-saving sample preparation protocol, for the simultaneous analysis of faecal biomarkers (6 sterols/stanols and 5 bile acids) in 14 soil samples from the archaeological site of "Le Colombare di Negrar" in northern Italy. Although the archaeological sediment samples examined are numerically exiguous, a comparative reading of our faecal biomarkers findings with new studies on faunal materials collected in the same stratigraphic detail during recent excavation campaigns will allow to better clarify the economic interest of the animal species farmed in the Colombare site (such as bovines, goats, sheep and pigs) and to shed light on the management of breeding. Together with archaeozoological and archaeobotanical analyses, the investigation of faecal biomarkers can increase our knowledge of how ancient local communities exploited natural resources and may allow us to deduce what their impact on the landscape was

Polarization effects in the reaction e++e−→ρ++ρ−e^++e^-\to \rho^+ +\rho^- and determination of the ρ−\rho - meson form factors in the time--like region

The electron positron annihilation reaction into four pion production has been studied, through the channel $e^++e^-\to \bar \rho+\rho$. The differential (and total) cross sections and various polarization observables for this reaction have been calculated in terms of the electromagnetic form factors of the corresponding $\gamma^*\rho\rho$ current. The elements of the spin--density matrix of the $\rho -$meson were also calculated. Numerical estimations have been done, with the help of phenomenological form factors obtained in the space--like region of the momentum transfer squared and analytically extended to the time-like region.Comment: 19 pages, 2 figures, to appear in Phys Rev

Influence of magmatic and magmatic-hydrothermal processes on the lithium endowment of micas in the Cornubian Batholith (SW England)

This is the final version. Available on open access from Springer via the DOI in this recordThe Cornubian Batholith (SW England) is an archetypal Variscan rare metal granite with potential for Li-mica mineralization. We present a petrographic, trace element and multivariate statistical study of micas from the Cornubian Batholith granite series and related hydrothermally altered units to assess the role of magmatic vs subsolidus processes and of fluxing elements (F and B) on the Li cycle during the evolution of the system. The mica types are as follows: (1) magmatic, which include Fe-biotite, protolithionite I and phengite-muscovite from the most primitive granites, and zinnwaldite I from more fractionated lithologies; (2) subsolidus, which encompass high-temperature autometasomatic Li-micas and low-temperature hydrothermal muscovite-phengite. Autometasomatic species include protolithionite II, zinnwaldite II and lepidolite, which were observed in the most fractionated and hydrothermally altered units, and occur as replacements of magmatic micas. Low-temperature hydrothermal Li-poor micas formed via alteration of magmatic and autometasomatic micas or as replacement of feldspars, and albeit occur in all studied lithologies they are best represented by the granite facies enriched in metasomatic tourmaline. The evolution of micas follows two major trends underlining a coupling and decoupling between the Li(F) and B fluxes. These include as follows: (1) a Li(F)-progressive trend explaining the formation of protolithionite I and zinnwaldite I, which fractionate Li along with Cs, Nb and Sn during the late-magmatic stages of crystallization, and of zinnwaldite II and lepidolite forming from the re-equilibration of primary micas with high-temperature Li-B-W-Tl-Cs-Mn-W-rich autometasomatic fluids; (2) a Li(F)-retrogressive trend explaining the low-temperature hydrothermal muscovitization, which represents the main Li depletion process. Trace element geochemistry and paragenesis of late muscovite-phengite support that muscovitization is a district-scale process that affected the upper parts of the granite cupolas through acidic and B(Fe-Sn)-saturated hydrothermal fluids associated with metasomatic tourmalinization, which were mixed with a low Eh meteoric component.Natural Environment Research Council (NERC)Ministry of Science and Higher Education of the Republic of Kazakhsta

Polarization effects in e++e−→dˉ+de^+ +e^-\to \bar d+d and determination of time like deuteron form factors

Polarization effects in the reaction $e^++e^-\to \bar d+d$ have been investigated for the case of longitudinally polarized electron beam and arbitrary polarization of the produced deuteron, with the aim of a determination of the time-like complex deuteron electromagnetic form factors. General expressions of polarization observables are derived and numerical estimations have been carried out by means of various models of deuteron electromagnetic form factors, for kinematical conditions near threshold.Comment: 19 pages, 3 figure