The ore deposits of Bou Caïd (Ouarsenis, Algeria) occur in Jurassic and Cretaceous sedimentary rocks. The barite and Pb-Zn (Fe, Cu, and F) ore deposits of Bou Caïd belong to vein- and karst-type. The mineralization is represented in the whole area by a mixture of barite (currently still exploited) and nonsulfides consisting of hemimorphite, smithsonite, cerussite, hydrozincite, and Fe-oxy-hydroxides, with remnants of galena and sphalerite in variable proportions. Mineralogical and geochemical analyses were carried out on the Bou Caïd nonsulfides. Several samples representing nonsulfide mineralization (Grand Pic and at Srâa Abdelkader) were subjected to a multidisciplinary analytical approach, using optical microscopy (OM), powder X-ray diffraction (PXRD), Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM-EDS). Nonsulfide mineralization consists of a mixture of hemimorphite, hydrozincite, smithsonite, cerussite, and Fe-oxy-hydroxides, often with zebra-like textures. In the proposed paragenetic scheme, covellite and chalcocite are followed by cerussite, jarosite, smithsonite, and hydrozincite. Then, hemimorphite crystallizes, accompanied by mimetite, traces of malachite and clay minerals (also Zn-bearing), precipitate. Fe-(Mn)-oxy-hydroxides can form during various phases of the supergene stage. Small amounts of late barite can be related to partial remobilization and occur as reprecipitation products. Stable isotope analyses were performed on the calcites and metal carbonates of the supergene ores. Carbon and oxygen isotope values of smithsonite and hydrozincite were comparable to published supergene Zn carbonate data. The isotope values of the Bou Caïd calcites fell both into the hydrothermal carbonate and in the supergene fields. Full article

Through integration of Pb-Zn ± Cu non-sulfide mineralogy, texture, and stable isotope (C, O, S) geochemistry, the world-class Touissit- Bou Beker and Jbel Bou Dahar Mississippi Valley-type districts of the Moroccan Atlasic system have been investigated in order to gain insights into the origin and processes that contributed to the formation of the base metal non-sulfide mineralization. In both districts, direct replacement (“red calamine”) and wallrock replacement (“white calamine”) ores are observed. Based on the mineral assemblages, ore textures, and crosscutting relations, three distinct mineralizing stages are recognized. The earliest, pre-non-sulfide gossanous stage was a prerequisite for the following supergene stages and constituted the driving force that ultimately promoted the leaching of most base metals such as Zn and Cu and alkalis from their rock sources. The following two stages, referred to as the main supergene “red calamine” and late “white calamine” ore stages, generated the bulk of mineable “calamine” ores in the Touissit-Bou Beker and Jbel Bou Dahar districts. Stable isotope compositions (δ¹³C_V-PDB, δ¹⁸O_V-SMOW, δ³⁴S_CDT) support a three-stage model whereby metals were released by supergene acidic fluids and then precipitated by bacteria and archaea-mediated metal-rich meteoric fluids due to a decrease in temperature and/or increase of f_O2. Oxygen isotope thermometry indicates decreasing precipitation temperatures with advancing paragenetic sequence from 33° to 18 °C, with wet to semi-arid to arid climatic conditions. The close spatial relationships between coexisting sulfide and non-sulfide mineralization along with stable isotope constraints suggest that the oxidation of sulfides occurred concurrently after the main stage of the Alpine orogeny between 15 Ma and the present. More importantly, the current data show for the first time the involvement of biologically controlled activity as the major driving process that triggered both oxidation and deposition of supergene mineralization at Jbel Bou Dahar and Touissit-Bou Beker districts. Conclusions drawn from this study therefore have implications for supergene Mississippi Valley-type (MVT) -derived non-sulfide deposits worldwide and account for the prominent role of biological processes in the genesis of this category of ore deposits. Full article

The mining district of Nefza-Sejnane (Tunisia) encloses numerous ores and raw material deposits, all formed in relation with successive Fe-rich fluids of meteoric and/or hydrothermal origins. Here, for the first time in Tunisia, (U-Th)/He ages were obtained on supergene goethite from various localities/deposits of the district highlight direct dating of significant weathering episodes during late Tortonian and late Pleistocene. These weathering events are most likely associated with favorable conditions that combine (i) wet climate displaying sufficient meteoric water/fluid; and (ii) regional exhumation, due to large-scale vertical lithospheric movements enhancing the percolation of fluids. Matched with previous works, these results refine the stratigraphic frame for the polymetallic mineralization and clay deposits in the district, confirming the influence of meteoric fluids circulation during the late Cenozoic. As a consequence of the new (U-Th)/He data, we moreover propose a taxonomic and stratigraphic revision of the well-known mammalian fauna from the Fe-rich Douahria locality, suggesting an early Tortonian age for the fossils, i.e., prior to the first episode of meteoric event in the area. Full article

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. Full article

The giant Tizert copper deposit is considered as the largest copper resource in the western Anti-Atlas (Morocco). The site is characterized by Cu mineralization carried by malachite, chalcocite, covellite, bornite and chalcopyrite; azurite is not observed. The host rocks are mainly limestones (Formation of Tamjout Dolomite) and sandstones/siltstones (Basal Series) of the Ediacaran/Cambrian transition. The supergene enrichment is most likely related to episodes of uplift/doming (last event since 30 Ma), which triggered the exhumation of primary/hypogene mineralization (chalcopyrite, pyrite, galena, chalcocite I and bornite I), generating their oxidation and the precipitation of secondary/supergene sulfides, carbonates and Fe-oxyhydroxides. The Tizert supergene deposit mainly consists of (i) a residual patchwork of laterite rich in Fe-oxyhydroxides; (ii) a saprolite rich in malachite, or “green oxide zone” where primary structures such as stratification are preserved; (iii) a cementation zone containing secondary sulfides (covellite, chalcocite II and bornite II). The abundance of Cu carbonates results from the rapid neutralization of acidic meteoric fluids, due to oxidation of primary sulfides, by carbonate host rocks. Chlorite is also involved in the neutralization processes in the sandstones/siltstones of the Basal Series, in which supergene clays, such as kaolinite and smectites, subsequently precipitated. At Tizert, as can be highlighted in other supergene Cu-deposits around the world, azurite is absent due to low pCO₂ and relatively high pH conditions. In addition to copper, Ag enrichment is also observed in weathered rocks; Fe-oxyhydroxides contain high Zn, As, and Pb contents. However, these secondary enrichments are quite low compared to Cu in the whole Tizert site, which is therefore, considered as relatively homogeneous. Full article

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. Full article