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Supergene nonsulfide ores form from the weathering of sulfide mineralization. Given the geochemical affinity of Ge to Si 4+ and Fe 3+ , weathering of Ge-bearing sulfides could potentially lead to Ge enrichments in silicate and Fe-oxy-hydroxide minerals, although bulk rock Ge concentrations in supergene nonsulfide deposits are rarely reported. Here, we present the results of an investigation into Ge concentrations and deportment in the Cristal supergene Zn nonsulfide prospect (Bongará, northern Peru), which formed from the weathering of a preexisting Mississippi Valley-type (MVT) sulfide deposit. Material examined in this study originates from drillcore recovered from oxidized Zn-rich bodies~15-20 m thick, containing~5-45 wt% Zn and Ge concentrations~100 ppm. Microanalysis and laser ablation-ICP-MS show that precursor sphalerite is rich in both Fe (mean Fe = 8.19 wt%) and Ge (mean Ge = 142 ppm). Using the mineral geothermometer GGIMFis-geothermometer for Ga, Ge, In, Mn, and Fe in sphalerite-proposed by Frenzel et al. (Ore Geol Rev 76:52-78, 2016), sphalerite trace element data from the Cristal prospect suggest a possible formation temperature (T GGIMFis ) of 225 ± 50°C, anomalously high for a MVT deposit. Germanium concentrations measured in both goethite (mean values 100 to 229 ppm, max 511 ppm) and hemimorphite (mean values 39 to 137 ppm, max 258 ppm) are similar to concentrations measured in hypogene sphalerite. Additionally, the Ge concentrations recorded in bulk rock analyses of sphalerite-bearing and oxidized samples are also similar. A persistent warm-humid climate is interpreted for the region, resulting in the development of an oxidation zone favoring the formation of abundant Zn hydrosilicates and Fe hydroxides, both able to incorporate Ge in their crystal structure. In this scenario, Ge has been prevented from dispersion during the weathering of the Ge-bearing sulfide bodies and remains in the resultant nonsulfide ore.

A preliminary C-O stable isotopes geochemical characterization of several nonsulfide Zn-Pb Tunisian deposits has been carried out, in order to evidence the possible differences in their genesis. Nonsulfide ores were sampled from the following deposits: Ain Allegua, Jebel Ben Amara, Jebel Hallouf (Nappe Zone), Djebba, Bou Grine, Bou Jaber, Fedj el Adoum, Slata Fer (Diapir Zone), Jebel Ressas, Jebel Azreg, Mecella (North South Axis Zone), Jebel Trozza, Sekarna (Graben Zone). After mineralogical investigation of selected specimens, the C-O stable isotopic study was carried out on smithsonite, hydrozincite, cerussite and calcite. The data have shown that all the carbonate generations in the oxidized zones of Ain Allegua and Jebel Ben Amara (Nappe Zone), Bou Jaber, Bou Grine and Fedj el Adoum (Diapir Zone), Mecella and Jebel Azreg (North South Zone) have a supergene origin, whereas the carbonates sampled at Sekarna (Graben Zone) (and in limited part also at Bou Jaber) precipitated from thermal waters at moderately high temperature. Most weathering processes that controlled the supergene alteration of the Zn-Pb sulfide deposits in Tunisia had probably started in the middle to late Miocene interval and at the beginning of the Pliocene, both periods corresponding to two distinct tectonic pulses that produced the exhumation of sulfide ores, but the alteration and formation of oxidized minerals could have also continued through the Quaternary. The isotopic characteristics associated with the weathering processes in the sampled localities were controlled by the different locations of the sulfide protores within the tectonic and climatic zones of Tunisia during the late Tertiary and Quaternary.