Boni, Maria

The Florida Canyon Zn deposit in the Bongará Province of northern Peru consists of sulfide and nonsulfide mineralizations within dolomitized strata of the Triassic Chambará Formation, a member of the Triassic-Jurassic Pucará Group. The nonsulfide mineralization, which represents one third of the total resource, formed by supergene alteration of Mississippi Valley-type sulfide bodies. The nonsulfide assemblages occur in stratabound or fault-related, discordant zones that mimic the shapes of the former sulfide zones. Two nonsulfide facies can be distinguished: facies 1 – red zinc ores, which are characterized by smithsonite, or hemimorphite-dominant bodies that formed by direct replacement of primary sulfide assemblages, and facies 2 – white zinc ores, which are characterized by masses of colloform smithsonite formed by replacement of wall rock. The facies are distinct in bulk chemical composition and stable isotope geochemistry. Facies 1 shows high concentrations of Zn, Pb, Fe, Ge, Mn, and As, whereas facies 2 shows only high Zn and Cd concentrations. Enrichments in Ge, which have been reported in other Zn deposits of the Bongará Province, are associated with hemimorphite, Fe hydroxides, and remnant sphalerite in facies 1. The δ13C and δ18O signatures of smithsonite in both facies suggest that meteoric waters infiltrating the precursor sulfide bodies were affected by kinetic fractionation and originated from multiple sources at different altitude.

The present research represents an approach toward the recycling of extractive waste inspired by circular economy and sustainability that is developed in accordance with Goal 12 of the United Nations 2030 Agenda for Sustainable Development Goals. A new procedure for the recovery of REEs from fluorite–barite–galena ores with calcite gangue from the Silius mine (Sardinia, Italy) is presented. The considered samples are waste materials of Silius mineralization, collected in the old processing plant of Assemini (near Cagliari). In this orebody, REE minerals consist of prevailing synchysite (a REE-bearing fluorocarbonate) and subordinate xenotime-Y (a Y-bearing phosphate). REE fluorocarbonates are extracted using 50% K2CO3 as the leaching solution, at 100 °C. Using a solution (mL)/sample (g) ratio of 25, about 10% of the total REE content of the considered sample is extracted within 1 h. At the laboratory scale, such alkaline leaching of REE from the waste materials allows the recovery of the CO2 produced as K2CO3 from concentrated KOH, in accordance with a circular flow. Further work is ongoing to scale up the process into a pilot plant, to prove that the method developed within this research can be economically feasible, socially suitable, and environmentally respectful.

Bauxites in southern France (Provence and Languedoc) have been exploited since the beginning of the last century. Though most of the deposits are now subeconomic or mined-out, these bauxites represent model analogs for other economic bauxites of the world. These Cretaceous karst-type deposits lie directly on Jurassic carbonates, and have been formed through a combination of di erent processes: in-situ alteration of siliciclastic sediments deposited on carbonate platforms, and reworking of early bauxites in the karst network. In this study, we present preliminary bulk rock geochemical and in-situ laser ablation (LA) -ICP-MS analyses on Al- and Fe-oxy-hydroxides of Provence (Les Baux-de-Provence) and Languedoc (Villeveyrac, Loupian) bauxites, with the aim of evaluating the concentrations of rare earth elements (REEs) and their deportment in these minerals. REEs have total average concentrations of 700 mg/kg in the analyzed samples, which are mostly composed of boehmite, -AlO(OH), and Fe-oxy-hydroxides (hematite and goethite). Maximum REEs concentrations are commonly associated with positive Ce anomalies in chondrite-normalized patterns. In contrast with other examples from the literature, it has been observed that high REE concentrations also occur in samples apparently devoid or poor of REE-minerals. In these samples, the total amount of REEs is positively correlated with that of Ga (commonly contained in boehmite). LA-ICP-MS trace element analyses on boehmite and Fe-oxy-hydroxides have shown that while the Al-hydroxide contains the suite of REEs, goethite and hematite are preferentially enriched only in Ce. Considering that Al-hydroxides are digested during the Bayer process, an interesting issue to develop in the future is whether (and how) REEs released during Al-hydroxide digestion could be recovered together with Al from the pregnant leach liquor, as routinely done for Ga.

The Cristal Zn prospect is located in the northernmost part of a wide mining district corresponding to the “Charlotte Bongará Zinc Project”, which covers an area of approximately 110 km2 in the Amazonas region in northern Peru. The mineralized area consists of many Zn occurrences that contain mixed sulfide and nonsulfide mineralizations. The nonsulfide ores are interpreted to be the product of weathering of primary MVT sulfide bodies. The Zn concentrations of the Cristal prospect are hosted by platform carbonates of the Condorsinga Formation (Early Jurassic), which belongs to the Pucará Group. The prospect extends over an area of approximately 2×1 km, with nearly continuous zones of Zn enrichment that has been detected in soil and rock samples. The nonsulfide mineralization consists mainly of semi-amorphous orange to brown zinc “oxides” that include hemimorphite, smithsonite and Fe-(hydr)oxides. The most important mineralized areas are the Esperanza and Yolanda occurrences, which were also most intensively explored. In both occurrences, the supergene Zn-carbonates and silicates infill solution cavities, or replace the carbonate host rocks and/or the primary sulfides, forming smithsonite- and hemimorphite-rich mineralizations. The analyzed drill core samples have on average 20 wt% Zn and maximum Ge concentrations of 200 ppm. The Bongará area experienced a prolonged phase of weathering from Miocene to Recent under tropical climatic conditions. In these conditions, the weathering processes affected many pre-existing sulfide deposits (e.g. Cristal, Florida Canyon, Mina Grande), where supergene profiles were developed under locally different settings that are defined primarily on the basis of mineralogical and geochemical data. Contrary to the Mina Grande deposit, at Cristal, the development of a karst network was minor due to limited uplift, and supergene alteration did not completely obliterate the roots of the original sulfide orebody. The mineralogy and geochemistry of Bongará nonsulfides is dependent on two main factors at the local scale: (1) uplift rates, and (2) host rock composition. The latter may have favored the development of more (e.g. Mina Grande) or less (e.g. Cristal) alkaline supergene environments. Uplift was controlled by the activity of local faults, which allowed the exposure of sulfide protores at variable elevations in different periods of time and hydrological settings. Such different settings resulted in the precipitation of isotopically different supergene carbonates (e.g. smithsonites and calcites at Mina Grande and Cristal).

The Abruzzi bauxite district includes the deposits located on the Campo Felice plateau and those of the Monti d’Ocre, which had been mined in the first part of the 20th century. Bauxite is of the karst type, with textures ranging between oolitic and oolitic-conglomeratic, the latter suggesting a partial reworking of evolved lateritic soils. The high contents of Al2O3 and Fe2O3 (average values 53.76 and 21.76 wt %, respectively) are associated with the presence of boehmite, hematite, and minor goethite. SiO2 and TiO2 have average values of 7.79 and 2.75 wt %, corresponding to the presence of kaolinite, anatase and rutile. Among the minor so-called “bauxitophile” elements V, Co, Ni, Cr and Zr, the most enriched is Cr, with an average value of 0.07 wt %. Nickel has an average value of 210.83 ppm. Vanadium shows an average value of 266.57 ppm, whereas the average Co concentration is 35.89 ppm. The total rare earth elements (REE) concentration in the sampled bauxite sites is variable between ca. 700 and 550 ppm. Among REEs, the most abundant element is Ce, with Ce anomalies commonly associated with authigenic REE-fluoro-carbonates, probably produced after the REEs remobilization from primary detrital minerals and their precipitation in neo-formed phases during the bauxitization process. Scandium and Ga occur in small amounts (57 and 60 ppm, respectively), but geochemical proxies of their remobilization and uptake in neo-formed minerals (Feand Al-(hydr)oxides, respectively) have been observed. The mean Eu/Eu* and Al2O3/TiO2 ratios and the Ni-Cr contents of the Abruzzi bauxites suggest that the parent rock of these deposits was amaterial of acid affinity, likely corresponding to volcanic tephra or eolic loess-type sands.

Supergene nonsulfide ores form from the weathering of sulfide mineralization. Given the geochemical affinity of Ge toSi4+ and Fe3+, 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 (TGGIMFis) 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 first paleomagnetic investigation aimed at constraining the age of the non-sulfide Zn-Pb ore deposits in the Iglesiente district (SW Sardinia, Italy) was carried out. In these ores, the oxidation of primary sulfides, hosted in Cambrian carbonate rocks, was related to several paleoweathering episodes spanning from the Mesozoic onward. Paleomagnetic analyses were performed on 43 cores from 4 different localities, containing: a) non-oxidized primary sulfides and host rock, b) oxidized Fe-rich hydrothermal dolomites and (c) supergene oxidation ore («Calamine»). Reliable data were obtained from 18 samples; the others show uninterpretable results due to low magnetic intensity or to scattered demagnetization trajectories. Three of them show a scattered Characteristic Remanent Magnetization (ChRM), likely carried by the original (i.e. Paleozoic) magnetic iron sulfides. The remaining 15 samples show a well defined and coherent ChRM, carried by high-coercivity minerals, acquired after the last phase of counterclockwise rotation of Sardinia (that is after 16 Myr), in a time interval long enough to span at least one reversal of the geomagnetic field. Hematite is the main magnetic carrier in the limestone, whereas weathered hydrothermal dolomite contains goethite or a mixture of both. The results suggest that paleomagnetism can be used to constrain the timing of oxidation in supergene-enriched ores.