Abstract
A multi-methodical characterization of a sauconite (Zn-bearing trioctahedral smectite) specimen from the Skorpion ore deposit (Namibia) was performed by combining X‑ray powder diffraction (XRPD), cation exchange capacity (CEC) analysis, differential thermal analysis (DTA), thermogravimetry (TG), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM-HRTEM-AEM). The X‑ray diffraction pattern exhibits the typical features of turbostratic stacking disorder with symmetrical basal 00l reflections and long-tailed hk bands, as confirmed by TEM observations. Besides sauconite, the sample contains minor amounts of kaolinite, dioctahedral smectite, and quartz. CEC analysis provides a total of Ca (~69%), Mg (~26%), Na (~4%), and K (0.7%) exchangeable cations. Therefore, Zn is located exclusively within the octahedral site of sauconite. TG analysis of the sample yields a total mass loss of about 17%. Three endothermic peaks can be observed in the DTA curve, associated with dehydration and dehydroxylation of the material. An exothermic peak at 820 °C is also present as a consequence of decomposition and recrystallization. The infrared spectrum shows the typical Zn3OH stretching signature at 3648 cm–1, whereas, in the OH/H2O stretching region two bands at 3585 and 3440 cm–1 can be attributed to stretching vibrations of the inner hydration sphere of the interlayer cations and to absorbed H2O stretching vibration, respectively. Diagnostic bands of kaolinite impurity at ~3698 and 3620 cm–1 are also found, whereas 2:1 dioctahedral layer silicates may contribute to the 3585 and 3620 cm–1 bands. Finally, using the one-layer supercell approach implemented in the BGMN software, a satisfactory XRPD profile fitting model for the Skorpion sauconite was obtained. These findings have implications not only for economic geology/recovery of critical metals but also, more generally, in the field of environmental sciences.
Funding statement: The XRPD laboratory at the Dipartimento di Scienze della Terra and Geoambientali, University of Bari Aldo Moro, was funded by Potenziamento Strutturale PONa3_00369 “Laboratorio per lo Sviluppo Integrato delle Scienze e delle TEcnologie dei Materiali Avanzati e per dispositivi innovativi (SISTEMA)”. The XRPD facility at the DiSTAR, University “Federico II” Napoli, is acknowledged. This work was partly supported by DiSTAR fund 2017 (University of Naples Federico II, Italy) granted to G. Balassone, as well as by the research projects PGC2018-094573-B-100 from the Spanish Government and the Research Group RNM-179 of the Junta de Andalucía granted to F. Nieto.
Acknowledgments
The authors acknowledge Annett Steudel and Katja Emmerich for CEC measurement at the Competence Center for Material Moisture, University of Karlshrue, Germany. G.B. and N.M. thank Maria Boni, who promoted the study of the economic geology of worldwide nonsulfide ore deposits, for invaluable scientific guide, and G. Arfè, who first characterized the Skorpion samples, for continuous help and fruitful discussions. Two anonymous referees are thanked for insightful comments that helped to improve the quality of the manuscript.
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