Light in the darkening on Naica gypsum crystals

Abstract

Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe2O3), β-MnO2, Mn2O3, MnO and/or MnCO3, PbS, PbCO3 and/or PbSO4, ZnO4, ZnS and/or smithsonite (ZnCO3), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.