The giant gypsum crystals of Naica cave have fascinated scientists since their discovery in 2000. Human activity has changed the microclimate inside the cave, making scientists wonder about the potential environmental impact on the crystals. Over the last 9 years, we have studied approximately 70 samples. This paper reports on the detailed chemical–structural characterization of the impurities present at the surface of these crystals and the experimental simulations of their potential deterioration patterns. Selected samples were studied by petrography, optical and electronic microscopy, and laboratory X-ray diffraction. 2D grazing incidence X-ray diffraction, X-ray μ-fluorescence, and X-ray μ-absorption near-edge structure were used to identify the impurities and their associated phases. These impurities were deposited during the latest stage of the gypsum crystal formation and have afterward evolved with the natural high humidity. The simulations of the behavior of the crystals in microclimatic chambers produced crystal dissolution by 1–4% weight fraction under high CO2 concentration and permanent fog, and gypsum phase dehydration under air and CO2 gaseous environment. Our work suggests that most surface impurities are of natural origin; the most significant anthropogenic damage on the crystals is the extraction of water from the caves.

The “espada” speleothems of Cueva de las Espadas (Naica Mine, Chihuahua, Mexico) comprise a high-purity selenite core overlain by successive deposits of calcite, gypsum and aragonite. Gypsum precipitated under water from a hydrothermal solution (~ 58°C) when the water table was above the cave level ca. 57 ka, during the last glaciation, and some intervals during deglaciation and the Holocene. Aragonite was deposited at lower temperatures (~ 26°C) in a perched lake occupying the cave bottom, when the water table dropped below the cave level during brief dry intervals during deglaciation and the early Holocene. The isotopic composition of gypsum water of crystallization shows that the deglaciation–Holocene aquifer water was enriched in deuterium by 12.8–8.7‰ relative to water from the last glaciation. This is attributed to an increased relative moisture contribution from the Gulf of Mexico during deglaciation and the Holocene compared to the last glaciation. This indicates that drier conditions occurred in the Naica area during the Holocene than around 57 ka. Furthermore, trace element analyses of gypsum served to deduce the circulation regime of the Naica aquifer during the past 60,000 yr, and also suggest that higher aquifer recharge occurred during the last glaciation.