Hydrothermal genesis and growth of the banded agates from the Allumiere-Tolfa volcanic district (Latium, Italy)

In this work, we studied the hydrothermal agates from the Neogene–Quaternary volcanic district of Allumiere-Tolfa, north-west of Rome (Latium, Italy) using a combination of micro-textural, spectroscopic, and geochemical data. The examined sample consists of (1) an outer cristobalite layer deposited during the early stages of growth, (2) a sequence of chalcedonic bands (including i.e., length-fast, zebraic, and minor length-slow chalcedony) with variable moganite content (up to ca. 48 wt%), (3) an inner layer of terminated hyaline quartz crystals. The textures of the various SiO₂ phases and their trace element content (Al, Li, B, Ti, Ga, Ge, As), as well as the presence of mineral inclusions (i.e., Fe-oxides and sulfates), is the result of physicochemical fluctuations of SiO₂-bearing fluids. Positive correlation between Al and Li, low Al/Li ratio, and low Ti in hyaline quartz points to low-temperature hydrothermal environment. Local enrichment of B and As in chalcedony-rich layers are attributed to pH fluctuations. Analysis of the FT-IR spectra in the principal OH-stretching region (2750–3750 cm⁻¹) shows that the silanol and molecular water signals are directly proportional. Strikingly, combined Raman and FT-IR spectroscopy on the chalcedonic bands reveals an anticorrelation between the moganite content and total water (SiOH + molH₂O) signal. The moganite content is compatible with magmatic-hydrothermal sulfate/alkaline fluids at a temperature of 100–200 °C, whereas the boron-rich chalcedony can be favored by neutral/acidic conditions. The final Bambauer quartz growth lamellae testifies diluted SiO₂-bearing solutions at lower temperature. These findings suggest a genetic scenario dominated by pH fluctuations in the circulating hydrothermal fluid.