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

Abstract

In this work, we studied the hydrothermal agates from the Neogene–Quaternary volcanic district of Allumiere-Tolfa, northwest 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 fuctuations of SiO2-bearing fuids. 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 fuctuations. 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 fuids at a temperature of 100–200 °C, whereas the boron-rich chalcedony can be favored by neutral/acidic conditions. The fnal Bambauer quartz growth lamellae testifes diluted SiO 2-bearing solutions at lower temperature. These fndings suggest a genetic scenario dominated by pH fuctuations in the circulating hydrothermal fuid