The acid sulfate zone and the mineral alteration styles of the Roman Puteoli (Neapolitan area, Italy): clues on fluid fracturing progression at the Campi Flegrei volcano

Abstract

Abstract. Active fumarolic solfataric zones represent important structures of dormant volcanoes, but unlike emitted fluids, their mineralizations are omitted in the usual monitoring activity. This is the case of the Campi Flegrei caldera in Italy, among the most hazardous and best-monitored explosive volcanoes in the world, where the landscape of Puteoli is characterized by an acid sulfate alteration that has been active at least since Roman time. This paper provides temperature, mineralogical, textural, compositional and stable isotope data for those solfataric terrains sampled at the crater and Pisciarelli slope of the Solfatara volcano between 2013 and 2019. Temperatures vary between 40 and 95 ∘C. Minerals include alunite with grain sizes generally larger than 20 µm, alunogen, native sulfur, well-ordered kaolinite, and, common at Pisciarelli, pyrite, illite and NH4 sulfates. Sulfate terrains have higher contents of Ti, Ba, Au, As, Hg and Tl relative to their parent substrate. The Pisciarelli slope is anomalous in terms of the presence of NH4. δ34S values for sulfides and native S range between −3.00 ‰ and 0.49 ‰ and from −4.42 ‰ to 0.80 ‰, respectively. Sulfates show δ34S and δ18O values in the range of −2.78 ‰ to 2.09 ‰ and between 4.60 ‰ and 31.33 ‰, respectively. The style of mineralization and the stable isotope geochemistry do produce complex and not completely consistent classifications and genetic constraints. We merge our data with volcanological information, data from exploration drillings and geophysical results. With the conceptual model, we suggest a series of shallow and deep aquifers interconnected like “communicating vessels” through a main fault system that downthrows Solfatara with respect to Pisciarelli. Fluid outflow from the different discrete aquifers hosted in sediments – and possibly bearing organic imprints – is the main dataset that allows determination of the steam-heated environment with a supergene setting superimposed. Supergene conditions and high-sulfidation relicts, together with the narrow sulfate alteration zone buried under the youngest volcanic deposits, point to the existence of an evolving paleo-conduit. The data will contribute to monitoring and evaluating the volcanic hazards.