Biotic and inorganic control on travertine deposition at Bullicame 3 spring (Viterbo, Italy): A multidisciplinary approach

A multidisciplinary characterization of an active thermal spring in central Italy has been undertaken with the aim of (i) ascertaining whether microbiological activity plays a relevant role in hot-depositing travertines and (ii) establishing an experimental protocol able to identify similar effects in fossil travertines. Water, gas, and travertine samples were investigated by chemical (ICP/MS, SEM/EDS), physical (DTA-DTG), isotopic (?18O, ?D, and ?13C), mineralogical (XRPD), and spectroscopic (EPR) techniques. Twenty-four samples (three for each phase) were collected every 5 °C temperature drop, along a ~100 m long artificial channel near Viterbo (Bullicame 3, Latium, central Italy). A microbiological characterization was carried out in parallel, sampling the channel every 10 °C temperature drop. The Bullicame 3 system is revealed to be composed of two markedly different subsystems: a water/gas interface, where a kinetically fast exchange allows equilibrium of components both in water and in gases; a solid/water interface, where travertine precipitation occurs, influenced by microbiological activity. A peculiar lattice shrinking of calcite was identified, as well as an anomalous value of the zero-field splitting parameter from the EPR measurements. The interpretation of these anomalies is confirmed by the identification of calcifying cyanobacteria throughout the channel path. Our results point out that microbiological activity can play a significant role in travertine deposition from hot springs. Furthermore, the proposed approach, representing a tool to identify crystal chemical remnants of past microbiological activity, could be applicable to fossil travertines.