Mercury content and speciation in the Phlegrean Fields volcanic complex: evidence from hydrothermal system and fumaroles

Mercury is outstanding among the global environmental pollutants of continuing concern. Although degassing of active volcanic areas represents an important natural source of mercury into the atmosphere, still little is known about the amount and behaviour of Hg in volcanic aquifers, especially regarding its chemical speciation. In order to assess the importance of mercury emissions from active volcanoes, thermal waters were sampled in the area surrounding La Solfatara, Pozzuoli bay. This is the most active zone of the Phlegraean Fields complex (coastal area north-west of Naples), with intense hydrothermal activity at present day. Studied groundwaters show total Hg (THg) concentrations range from 56 to 171 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization (WHO, 1993). We also carefully discriminated the different aqueous species of Hg in the collected water samples. Besides, original data on Hg determination in gaseous manifestations at La Solfatara crater are also reported. We measured volcanogenic mercury concentration and Hg/Stot ratio both in the volcanic plume and in fumarolic condensates in order to better constrain Hg reactivity once emitted into the atmosphere. Data on Hg/Stot reveal that there is no significant difference between Hg volcanic composition at the venting source (fumaroles) and in near-vent diluted volcanic plumes (1,6×10-5 and 1,9×10-5, respectively), suggesting that there is limited Hg chemical processing in volcanic fumarole plumes, at least on the timescales of a few seconds investigated here. Combining the mean fumaroles Hg/CO2 mass ratio of about 1.3×10-8 (molar ratio: 2.1×10-9) with the hydrothermal soil diffuse CO2 degassing of the area, the annual Hg flux from La Solfatara is estimated as 7 kg y-1 (0.007 t y-1). Current mercury emission from La Solfatara volcano represents a very small contribution to the estimated global volcanic budget for this element, and the estimated Hg flux is considerably lower than that estimated from open conduit active basaltic volcanoes.