Mario Paolieri

Arsenic-bearing calcite in natural travertines: evidence from sequential extraction, μXAS, and μXRF.

Recent studies demonstrated that synthetic calcite may host considerable amounts of arsenic (As). In this paper, the concentration of As in natural calcite was determined using two novel, specifically designed, sequential extraction procedures. In addition, the oxidation state of As and its distribution between calcite and coexisting Fe-oxyhydroxides was unravelled by μXRF elemental mapping and As K-edge μXAS spectroscopy. Our results conclusively demonstrate that arsenic can be found in natural calcite up to 2 orders of magnitude over the normal crustal As abundances. Because of the large diffusion of calcite in the environment, this phase may exert an important control on As geochemistry, mobility, and bioavailability.

Metallogeny, exploitation and environmental impact of the Mt. Amiata mercury ore district (Southern Tuscany, Italy)

The Mt. Amiata mining district (Southern Tuscany, Italy) is a world class Hg district, with a cumulate production of more than 100,000 tonnes of Hg, mostly occurring between 1870 and 1980. The Hg mineralization at Mt. Amiata is younger than 0.3 Ma, and is directly related to shallow hydrothermal systems similar to presentday geothermal fields of the region. There is likely a continuum of Hg deposition to present day, because Hg emission from geothermal power plants is on-going. In this sense, the Mt. Amiata deposits present some analogies with hot-spring type deposits of western USA, although an ore deposit model for the district has not been established. Specifically, the source of Hg remains highly speculative. The mineralizing hydrothermal fluids are of low temperature, and of essentially meteoric origin. Recent results by our research group indicate that, 30 years after mine closure, the environmental effects of Hg contamination related to mining are still recorded by the ecosystem, namely on waterways of the Paglia and Tiber River basins. In particular, the close spatial connection between the town of Abbadia San Salvatore, the Hg mine within its immediate neighborhood, and the drainage catchment of the Paglia River has an influence also on Hg speciation, transported mainly in the particulate form by the river system. The extent of Hg contamination has been identified at least 100 km from Abbadia San Salvatore along the Paglia-Tiber River system. Estimated annual Hg mass loads transported by the Paglia River to the Tiber River were about 11 kg yr-1. However, there is evidence that flood events may enhance Hg mobilization in the Paglia River basin, increasing Hg concentrations in stream sediment. The high methyl-Hg/Hg ratio in water in this area is an additional factor of great concern due to the potential harmful effects on human and wildlife health. Results of our studies indicate that the Mt. Amiata region is at present a source of Hg of remarkable environmental concern at the local, regional (Tiber River), and Mediterranean scales. Ongoing studies are aimed to a more detailed quantification of the Hg mass load input to the Mediterranean Sea, and to unravel the processes concerning Hg transport and fluid dynamics.