Mineral paragenesis and fluid inclusion constraints on the Torre di Rio skarn, Island of Elba

The historical iron ore deposits of eastern Elba held great importance for the region and were its primary source of iron. The Torre di Rio skarn, despite its easily accessible outcrop and vicinity to the larger Rio Marina deposit, was never properly characterized. The results of petrographic and microthermometric study presented in this work provide new constraints on the Torre di Rio skarn. Mineral assemblage of ilvaite, calcite, quartz, iron oxides and sulphides combined with textural evidence indicate that Torre di Rio skarn does not fit into classical skarn model. The complex paragenetic sequence and overlapping of skarn and ore mineralogy is result of fast formation at relatively low temperatures evidenced by the silicon enrichment and pervasive nature of limonite alteration. Hematite-magnetite textural relationship points to boundary conditions of the ore fluid in terms of oxygen fugacity. Eutectic temperatures range from -16 to -33 °C indicating complex fluids. Calculated salinities range from 1.4 to 17.4 wt% NaCleq suggesting multiple fluids of different compositions. Total homogenization temperatures vary from 330 °C to 150 °C with both homogeneously and heterogeneously trapped FIAs. Ore deposition is concentrated where skarn formation was controlled primarily by phase separation during boiling. Calculated fluid pressure at boiling suggest shallow formation depth of a few hundred meters and constrains maximum temperature of ore deposition to c. 260 °C. This work suggest that relatively low salinities of fluid inclusions could indicate dominant marine origin of the hydrothermal fluids that were activated by the Porto Azzurro pluton emplacement and that scavenged Fe from sedimentary host rocks. During boiling at shallow depths and decreasing iron solubility, these fluids started precipitating Fe-minerals at Torre di Rio mineralization. Mixing with batches of more saline fluids at around 236 °C increased salinity abruptly and marked the end of ore deposition.

Anaerobic oxidation of ethanol over spinel mixed oxides: the first step in the steam-iron process for H2 production

The future hydrogen demand is expected to increase, both in existing industries (including upgrading of fossil fuels or ammonia production) and in new technologies, like fuel cells. Nowadays, hydrogen is obtained predominantly by steam reforming of methane, but it is well known that hydrocarbon based routes result in environmental problems and besides the market is dependent on the availability of this finite resource which is suffering of rapid depletion. Therefore, alternative processes using renewable sources like wind, solar energy and biomass, are now being considered for the production of hydrogen. One of those alternative methods is the so-called “steam-iron process” which consists in the reduction of a metal-oxide by hydrogen-containing feedstock, like ethanol for instance, and then the reduced material is reoxidized with water to produce “clean” hydrogen (water splitting). This kind of thermochemical cycles have been studied before but currently some important facts like the development of more active catalysts, the flexibility of the feedstock (including renewable bio-alcohols) and the fact that the purification of hydrogen could be avoided, have significantly increased the interest for this research topic. With the aim of increasing the understanding of the reactions that govern the steam-iron route to produce hydrogen, it is necessary to go into the molecular level. Spectroscopic methods are an important tool to extract information that could help in the development of more efficient materials and processes. In this research, ethanol was chosen as a reducing fuel and the main goal was to study its interaction with different catalysts having similar structure (spinels), to make a correlation with the composition and the mechanism of the anaerobic oxidation of the ethanol which is the first step of the steam-iron cycle. To accomplish this, diffuse reflectance spectroscopy (DRIFTS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Furthermore, mass spectrometry was used to monitor the desorbed products. The set of studied materials include Cu, Co and Ni ferrites which were also characterized by means of X-ray diffraction, surface area measurements, Raman spectroscopy, and temperature programmed reduction.