Asphaltene-bearing mantle xenoliths from Hyblean diatremes, Sicily

Microscopic blebs of sulfur-bearing organic matter (OM) commonly occur between the secondary calcite grains and fibrous phyllosilicates in extensively serpentinized and carbonated mantle-derived ultramafic xenoliths from Hyblean nephelinite diatremes, Sicily, Italy. Rarely, coarse bituminous patches give the rock a blackish color. Micro Fourier transform infrared spectra (μ-FTIR) point to asphaltene-like structures in the OM, due to partially condensed aromatic rings with aliphatic tails consisting of a few C atoms. X-ray photoelectron spectroscopy (XPS) analysis indicates the occurrence of minor S═O (either sulphonyl or sulphoxide) functional groups in the OM. Solubility tests in toluene, thermo-gravimetric (TGA) and differential thermal (DTA) analyses confirm the presence of asphaltene structures. It is proposed that asphaltenes derive from the in situ aromatization (with decrease in H/C ratio) of previous light aliphatic hydrocarbons. Field evidence excludes that hydrocarbon from an external source percolated through the xenolith bearing tuff-breccia. The discriminating presence of hydrocarbon in a particular type of xenolith only and the lack of hydrocarbon in the host breccia matrix, are also inconsistent with an interaction between the ascending eruptive system and a supposed deep-seated oil reservoir. Assuming that the Hyblean unexposed basement consists of mantle ultramafics and mafic intrusive rocks having hosted an early abyssal-type hydrothermal system, one can put forward the hypothesis that the hydrocarbon production was related to hydrothermal activity in a serpentinite system. Although a bacteriogenesis or thermogenesis cannot be ruled out, the coexisting serpentine, Ni–Fe ores and hydrocarbon strongly suggest a Fischer–Tropsch-type (FTT) synthesis. Subsequent variations in the chemical and physical conditions of the system, for example an increase in the water/rock ratio, gave rise to partial oxidation and late carbonation of the serpentinite hosted hydrocarbon. Admitting an authigenic origin for most of the modal calcite (30–50% by volume) in these rocks, one can conclude as a general rule that un-carbonated serpentinites tectonically emplaced at shallow crustal levels are potential reservoir rocks (as well putative source rocks) for exploitable petroleum reserves.

Research highlights
► Petroleum asphaltenes occur in serpentinized mantle xenoliths from Sicily
► Field evidence excludes oil infiltration in the xenolith-bearing tuff-breccia
► Asphaltenes derive from in-situ aromatization of primary light hydrocarbons
► Coexisting serpentine, hydrocarbon and Ni–Fe ores point to a FTT organic synthesis
► Hydrocarbon experienced late oxidation and extensive carbonation