Hydrogen content in clinopyroxene phenocrysts from Salina mafic lavas (Aeolian arc,Italy)

Clinopyroxene phenocrysts from the mafic calc-alkaline lavas of Salina (Aeolian arc, southern Tyrrhenian Sea, Italy) have been analysed to determine the hydrogen content and iron oxidation state of this early crystallized phase. The volcanic activity of Salina, starting at 168 ka and developed in several centres up to 24 ka, was dominated by calc-alkaline and high-K calc-alkaline basalts and andesites, with minor dacites and rhyolites. The presence of OH vibrational bands was detected in the IR spectra of clinopyroxenes phenocrysts from Corvo, Rivi-Capo (168–87 ka), Fossa delle Felci (108–59 ka) and Monte dei Porri (57 ka) eruptions. Corvo-Rivi-Capo basalts have clinopyroxenes with the lowest water contents 75–97 ppm H₂O by weight, whereas an increase in the hydrogen contents of clinopyroxenes from Fossa delle Felci centre, with 171–286 ppm H₂O by weight, and Monte dei Porri with 343–390 ppm H₂O by weight, was observed. Mössbauer spectroscopy showed only a limited variation on the Fe³⁺/Fe_tot ratio of the studied samples, and a very similar atomic Fe³⁺ content (0.042–0.047 a.p.f.u.) suggesting that only minor variation on fO₂ occurred during the crystallization of these clinopyroxenes. The water content of parental melts, calculated by applying an ^IVAl-dependent partition coefficient to the measured hydrogen contents of clinopyroxenes, is 0.4–0.8 wt% of water in melt for the Rivi-Capo-Corvo basalts, 0.5–3.7 wt% water in melt for Fossa delle Felci lavas and 1.6–2.6 wt% of water in melt for Monte dei Porri lavas. An increase in the maximum hydrogen contents of clinopyroxenes can be recognized during the evolution of the Salina volcano, with the highest hydrogen content measured in clinopyroxenes from Monte dei Porri where the eruptions were characterized by a high degree of explosivity, suggesting a key role of volatiles.