Multi O- and S-isotopes as tracers of black crusts formation under volcanic and non-volcanic atmospheric conditions in Sicily (Italy).

The deterioration of monument or building stone materials is mostly due to the growth of black crusts that cause blackening and disaggregation of the exposed surface. This study reports on new oxygen (δO, δO and ΔO) and sulphur (δS, δS, δS, ΔS and ΔS) isotopic analyses of black crust sulphates formed on building stones in Sicily (Southern Italy). The measurements are used to identify the possible influence of volcanic emissions on black crust formation. Black crusts were mostly sampled on carbonate stone substrate in different locations subject to various sulphur emission sources (marine, anthropogenic and volcanic). Unlike atmospheric sulphate aerosols that mostly exhibit ΔS > 0‰, here most of the analysed black crust sulphates show negative ΔS. This confirms that black crust sulphates do not result from deposition of sulphate aerosols or of rainwater but mostly from the oxidation of dry deposited SO onto the stone substrate. The δS and δO values indicate that most of black crust sulphate originates from anthropogenic activities. ΔO values are found to be related to the sampling location. The largest O-anomalies (up to ~4‰) are measured in black crust from areas highly influenced by volcanic emissions, which demonstrates the strong involvement of ozone in the formation of black crusts in volcanically influenced environments.