Constraining the ship contribution to the aerosol of the central Mediterranean

Particulate matter with aerodynamic diameters lower than 10 mu m, (PM10) aerosol samples were collected during summer 2013 within the framework of the Chemistry and Aerosol Mediterranean Experiment (ChArMEx) at two sites located north (Capo Granitola) and south (Lampedusa Island), respectively, of the main Mediterranean shipping route in the Straight of Sicily. The PM10 samples were collected with 12 h time resolutions at both sites. Selected metals, main anions, cations and elemental and organic carbon were determined. The evolution of soluble V and Ni concentrations (typical markers of heavy fuel oil combustion) was related to meteorology and ship traffic intensity in the Straight of Sicily, using a high-resolution regional model for calculation of back trajectories. Elevated concentration of V and Ni at Capo Granitola and Lampedusa are found to correspond with air masses from the Straight of Sicily and coincidences between trajectories and positions of large ships; the vertical structure of the planetary boundary layer also appears to play a role, with high V values associated with strong inversions and a stable boundary layer. The V concentration was generally lower at Lampedusa than at Capo Granitola V, where it reached a peak value of 40 ngm(-3). Concentrations of rare earth elements (REEs), La and Ce in particular, were used to identify possible contributions from refineries, whose emissions are also characterized by elevated V and Ni amounts; refinery emissions are expected to display high La / Ce and La / V ratios due to the use of La in the fluid catalytic converter systems. In general, low La / Ce and La / V ratios were observed in the PM samples. The combination of the analyses based on chemical markers, air mass trajectories and ship routes allows us to unambiguously identify the large role of the ship source in the Straight of Sicily. Based on the sampled aerosols, ratios of the main aerosol species arising from ship emission with respect to V were estimated with the aim of deriving a lower limit for the total ship contribution to PM10. The estimated minimum ship emission contributions to PM10 were 2.0 mu gm(-3) at Lampedusa and 3.0 mu gm(-3) at Capo Granitola, corresponding with 11 and 8.6% of PM10, respectively.