Saharan dust aerosol over the central Mediterranean Sea: optical columnar measurements vs. aerosol load, chemical composition and marker solubility at ground level

This study aims at the determination of the mineral contribution to PM10 in the central Mediterranean Sea on the basis of 7 yr of PM10 chemical composition daily measurements made on the island of Lampedusa (35.5° N, 12.6° E). Aerosol optical depth measurements are carried out in parallel while sampling with a multi-stage impactor, and observations with an optical particle counter were performed in selected periods. Based on daily samples, the total content and soluble fraction of selected metals are used to identify and characterize the dust events. The total contribution is determined by PIXE (particle-induced X-ray emission) while the composition of the soluble fraction by ICP-AES (inductively coupled plasma atomic emission spectroscopy) after extraction with HNO3 at pH 1.5. The average PM10 concentration at Lampedusa calculated over the period June 2004–December 2010 is 31.5 μg m−3, with low interannual variability. The annual means are below the EU annual standard for PM10, but 9.9% of the total number of daily data exceed the daily threshold value established by the European Commission for PM (50 μg m−3, European Community, EC/30/1999). The Saharan dust contribution to PM10 was derived by calculating the contribution of Al, Si, Fe, Ti, non-sea-salt (nss) Ca, nssNa, and nssK oxides in samples in which PIXE data were available. Cases with crustal content exceeding the 75th percentile of the crustal oxide content distribution were identified as dust events. Using this threshold we identify 175 events; 31.6% of them (55 events) present PM10 higher than 50 μg m−3, with dust contributing by 33% on average. The annual average crustal contribution to PM10 is 5.42 μg m−3, reaching a value as high as 67.9 μg m−3, 49% of PM10, during an intense Saharan dust event. The crustal aerosol amount and contribution to PM10 shows a very small seasonal dependence; conversely, the dust columnar burden displays an evident annual cycle, with a strong summer maximum (monthly average aerosol optical depth at 495.7 nm up to 0.28 in June–August). We found that 71.3% of the events identified from optical properties over the air column display a high dust content at the ground level. Conversely, the remaining 28.7% of cases present a negligible or small impact of dust on the surface aerosol composition due to the Saharan dust transport processes over the Mediterranean that frequently occur above the marine boundary layer especially in spring, summer and early autumn. The solubility of different elements presents a large variability. In general, the solubility is lower in Saharan dust samples than for non-Saharan dust events. The solubility also displays a marked dependency on size for Saharan dust samples. Crustal markers show two relative maxima in the size range 2.1–3.3 μm and 5.8–9 μm, generally characterized by low solubility. Optical particle counter measurements present similar values of median radii for the dust size distribution. Conversely, elements mainly due to anthropic sources display a maximum in the finest fraction, and a high solubility. For instance, Fe, K, and Co present a very low solubility in the coarse fraction (8% in the size range 2.1–3.3 μm for Fe), while the finest fraction is characterized by high solubility (69% in the size range 0.4–0.7 μm for Fe). A ionic balance analysis on multi-stage impactor samples shows that exchange reactions involving anthropic acids, and crustal matter may play a significant role in cases of mixing. These reactions may affect the solubility and bioavailability of the crustal elements.