Abstract. Measurements of aerosol chemical composition made on the island of Lampedusa, south of the Sicily channel, during years [2004][2005][2006][2007][2008], are used to identify the influence of heavy fuel oil (HFO) combustion emissions on aerosol particles in the Central Mediterranean. Aerosol samples influenced by HFO are characterized by elevated Ni and V soluble fraction (about 80 % for aerosol from HFO combustion, versus about 40 % for crustal particles), high V and Ni to Si ratios, and values of V sol > 6 ng m −3 . Evidence of HFO combustion influence is found in 17 % of the daily samples. Back trajectories analysis on the selected events show that air masses prevalently come from the Sicily channel region, where an intense ship traffic occurs. This behavior suggests that single fixed sources like refineries are not the main responsible for the elevated V and Ni events, which are probably mainly due to ships emissions.V sol , Ni sol , and non-sea salt SO 2− 4 (nssSO 2− 4 ) show a marked seasonal behaviour, with an evident summer maximum. Such a pattern can be explained by several processes: (i) increased photochemical activity in summer, leading to a faster production of secondary aerosols, mainly nssSO 2− 4 , from the oxidation of SO 2 (ii) stronger marine boundary layer (MBL) stability in summer, leading to higher concentration of emitted compounds in the lowest atmospheric layers. A very intense event in spring 2008 was studied in detail, also using size segregated chemical measurements. These data show that elements arising from heavy oil combustion (V, Ni, Al, Fe) are distributed in the sub-micrometric fraction of the aerosol, and the metals are present as free metals, carbonates, oxides hydrates or labile complex with organic ligands, so that they are dissolved in mild condition (HNO 3 , pH1.5).Data suggest a characteristic nssSO 2− 4 /V ratio in the range 200-400 for HFO combustion aerosols in summer at Lampedusa. By using the value of 200 a lower limit for the HFO contribution to total sulphates is estimated. HFO combustion emissions account, as a summer average, at least for 1.2 µg m −3 , representing about 30 % of the total nssSO 2− 4 , 3.9 % of PM 10 , 8 % of PM 2.5 , and 11 % of PM1. Within the used dataset, sulphate from HFO combustion emissions reached the peak value of 6.1 µg m −3 on 26 June 2008, when it contributed by 47 % to nssSO 2− 4 , and by 15 % to PM 10 .

Abstract. This study aims to determine the mineral contribution to PM 10 in the central Mediterranean Sea, based on 7 yr of daily PM 10 samplings made on the island of Lampedusa (35.5 • N, 12.6 • E).The chemical composition of the PM 10 samples was determined by ion chromatography for the main ions, and, on selected samples, by particle-induced X-ray emission (PIXE) for the total content of crustal markers. Aerosol optical depth measurements were carried out in parallel to the PM 10 sampling.The average PM 10 concentration at Lampedusa 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 PM 10 , but 9.9 % of the total number of daily data exceeds 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 PM 10 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 in which crustal content exceeded the 75th percentile of the crustal oxide content distribution were identified as elevated dust events. Using this threshold, we obtained 175 events. Fifty-five elevated dust events (31.6 %) displayed PM 10 higher than 50 µg m −3 , with dust contributing by 33 % on average.The crustal contribution to PM 10 has an annual average value of 5.42 µg m −3 , and reaches a value as high as 67.9 µg m −3 (corresponding to 49 % of PM 10 ) during an intense Saharan dust event.The crustal content estimated from a single tracer, such as Al or Ca, is in good agreement with the one calculated as the sum of the metal oxides. Conversely, larger crustal contents are derived by applying the EU guidelines for demonstration and subtraction of exceedances in PM 10 levels due to high background of natural aerosol. The crustal aerosol amount and contribution to PM 10 showed 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 500 nm up to 0.28 in June-August). We found that 71.3 % of the dust events identified from optical properties over the atmospheric column display a high dust content at the ground level. Conversely, the remaining 28.7 % of cases present a negligible or small impact on the surface aerosol composition due to the transport processes over the Mediterranean Sea, where dust frequently travels above the marine boundary layer, especially in summer.Published by Copernicus Publications on behalf of the European Geosciences Union. M. Marconi et al.: Saharan dust aerosol over the central Mediterranean SeaBased on backward trajectories, two regions, one in Algeria-Tunisia, and one in Libya, are identified as main source areas for intense dust episodes occurring mainly in autumn and winter. Data on the bulk composition of mineral aerosol arising from these two source areas are scarce; results on characteristic ratios between ele...

Aerosol optical properties have been measured on the island of Lampedusa (35.5°N, 12.6°E) with seven-band multifilter rotating shadowband radiometers (MFRSRs) and a CE 318 Cimel sunphotometer (part of the AERONET network) since 1999. Four different MFRSRs have operated since 1999. The Cimel sunphotometer has been operational for a short period in 2000 and in 2003-2006 and 2010-present. Simultaneous determinations of the aerosol optical depth (AOD) from the two instruments were compared over a period of almost 4 years at several wavelengths between 415 and 870 nm. This is the first long-term comparison at a site strongly influenced by desert dust and marine aerosols and characterized by frequent cases of elevated AOD. The datasets show a good agreement, with MFRSR underestimating the Cimel AOD in cases with low Ångström exponent; the underestimate decreases for increasing wavelength and increases with AOD. This underestimate is attributed to the effect of aerosol forward scattering on the relatively wide field of view of the MFRSR. An empirical correction of the MFRSR data was implemented. After correction, the mean bias (MB) between MFRSR and Cimel simultaneous AOD determinations is always smaller than 0.004, and the root mean square difference is ≤0.031 at all wavelengths. The MB between MFRSR and Cimel monthly averages (for months with at least 20 days with AOD determinations) is 0.0052. Thus, by combining the MFRSR and Cimel observations, an integrated long-term series is obtained, covering the period 1999-present, with almost continuous measurements since early 2002. The long-term data show a small (nonstatistically significant) decreasing trend over the period 2002-2013, in agreement with independent observations in the Mediterranean. The integrated Lampedusa dataset will be used for aerosol climatological studies and for verification of satellite observations and model analyses.

Abstract. The Mediterranean Basin atmosphere is influenced by both strong natural and anthropogenic aerosol emissions and is also subject to important climatic forcings. Several programs have addressed the study of the Mediterranean basin; nevertheless important pieces of information are still missing. In this framework, PM10 samples were collected on a daily basis on the island of Lampedusa (35.5° N, 12.6° E; 45 m a.s.l.), which is far from continental pollution sources (the nearest coast, in Tunisia, is more than 100 km away). After mass gravimetric measurements, different portions of the samples were analyzed to determine the ionic content by ion chromatography (IC), the soluble metals by inductively coupled plasma atomic emission spectrometry (ICP-AES), and the total (soluble + insoluble) elemental composition by particle-induced x-ray emission (PIXE). Data from 2007 and 2008 are used in this study. The Positive Matrix Factorization (PMF) model was applied to the 2-year long data set of PM10 mass concentration and chemical composition to assess the aerosol sources affecting the central Mediterranean basin. Seven sources were resolved: sea salt, mineral dust, biogenic emissions, primary particulate ship emissions, secondary sulfate, secondary nitrate, and combustion emissions. Source contributions to the total PM10 mass were estimated to be about 40 % for sea salt, around 25 % for mineral dust, 10 % each for secondary nitrate and secondary sulfate, and 5 % each for primary particulate ship emissions, biogenic emissions, and combustion emissions. Large variations in absolute and relative contributions are found and appear to depend on the season and on transport episodes. In addition, the secondary sulfate due to ship emissions was estimated and found to contribute by about one-third to the total sulfate mass. Results for the sea-salt and mineral dust sources were compared with estimates of the same contributions obtained from independent approaches, leading to an estimate of the water content bound to the sea salt in the marine source.

Abstract. Particulate matter with aerodynamic diameters lower than 10 µm, (PM 10 ) 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 PM 10 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 ng m −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 PM 10 . The estimated minimum ship emission contributions to PM 10 were 2.0 µg m −3 at Lampedusa and 3.0 µg m −3 at Capo Granitola, corresponding with 11 and 8.6 % of PM 10 , respectively.