Chemical fingerprint and impact of shipping emissions over a western Mediterranean metropolis: primary and aged contributions.

An intensive monitoring campaign was carried out in the harbor of Barcelona (Spain) to quantify the contribution of primary shipping emissions (PSE) on PM10. Chemical composition of inorganic species, as well as OC and EC, was completed, and a source apportionment analysis by Positive Matrix Factorization was conducted. Among the 6 sources extracted, two were linked to harbor emissions: dusty materials released in different areas along the harbor and fuel-oil combustion. On average, harbor emissions accounted for 31% of the PM10 mass. Since the chemical signature of PSE was not determined neither their contribution was obtained, additional approaches were followed and mainly consisted in: 1) the evaluation of V/Ni and V/Cu ratios to identify those days affected by PSE; 2) the identification of the chemical components increasing under the influence of PSE; 3) the calculation of the daily and average PSE from their experimentally-determined chemical signature and the experimental concentrations of vanadium. As a result, the contribution of PSE was estimated in 0.84 μg m(-3) (2.7% of PM10) and the residual fuel-oil combustion factor (3.6 μg m(-3), 12% of PM10) was interpreted as aged shipping emissions. The present study splits the contribution of shipping emissions into primary and aged, and highlights the importance of atmospheric mixing and aging processes in western Mediterranean atmospheres. In the case of shipping emissions, the aged products were found to be dominant with respect to the primary ones even in the vicinity of the source.