Sources and mixing state of summertime background aerosol in the north-western Mediterranean basin

Abstract

An aerosol time-of-flight mass spectrometer (ATOFMS) was employed to provide real-time single particle mixing state and thereby source information for aerosols impacting the western Mediterranean basin during the ChArMEx-ADRIMED and SAF-MED campaigns in summer 2013. The ATOFMS measurements were made at a ground-based remote site on the northern tip of Corsica. Twenty-seven distinct ATOFMS particle classes were identified and subsequently grouped into eight general categories: EC-rich (elemental carbon), K-rich, Na-rich, amines, OC-rich (organic carbon), V-rich, Fe-rich and Ca-rich particles. Mass concentrations were reconstructed for the ATOFMS particle classes and found to be in good agreement with other co-located quantitative measurements (PM1, black carbon (BC), organic carbon, sulfate mass and ammonium mass). Total ATOFMS reconstructed mass (PM2. 5) accounted for 70–90 % of measured PM10 mass and was comprised of regionally transported fossil fuel (EC-rich) and biomass burning (K-rich) particles. The accumulation of these transported particles was favoured by repeated and extended periods of air mass stagnation over the western Mediterranean during the sampling campaigns. The single particle mass spectra proved to be valuable source markers, allowing the identification of fossil fuel and biomass burning combustion sources, and was therefore highly complementary to quantitative measurements made by Particle into Liquid Sampler ion chromatography (PILS-IC) and an aerosol chemical speciation monitor (ACSM), which have demonstrated that PM1 and PM10 were comprised predominantly of sulfate, ammonium and OC. Good temporal agreement was observed between ATOFMS EC-rich and K-rich particle mass concentrations and combined mass concentrations of BC, sulfate, ammonium and low volatility oxygenated organic aerosol (LV-OOA). This combined information suggests that combustion of fossil fuels and biomass produced primary EC- and OC-containing particles, which then accumulated ammonium, sulfate and alkylamines during regional transport. Three other sources were also identified: local biomass burning, marine and shipping. Local combustion particles (emitted in Corsica) contributed little to PM2. 5 particle number and mass concentrations but were easily distinguished from regional combustion particles. Marine emissions comprised fresh and aged sea salt: the former was detected mostly during a 5-day event during which it accounted for 50–80 % of sea salt aerosol mass, while the latter was detected throughout the sampling period. Dust was not efficiently detected by the ATOFMS, and support measurements showed that it was mainly in the PM2. 5–10 fraction. Shipping particles, identified using markers for heavy fuel oil combustion, were associated with regional emissions and represented only a small fraction of PM2. 5 particle number and mass concentration at the site.