Polycyclic aromatic hydrocarbons (PAHs) and their alkylated-, nitro- and oxy-derivatives in the atmosphere over the Mediterranean and Middle East seas

Abstract. Polycyclic aromatic hydrocarbons (PAHs), their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants has hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑27PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phase, were 2.85 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as Persian Gulf). 1,4 Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2 nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-NFLT, which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-nitrofluoranthene (2-NFLT) and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, also benz(a)anthracene-7,12-dione and 1,4-O2NAP had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).