Shipborne measurements of ClNO2 in the Mediterranean Sea and around the Arabian Peninsula during summer

Abstract

Shipborne measurements of nitryl chloride (ClNO₂), hydrogen chloride (HCl) and sulfur dioxide (SO₂) were made during the AQABA (Air Quality and climate change in the Arabian BAsin) ship campaign in summer 2017. The dataset includes measurements over the Mediterranean Sea, the Suez Canal, the Red Sea, the Gulf of Aden, the Arabian Sea, the Gulf of Oman, and the Arabian Gulf (also known as Persian Gulf) with observed ClNO₂ mixing ratios ranging from the limit of detection to ≈600 pptv. We examined the regional variability in the generation of ClNO₂ via the uptake of dinitrogen pentoxide (N₂O₅) to Cl-containing aerosol and its importance for Cl atom generation in a marine boundary layer under the (variable) influence of emissions from shipping and the oil industry. The yield of ClNO₂ formation per NO₃ radical generated was generally low (median of ≈1 %–5 % depending on the region), mainly as a result of gas-phase loss of NO₃ dominating over heterogeneous loss of N₂O₅, the latter being disfavoured by the high temperatures found throughout the campaign. The contributions of ClNO₂ photolysis and OH-induced HCl oxidation to Cl-radical formation were derived and their relative contributions over the diel cycle compared. The results indicate that over the northern Red Sea, the Gulf of Suez, and the Gulf of Oman the formation of Cl atoms will enhance the oxidation rates of some volatile organic compounds (VOCs), especially in the early morning.