Reactive nitrogen around the Arabian Peninsula and in the Mediterranean Sea during the 2017 AQABA ship campaign

Abstract

Abstract. We present ship-borne measurements of NOx (≡ NO + NO2) and NOy (≡ NOx + gas- and particle-phase organic and inorganic oxides of nitrogen) in summer 2017 as part of the expedition Air Quality and climate change in the Arabian Basin (AQABA). The NOx and NOz (≡ NOy–NOx) measurements, made with a thermal dissociation cavity-ringdown-spectrometer (TD-CRDS), were used to examine the chemical mechanisms involved in the processing of primary NOx emissions and their influence on the NOy budget in chemically distinct marine environments, including the Mediterranean Sea, the Red Sea, and the Arabian Gulf which were influenced to varying extents by emissions from shipping and oil and gas production. In all regions, we find that NOx is strongly connected to ship emissions, both via direct emission of NO and via the formation of HONO and its subsequent photolytic conversion to NO. Mean NO2 lifetimes were 3.9 hours in the Mediterranean Sea, 4.0 hours in the Arabian Gulf and 5.0 hours in the Red Sea area. The cumulative loss of NO2 during the night (reaction with O3) was more important than daytime losses (reaction with OH) over the Arabian Gulf (by a factor 2.8) and over the Red Sea (factor 2.9), whereas over the Mediterranean Sea, where OH levels were high, daytime losses dominated (factor 2.5). Regional ozone production efficiencies (OPE) ranged from 10.5 ± 0.9 to 19.1 ± 1.1. This metric quantifies the relative strength of photochemical O3 production from NOx, compared to the competing sequestering into NOz species. The largest values were found over the Arabian Gulf, consistent with high levels of O3 found in that region (10–90 percentiles range: 23–108 ppbv). The fractional contribution of individual NOz species to NOy exhibited a large regional variability, with HNO3 generally the dominant component (on average 33 % of NOy) with significant contributions from organic nitrates (11 %) and particulate nitrates in the PM1 size range (8 %).

Comment on acp-2021-42

“…In some (especially marine) environments (Osthoff et al, 2008;Kercher et al, 2009), loss of N2O5 to particles can result in formation of ClNO2 (R18) which, via photolysis, reforms NO2 the next day. The above reactions illustrate that NOx and VOCs provide the catalyst and fuel for photochemical ozone formation, the efficiency of which is determined by the competition between photolysis of NO2 to ozone and its conversion to NOz (Day et al, 2003;Wild et al, 2014;Wild et al, 2016;Womack et al, 2017). Modelling studies have identified the Arabian Gulf as a hotspot for O3 pollution and photochemical smog, with O3 mixing ratios exceeding 100 ppbv (Lelieveld et al, 2009).…”