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External cycling regenerating nitrogen oxides (NO_x ≡ NO + NO₂) from their oxidative reservoir, NO_z, is proposed to reshape the temporal–spatial distribution of NO_xand consequently hydroxyl radical (OH), the most important oxidant in the atmosphere. Here we verify the in situ external cycling of NO_xin various environments with nitrous acid (HONO) as an intermediate based on synthesized field evidence collected onboard aircraft platform at daytime. External cycling helps to reconcile stubborn underestimation on observed ratios of HONO/NO₂and NO₂/NO_zby current chemical model schemes and rationalize atypical diurnal concentration profiles of HONO and NO₂lacking noontime valleys specially observed in low-NO_xatmospheres. Perturbation on the budget of HONO and NO_xby external cycling is also found to increase as NO_xconcentration decreases. Consequently, model underestimation of OH observations by up to 41% in low NO_xatmospheres is attributed to the omission of external cycling in models.

 

Abstract. Here we present measurement results of temporal distributions of nitrous acid (HONO) along with several chemical and meteorologicalparameters during the spring and the late summer of 2019 at Tudor Hill Marine Atmospheric Observatory in Bermuda. Large temporal variations inHONO concentration were controlled by several factors including local pollutant emissions, air mass interaction with the island, andlong-range atmospheric transport of HONO precursors. In polluted plumes emitted from local traffic, power plant, and cruise ship emissions,HONO and nitrogen oxides (NOx) existed at substantial levels (up to 278 pptv and 48 ppbv, respectively),and NOx-related reactions played dominant roles in daytime formation of HONO. The lowest concentration of HONO wasobserved in marine air, with median concentrations at ∼ 3 pptv around solar noon and < 1 pptv during thenighttime. Considerably higher levels of HONO were observed during the day in the low-NOx island-influenced air([NO2] < 1 ppbv), with a median HONO concentration of ∼ 17 pptv. HONO mixing ratios exhibiteddistinct diurnal cycles that peaked around solar noon and were lowest before sunrise, indicating the importance of photochemical processes forHONO formation. In clean marine air, NOx-related reactions contribute to ∼ 21 % of the daytime HONOsource, and the photolysis of particulate nitrate (pNO3) can account for the missing source assuming a moderate enhancement factorof 29 relative to gaseous nitric acid photolysis. In low-NOx island-influenced air, the contribution from bothNOx-related reactions and pNO3 photolysis accounts for only ∼ 48 % of the daytime HONOproduction, and the photochemical processes on surfaces of the island, such as the photolysis of nitric acid on the forest canopy, might contributesignificantly to the daytime HONO production. The concentrations of HONO, NOx, and pNO3 were lowerwhen the site was dominated by the aged marine air in the summer and were higher when the site was dominated by North American air in the spring,reflecting the effects of long-range transport on the reactive nitrogen chemistry in background marine environments.