Nitrous acid in marine boundary layer over eastern Bohai Sea, China: Characteristics, sources, and implications

Nitrous acid (HONO) serves as a key source of hydroxyl radicals and plays important roles in atmospheric photochemistry. In this study, gaseous HONO and related species and parameters were measured in autumn of 2016 at a marine background site on Tuoji Island in eastern Bohai Sea, China. The HONO concentration in marine boundary layer (MBL) was on average 0.20 ± 0.20 ppbv (average ± standard deviation) with a maximum hourly value of 1.38 ppbv. It exhibited distinct diurnal variations featuring with elevated concentrations in the late night and frequent concentration peaks in the early afternoon. During nighttime, the HONO was produced at a fast rate with the NO₂-HONO conversion rate ranging from 0.006 to 0.036 h^-1. The fast HONO production and the strong dependence of temperature implied the enhancement of nocturnal HONO formation caused by air-sea interactions at high temperature. At daytime, HONO concentration peaks were frequently observed between 13:00-15:00. The observed daytime HONO concentrations were substantially higher than those predicted in the photostationary state in conditions of intensive solar radiation and high temperature. Strong or good correlations between the missing HONO production rate and temperature or photolysis frequency suggest a potential source of HONO from the photochemical conversions of nitrogen-containing compounds in sea microlayer. The source intensity strengthened quickly when the temperature was high. The abnormally high concentrations of daytime HONO contributed a considerable fraction to the primary OH radicals in the MBL.