Chlorine activation in marine air: Insights from chemical budgets of
molecular chlorine and hypochlorous acid
Abstract
Chlorine chemistry considerably affects air quality and climate in
marine environments. Nitrogen oxides (NOx), emitted by ocean-going
vessels, react with sea salt chloride to generate reactive chlorine
species. However, the exact mechanisms and chemical budget of chlorine
remain poorly understood. In this study, we explore chlorine activation
through field observations in Hong Kong, complemented by box modeling.
Over the two-week measurement period, the summer monsoon introduced
abundant NOx, producing molecular chlorine (Cl2, 0.64 ± 0.69 ppt) and
hypochlorous acid (HOCl, 8.9 ± 5.1 ppt). Daytime Cl2 production was
attributable to nitrate (NO3-) photolysis and the uptake of hydroxyl
radicals (OH·) on aerosols. A budget analysis using the box model
revealed that the production rate of HOCl, primarily driven by chlorine
nitrate (ClONO2) hydrolysis, was substantially lower than its loss rate.
This discrepancy indicates either uncertainties in known HOCl sources or
a missing source of chlorine atoms (Cl·). We examined the potential
precursors of Cl· by incorporating emerging reactive chlorine species,
such as, trichloramine (NCl3) and iodine chloride (ICl), into the model.
However, the inclusion of NCl3 caused an overestimation of ambient Cl2
levels, while adding ICl led to excessive ozone (O3) depletion.
Incorporating an unknown Cl· source (equivalent to ~46.0
ppt Cl2) remarkably enhanced atmospheric oxidation capacity, increasing
daytime OH· levels by 12.8% and net ozone production by 35.7% while
decreasing the mercury (Hg) lifetime by a factor of 3. These findings
highlight the incomplete understanding of chlorine chemistry and suggest
the existence of unidentified Cl· sources in coastal environments.