Surface Nitrate Enrichment and Enhanced HONO Production from Ionic Surfactant Aggregation at the Aqueous-Air Interface

Significant discrepancies persist between field observations and model simulations regarding the strength of marine-derived HONO sources, underscoring the urgency to resolve unidentified HONO sources. In this study, sodium dodecyl sulfate (SDS) was chosen as a proxy for marine surfactants to investigate its impact on aqueous nitrate photolysis for the first time. Remarkable increases in HONO and NO₂ production rates by factors of 3.3 and 5.6, respectively, along with a 1.9-fold rise in NO₂^- concentration, were observed at a very low SDS concentration of 0.01 mM, strongly illustrating the promoting effect on nitrate photolysis. Furthermore, at an SDS concentration of 2 mM, intriguingly aligned with the critical micelle concentration, there was an additional 41.7% increase in HONO production rates. Vertically resolved Raman measurements indicated that SDS anions at the aqueous-air interface attracted NO₃^- closer to the aqueous surfaces, increasing the amount of incompletely solvated surface nitrate. Importantly, the anionic surfactant exhibited a greater promoting effect on HONO production compared to other typical nitrate photochemistry systems with the addition of a marine dissolved organic matter proxy, halogen, photosensitizer, or OH scavenger. These findings offer new insights into marine-derived HONO sources and should be considered in model simulations concerning the budgets of NO_x, OH, and O₃.