Continuous Measurement and Molecular Compositions of Atmospheric Water‐Soluble Brown Carbon in the Nearshore Marine Boundary Layer of Northern China: Secondary Formation and Influencing Factors

Abstract

Abstract Understanding the evolution of brown carbon (BrC) in the atmosphere is essential for investigating its climate effects. This study deployed a novel in‐situ BrC continuous observation system to firstly measure water‐soluble BrC absorption (Abs WS‐BrC ) in an offshore island over the Bohai Sea in the winter of 2020. The Abs WS‐BrC abundance before the cold wave (BCW) was more than twice higher than that after the cold wave (ACW). This was mainly ascribed to the substantially suppressed formation of secondary WS‐BrC (WS‐BrC sec ). Diurnal patterns of Abs WS‐BrC exhibited nighttime peaks, which derived from enhanced primary emissions and strong aqueous‐phase processes. Photochemical processes bleached daytime WS‐BrC during BCW, while daytime peaks of WS‐BrC sec emerged during ACW due to the weakened photobleaching effect. Statistical analysis indicated ambient temperature and relative humidity as well as total oxidized nitrogen (NO 2 + NO 3 − ) and reduced nitrogen (NH 4 + + NH 3 ) were the dominant factors promoting WS‐BrC sec . Moderate aerosol pH (>2.5) also facilitated the formation of WS‐BrC sec while no obvious dependences of WS‐BrC sec on gas‐particle partitioning of ammonia, O 3 , and sulfur precursors were found. At the molecular level, BrC chromophores with the identified compositions, carbon oxidation state, O/C, H/C, and absorption spectra were compared between the two periods. Characteristics of water‐soluble CHO‐ and CHON‐BrC were more of secondary origin during BCW, while primary emissions contributed significantly to BrC chromophores during ACW. This study highlights the advantage of high resolution BrC measurement in probing its dynamic evolution and influencing factors.