ABSTRACT
The pollution burdens and compositions of atmospheric brown carbon (BrC) that determine their impacts on climate-health-ecosystems have not been well studied, particularly in some mega-economic coastal areas. Herein, atmospheric BrC samples synchronously collected from urban Shanghai (SH) and Huaniao Island (HNI) in the East China Sea during winter were characterized through ultrahigh-performance liquid chromatography-diode array detector-high resolution mass spectrometry (UHPLC-DAD-HRMS). The three polarity-dependent BrC fractions exhibited significant differences in both light absorption and chromophore composition. The average light absorption coefficients of BrC subfractions at 365 nm in SH were 2.6-3.7 times higher than those in HNI. The water-insoluble BrC (WIS-BrC) and humic-likes BrC (HULIS-BrC) dominated the total BrC absorption in SH (45 ± 7 %) and HNI (43 ± 6 %), respectively. Compared with SH, the higher O/Cw, lower molecule conjugation degree, and reduced mass absorption efficiency at 365 nm (MAE365) in HNI imply a potential bleaching mechanism during the transportation oxidation process. Thousands of BrC chromophores were detected at both sites. >20 major chromophores with strong absorption were unambiguously identified in HULIS-BrC and accounted for â¼40 % of the HULIS light absorption at 365 nm at both sites. These chromophores in SH HULIS-BrC featured oxygenated aromatics and nitroaromatics, while alkyl benzenesulfonic acids with emissions from cargo ships were found in HNI HULIS-BrC. Moreover, 22 major chromophores identified in WIS-BrC included alkaloids, polyaromatic hydrocarbons (PAHs), and carbonyl oxygenated PAHs, contributing 39 % and 49 % of the WIS-BrC light absorption at 365 nm in SH and HNI, respectively. Ascertaining the molecular-specific optical properties of BrC chromophores over the mega-economic coastal area is helpful for the predictive understanding of the sources and evolution of BrC, as well as its atmospheric behavior from land to sea.
ABSTRACT
Reduced nitrogen-containing organic compounds (NOCs) in aerosols play a crucial role in altering their light-absorption properties, thereby impacting regional haze and climate. Due to the low concentration levels of individual NOCs in the air, the utilization of accurate detection and quantification technologies becomes essential. For the first time, this study investigated the diurnal variation, chemical characteristics, and potential formation pathways of NOCs in urban ambient aerosols in Shanghai using a versatile aerosol concentration enrichment system (VACES) coupled with HPLC-Q-TOF-MS. The results showed that NOCs accounted over 60% of identified components of urban organic aerosols, with O/N < 3 compounds being the major contributors (>70%). The predominance of the positive ionization mode suggested the prevalence of reduced NOCs. Higher relative intensities and number fractions of NOCs were observed during nighttime, while CHO compounds showed an opposite trend. Notably, a positive correlation between the intensity of NOCs and ammonium during the nighttime was observed, suggesting that the reaction of ammonium to form imines may be a potential pathway for the formation of reduced NOCs during the nighttime. Seven prevalent types of reduced NOCs in autumn and winter were identified and characterized by an enrichment of CH2 long-chain homologues. These NOCs included alkyl, cyclic, and aromatic amides in CHON compounds, as well as heterocyclic or cyclic amines and aniline homologue series in CHN compounds, which were associated with anthropogenic activities and may be capable of forming light-absorbing chromophores or posing harm to human health. The findings highlight the significant contributions of both primary emissions and ammonium chemistry, particularly amination processes, to the pollution of reduced NOCs in Shanghai's atmosphere.
