Mixing state and influence factors controlling diurnal variation of particulate nitrophenol compounds at a suburban area in northern China.

Nitrophenols have received extensive attention due to their strong light-absorbing ability in the near-ultraviolet-visible region, which could be influenced by the atmospheric processes of nitrophenols. However, our knowledge and understanding of the formation and evolution of nitrophenols are still in the nascent stages. In the present study, the mixing states of four mononitrophenol particles (i.e., nitrophenol, methynitrophenol, nitrocatechol, and methoxynitrophenol), and one nitropolycyclic aromatic hydrocarbon particles (i.e., nitronaphthol (NN)) were investigated using a single-particle aerosol mass spectrometer (SPAMS) in November 2019 in Qingdao, China. The results showed, for the first time, that mononitrophenols and NN exhibit different mixing states and diurnal variations. Four mononitrophenols were internally mixed well with each other, and with organic acids, nitrates, potassium, and naphthalene. The diurnal variation in the number fraction of mononitrophenols presented two peaks at 07:00 to 09:00 and 18:00 to 20:00, and a valley at noon. Atmospheric environmental conditions, including NO2, O3, relative humidity, and temperature, can significantly influence the diurnal variation of mononitrophenols. Multiple linear regression and random forest regression models revealed that the main factors controlling the diurnal variation of mononitrophenols were photochemical reactions during the day and aqueous-phase reactions during the night. Unlike mononitrophenols, about 62-83% of NN were internally mixed with [NH4]+ and [H(NO3)2]-, but not with organic acids and potassium. The diurnal variation of NN was also different from that of mononitrophenols, generally increased from 17:00 to 10:00 and then rapidly decreaed from 11:00 to 16:00. These results imply that NN may have sources and atmospheric processes that are different from mononitrophenols. We speculate that this is mostly controlled by photochemical reactions and mixing with [NH4]+, which may influence the diurnal variation of NN in the ambient particles; however, this requires further confirmation. These findings extend our current understanding of the atmospheric formation and evolution of nitrophenols.

Molecular characteristics, sources and transformation of water-insoluble organic matter in cloud water.

Studies have shown that water-insoluble organic matter (WIOM) accounts for a large part of the organic components in cloud water and significantly contributes to brown carbon. However, the molecular characteristics of WIOM in cloud droplets remain unclear, hampering the understanding of their climate effects. In this study, cloud water was collected at a remote mountain site in South China during the winter of 2020, and WIOM was separated by membrane filtration, extracted by methanol, and characterized using Fourier transform ion cyclotron resonance mass spectrometry coupled with an electrospray ionization source. A total of 697-1637 molecules were identified in WIOM. WIOM is characterized by lower oxidation states of carbon atoms (-1.10 âˆ¼ -0.84 in WIOM vs. -0.58 âˆ¼ -0.51 in water-soluble organic matter (WSOM) on average), higher carbon number (14.12-20.59 vs. 9.87-10.56) and lower unsaturation (double-bond equivalent 4.55-4.95 vs. 4.84-5.23) relative to WSOM. More abundant lipid-like compounds (12.2-41.9% in WIOM vs. <2% in WSOM) but less highly oxygenated compounds (<7% vs. 28.6-35.3%) exist in WIOM. More than 30% of WIOM molecules in cloud water are common with interstitial particles, implying that WIOM in cloud water may originate from aerosol activation and/or collision. Some unique molecules in WIOM in cloud water are identified as aqueous-phase oligomerization products, indicating the aqueous-phase formation of WIOM. Further analysis of the intermolecular relationship shows that WIOM has the potential to transform into WSOM by partitioning into the dissolved phase, oxidation and functionalization by heteroatom-containing groups, representing a previously unidentified pathway for WSOM formation in cloud water. The results provide new insights into the in-cloud chemistry, which would assist in the understanding of the aqueous formation and evolution of WIOM.

Filter-based absorption enhancement measurement for internally mixed black carbon particles over southern China.

The effect of the mixing state of black carbon (BC) on light absorption is of enduring interest due to its close connection to regional/global climate. Herein, we present concurrent measurements of both BC absorption enhancement (Eabs) and the chemical mixing state in southern China. Eabs was obtained by simultaneous measuring the light absorption coefficient using an aethalometer before and after being heated. The observed Eabs was categorized into non- (Eabs ≤ 1.0), slight (1.0 < Eabs ≤ 1.2), and higher (Eabs > 1.2) enhancement groups, and it was compared to the mixing state of elemental carbon (EC) particles detected by a single particle aerosol mass spectrometer (SPAMS). The individual EC-containing particles were classified into four types, including EC with sodium and potassium ion peaks (NaK-EC), long EC cluster ions (Cn+/-, n ≥ 6) with sulfate (EC-Sul1), short EC cluster ions (Cn+/-, n < 6) with sulfate (EC-Sul2), and EC with OC and sulfate (ECOC-Sul). NaK-EC and EC-Sul2 are the dominant EC types. Slight enhancement group is mainly explained by the photochemical production of ammonium sulfate and organics on EC-Sul2 during afternoon hours. In contrast, the higher Eabs is primarily attributed to the enhanced mixing of ammonium chloride with NaK-EC during morning hours, without photochemistry. The characterization of source emissions indicates that NaK-EC is likely from coal combustion and is associated with a relatively higher amount of ammonium chloride. To our knowledge, this is the first report to state that EC particles associated with ammonium chloride have a relatively higher Eabs.