Despite their crucial roles in health and climate concerns, the gas-particle partitioning of carbonyl compounds is poorly characterized in the ambient atmosphere. In this study, we investigate their partitioning by simultaneously measuring six carbonyl compounds (formaldehyde, acetaldehyde, acetone, propionaldehyde, glyoxal, and methylglyoxal) in the gas and particle phase at an urban site in Beijing. The field-derived partitioning coefficients ( K) are in the range of 10-10 m μg, and the corresponding effective Henry's law coefficients ( K) should be 10-10 M atm. The Pankow's absorptive partitioning theory and Henry's law both significantly underestimate concentrations of particle-phase carbonyl compounds (10-10 times and >10 times, respectively). The observed "salting-in" effects only partially explain the enhanced partitioning to particles, which is approximately 1 order of magnitude. The measured K values are higher at low relative humidity, and the overall effective vapor pressure of these carbonyl species are lower than their hydrates, indicating that carbonyl oligomers potentially formed in highly concentrated particle phase. The reaction kinetics of oligomer formation should be included if applying Henry's law to low-to-moderate relative humidity, and the high partitioning coefficients observed need to be proved by further field and laboratory studies. These findings provide deeper insights into the formation of carbonyl secondary organic aerosols in the ambient atmosphere.

This report focuses on studying generation and/or evolution of sea-salt aerosols (SSA) on basis of measurements in the Northwest Pacific Ocean (NWPO), the marginal seas of China, at sea-beach sites and a semi-urban coastal site in 2012–2015. From measurements in the NWPO, we obtained the smallest generation function of the super-micron SSA mass ([MSSA]) by the local wind comparing to those previously reported. Vessel-caused wave-breaking was found to greatly enhance generation of SSA and increase [MSSA], which was subject to non-natural generation of SSA. However, naturally enhanced generation of SSA was indeed observed in the marginal seas and at the sea-beach site. The two enhancement mechanisms may explain the difference among this and previous studies. Size distributions of super-micron SSA exhibited two modes, i.e., 1–2 μm mode and ~5 μm mode. The 1–2 μm mode of SSA was enhanced more and comparable to the ~5 μm mode under the wind speed >7 m/s. However, the smaller mode SSA was largely reduced from open oceans to sea-beach sites with reducing wind speed. The two super-micron modes were comparable again at a semi-urban coastal site, suggesting that the smaller super-micron mode SSA may play more important roles in atmospheres.

Abstract. Hydrogen peroxide (H2O2) is a vital oxidant in the atmosphere and plays critical roles in the oxidation chemistry of both liquid and aerosol phases. The partitioning of H2O2 between the gas and liquid phases, or the aerosol phase, could affect its abundance in these condensed phases and eventually the formation of secondary components. However, the partitioning processes of H2O2 in gas-liquid and gas-aerosol phases are still unclear, especially in the ambient atmosphere. In this study, field observations of gas-, liquid-, and aerosol-phase H2O2 were carried out in the urban atmosphere of Beijing during the summer and winter of 2018. The effective field-derived mean value of Henry's law constant (HAm, 2.1×105 M atm−1) was 2.5 times of the theoretical value in pure water (HAt, 8.4×104 M atm−1) at 298±2 K. The effective derived gas-aerosol partitioning coefficient (KPm, 3.8×10-3 m3 µg−1) was 4 orders of magnitude higher on average than the theoretical value (KPt, 2.8×10-7 m3 µg−1) at 270±4 K. Beyond following Henry's law or Pankow's absorptive partitioning theory, the partitioning of H2O2 in the gas-liquid and gas-aerosol phases in the ambient atmosphere was also influenced by certain physical and chemical reactions. The average concentration of liquid-phase H2O2 in rainwater during summer was 44.12±26.49 µM. In 69 % of the collected rain samples, the measured level of H2O2 was greater than the predicted value in pure water calculated by Henry's law. In these samples, 41 % of the measured H2O2 was from gas-phase partitioning, while most of the rest may be from residual H2O2 in raindrops. In winter, the level of aerosol-phase H2O2 was 0.093±0.085 ng µg−1, which was much higher than the predicted value based on Pankow's absorptive partitioning theory. The contribution of partitioning of the gas-phase H2O2 to the aerosol-phase H2O2 formation was negligible. The decomposition/hydrolysis rate of aerosol-phase organic peroxides could account for 11 %–74 % of the consumption rate of aerosol-phase H2O2, and the value depended on the composition of organic peroxides in the aerosol particles. Furthermore, the heterogeneous uptake of HO2 and H2O2 on aerosols contributed to 22 % and 2 % of the aerosol-phase H2O2 consumption, respectively.

No abstract

No abstract

No abstract

No abstract

No abstract