Elucidating the Mechanism on the Transition-Metal Ion-Synergetic-Catalyzed Oxidation of SO2 with Implications for Sulfate Formation in Beijing Haze.

Currently, atmospheric sulfate aerosols cannot be predicted reliably by numerical models because the pathways and kinetics of sulfate formation are unclear. Here, we systematically investigated the synergetic catalyzing role of transition-metal ions (TMIs, Fe3+/Mn2+) in the oxidation of SO2 by O2 on aerosols using chamber experiments. Our results showed that the synergetic effect of TMIs is critically dependent on aerosol pH due to the solubility of Fe(III) species sensitive to the aqueous phase acidity, which is effective only under pH < 3 conditions. The sulfate formation rate on aerosols is 2 orders of magnitude larger than that in bulk solution and increases significantly on smaller aerosols, suggesting that such a synergetic-catalyzed oxidation occurs on the aerosol surface. The kinetic reaction rate can be described as R = k*[H+]-2.95[Mn(II)][Fe(III)][S(IV)] (pH ≤ 3.0). We found that TMI-synergetic-catalyzed oxidation is the dominant pathway of sulfate formation in Beijing when haze particles are very acidic, while heterogeneous oxidation of SO2 by NO2 is the most important pathway when haze particles are weakly acidic. Our work for the first time clarified the role and kinetics of TMI-synergetic-catalyzed oxidation of SO2 by O2 in haze periods, which can be parameterized into models for future studies of sulfate formation.

Secondary Formation of Atmospheric Brown Carbon in China Haze: Implication for an Enhancing Role of Ammonia.

Optical characteristics and molecular compositions of brown carbon (BrC) were investigated during winter 2019 at a rural site of China with a focus on nitro-aromatic compounds (NACs) and imidazoles (IMs). The abundance of gaseous nitrophenols relative to CO during the campaign maximized at noontime, being similar to O3, while the particulate NACs during the haze periods strongly correlated with toluene and NO2, suggesting that NACs in the region are largely formed from the gas-phase photooxidation. Strong correlations of particulate IMs in the dry haze periods with the mass ratio of EC/PM2.5 and the concentration of levoglucosan were observed, indicating that IMs during the dry events are largely derived from biomass burning emissions. However, an increase in IMs with the increasing aerosol liquid water content and pH was observed in the humid haze events, along with much lower abundances of levoglucosan and K+ relative to PM2.5, suggesting that IMs were mostly formed from aqueous reactions in the humid haze periods. These IMs exponentially increased with an increasing NH3 owing to an aqueous reaction of carbonyls with free ammonia. Our findings for the first time revealed an enhancing effect of ammonia on BrC formation in China, especially in humid haze periods.

Effects of NO2 and RH on secondary organic aerosol formation and light absorption from OH oxidation of ο-xylene.

Ο-xylene is an important aromatic volatile organic compound (VOC) in the atmosphere over urban areas. In this work, the effect of nitrogen dioxide (NO2) concentration and relative humidity (RH) on the mass concentration of secondary organic aerosols (SOA) formed from ο-xylene OH oxidization was investigated in a photooxidation chamber. The ο-xylene SOA mass concentration increased from 54.2 µg m-3 to 127.2 µg m-3 during dry conditions, but decreased from 177.7 µg m-3 to 146.5 µg m-3 during high RH conditions when the initial NO2 concentration increased form 0 ppbv to about 900 ppbv. An increase in the ratio of [NO3-]/[Org] and a decrease in the oxidation state of carbon (OSC) of SOA suggested that acid-catalyzed heterogeneous reaction was responsible for enhancing SOA formation with increasing NO2 concentrations in dry conditions. In contrast, in humid conditions, the high molecular diffusion capacity of SOA could promote the reactivity of OH towards the interior of SOA, and the enhancement of nitrous acid (HONO) formation under high NO2 conditions could promote the SOA aging processes and be responsible for the decreasing trend of SOA formation with NO2. Light absorption by SOA was also measured, and both NO2 and RH enhanced the mass absorption coefficient (MACλ = 365 nm) value for the optical properties of ο-xylene SOA. The highest MACλ = 365 nm value of ο-xylene SOA was 0.89 m2 g-1, observed during humid conditions with an initial NO2 concentration of 862 ppbv, which was 3.9 times higher than in the experiment conducted in the absence of NO2 under dry conditions. The formation of nitrogen-containing organic compounds (NOCs) and humic-like substances (HULIS) were responsible for the increased MACλ = 365 nm values of ο-xylene derived SOA. This study provides new insight into the effect of NO2 on SOA formation through the change in ο-xylene photooxidation under different RH conditions, and the complex effect of multiple environmental factors on SOA formation was also important and should not be ignored.

Smog chamber simulation on heterogeneous reaction of O3 and NO2 on black carbon under various relative humidity conditions.

In this study, heterogeneous formation of nitrate from O3 reaction with NO2 on black carbon (BC) and KCl-treated BC surface in the presence of NH3 was simulated under 30-90% RH conditions by using a laboratory smog chamber. We found that O3 and NO2 in the chamber quickly reacted into N2O5 in the gas phase, which subsequently hydrolyzed into HNO3 and further neutralized with NH3 into NH4NO3 on the BC surface, along with a small amount of N2O5 decomposed into NO and NO2 through a reaction with the BC surface active site. Meanwhile, the fractal BC aggregates restructured and condensed to spherical particles during the NH4NO3 coating process. Compared to that during the exposure to NO2 or O3 alone, the presence of strong signals of CH2O+, CH2O2+ and CH4NO+ during the simultaneous exposure to both NO2 and O3 suggested a synergetic oxidizing effect of NO2 and O3, which significantly activated the BC surface by forming carbonyl, carboxylic and nitro groups, promoted the adsorption of water vapor onto the BC surface and enhanced the NH4NO3 formation. Under <75 ± 2% RH conditions the coating process of NH4NO3 on the BC surface consisted of a diffusion of N2O5 onto the surface and a subsequent hydrolysis, due to the limited number of water molecules adsorbed. However, under 90 ± 2% RH conditions N2O5 directly hydrolyzed on the aqueous phase of the BC surface due to the multilayer water molecules adsorbed, which caused an instant NH4NO3 formation on the surface without any delay. The coating rate of NH4NO3 on KCl-treated BC particles was 3-4 times faster than that on the pure BC particles at the initial stage, indicating an increasing formation of NH4NO3, mainly due to an enhanced hygroscopicity of BC by KCl salts.

Source apportionment of PM2.5 and sulfate formation during the COVID-19 lockdown in a coastal city of southeast China.

Revealing the changes in chemical compositions and sources of PM2.5 is important for understanding aerosol chemistry and emission control strategies. High time-resolved characterization of water-soluble inorganic ions, elements, organic carbon (OC), and elemental carbon (EC) in PM2.5 was conducted in a coastal city of southeast China during the COVID-19 pandemic. The results showed that the average concentration of PM2.5 during the city lockdown (CLD) decreased from 46.2 µg m-3 to 24.4 µg m-3, lower than the same period in 2019 (PM2.5: 37.1 µg m-3). Concentrations of other air pollutants, such as SO2, NO2, PM10, OC, EC, and BC, were also decreased by 27.3%-67.8% during the CLD, whereas O3 increased by 28.1%. Although SO2 decreased from 4.94 µg m-3to 1.59 µg m-3 during the CLD, the concentration of SO42- (6.63 µg m-3) was comparable to that (5.47 µg m-3) during the non-lockdown period, which were attributed to the increase (16.0%) of sulfate oxidation rate (SOR). Ox (O3+NO2) was positively correlated with SO42-, suggesting the impacts of photochemical oxidation. A good correlation (R2 = 0.557) of SO42- and Fe and Mn was found, indicating the transition-metal ion catalyzed oxidation. Based on positive matrix factorization (PMF) analysis, the contribution of secondary formation to PM2.5 increased during the epidemic period, consisting with the increase of secondary organic carbon (SOC), while other primary sources including traffic, dust, and industry significantly decreased by 9%, 8.5%, and 8%, respectively. This study highlighted the comprehensive and nonlinear response of chemical compositions and formation mechanisms of PM2.5 to anthropogenic emissions control under relatively clean conditions.

Air pollution increases human health risks of PM2.5-bound PAHs and nitro-PAHs in the Yangtze River Delta, China.

Identifying the nature and extent of atmospheric PM2.5-bound toxic organic pollutants is beneficial to evaluate human health risks of air pollution. Seasonal observations of PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in the Yangtze River Delta (YRD) were investigated, along with criteria air pollutants and meteorological parameters. With the elevated PM2.5 level, the percentage of 4-ring PAHs and typical NPAH including 3-Nitrobiphenyl (3-NBP) and 2-Nitrofluoranthene (2-NFLT) increased by 19-40%. PM2.5-bound 2-NFLT was positively correlated with O3 and NO2, suggesting the contribution of atmospheric oxidation capacity to enhance the secondary formation of NPAHs in the atmosphere. Positive matrix factorization (PMF) analysis indicated that traffic emissions (44.9-48.7%), coal and biomass combustion (27.6-36.0%) and natural gas and volatilization (15.3-27.5%) were major sources of PAHs, and secondary formation (39.8-53.8%) was a predominant contributor to total NPAH concentrations. Backward trajectory analysis showed that air masses from North China transported to the YRD region increased PAH and NPAH concentrations. Compare to clean days, the BaP equivalent concentrations of total PAHs and NPAHs during haze pollution days were enhanced by 10-25 and 2-6 times, respectively. The Incremental Lifetime Cancer Risks (ILCRs) of PAHs by inhalation exposure also indicated high potential health risks in the YRD region. The results implied that the health risks of PM2.5-bound PAHs and NPAHs could be sharply enhanced with the increase of PM2.5 concentrations.