Severe winter haze events in Beijing and North China Plain are characterized by rapid production of sulfate aerosols with unresolved mechanisms. Oxidation of SO2 by O2 in the absence of metal catalysts (uncatalyzed autoxidation) represents the most ubiquitous SO2 conversion pathway in the atmosphere. However, this reaction has long been regarded as too slow to be atmospherically meaningful. This traditional view was based on the kinetic studies conducted in bulk dilute solutions that mimic cloudwater but deviate from urban aerosols. Here, we directly measure the sulfate formation rate via uncatalyzed SO2 autoxidation in single (NH4)2SO4 microdroplets, by using an aerosol optical tweezer coupled with a cavity-enhanced Raman spectroscopy technique. We find that the aqueous reaction of uncatalyzed SO2 autoxidation is accelerated by two orders of magnitude at the high ionic strength (∼36 molal) conditions in the supersaturated aerosol water. Furthermore, at acidic conditions (pH 3.5–4.5), uncatalyzed autoxidation predominately occurs on droplet surface, with a reaction rate unconstrained by SO2 solubility. With these rate enhancements, we estimate that the uncatalyzed SO2 autoxidation in aerosols can produce sulfate at a rate up to 0.20 μg m–3 hr–1, under the winter air pollution condition in Beijing.
There is a large gap between the simulated and observed sulfate concentrations during winter haze events in North China. Although multiphase sulfate formation mechanisms have been proposed, they have not been evaluated using chemical transport models. In this study, the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) was used to apportion sulfate formation. It was found that Mncatalyzed oxidation on aerosol surfaces was the dominant sulfate formation pathway, accounting for 92.3 ± 3.5% of the sulfate formation during haze events. Gas-phase oxidation contributed 3.1 ± 0.5% to the sulfate formation due to the low OH levels. The H 2 O 2 oxidation in aerosol water accounted for 4.2 ± 3.6% of the sulfate formation, caused by the rapid consumption of H 2 O 2 . The contributions of O 3 , NO 2 oxidation, and transition metal ion-catalyzed reactions in aerosol water could be negligible owing to the low aerosol water content, low pH, and high ionic strength. The contributions from in-cloud reactions were negligible due to the barrier provided by stable stratification during winter haze events.
<p><strong>Abstract.</strong> Gaseous sulfuric acid is known as one of the key precursors for atmospheric new particle formation processes, but its measurement remains a major challenge. A proxy method that is able to derive gaseous sulfuric acid concentrations from parameters that can be measured relatively easily and accurately is therefore highly desirable among the atmospheric chemistry community. Although such methods are available for clean atmospheric environments, a proxy that works well in a polluted atmosphere, such as those in Chinese megacities, is yet to be developed. In this study, the gaseous sulfuric acid concentration was measured in February&#8211;March, 2018, in urban Beijing by a nitrate based &#8211; Long Time-of-Flight Chemical Ionization Mass Spectrometer (LToF-CIMS). A number of atmospheric parameters were recorded concurrently including the ultraviolet radiation B (UVB) intensity, concentrations of O<sub>3</sub>, NO<sub><i>x</i></sub>, SO<sub>2</sub> and HONO, and aerosol particle number size distributions. A proxy for atmospheric daytime gaseous sulfuric acid concentration was derived using a statistical analysis method by using the UVB intensity, [SO<sub>2</sub>], condensation sink (CS), [O<sub>3</sub>], and [HONO] (or [NO<sub><i>x</i></sub>]) as the predictor variables. In this proxy method, we considered the formation of gaseous sulfuric acid from reactions of SO<sub>2</sub> and OH radicals during the daytime, and loss of gaseous sulfuric acid due to its condensation onto the pre-existing particles. In addition, we explored formation of OH radicals from the conventional gas-phase photochemistry using ozone as a proxy and from the photolysis of heterogeneously-formed HONO using HONO (and subsequently NO<sub><i>x</i></sub>) as a proxy. Our results showed that the UVB intensity and [SO<sub>2</sub>] are dominant factors for the production of gaseous sulfuric acid, and that the simplest proxy could be constructed with the UVB intensity and [SO<sub>2</sub>] alone, resulting in up to 29&#8201;% relative deviations when sulfuric acid concentrations were larger than 2.0&#8201;&#215;&#8201;10<sup>6</sup>&#8201;molecules&#8201;cm<sup>&#8722;3</sup>. When the OH radical production from both homogenously- and heterogeneously-formed precursors were considered, the relative deviations were lower than 24&#8201;%.</p>
23Calcium-and magnesium-containing salts are important components for mineral dust and 24 sea salt aerosols, but their physicochemical properties are not well understood yet.
Long-chain alkanes are a type of intermediate volatility organic compound (IVOC) in the atmosphere and a potential source of secondary organic aerosols (SOAs). C 12 −C 14 nalkylcyclohexanes are important compositions of IVOCs, with considerable concentrations and emission rates. The reaction rate constants and SOA formation of the reactions of C 12 −C 14 nalkylcyclohexanes with Cl atoms were investigated in the present study. The reaction rate constants of the long-chain alkanes obtained via the relative-rate method at 298 ± 0.2 K (in units of ×10 −10 cm 3 molecule −1 s −1 ) were as follows: k hexylcyclohexane = 5.11 ± 0.28, k heptylcyclohexane = 5.56 ± 0.30, and k octylcyclohexane = 5.74 ± 0.31. The gas-phase products of the reactions were identified as mainly small molecules of aldehydes, ketones, and acids. The particlephase products were mostly monomers and oligomers, but there were still trimers even under high-NO x conditions. Moreover, under high-NO x conditions (urban atmosphere), the SOA yields of hexylcyclohexane are higher than that under low-NO x conditions (remote atmosphere), indicating that more attention should be given to the SOA formation of Cl-initiated n-alkylcyclohexane oxidations in polluted regions. This research can further clarify the oxidation processes and SOA formation of n-alkylcyclohexanes in the atmosphere.
Abstract. Co-occurrences of high concentrations of PM2.5 and ozone (O3) have been frequently observed in haze-aggravating processes in the North China Plain (NCP) over the past few years. Higher O3 concentrations on hazy days were hypothesized to be related to nitrous acid (HONO), but the key sources of HONO enhancing O3 during haze-aggravating processes remain unclear. We added six potential HONO sources, i.e., four ground-based (traffic, soil, and indoor emissions, and the NO2 heterogeneous reaction on ground surface (Hetground)) sources, and two aerosol-related (the NO2 heterogeneous reaction on aerosol surfaces (Hetaerosol) and nitrate photolysis (Photnitrate)) sources into the WRF-Chem model and designed 23 simulation scenarios to explore the unclear key sources. The results indicate that ground-based HONO sources producing HONO enhancements showed a rapid decrease with height, while the NO + OH reaction and aerosol-related HONO sources decreased slowly with height. Photnitrate contributions to HONO concentrations were enhanced with aggravated pollution levels. The enhancement of HONO due to Photnitrate on hazy days was about 10 times greater than on clean days and Photnitrate dominated daytime HONO sources (∼ 30 %–70 % when the ratio of the photolysis frequency of nitrate (Jnitrate) to gas nitric acid (JHNO3) equals 30) at higher layers (>800 m). Compared with that on clean days, the Photnitrate contribution to the enhanced daily maximum 8 h averaged (DMA8) O3 was increased by over 1 magnitude during the haze-aggravating process. Photnitrate contributed only ∼ 5 % of the surface HONO in the daytime with a Jnitrate/JHNO3 ratio of 30 but contributed ∼ 30 %–50 % of the enhanced O3 near the surface in NCP on hazy days. Surface O3 was dominated by volatile organic compound-sensitive chemistry, while O3 at higher altitudes (>800 m) was dominated by NOx-sensitive chemistry. Photnitrate had a limited impact on nitrate concentrations (<15 %) even with a Jnitrate/JHNO3 ratio of 120. These results suggest the potential but significant impact of Photnitrate on O3 formation, and that more comprehensive studies on Photnitrate in the atmosphere are still needed.
HONO concentrations in Beijing (BJ) and Sanmenxia (SMX) were simultaneously measured in winter with a duration of 1 month, and the sources and sinks of HONO in the two cities were comparably analyzed. BJ and SMX had different pollution characteristics. Direct vehicle emission made a contribution to observed HONO of about 28% in BJ, whereas it contributed to HONO only about 12% in SMX. Additionally, direct emission from coal combustion in SMX also made a significant contribution to atmospheric HONO, which could achieve to be 13%. In BJ, nighttime NO2 conversion on the aerosol and ground surfaces contributed to HONO sources of 15% and 27%, respectively. In SMX, nighttime NO2 conversion on the aerosol and ground surfaces contributed to HONO sources of 40% and 30%, respectively. Daytime NO2 heterogeneous conversion (including photo‐enhanced conversion) on the aerosol and ground surfaces was important in SMX. Daytime NO3− photolysis contributed 9% HONO in SMX and 4% in BJ. The primary OH production rates from photolysis of daytime HONO in both BJ and SMX were three orders of magnitude faster than those from photolysis of O3, revealing the dominant role of HONO in local atmospheric chemistry of the two cities in winter.
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