Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013–2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

Abstract. Elemental carbon (EC) has been widely used as a tracer to track the portion of co-emitted primary organic carbon (OC) and, by extension, to estimate secondary OC (SOC) from ambient observations of EC and OC. Key to this EC tracer method is to determine an appropriate OC / EC ratio that represents primary combustion emission sources (i.e., (OC / EC)pri) at the observation site. The conventional approaches include regressing OC against EC within a fixed percentile of the lowest (OC / EC) ratio data (usually 5–20 %) or relying on a subset of sampling days with low photochemical activity and dominated by local emissions. The drawback of these approaches is rooted in its empirical nature, i.e., a lack of clear quantitative criteria in the selection of data subsets for the (OC / EC)pri determination. We examine here a method that derives (OC / EC)pri through calculating a hypothetical set of (OC / EC)pri and SOC followed by seeking the minimum of the coefficient of correlation (R2) between SOC and EC. The hypothetical (OC / EC)pri that generates the minimum R2(SOC,EC) then represents the actual (OC / EC)pri ratio if variations of EC and SOC are independent and (OC / EC)pri is relatively constant in the study period. This Minimum R Squared (MRS) method has a clear quantitative criterion for the (OC / EC)pri calculation. This work uses numerically simulated data to evaluate the accuracy of SOC estimation by the MRS method and to compare with two commonly used methods: minimum OC / EC (OC / ECmin) and OC / EC percentile (OC / EC10 %). Log-normally distributed EC and OC concentrations with known proportion of SOC are numerically produced through a pseudorandom number generator. Three scenarios are considered, including a single primary source, two independent primary sources, and two correlated primary sources. The MRS method consistently yields the most accurate SOC estimation. Unbiased SOC estimation by OC / ECmin and OC / EC10 % only occurs when the left tail of OC / EC distribution is aligned with the peak of the (OC / EC)pri distribution, which is fortuitous rather than norm. In contrast, MRS provides an unbiased SOC estimation when measurement uncertainty is small. MRS results are sensitive to the magnitude of measurement uncertainty but the bias would not exceed 23 % if the uncertainty is within 20 %.

The optical properties of atmospheric secondary brown carbon (BrC) aerosol are poorly understood because of its chemical complexity, and this has hampered quantitative assessments of the impacts of this light‐absorbing material on glaciers on the Tibetan Plateau. For this study, a statistical approach was developed to investigate BrC light absorption over the southeastern margin of the Tibetan Plateau. Secondary sources for BrC were more important for absorption than primary ones. A diurnal cycle in secondary BrC absorption was explained by the formation of light‐absorbing chromophores by photochemical oxidation after sunrise followed by photobleaching of the chromophores under the more oxidizing conditions as the day progressed. Multimethod analyses showed that biomass burning in northern Burma and along the Sino‐Burmese border was the most important source for the secondary BrC. The mean integrated simple forcing efficiency was 79 W/g, indicating that secondary BrC can cause substantial radiative effects.

Submicron aerosol (PM1) species measured by aerosol mass spectrometers have been widely used to validate chemical transport models; however, the uncertainties due to chemical differences between PM1 and PM2.5 are poorly constrained. Here we characterized such differences in a highly polluted environment in north China in winter. Our results showed that the changes in PM1/PM2.5 ratios as a function of relative humidity (RH) were largely different for primary and secondary species. Secondary organic and inorganic aerosol (SOA and SIA) presented clear decreases in PM1/PM2.5 ratios at RH > 60% during periods with high SIA contributions (>50%), likely driven by the changes in aerosol hygroscopicity and phase states, while the traffic and coal combustion OA had limited dependence on RH. Thermodynamic modeling showed negligible impacts of PM differences on predictions of particle acidity, yet these impacts can cause a difference in aerosol water content by up to 50–70%.