Catalytic role of formaldehyde in particulate matter formation.

Formaldehyde (HCHO), the simplest and most abundant carbonyl in the atmosphere, contributes to particulate matter (PM) formation via two in-cloud processing pathways. First, in a catalytic pathway, HCHO reacts with hydrogen peroxide (H2O2) to form hydroxymethyl hydroperoxide (HMHP), which rapidly oxidizes dissolved sulfur dioxide (SO2,aq) to sulfate, regenerating HCHO. Second, HCHO reacts with dissolved SO2,aq to form hydroxymethanesulfonate (HMS), which upon oxidation with the hydroxyl radical (OH) forms sulfate and also reforms HCHO. Chemical transport model simulations using rate coefficients from laboratory studies of the reaction rate of HMHP with SO2,aq show that the HMHP pathways reduce the SO2 lifetime by up to a factor of 2 and contribute up to ∼18% of global sulfate. This contribution rises to >50% in isoprene-dominated regions such as the Amazon. Combined with recent results on HMS, this work demonstrates that the one-carbon molecules HMHP and HCHO contribute significantly to global PM, with HCHO playing a crucial catalytic role.

Aerosol-Radiation Interactions in China in Winter: Competing Effects of Reduced Shortwave Radiation and Cloud-Snowfall-Albedo Feedbacks Under Rapidly Changing Emissions.

Since 2013, Chinese policies have dramatically reduced emissions of particulates and their gas-phase precursors, but the implications of these reductions for aerosol-radiation interactions are unknown. Using a global, coupled chemistry-climate model, we examine how the radiative impacts of Chinese air pollution in the winter months of 2012 and 2013 affect local meteorology and how these changes may, in turn, influence surface concentrations of PM2.5, particulate matter with diameter <2.5 µm. We then investigate how decreasing emissions through 2016 and 2017 alter this impact. We find that absorbing aerosols aloft in winter 2012 and 2013 heat the middle- and lower troposphere by ∼0.5-1 K, reducing cloud liquid water, snowfall, and snow cover. The subsequent decline in surface albedo appears to counteract the ∼15-20 W m-2 decrease in shortwave radiation reaching the surface due to attenuation by aerosols overhead. The net result of this novel cloud-snowfall-albedo feedback in winters 2012-2013 is a slight increase in surface temperature of ∼0.5-1 K in some regions and little change elsewhere. The aerosol heating aloft, however, stabilizes the atmosphere and decreases the seasonal mean planetary boundary layer (PBL) height by ∼50 m. In winter 2016 and 2017, the ∼20% decrease in mean PM2.5 weakens the cloud-snowfall-albedo feedback, though it is still evident in western China, where the feedback again warms the surface by ∼0.5-1 K. Regardless of emissions, we find that aerosol-radiation interactions enhance mean surface PM2.5 pollution by 10%-20% across much of China during all four winters examined, mainly though suppression of PBL heights.

Global Importance of Hydroxymethanesulfonate in Ambient Particulate Matter: Implications for Air Quality.

Sulfur compounds are an important constituent of particulate matter, with impacts on climate and public health. While most sulfur observed in particulate matter has been assumed to be sulfate, laboratory experiments reveal that hydroxymethanesulfonate (HMS), an adduct formed by aqueous phase chemical reaction of dissolved HCHO and SO2, may be easily misinterpreted in measurements as sulfate. Here we present observational and modeling evidence for a ubiquitous global presence of HMS. We find that filter samples collected in Shijiazhuang, China, and examined with ion chromatography within 9 days show as much as 7.6 µg m-3 of HMS, while samples from Singapore examined 9-18 months after collection reveal ~0.6 µg m-3 of HMS. The Shijiazhuang samples show only minor traces of HMS 4 months later, suggesting that HMS had decomposed over time during sample storage. In contrast, the Singapore samples do not clearly show a decline in HMS concentration over 2 months of monitoring. Measurements from over 150 sites, primarily derived from the IMPROVE network across the United States, suggest the ubiquitous presence of HMS in at least trace amounts as much as 60 days after collection. The degree of possible HMS decomposition in the IMPROVE observations is unknown. Using the GEOS-Chem chemical transport model, we estimate that HMS may account for 10% of global particulate sulfur in continental surface air and over 25% in many polluted regions. Our results suggest that reducing emissions of HCHO and other volatile organic compounds may have a co-benefit of decreasing particulate sulfur.