Extensive field evidence for the release of HONO from the photolysis of nitrate aerosols.

Particulate nitrate ([Formula: see text]) has long been considered a permanent sink for NOx (NO and NO2), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of [Formula: see text] can recycle HONO and NOx back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in "renoxification" photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of [Formula: see text], thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O3 in both polluted and clean environments.

Emissions Measurements from Household Solid Fuel Use in Haryana, India: Implications for Climate and Health Co-benefits.

A large concern with estimates of climate and health co-benefits of "clean" cookstoves from controlled emissions testing is whether results represent what actually happens in real homes during normal use. A growing body of evidence indicates that in-field emissions during daily cooking activities differ substantially from values obtained in laboratories, with correspondingly different estimates of co-benefits. We report PM2.5 emission factors from uncontrolled cooking (n = 7) and minimally controlled cooking tests (n = 51) using traditional chulha and angithi stoves in village kitchens in Haryana, India. Minimally controlled cooking tests (n = 13) in a village kitchen with mixed dung and brushwood fuels were representative of uncontrolled field tests for fine particulate matter (PM2.5), organic and elemental carbon (p > 0.5), but were substantially higher than previously published water boiling tests using dung or wood. When the fraction of nonrenewable biomass harvesting, elemental, and organic particulate emissions and modeled estimates of secondary organic aerosol (SOA) are included in 100 year global warming commitments (GWC100), the chulha had a net cooling impact using mixed fuels typical of the region. Correlation between PM2.5 emission factors and GWC (R2 = 0.99) implies these stoves are climate neutral for primary PM2.5 emissions of 8.8 ± 0.7 and 9.8 ± 0.9 g PM2.5/kg dry fuel for GWC20 and GWC100, respectively, which is close to the mean for biomass stoves in global emission inventories.

Comprehensive Molecular Characterization of Atmospheric Brown Carbon by High Resolution Mass Spectrometry with Electrospray and Atmospheric Pressure Photoionization.

Light-absorbing components of atmospheric organic aerosols, which are collectively termed "brown carbon" (BrC), are ubiquitous in the atmosphere. They affect absorption of solar radiation by aerosols in the atmosphere and human health as some of them have been identified as potential toxins. Understanding the sources, formation, atmospheric evolution, and environmental effects of BrC requires molecular identification and characterization of light-absorption properties of BrC chromophores. Identification of BrC components is challenging due to the complexity of atmospheric aerosols. In this study, we employ two complementary ionization techniques, atmospheric pressure photo ionization (APPI) and electrospray ionization (ESI), to obtain broad coverage of both polar and nonpolar BrC components using high-resolution mass spectrometry (HRMS). These techniques are combined with chromatographic separation of BrC compounds with high performance liquid chromatography (HPLC), characterization of their light absorption with a photodiode array (PDA) detector, and chemical composition with HRMS. We demonstrate that this approach enables more comprehensive characterization of BrC in biomass burning organic aerosols (BBOAs) emitted from test burns of sage brush biofuel. In particular, we found that nonpolar BrC chromophores such as PAHs are only detected using positive mode APPI. Meanwhile, negative mode ESI results in detection of polar compounds such as nitroaromatics, aromatic acids, and phenols. For the BrC material examined in this study, over 40% of the solvent-extractable BrC light absorption is attributed to water insoluble, nonpolar to semipolar compounds such as PAHs and their derivatives, which require APPI for their identification. In contrast, the polar, water-soluble BrC compounds, which are detected in ESI, account for less than 30% of light absorption by BrC.