Atmospheric particulate matter plays an important role in the Earth's radiative balance. Over the past two decades, it has been established that a portion of particulate matter, black carbon, absorbs significant amounts of light and exerts a warming e ect rivalling that of anthropogenic carbon dioxide 1,2 . Most climate models treat black carbon as the sole light-absorbing carbonaceous particulate. However, some organic aerosols, dubbed brown carbon and mainly associated with biomass burning emissions 3-6 , also absorbs light 7 . Unlike black carbon, whose light absorption properties are well understood 8 , brown carbon comprises a wide range of poorly characterized compounds that exhibit highly variable absorptivities, with reported values spanning two orders of magnitude 3-6,9,10 . Here we present smog chamber experiments to characterize the e ective absorptivity of organic aerosol from biomass burning under a range of conditions. We show that brown carbon in emissions from biomass burning is associated mostly with organic compounds of extremely low volatility 11 . In addition, we find that the e ective absorptivity of organic aerosol in biomass burning emissions can be parameterized as a function of the ratio of black carbon to organic aerosol, indicating that aerosol absorptivity depends largely on burn conditions, not fuel type. We conclude that brown carbon from biomass burning can be an important factor in aerosol radiative forcing.Black carbon (BC) in atmospheric particulate matter is an important global warming agent (potentially second only to CO 2 ) with estimates of its direct radiative forcing (DRF) ranging between 0.17 and 1.48 W m −2 (ref. 2). The large uncertainty in BC DRF stems partly from the mismatch between BC light absorption (hence its DRF) estimated by climate models and that retrieved using remote sensing, with models usually reporting smaller values 2 . Open biomass burning contributes one-third of the global BC budget. Biomass burning is also a major source of organic aerosol (OA), contributing two-thirds of the global primary OA budget 2,12 , which most climate models treat as purely scattering. The cooling due to this scattering offsets the warming by BC from biomass burning, resulting in negative net DRF for biomass burning emissions 13 . However, there is a growing body of evidence that biomass burning OA contains substantial amounts of light-absorbing brown carbon 3-6 (BrC), which can shift the net biomass burning DRF to positive values 14 . Neglecting absorption by biomass burning OA might lead to misattribution of observed atmospheric particulate matter absorption to BC, contributing to the discrepancy between models and observations. There are substantial uncertainties in quantifying the effect of BrC. A major obstacle is the very high variability in reported light absorption properties of biomass burning OA, often attributed to fuel type and burn conditions 4,6 , which complicates their treatment in climate models.In this study, we show that the least volatile fraction (extreme...

Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3 to 4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration to 0.7 in experiments where photo-oxidation resulted in a 30 % loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17 % of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.

We report secondary organic aerosol (SOA) yields from the ozonolysis of alpha-pinene in the presence of NO and NO2. Experimental conditions are characterized by the [VOC]0/ [NOx]0 ratio (ppbC/ppb), which varies from approximately 1 to approximately 300. SOA yield is constant for [VOC]0/[NOx]0 > approximately 15 and decreases dramatically (by more than a factor of 4) as [VOC]0/[NOx]0 decreases. Aerosol production is completely suppressed in the presence of NO for [VOC]0/[NOx]0 < or = 4.5. Fouriertransform IR analysis of filter samples reveals that nitrate-containing species contribute significantly to the total aerosol mass at low [VOC]0/[NOx]0. Yield reduction is a result of the formation of a more volatile product distribution as [VOC]0/[NOx]0 decreases; we propose that the change in the product distribution is driven by changes in the gas-phase chemistry as NOx concentration increases. We also present two-product model parameters to describe aerosol production from the alpha-pinene/0/NOx system under both high- and low-NOx conditions.

Methods for removing mercury from flue gas have received increased attention because of recent limitations placed on mercury emissions from coal-fired utility boilers by the U. S. Environmental Protection Agency and various states. A promising method for mercury removal is catalytic oxidation of elemental mercury (Hg0) to oxidized mercury (Hg2+), followed by wet flue gas desulfurization (FGD). FGD cannot remove Hg0, but easily removes Hg2+ because of its solubility in water. To date, research has focused on three broad catalyst areas: selective catalytic reduction catalysts, carbon-based materials, and metals and metal oxides. We review published results for each type of catalyst and also present a discussion on the possible reaction mechanisms in each case. One of the major sources of uncertainty in understanding catalytic mercury oxidation is a lack of knowledge of the reaction mechanisms and kinetics. Thus, we propose that future research in this area should focus on two major aspects: determining the reaction mechanism and kinetics and searching for more cost-effective catalyst and support materials.