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...

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 μg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.

Intermediate volatility organic compounds (IVOCs) are an important class of secondary organic aerosol (SOA) precursors that have not been traditionally included in chemical transport models. A challenge is that the vast majority of IVOCs cannot be speciated using traditional gas chromatography-based techniques; instead they are classified as an unresolved complex mixture (UCM) that is presumably made up of a complex mixture of branched and cyclic alkanes. To better understand SOA formation from IVOCs, a series of smog chamber experiments was conducted with different alkanes, including cyclic, branched, and linear compounds. The experiments focused on freshly formed SOA from hydroxyl (OH) radical-initiated reactions under high-NO(x) conditions at typical atmospheric organic aerosol concentrations (C(OA)). SOA yields from cyclic alkanes were comparable to yields from linear alkanes three to four carbons larger in size. For alkanes with equivalent carbon numbers, branched alkanes had the lowest SOA mass yields, ranging between 0.05 and 0.08 at a C(OA) of 15 μg m(-3). The SOA yield of branched alkanes also depends on the methyl branch position on the carbon backbone. High-resolution aerosol mass spectrometer data indicate that the SOA oxygen-to-carbon ratios were largely controlled by the carbon number of the precursor compound. Depending on the precursor size, the mass spectrum of SOA produced from IVOCs is similar to the semivolatile-oxygenated and hydrocarbon-like organic aerosol factors derived from ambient data. Using the new yield data, we estimated SOA formation potential from diesel exhaust and predict the contribution from UCM vapors to be nearly four times larger than the contribution from single-ring aromatics and comparable to that of polycyclic aromatic hydrocarbons after several hours of oxidation at typical atmospheric conditions. Therefore, SOA from IVOCs may be an important contributor to urban OA and should be included in SOA models; the yield data presented in this study are suitable for such use.

Facility-level methane emissions were measured at 114 gathering facilities and 16 processing plants in the United States natural gas system. At gathering facilities, the measured methane emission rates ranged from 0.7 to 700 kg per hour (kg/h) (0.6 to 600 standard cubic feet per minute (scfm)). Normalized emissions (as a % of total methane throughput) were less than 1% for 85 gathering facilities and 19 had normalized emissions less than 0.1%. The range of methane emissions rates for processing plants was 3 to 600 kg/h (3 to 524 scfm), corresponding to normalized methane emissions rates <1% in all cases. The distributions of methane emissions, particularly for gathering facilities, are skewed. For example, 30% of gathering facilities contribute 80% of the total emissions. Normalized emissions rates are negatively correlated with facility throughput. The variation in methane emissions also appears driven by differences between inlet and outlet pressure, as well as venting and leaking equipment. Substantial venting from liquids storage tanks was observed at 20% of gathering facilities. Emissions rates at these facilities were, on average, around four times the rates observed at similar facilities without substantial venting.