Brown carbon in fresh and aged biomass burning emissions

To date, most climate forcing calculations treat black carbon (BC) and dust as the only particulate light absorbers. Numerous studies have shown that some organic aerosols (OA), referred to as brown carbon (BrC), also absorb light. BrC has been identified in biomass burning emissions; however, its light absorption properties are poorly constrained. Literature values of the imaginary part of the refractive indices of biomass burning OA (kOA) span two orders of magnitude. This variability, attributed to differences in fuel type and burning conditions, complicates the representation of biomass burning BrC in climate models. Proper accounting for BrC absorption in climate forcing calculations is of great importance. It can enhance the models' performance, bringing estimates of climate sensitivity to better agreement with observations. Here, we investigate the source of variability in absorptivity of biomass-burning OA observed in this study. We show that absorptivity is closely linked to OA volatility. Specifically, low-volatility organic compounds (LVOCs) are responsible for most of the light absorption, with effective kOA 1-2 orders of magnitude greater than the semi-volatile organic compounds (SVOCs). The effective kOA of biomass-burning emissions thus depends on the extent to which SVOCs partition to the condensed phase, which is sensitive to OA loading. kOA increases by a factor of 3-4 when the emissions are diluted from source concentrations (1-10 mg/m3) to atmospheric-like concentrations (1-10 μg/m3), as the partitioning of SVOCs shifts towards the gas phase. More importantly, we demonstrate that the effective kOA depends largely on burn conditions, and not fuel type. Burns which produce high levels of BC emit OA that is more absorptive than burns which produce low levels of BC. The dependence of kOA on OA loading and burn conditions can be parameterized as a function of a single property of the emissions, namely the BC-to-OA ratio. Specifically, kOA at wavelength (lambda) of 550 nm increases linearly with the BC-to-OA ratio, while the spectral-dependence, w, where k¬OA = kOA,550nm*(550/lambda)w, is inversely proportional to the BC-to-OA ratio. These correlations were determined by examining emissions from small scale laboratory burns of six globally relevant fuels (black spruce, ponderosa pine, hay, rice straw, saw grass, and wire grass), assuming that their behavior can be extrapolated to other biomass fuels. Experiments were conducted during the Fire Laboratory at Missoula Campaign (FLAME 4). The BC-to-OA ratios in the experiments were between 0.01 and 0.2. Aging of the emissions (photo-oxidation or dark ozonolysis) was performed in a smog chamber. To determine the dependence of absorptivity on volatility, the SVOCs were stripped from the condensed phase by heating the emissions to 250 C inside a thermodenuder. This allowed for constraining the optical properties of the low-volatility residue. kOA values were retrieved by performing optical closure, which combines Mie theory calculations with measurements of light absorption, and total and BC size distributions.