Chelsea E. Stockwell

Aerosol single scattering albedo dependence on biomass combustion efficiency: Laboratory and field studies

Single scattering albedo (ω) of fresh biomass burning (BB) aerosols produced from 92 controlled laboratory combustion experiments of 20 different woods and grasses was analyzed to determine the factors that control the variability in ω. Results show that ω varies strongly with fire-integrated modified combustion efficiency (MCEFI)—higher MCEFI results in lower ω values and greater spectral dependence of ω. A parameterization of ω as a function of MCEFI for fresh BB aerosols is derived from the laboratory data and is evaluated by field observations from two wildfires. The parameterization suggests that MCEFI explains 60% of the variability in ω, while the 40% unexplained variability could be accounted for by other parameters such as fuel type. Our parameterization provides a promising framework that requires further validation and is amenable for refinements to predict ω with greater confidence, which is critical for estimating the radiative forcing of BB aerosols.

Emissions of Fine Particle Fluoride from Biomass Burning

The burning of biomasses releases fluorine to the atmosphere, representing a major and previously uncharacterized flux of this atmospheric pollutant. Emissions of fine particle (PM2.5) water-soluble fluoride (F-) from biomass burning were evaluated during the fourth Fire Laboratory at Missoula Experiment (FLAME-IV) using scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDX) and ion chromatography with conductivity detection. F- was detected in 100% of the PM2.5 emissions from conifers (n=11), 94% of emissions from agricultural residues (n=16), and 36% of the grasses and other perennial plants (n=14). When F- was quantified, it accounted for an average (±standard error) of 0.13±0.02% of PM2.5. F- was not detected in remaining samples (n=15) collected from peat burning, shredded tire combustion, and cook-stove emissions. Emission factors (EF) of F- emitted per kilogram of biomass burned correlated with emissions of PM2.5 and combustion efficiency, and also varied with the type of biomass burned and the geographic location where it was harvested. Based on recent evaluations of global biomass burning, we estimate that biomass burning releases 76 Gg F- yr(-1) to the atmosphere, with upper and lower bounds of 40-150 Gg F- yr(-1). The estimated F- flux from biomass burning is comparable to total fluorine emissions from coal combustion plus other anthropogenic sources. These data demonstrate that biomass burning represents a major source of fluorine to the atmosphere in the form of fine particles, which have potential to undergo long-range transport.

Rapidly evolving ultrafine and fine mode biomass smoke physical properties: Comparing laboratory and field results

Combining field and laboratory results, we present biomass smoke physical properties. We report sub-0.56 µm diameter (Dp) particle sizing (fast mobility particle sizer, FMPS) plus light absorption and scattering at 870 nm (photoacoustic extinctiometer). For Dp   100 nm), while flaming combustion produced very high number concentrations of smaller (Dp ~ 50 nm) absorbing particles. Due to smoldering and particle growth processes, Dp approached 100 nm within 3 h after emission. Increased particle cross-sectional area and Mie scattering efficiency shifted the relative importance of light absorption (flaming maximum) and light scattering (smoldering maximum), increasing ω over time. Measurements showed a consistent picture of smoke properties from emission to aging.

A New Method to Determine the Number Concentrations of Refractory Black Carbon Ice Nucleating Particles

Ice nucleating particles (INP) initiate heterogeneous ice nucleation in mixed-phase clouds, influencing cloud phase and onset temperatures for ice formation. Determination of particle types contributing to atmospheric INP populations requires isolation of the relatively rare INP from a total particle sample, typically followed by time-consuming single-particle characterization. We propose a method to estimate the contributions of light-absorbing, primarily refractory black carbon (rBC), particles to INP populations by selectively removing them prior to determination of INP concentrations. Absorbing particles are heated to their vaporization temperature using laser induced incandescence in a single particle soot photometer (SP2) and the change in INP number concentrations, compared to unheated samples, is assessed downstream in the CSU Continuous Flow Diffusion Chamber (CFDC). We tested this approach in the laboratory using strongly-absorbing and nonabsorbing aerosol types to confirm effective removal of rBC INP and to explore the impact of the processing on non-light-absorbing INP. An INP-active rBC particle type was efficiently removed, while nonabsorbing kaolinite and a soil-based INP were not affected by laser exposure. Results for the products of wiregrass combustion indicated that absorbing particles, primarily rBC, accounted for about 40% of all INP, consistent with electron microscopy of INP emitted during prescribed burns of this fuel type. However, kaolinite internally mixed with rBC exhibited reduced activity after passing through the SP2, suggesting that the validity of the method for realistic internal mixtures needs additional research. The sensitivity of the CFDC presently limits applicability of the method to relatively high INP number concentration samples. Copyright 2014 American Association for Aerosol Research

Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): Emissions of particulate matter from wood and dung cooking fires, garbage and crop residue burning, brick kilns, and other sources

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) characterized widespread and under-sampled combustion sources common to South Asia, including brick kilns, garbage burning, diesel and gasoline generators, diesel groundwater pumps, idling motorcycles, traditional and modern cooking stoves and fires, crop residue burning, and heating fire. Fuel-based emission factors (EFs; with units of pollutant mass emitted per kilogram of fuel combusted) were determined for fine particulate matter (PM2.5), organic carbon (OC), elemental carbon (EC), inorganic ions, trace metals, and organic species. For the forced-draft zigzag brick kiln, EFPM2.5 ranged from 12 to 19 g kg−1 with major contributions from OC (7 %), sulfate expected to be in the form of sulfuric acid (31.9 %), and other chemicals not measured (e.g., particle-bound water). For the clamp kiln, EFPM2.5 ranged from 8 to 13 g kg −1, with major contributions from OC (63.2 %), sulfate (23.4 %), and ammonium (16 %). Our brick kiln EFPM2.5 values may exceed those previously reported, partly because we sampled emissions at ambient temperature after emission from the stack or kiln allowing some particle-phase OC and sulfate to form from gaseous precursors. The combustion of mixed household garbage under dry conditions had an EFPM2.5 of 7.4± 1.2 g kg−1, whereas damp conditions generated the highest EFPM2.5 of all combustion sources in this study, reaching up to 125± 23 g kg−1. Garbage burning emissions contained triphenylbenzene and relatively high concentrations of heavy metals (Cu, Pb, Sb), making these useful markers of this source. A variety of cooking stoves and fires fueled with dung, hardwood, twigs, and/or other biofuels were studied. The use of dung for cooking and heating produced higher EFPM2.5 than other biofuel sources and consistently emitted more PM2.5 and OC than burning hardwood and/or twigs; this trend was consistent across traditional mud stoves, chimney stoves, and three-stone cooking fires. The comparisons of different cooking stoves and cooking fires revealed the highest PM emissions from threestone cooking fires (7.6–73 g kg−1), followed by traditional mud stoves (5.3–19.7 g kg−1), mud stoves with a chimney for exhaust (3.0–6.8 g kg−1), rocket stoves (1.5–7.2 g kg−1), induced-draft stoves (1.2–5.7 g kg−1), and the bhuse chulo stove (3.2 g kg−1), while biogas had no detectable PM emisPublished by Copernicus Publications on behalf of the European Geosciences Union. 2260 T. Jayarathne et al.: Emissions of particulate matter sions. Idling motorcycle emissions were evaluated before and after routine servicing at a local shop, which decreased EFPM2.5 from 8.8± 1.3 to 0.71± 0.45 g kg −1 when averaged across five motorcycles. Organic species analysis indicated that this reduction in PM2.5 was largely due to a decrease in emission of motor oil, probably from the crankcase. The EF and chemical emissions profiles developed in this study may be used for source apportionment and to update regional emission inventories.

A dual‐chamber method for quantifying the effects of atmospheric perturbations on secondary organic aerosol formation from biomass burning emissions

Biomass burning (BB) is a major source of atmospheric pollutants. Field and laboratory studies indicate that secondary organic aerosol (SOA) formation from BB emissions is highly variable. We investigated sources of this variability using a novel dual-smog-chamber method that directly compares the SOA formation from the same BB emissions under two different atmospheric conditions. During each experiment, we filled two identical Teflon smog chambers simultaneously with BB emissions from the same fire. We then perturbed the smoke with UV-lights, UV-lights plus HONO, or dark ozone in one or both chambers. These perturbations caused SOA formation in nearly every experiment with an average organic aerosol (OA) mass enhancement ratio of 1.78 ± 0.91 (mean ± 1σ). However, the effects of the perturbations were highly variable ranging with OA mass enhancement ratios ranging from 0.7 (30% loss of OA mass) to 4.4 across the set of perturbation experiments. There was no apparent relationship between OA enhancement and perturbation type, fuel type, and modified combustion efficiency. To better isolate the effects of different perturbations, we report dual-chamber enhancements (DUCE), which quantity the effects of a perturbation relative to a reference condition. DUCE values were also highly variable, even for the same perturbation and fuel type. Gas measurements indicate substantial burn-to-burn variability in the magnitude and composition of SOA precursor emissions, even in repeated burns of the same fuel under nominally identical conditions. Therefore, the effects of different atmospheric perturbations on SOA formation from BB emissions appear to be less important than burn-to-burn variability.

Speciated On-line PM 1 from South Asian Combustion Sources: Part I, Fuel-based Emission Factors and Size Distributions

Combustion of biomass, garbage, and fossil fuels in South Asia has led to poor air quality in the region and has uncertain climate forcing impacts. Online measurements of submicron aerosol (PM1) emissions were conducted as part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) to investigate and report emission factors (EFs) and vacuum aerodynamic diameter (dva) size distributions from prevalent but poorly characterized combustion sources. The online aerosol instrumentation included a “mini” aerosol mass spectrometer (mAMS) and a dual-spot eight-channel aethalometer (AE33). The mAMS measured non-refractory PM1 mass, composition, and size. The AE33-measured black carbon (BC) mass and estimated light absorption at 370 nm due to organic aerosol or brown carbon. Complementary gas-phase measurements of carbon dioxide (CO2), carbon monoxide (CO), and methane (CH4) were collected using a Picarro Inc. cavity ring-down spectrometer (CRDS) to calculate fuel-based EFs using the carbon mass balance approach. The investigated emission sources include open garbage burning, diesel-powered irrigation pumps, idling motorcycles, traditional cookstoves fueled with dung and wood, agricultural residue fires, and coal-fired brick-making kilns, all of which were tested in the field. Open-garbage-burning emissions, which included mixed refuse and segregated plastics, were found to have some of the largest PM1 EFs (3.77–19.8 g kg−1) and the highest variability of the investigated emission sources. Nonrefractory organic aerosol (OA) size distributions measured by the mAMS from garbage-burning emissions were observed to have lognormal mode dva values ranging from 145 to 380 nm. Particle-phase hydrogen chloride (HCl) was observed from open garbage burning and was attributed to the burning of chlorinated plastics. Emissions from two diesel-powered irrigation pumps with different operational ages were tested during NAMaSTE. Organic aerosol and BC were the primary components of the emissions and the OA size distributions were centered at ∼ 80 nm dva. The older pump was observed to have significantly larger EFOA than the newer pump (5.18 g kg−1 compared to 0.45 g kg−1) and similar EFBC. Emissions from two distinct types of coal-fired brick-making kilns were investigated. The less advanced, intermittently fired clamp kiln was observed to Published by Copernicus Publications on behalf of the European Geosciences Union. 14654 J. D. Goetz et al.: PM1 from South Asian combustion sources have relatively large EFs of inorganic aerosol, including sulfate (0.48 g kg−1) and ammonium (0.17 g kg−1), compared to the other investigated emission sources. The clamp kiln was also observed to have the largest absorption Ångström exponent (AAE= 4) and organic carbon (OC) to BC ratio (OC :BC= 52). The continuously fired zigzag kiln was observed to have the largest fraction of sulfate emissions with an EFSO4 of 0.96 g kg −1. Non-refractory aerosol size distributions for the brick kilns were centered at ∼ 400 nm dva. The biomass burning samples were all observed to have significant fractions of OA and non-refractory chloride; based on the size distribution results, the chloride was mostly externally mixed from the OA. The dung-fueled traditional cookstoves were observed to emit ammonium, suggesting that the chloride emissions were partially neutralized. In addition to reporting EFs and size distributions, aerosol optical properties and mass ratios of OC to BC were investigated to make comparisons with other NAMaSTE results (i.e., online photoacoustic extinctiometer (PAX) and off-line filter based) and the existing literature. This work provides critical field measurements of aerosol emissions from important yet undercharacterized combustion sources common to South Asia and the developing world.