Search

Agricultural and prescribed burning activities emit large amounts of trace gases and aerosols on regional to global scales. We present a compilation of emission factors (EFs) and emission ratios from the eastern portion of the Fire Influence on Regional to Global Environments and Air Quality (FIREX‐AQ) campaign in 2019 in the United States, which sampled burning of crop residues and other prescribed fire fuels. FIREX‐AQ provided comprehensive chemical characterization of 53 crop residue and 22 prescribed fires. Crop residues burned at different modified combustion efficiencies (MCE), with corn residue burning at higher MCE than other fuel types. Prescribed fires burned at lower MCE (<0.90) which is typical, while grasslands burned at lower MCE (0.90) than normally observed due to moist, green, growing season fuels. Most non‐methane volatile organic compounds (NMVOCs) were significantly anticorrelated with MCE except for ethanol and NMVOCs that were measured with less certainty. We identified 23 species where crop residue fires differed by more than 50% from prescribed fires at the same MCE. Crop residue EFs were greater for species related to agricultural chemical use and fuel composition as well as oxygenated NMVOCs possibly due to the presence of metals such as potassium. Prescribed EFs were greater for monoterpenes (5×). FIREX‐AQ crop residue average EFs generally agreed with the previous agricultural fire study in the US but had large disagreements with global compilations. FIREX‐AQ observations show the importance of regionally‐specific and fuel‐specific EFs as first steps to reduce uncertainty in modeling the air quality impacts of fire emissions. Plain Language Summary: Crop residue and prescribed fires emit pollution that impacts air quality. FIREX‐AQ provided observations of these emissions to better characterize their variability with a detailed set of chemical observations. These observations showed significant differences in the emissions from burning different crops (corn, rice, soybean, wheat) compared to other prescribed fires or grasslands that may be due to differences in the fuel composition, the use of agricultural chemicals, and moisture levels. Overall, FIREX‐AQ observations for crop residue fires compared better with previous results in the region than with globally averaged information. The campaign observed even greater variability across EFs than previous studies, suggesting that new methods must be developed to take this into account to improve predictions of the air quality impacts of burning these fuels. Key Points: Corn residue burned at higher modified combustion efficiency than rice or soybean residueImpacts of fire emissions >6 hr downwind on OH reactivity will be more influenced by species that are less important at the sourceEmission factors from crop residue fires agreed better with previous results from the same region than with global compilations [ABSTRACT FROM AUTHOR]

The impact of biomass burning (BB) on the atmospheric burden of volatile organic compounds (VOCs) is highly uncertain. Here we apply the GEOS-Chem chemical transport model (CTM) to constrain BB emissions in the western USA at ∼ 25 km resolution. Across three BB emission inventories widely used in CTMs, the inventory–inventory comparison suggests that the totals of 14 modeled BB VOC emissions in the western USA agree with each other within 30 %–40 %. However, emissions for individual VOCs can differ by a factor of 1–5, driven by the regionally averaged emission ratios (ERs, reflecting both assigned ERs for specific biome and vegetation classifications) across the three inventories. We further evaluate GEOS-Chem simulations with aircraft observations made during WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption and Nitrogen) and FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality) field campaigns. Despite being driven by different global BB inventories or applying various injection height assumptions, the model–observation comparison suggests that GEOS-Chem simulations underpredict observed vertical profiles by a factor of 3–7. The model shows small to no bias for most species in low-/no-smoke conditions. We thus attribute the negative model biases mostly to underestimated BB emissions in these inventories. Tripling BB emissions in the model reproduces observed vertical profiles for primary compounds, i.e., CO , propane, benzene, and toluene. However, it shows no to less significant improvements for oxygenated VOCs, particularly for formaldehyde, formic acid, acetic acid, and lumped ≥ C3 aldehydes, suggesting the model is missing secondary sources of these compounds in BB-impacted environments. The underestimation of primary BB emissions in inventories is likely attributable to underpredicted amounts of effective dry matter burned, rather than errors in fire detection, injection height, or ERs, as constrained by aircraft and ground measurements. We cannot rule out potential sub-grid uncertainties (i.e., not being able to fully resolve fire plumes) in the nested GEOS-Chem which could explain the negative model bias partially, though back-of-the-envelope calculation and evaluation using longer-term ground measurements help support the argument of the dry matter burned underestimation. The total ERs of the 14 BB VOCs implemented in GEOS-Chem only account for half of the total 161 measured VOCs (∼ 75 versus 150 ppbppm-1). This reveals a significant amount of missing reactive organic carbon in widely used BB emission inventories. Considering both uncertainties in effective dry matter burned (× 3) and unmodeled VOCs (× 2), we infer that BB contributed to 10 % in 2019 and 45 % in 2018 (240 and 2040 GgC) of the total VOC primary emission flux in the western USA during these two fire seasons, compared to only 1 %–10 % in the standard GEOS-Chem. [ABSTRACT FROM AUTHOR]

The impact of biomass burning (BB) on the atmospheric burden of volatile organic compounds (VOCs) is highly uncertain. Here we apply the GEOS-Chem chemical transport model (CTM) to constrain BB emissions in the western US at ~25 km resolution. Across three BB emission inventories widely used in CTMs, the total of 14 modeled BB VOC emissions in the western US agree with each other within 30–40 %. However, emissions for individual VOC differ by up to a factor of 5 (i.e. , lumped ≥ C4 alkanes), driven by the regionally averaged emission ratios (ERs) among inventories. We further evaluate GEOS-Chem simulations with aircraft observations made during WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen) and FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality) field campaigns. Despite being driven by different global BB inventories or applying various injection height assumptions, GEOS-Chem simulations underpredict observed vertical profiles by a factor of 3–7. The model shows small-to-no bias for most species in low/no smoke conditions. We thus attribute the negative model biases mostly to underestimated BB emissions in these inventories. Tripling BB emissions in the model reproduces observed vertical profiles for primary compounds, i.e., CO, propane, benzene, and toluene. However, it shows no-to-less significant improvements for oxygenated VOCs, particularly formaldehyde, formic acid, acetic acid, and lumped ≥ C3 aldehydes, suggesting the model is missing secondary sources of these compounds in BB-impacted environments. The underestimation of primary BB emissions in inventories is likely attributable to underpredicted amounts of effective dry matter burned, rather than errors in fire detection, injection height, or ERs. We cannot rule out potential sub-grid uncertainties (i.e. , not being able to fully resolve fire plumes) in the nested GEOS-Chem which could explain the model negative bias partially, though the back-of-the-envelope calculation and evaluation using longer-term ground measurements help increase the argument of the dry matter burned underestimation. The ERs of the 14 BB VOCs implemented in GEOS-Chem account for about half of the total 161 measured VOCs (~75 versus 150 ppb ppm-1). This reveals a significant amount of missing reactive organic carbon in widely-used BB emission inventories. Considering both uncertainties in effective dry matter burned and unmodeled VOCs, we infer that BB contributed up to 10 % in 2019 and 45 % in 2018 (240 and 2040 GgC) of the total VOC primary emission flux in the western US during these two fire seasons, compared to only 1–10 % in the standard GEOS-Chem. [ABSTRACT FROM AUTHOR]

The evolution of organic aerosol (OA) and aerosol size distributions within smoke plumes is uncertain due to the variability in rates of coagulation and OA condensation/evaporation between different smoke plumes and at different locations within a single plume. We use aircraft data from the FIREX-AQ campaign to evaluate differences in evolving aerosol size distributions, OA, and oxygen to carbon ratios (O:C) between and within smoke plumes during the first several hours of aging as a function of smoke concentration. The observations show that the median particle diameter increases faster in smoke of a higher initial OA concentration (>1000 µ g m -3), with diameter growth of over 100 nm in 8 h – despite generally having a net decrease in OA enhancement ratios – than smoke of a lower initial OA concentration (<100 µ g m -3), which had net increases in OA. Observations of OA and O:C suggest that evaporation and/or secondary OA formation was greater in less concentrated smoke prior to the first measurement (5–57 min after emission). We simulate the size changes due to coagulation and dilution and adjust for OA condensation/evaporation based on the observed changes in OA. We found that coagulation explains the majority of the diameter growth, with OA evaporation/condensation having a relatively minor impact. We found that mixing between the core and edges of the plume generally occurred on timescales of hours, slow enough to maintain differences in aging between core and edge but too fast to ignore the role of mixing for most of our cases. [ABSTRACT FROM AUTHOR]

Peat fires in Southeast Asia are a major source of trace gases and particles to the regional-global atmosphere that influence atmospheric chemistry, climate, and air quality. During the November 2015 record-high Ocean Niño Index (ONI, 2.6) our mobile smoke sampling team made the first, or rare, field measurements of numerous trace gases, aerosol optical properties, and aerosol chemistry and mass emissions for fires burning only peat in the Indonesian province of Central Kalimantan (on the island of Borneo). The measurements used Fourier transform infrared spectroscopy (FTIR), whole air sampling (WAS), photoacoustic extinctiometers (PAX, 401 and 870 nm), and detailed off-line analyses of particulate matter (PM) collected on filters. In September–November 2019 we measured peat fire trace gas emissions again, using WAS only, under El Niño–Southern Oscillation (ENSO)-neutral conditions (ONI, 0.3) in more remote areas of Central Kalimantan and also the Indonesian provinces of Riau, Jambi, and South Sumatra, all on the island of Sumatra. The 2019 measurements significantly expanded the geographic range and climate conditions sampled. This paper presents the 2019 results and synthesizes them with the previous fieldwork to converge on more robust regional average emission factors (EFs; grams of compound per kilogram of biomass burned) for authentic peat fires. In addition, samples of peat imported from Indonesia were burned in US laboratories, and the EFs and optical properties were characterized in more detail than in the field by a larger suite of instrumentation. We use the improved knowledge of regional emissions based on the expanded field measurements to select the most representative lab data and compute a synthesized, more "chemically complete" set of EFs and aerosol optical properties for tropical peat fires. The modified combustion efficiency (MCE) values for the peat smoke sampled in 2019 were within the range of MCEs sampled in 2015, but with a lower average in 2019 (0.718±0.021 , range 0.687–0.736) than 2015 (0.772±0.035 , range 0.693–0.835). Averaging the new and older data together suggests an updated MCE for tropical peat fires of ∼0.76. Despite the difference in MCE, the study-average methane emission factors (EF CH 4) were remarkably similar across the 2 years probing different regions: 9.42±2.51 g kg -1 in 2019 and 9.51±4.74 g kg -1 in 2015. When parsing the 2019 samples by province, the EFs for non-methane organic gases (NMOGs) were about 3 times higher in South Sumatra and Central Kalimantan than in Jambi and Riau, but the overall 2019 study average was only ∼15 % higher than the 2015 study average. South Sumatra peat fires emitted higher amounts of carbonyl and dimethyl sulfide, suggesting a volcanic or marine influence or effects of agricultural chemicals. The lab and fieldwork taken together provide EFs for 230 trace gases including CO 2 (1544 g kg -1), CO (315 g kg -1), and CH 4 (9.8 g kg -1). These are significant adjustments to IPCC-recommended EFs, -9 %, +50 %, and -53 %, respectively. We also report EFs for numerous NMOGs, 46 N-containing compounds, and 14 sulfur- or halogen-containing species. The use of high-resolution mass spectrometry in the lab allowed measurement of 82 % more NMOG mass than in the field. Gravimetrically measured EF PM 2.5 in the field in 2015 (17.3±5.8 g kg -1) was ∼20 % lower than the average from lab studies (22.4±10.4 g kg -1), perhaps due to higher field temperatures. Taken together the lab and field data show that the single-scattering albedo (SSA) was largely independent of wavelength and MCE in the visible (∼0.998), but lower at low MCE at 401 and 405 nm with a value of 0.958 at the study-average MCE. The absorption Ångström exponent (AAE) at the average MCE was 5.7. By far the largest PM component was weakly absorbing insoluble organic carbon. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) events are occurring globally with increasing frequency, and their emissions are having more impacts on human health and climate. Large ash particles are recognized as a BB product with major influences on soil and water environments. However, fine‐ash particles, which have diameters smaller than several microns and characteristic morphologies and compositions (mainly Ca and Mg carbonates), have not yet been explicitly considered as a major BB aerosol component either in field observations or climate models. This study measured BB aerosol samples using transmission electron microscopy (TEM) and ion chromatography during the Fire Influence on Regional to Global Environments and Air Quality (FIREX‐AQ) campaign. We show that significant amounts of fine ash‐bearing particles are transported >100 km from their fire sources. Our environmental chamber experiments suggest that they can act as cloud condensation and ice nuclei. We also found considerable amounts of fine ash‐bearing particles in the TEM samples collected during previous campaigns (Biomass Burning Observation Project and Megacity Initiative: Local and Global Research Observations). These ash particles are commonly mixed with organic matter and make up ∼8% and 5% of BB smoke by number and mass, respectively, in samples collected during the FIREX‐AQ campaign. The measured ash‐mass concentrations are approximately five times and six times greater than those of BB black carbon and potassium, respectively, scaling to an estimated global emission of 11.6 Tg yr−1 with a range of 8.8–16.3 Tg yr−1. Better characterization and constraints on these fine ash‐bearing particles will improve BB aerosol measurements and strengthen assessments of BB impacts on human health and climate. Plain Language Summary: Biomass burning (BB) events occur globally and impact climate and human health. Ash particles larger than ∼10 μm are well known as the main products of BB that contaminate the soil and water near the source regions. On the other hand, ash particles having diameters smaller than several microns, which are inhalable and can be transported long distances, are not yet recognized as a major aerosol component of BB smoke. This study reveals that such fine ash‐bearing particles are abundant in number (∼8%) and mass (∼5%) within BB smoke. The global emission of fine ash particles is estimated to be 11.6 Tg yr−1 with a range of 8.8–16.3 Tg yr−1. By considering their abundance and properties, we will strengthen assessments of BB impacts on human health and climate. Key Points: Ash‐bearing particles with diameters smaller than several microns can be one of the major aerosol components in biomass burning (BB) smokeFine ash‐bearing particles can act as cloud condensation or ice nuclei and influence cloud propertiesThe global emission of fine ash aerosol mass from BB is estimated to be ∼11.6 Tg yr−1 [ABSTRACT FROM AUTHOR]

Trichlorofluoromethane (CFC-11) is an ozone-depleting substance whose production and consumption are regulated under the Montreal Protocol. Global atmospheric CFC-11 levels declined less quickly than expected during 2012-2018, largely because of ongoing emissions from eastern Asia. Satellite measurements suggest additional CFC-11 hotspots in the Arabian Peninsula and north India/Nepal. Here we present CFC-11 levels measured in dozens of Asian cities during 1998-2018, including China and Pakistan before the 2010 phaseout of CFC-11, and China, Nepal, Pakistan, Saudi Arabia and South Korea after the phaseout. Surface measurements of CFCs in Nepal, Pakistan and Saudi Arabia are very rare, and these surveys provide important observational constraints from understudied regions. During pre-phaseout campaigns, higher CFC-11 levels were measured in Beijing than Karachi, despite much higher overall volatile organic compound (VOC) levels in Karachi. During post-phaseout campaigns, average CFC-11 levels were higher in inland Shandong Province and Seoul (1.11-1.23× background) than in western Saudi Arabia, Lahore and Kathmandu (1.02-1.11× background), despite higher levels of other VOCs in the latter regions. While China is known to emit excess CFC-11, elevated CFC-11 levels in Seoul, especially during stagnant meteorological conditions, suggest local emissions in 2015-2016. Rough emission estimates suggest that South Korea is likely a relatively minor global source of excess CFC-11. Hotspot CFC-11 levels were measured from a landfill fire in Mecca (average of 1.8× background) and from garbage burning in Nepal (1.5× background). Because garbage burning and open burning in dumps are common practices, further investigation of CFC-11 emissions at dumps and landfills worldwide is encouraged to determine their global impact. [ABSTRACT FROM AUTHOR]

We present emission measurements of volatile organic compounds (VOCs) for western U.S. wildland fires made on the NSF/NCAR C‐130 research aircraft during the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign in summer 2018. VOCs were measured with complementary instruments onboard the C‐130, including a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR‐ToF‐MS) and two gas chromatography (GC)‐based methods. Agreement within combined instrument uncertainties (<60%) was observed for most co‐measured VOCs. GC‐based measurements speciated the isomeric contributions to selected PTR‐ToF‐MS ion masses and generally showed little fire‐to‐fire variation. We report emission ratios (ERs) and emission factors (EFs) for 161 VOCs measured in 31 near‐fire smoke plume transects of 24 specific individual fires sampled in the afternoon when burning conditions are typically most active. Modified combustion efficiency (MCE) ranged from 0.85 to 0.94. The measured campaign‐average total VOC EF was 26.1 ± 6.9 g kg−1, approximately 67% of which is accounted for by oxygenated VOCs. The 10 most abundantly emitted species contributed more than half of the total measured VOC mass. We found that MCE alone explained nearly 70% of the observed variance for total measured VOC emissions (r2 = 0.67) and >50% for 57 individual VOC EFs representing more than half the organic carbon mass. Finally, we found little fire‐to‐fire variability for the mass fraction contributions of individual species to the total measured VOC emissions, suggesting that a single speciation profile can describe VOC emissions for the wildfires in coniferous ecosystems sampled during WE‐CAN. Key Points: A total of 161 measured volatile organic compound emission factors is 26.1 ± 6.9 g kg−1, 67% of which is from oxygenated species76% of the total volatile organic compound emitted mass shows statistically significant dependence on modified combustion efficiencyMass fraction contributions of individual species to the total measured emissions have little variability in 24 western U.S. fires [ABSTRACT FROM AUTHOR]

During the first phase of the Biomass Burn Operational Project (BBOP) field campaign, conducted in the Pacific Northwest, the DOE G-1 aircraft was used to follow the time evolution of wildfire smoke from near the point of emission to locations 2–3.5 h downwind. In nine flights we made repeated transects of wildfire plumes at varying downwind distances and could thereby follow the plume's time evolution. On average there was little change in dilution-normalized aerosol mass concentration as a function of downwind distance. This consistency hides a dynamic system in which primary aerosol particles are evaporating and secondary ones condensing. Organic aerosol is oxidized as a result. On all transects more than 90 % of aerosol is organic. In freshly emitted smoke aerosol, NH4+ is approximately equivalent to NO3. After 2 h of daytime aging, NH4+ increased and is approximately equivalent to the sum of Cl, SO42 , and NO3. Particle size increased with downwind distance, causing particles to be more efficient scatters. Averaged over nine flights, mass scattering efficiency (MSE) increased in ∼ 2 h by 56 % and doubled in one flight. Mechanisms for redistributing mass from small to large particles are discussed. Coagulation is effective at moving aerosol from the Aitken to accumulation modes but yields only a minor increase in MSE. As absorption remained nearly constant with age, the time evolution of single scatter albedo was controlled by age-dependent scattering. Near-fire aerosol had a single scatter albedo (SSA) of 0.8–0.9. After 1 to 2 h of aging SSAs were typically 0.9 and greater. Assuming global-average surface and atmospheric conditions, the observed age dependence in SSA would change the direct radiative effect of a wildfire plume from near zero near the fire to a cooling effect downwind. [ABSTRACT FROM AUTHOR]

Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include inert tracers to test production and transport and reactive species to test chemical mechanisms. We characterized smoke from fires in coniferous forest fuels for >1,000 hr over two summers (2017 and 2018) at our Missoula, Montana, surface station and found a narrow range for key properties. ΔPM2.5/ΔCO was 0.1070 ± 0.0278 (g/g) or about half the age‐independent ratios obtained at free troposphere elevations (0.2348 ± 0.0326). The average absorption Ångström exponent across both years was 1.84 ± 0.18, or about half the values available for very fresh smoke. Brown carbon (BrC) was persistent (~50% of absorption at 401 nm) in both years, despite differences in smoke age. ΔBC/ΔCO doubled from 2017 to 2018, but the average across 2 years was within 33% of recent airborne measurements, suggesting low sampling bias among platforms. Switching from a 1.0 to a 2.5 micron cutoff increased the mass scattering and mass absorption coefficients, suggesting often overlooked supermicron particles impact the optical properties of moderately aged smoke. O3 was elevated ~6 ppb on average over a full diurnal period when wildfire smoke was present, and smoke‐associated O3 increases were highest (~9 pbb) at night, suggesting substantial upwind production. NOx was mostly local in origin. NOx spurred high rates of NO3 production, including in the presence of wildfire smoke (up to 2.44 ppb hr−1) and at least one nighttime BrC secondary formation event that could have impacted next‐day photochemistry. Plain Language Summary: Wildfires are complicated and difficult to sample. We characterized smoke for over 1,000 hr downwind of a large number of wildfires burning at all stages and measured species sensitive to total smoke production, the combustion characteristics, and plume evolution. The PM/CO ratio was about half that in fresh smoke, suggesting that aerosol evaporation dominates at the surface at smoke ages up to ~1–2 days. Brown carbon accounted for about half of aerosol absorption at 401 nm. O3 levels increased significantly during smoke episodes. High NO3 production rates were driven by local (nonfire) NO2 sources. Key Points: Nonfire NO2 sources can promote NO3 and BrC production in smoke‐influenced urban airThe ratio of both particulate matter and brown carbon to carbon monoxide was consistently about half the usual ratio in fresh smokeOzone was enhanced by more than 10% during aged smoke episodes in a diurnal pattern, suggesting significant regional enhancement [ABSTRACT FROM AUTHOR]

Reactive nitrogen (Nr , defined as all nitrogen-containing compounds except for N2 and N2O) is one of the most important classes of compounds emitted from wildfire, as Nr impacts both atmospheric oxidation processes and particle formation chemistry. In addition, several Nr compounds can contribute to health impacts from wildfires. Understanding the impacts of wildfire on the atmosphere requires a thorough description of Nr emissions. Total reactive nitrogen was measured by catalytic conversion to NO and detection by NO– O3 chemiluminescence together with individual Nr species during a series of laboratory fires of fuels characteristic of western US wildfires, conducted as part of the FIREX Fire Lab 2016 study. Data from 75 stack fires were analyzed to examine the systematics of nitrogen emissions. The measured Nr / total-carbon ratios averaged 0.37 % for fuels characteristic of western North America, and these gas-phase emissions were compared with fuel and residue N/C ratios and mass to estimate that a mean (±SD) of 0.68 (±0.14) of fuel nitrogen was emitted as N2 and N2O. The Nr detected as speciated individual compounds included the following: nitric oxide (NO), nitrogen dioxide (NO2), nitrous acid (HONO), isocyanic acid (HNCO), hydrogen cyanide (HCN), ammonia (NH3), and 44 nitrogen-containing volatile organic compounds (NVOCs). The sum of these measured individual Nr compounds averaged 84.8 (±9.8) % relative to the total Nr , and much of the 15.2 % "unaccounted" Nr is expected to be particle-bound species, not included in this analysis. A number of key species, e.g., HNCO, HCN, and HONO, were confirmed not to correlate with only flaming or with only smoldering combustion when using modified combustion efficiency, MCE=CO2/(CO+CO2) , as a rough indicator. However, the systematic variations in the abundance of these species relative to other nitrogen-containing species were successfully modeled using positive matrix factorization (PMF). Three distinct factors were found for the emissions from combined coniferous fuels: a combustion factor (Comb-N) (800–1200 ∘C) with emissions of the inorganic compounds NO, NO2 , and HONO, and a minor contribution from organic nitro compounds (R- NO2); a high-temperature pyrolysis factor (HT-N) (500–800 ∘C) with emissions of HNCO, HCN, and nitriles; and a low-temperature pyrolysis factor (LT-N) (<500 ∘C) with mostly ammonia and NVOCs. The temperature ranges specified are based on known combustion and pyrolysis chemistry considerations. The mix of emissions in the PMF factors from chaparral fuels (manzanita and chamise) had a slightly different composition: the Comb-N factor was also mostly NO, with small amounts of HNCO, HONO, and NH3 ; the HT-N factor was dominated by NO2 and had HONO, HCN, and HNCO; and the LT-N factor was mostly NH3 with a slight amount of NO contributing. In both cases, the Comb-N factor correlated best with CO2 emission, while the HT-N factors from coniferous fuels correlated closely with the high-temperature VOC factors recently reported by Sekimoto et al. (2018), and the LT-N had some correspondence to the LT-VOC factors. As a consequence, CO2 is recommended as a marker for combustion Nr emissions, HCN is recommended as a marker for HT-N emissions, and the family NH3 / particle ammonium is recommended as a marker for LT-N emissions. [ABSTRACT FROM AUTHOR]

The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM 2.5 and PM 10 , respectively), online PM 1 , inorganic trace gases (NH3 , HNO3 , SO2 , and HCl), and carbon-containing gases (CO2 , CO, CH4 , and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM 2.5 concentrations ranged from 30 to 207 µ g m -3 , which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM 2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3 , HNO3 , and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m -3), 1,3,5-triphenylbenzene (0.8±0.6 ng m -3), cholesterol (2.9±6.6 ng m -3), stigmastanol (1.0 ±0.8 ng m -3), and cis-pinonic acid (4.5±1.9 ng m -3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM 2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM 2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM 2.5 and, as such, should be considered primary targets for controlling ambient PM pollution. [ABSTRACT FROM AUTHOR]

Total reactive nitrogen (Nr, defined as all nitrogen-containing compounds except for N2 and N2O) was measured by catalytic conversion to NO and detection by NO-O3 chemiluminescence together with individual Nr species during a series of laboratory fires of fuels characteristic of Western U.S. wildfires, conducted as part of the FIREX FireLab 2016 study. Data from 75 stack fires were analyzed to examine the systematics of nitrogen emissions. The Nr/total-carbon ratios measured in the emissions were compared with fuel and ash N/C ratios and mass to estimate that a mean (± std. dev.) of 0.68 (± 0.14) of fuel nitrogen was emitted as N2 and N2O. The remaining fraction of Nr was emitted as individual compounds: nitric oxide (NO), nitrogen dioxide (NO2), nitrous acid (HONO), isocyanic acid (HNCO), hydrogen cyanide (HCN), ammonia (NH3), and 44 nitrogen-containing volatile organic compounds (NVOCs). The relative difference between the total reactive nitrogen measurement, Nr, and the sum of measured individual Nr compounds had a mean (± std. dev) of 0.152 (± 0.098). Much of this unaccounted Nr is expected to be particle-bound species, not included in this analysis. A number of key species, e.g. HNCO, HCN and HONO, were confirmed not to correlate only with flaming or only with smoldering combustion when using modified combustion efficiency (MCE = CO2/(CO + CO2)) as a rough indicator. However, the systematic variations of the abundance of these species relative to other nitrogen-containing species were successfully modeled using positive matrix factorization (PMF). Three distinct factors were found for the emissions from combined coniferous fuels, aligning with our understanding of combustion chemistry in different temperature ranges: a combustion factor (Comb-N) (800–1200 °C) with emissions of the inorganic compounds NO, NO2 and HONO, and a minor contribution from organic nitro compounds (R-NO2); a high-temperature pyrolysis factor (HT-N) (500–800 °C) with emissions of HNCO, HCN and nitriles; and a low-temperature pyrolysis factor (LT-N) (< 500 °C) with mostly ammonia, and NVOCs, with the temperature ranges being based on known combustion and pyrolysis chemistry considerations. The mix of emissions in the PMF factors from the chaparral fuels had a slightly different composition: the Comb-N factor was also mostly NO, with small amounts of HNCO, HONO and NH3, the HT-N factor was dominated by NO2 and had HONO, HCN, and HNCO, and the LT-N factor was mostly NH3 with a slight amount of NO contributing. In both cases, the Comb-N factor correlated best with CO2 emission, while the HT-N factors from coniferous fuels correlated closely with the high temperature VOC factors recently reported by Sekimoto et al., (2018) and the LT-N had some correspondence to the LT-VOC factors. As a consequence, CO2 is recommended as a marker for combustion Nr emissions, HCN is recommended as a marker for HT-N emissions and the family NH3/particle ammonium is recommended as a marker for LT-N emissions. [ABSTRACT FROM AUTHOR]

Biomass combustion produces black carbon (BC) and brown carbon (BrC) aerosols that contribute substantially to warming the Earth's atmosphere. Accurate knowledge of their emissions and absorption per unit mass (mass absorption cross-section; MAC) can be used to quantify the radiative impact of these combustion products. We isolated particles generated from laboratory biomass burning fires by morphology and found that some particles from biomass burning do not correspond to either BC or BrC according to common operational definitions. Unlike BrC, these particles strongly absorb red light, with a MAC and spectral dependence of absorption between that of BrC and BC. They also have intermediate volatility: they survive thermodenuding at 250 °C but do not heat to incandescence in a single particle soot photometer (SP2) instrument. We also found evidence for intermediate properties in ambient wildfire smoke from the 2013 Rim Fire in California. More work is needed to understand how much this intermediate material contributes to atmospheric light absorption from typical combustion, whether or not it corresponds to "tar balls," and how it may affect previous MAC measurements that were attributed to enhanced absorption by transparent coatings. Copyright © 2019 American Association for Aerosol Research [ABSTRACT FROM AUTHOR]

Air pollution is one of the most pressing environmental issues in the Kathmandu Valley, where the capital city of Nepal is located. We estimated emissions from two of the major source types in the valley (vehicles and brick kilns) and analyzed the corresponding impacts on regional air quality. First, we estimated the on-road vehicle emissions in the valley using the International Vehicle Emissions (IVE) model with local emissions factors and the latest available data for vehicle registration. We also identified the locations of the brick kilns in the Kathmandu Valley and developed an emissions inventory for these kilns using emissions factors measured during the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) field campaign in April 2015. Our results indicate that the commonly used global emissions inventory, the Hemispheric Transport of Air Pollution (HTAP_v2.2), underestimates particulate matter emissions from vehicles in the Kathmandu Valley by a factor greater than 100. HTAP_v2.2 does not include the brick sector and we found that our sulfur dioxide (SO2) emissions estimates from brick kilns are comparable to 70 % of the total SO2 emissions considered in HTAP_v2.2. Next, we simulated air quality using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for April 2015 based on three different emissions scenarios: HTAP only, HTAP with updated vehicle emissions, and HTAP with both updated vehicle and brick kilns emissions. Comparisons between simulated results and observations indicate that the model underestimates observed surface elemental carbon (EC) and SO2 concentrations under all emissions scenarios. However, our updated estimates of vehicle emissions significantly reduced model bias for EC, while updated emissions from brick kilns improved model performance in simulating SO2. These results highlight the importance of improving local emissions estimates for air quality modeling. We further find that model overestimation of surface wind leads to underestimated air pollutant concentrations in the Kathmandu Valley. Future work should focus on improving local emissions estimates for other major and underrepresented sources (e.g., crop residue burning and garbage burning) with a high spatial resolution, as well as the model's boundary-layer representation, to capture strong spatial gradients of air pollutant concentrations. [ABSTRACT FROM AUTHOR]

The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM2.5 and PM10, respectively), online PM1, inorganic trace gases (NH3, HNO3, SO2, and HCl), and carbon-containing gases (CO2, CO, CH4, and 85 non-methane volatile organic compounds; NMVOC) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated that origins primarily from poorly-maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those two weeks, daily average PM2.5 concentrations ranged from 30 to 207 μg m-3, which exceeded the World Health Organization 24 hour guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas-aerosol phase partitioning of NH3, HNO3, and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (1230 ± 1153 ng m-3), 1,3,5-triphenylbenzene (0.8 ±0.5 ng m-3), cholesterol (3.0 ± 6.7 ng m-3), stigmastanol (1.4 ± 6.7 ng m-3), and cis-pinonic acid (4.5 ± 0.6 ng m-3) indicate contributions from biomass burning, garbage burning, food cooking, cow-dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18 ± 5 %), biomass burning (17 ± 10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18 ± 9 %). Model sensitivity tests with newly-developed source profiles indicated contributions from biomass burning within a factor of two of previous estimates, but relatively greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM2.5 OC included those originating from anthropogenic precursors for naphthalene (10 ± 4 %) and methylnaphthalene (0.3 ± 0.1 %) and biogenic precursors for monoterpenes (0.13 ± 0.07 %) and sesquiterpenes (5 ± 2 %). An average of 25 % of the PM2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil-fuel combustion) were the greatest contributors to PM2.5 and, as such, should be considered primary targets for controlling ambient PM pollution. [ABSTRACT FROM AUTHOR]

In mid-August through mid-September of 2017 a major wildfire smoke and haze episode strongly impacted most of the NW US and SW Canada. During this period our ground-based site in Missoula, Montana, experienced heavy smoke impacts for ∼500 h (up to 471 µ g m -3 hourly average PM 2.5). We measured wildfire trace gases, PM 2.5 (particulate matter ≤2.5 µ m in diameter), and black carbon and submicron aerosol scattering and absorption at 870 and 401 nm. This may be the most extensive real-time data for these wildfire smoke properties to date. Our range of trace gas ratios for ΔNH3/ΔCO and ΔC2H4/ΔCO confirmed that the smoke from mixed, multiple sources varied in age from ∼2 –3 h to ∼1 –2 days. Our study-average ΔCH4/ΔCO ratio (0.166±0.088) indicated a large contribution to the regional burden from inefficient smoldering combustion. Our ΔBC/ΔCO ratio (0.0012±0.0005) for our ground site was moderately lower than observed in aircraft studies (∼0.0015) to date, also consistent with a relatively larger contribution from smoldering combustion. Our ΔBC/ΔPM2.5 ratio (0.0095±0.0003) was consistent with the overwhelmingly non-BC (black carbon), mostly organic nature of the smoke observed in airborne studies of wildfire smoke to date. Smoldering combustion is usually associated with enhanced PM emissions, but our ΔPM2.5/ΔCO ratio (0.126±0.002) was about half the ΔPM1.0/ΔCO measured in fresh wildfire smoke from aircraft (∼0.266). Assuming PM 2.5 is dominated by PM 1 , this suggests that aerosol evaporation, at least near the surface, can often reduce PM loading and its atmospheric/air-quality impacts on the timescale of several days. Much of the smoke was emitted late in the day, suggesting that nighttime processing would be important in the early evolution of smoke. The diurnal trends show brown carbon (BrC), PM 2.5 , and CO peaking in the early morning and BC peaking in the early evening. Over the course of 1 month, the average single scattering albedo for individual smoke peaks at 870 nm increased from ∼0.9 to ∼0.96. Bscat401/Bscat870 was used as a proxy for the size and "photochemical age" of the smoke particles, with this interpretation being supported by the simultaneously observed ratios of reactive trace gases to CO. The size and age proxy implied that the Ångström absorption exponent decreased significantly after about 10 h of daytime smoke aging, consistent with the only airborne measurement of the BrC lifetime in an isolated plume. However, our results clearly show that non-BC absorption can be important in "typical" regional haze and moderately aged smoke, with BrC ostensibly accounting for about half the absorption at 401 nm on average for our entire data set. [ABSTRACT FROM AUTHOR]

Spectra of the 3d Rydberg state region of O2 have been obtained by two-photon resonant ionization of the ground electronic state. By varying the rotational distribution and radiation polarization, all observed bands were identified and attributed to excitation of Σ, Δ, and [uppercase_phi_synonym] states. Earlier assignments were corrected. The Δ and [uppercase_phi_synonym] assignments are complete while the Σ assignments are so far incomplete. [ABSTRACT FROM AUTHOR]

In mid-August through mid-September of 2017 a major wildfire smoke/haze episode strongly impacted most of the NW US and SW Canada. During this period our ground-based site in Missoula, MT experienced heavy smoke impacts for ~500 hours (up to 471µgm−3 hourly average PM2.5). We measured wildfire trace gases, PM2.5, and black carbon and sub-micron aerosol scattering and absorption at 870 and 401nm. This may be the most extensive real-time data for these wildfire smoke properties to date. Our range of trace gas ratios for ΔNH3/ΔCO and ΔC2H4/ΔCO confirmed that the smoke from mixed, multiple sources varied in age from ~2–3 hours to ~1–2 days. Our study-average ΔCH4/ΔCO ratio (0.166±0.088) indicated a large contribution to the regional burden from inefficient “smoldering” combustion. Our ΔBC/ΔCO ratio (0.0012±0.0005) for our ground site was moderately lower than observed in aircraft studies (~0.0015) to date, also consistent with a relatively larger contribution from smoldering combustion. Our ΔBC/ΔPM2.5 ratio (0.0095±0.0003) was consistent with the overwhelmingly non-BC, mostly organic nature of the smoke observed in airborne studies of wildfire smoke to date. Smoldering combustion is usually associated with enhanced PM emissions, but our ΔPM2.5/ΔCO ratio (0.126±0.002) was about half the ΔPM1.0/ΔCO measured in fresh wildfire smoke from aircraft (~0.266). Assuming PM2.5 is dominated by PM1, this suggests that aerosol evaporation, at least near the surface, can often reduce PM loading and its atmospheric/air-quality impacts on the time scale of several days. Much of the smoke was emitted late in the day suggesting that nighttime processing would be important in the early evolution of smoke. The diurnal trends show BrC, PM2.5, and CO peaking in early morning and BC peaking in early evening. Over the course of one month, the average single scattering albedo for individual smoke peaks at 870nm increased from ~0.9 to ~0.96. Bscat401/Bscat870 was used as a proxy for the size and “photochemical age” of the smoke particles with this interpretation being supported by the simultaneously-observed ratios of reactive trace gases to CO. The size/age proxy implied that the Ångström absorption exponent decreased significantly after about ten hours of daytime smoke aging, consistent with the only airborne measurement of the brown carbon (BrC) lifetime in an isolated plume. However, our results clearly show that non-BC absorption can be important in “typical” regional haze/moderately-aged plumes with BrC ostensibly accounting for about half the absorption at 401nm on average for our entire data set. [ABSTRACT FROM AUTHOR]

We report the emissions of glyoxal and methylglyoxal from the open burning of biomass during the NOAAled 2016 FIREX intensive at the Fire Sciences Laboratory in Missoula, MT. Both compounds were measured using cavity-enhanced spectroscopy, which is both more sensitive and more selective than methods previously used to determine emissions of these two compounds. A total of 75 burns were conducted, using 33 different fuels in 8 different categories, providing a far more comprehensive dataset for emissions than was previously available. Measurements of methylglyoxal using our instrument suffer from spectral interferences from several other species, and the values reported here are likely underestimates, possibly by as much as 70 %. Methylglyoxal emissions were 2-3 times higher than glyoxal emissions on a molar basis, in contrast to previous studies that report methylglyoxal emissions lower than glyoxal emissions. Methylglyoxal emission ratios for all fuels averaged 3.6±2.4 ppbv methylglyoxal (ppmv CO)-1 while emission factors averaged 0.66-0.50 g methylglyoxal (kg fuel burned)-1. Primary emissions of glyoxal from biomass burning were much lower than previous laboratory measurements but consistent with recent measurements from aircraft. Glyoxal emission ratios for all fuels averaged 1.4±0.7 ppbv glyoxal (ppmv CO)-1, while emission factors averaged 0.20±0.12 g glyoxal (kg fuel burned)-1, values that are at least a factor of 4 lower than assumed in previous estimates of the global glyoxal budget. While there was significant variability in the glyoxal emission ratios and factors between the different fuel groups, glyoxal and formaldehyde were highly correlated during the course of any given fire, and the ratio of glyoxal to formaldehyde, RGF, was consistent across many different fuel types, with an average value of 0.068±0.018. While RGF values for fresh emissions were consistent across many fuel types, further work is required to determine how this value changes as the emissions age. [ABSTRACT FROM AUTHOR]

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 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 (AAED4) and organic carbon (OC) to BC ratio (OC V BCD52). 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. [ABSTRACT FROM AUTHOR]

Western U.S. wildlands experience frequent and large-scale wildfires which are predicted to increase in the future. As a result, wildfire smoke emissions are expected to play an increasing role in atmospheric chemistry while negatively impacting regional air quality and human health. Understanding the impacts of smoke on the environment is informed by identifying and quantifying the chemical compounds that are emitted during wildfires and by providing empirical relationships that describe how the amount and composition of the emissions change based upon different fire conditions and fuels. This study examined particulate organic compounds emitted from burning common western U.S. wildland fuels at the U.S. Forest Service Fire Science Laboratory. Thousands of intermediate and semi-volatile organic compounds (I/SVOCs) were separated and quantified into fire-integrated emission factors (EFs) using thermal desorption, two-dimensional gas chromatograph with online derivatization coupled to an electron ionization/vacuum ultra-violet high-resolution time of flight mass spectrometer (TD-GC×GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of modified combustion efficiency (MCE), fuel source, and other defining characteristics for the separated compounds are provided in the accompanying mass spectral library. Results show that EFs for total organic carbon (OC), chemical families of I/SVOCs, and most individual I/SVOCs span 2-5 orders of magnitude, with higher EFs at smoldering conditions (low MCE) than flaming. Logarithmic fits applied to the observations showed that log(EF) for particulate organic compounds were inversely proportional to MCE. These measurements and relationships provide useful estimates of EFs for OC, elemental carbon (EC), organic chemical families, and individual I/SVOCs as a function of fire conditions. [ABSTRACT FROM AUTHOR]

Air pollution is one of the most pressing environmental issues in the Kathmandu Valley, where the capital city of Nepal is located. We estimated emissions from two of the major source types in the valley (vehicles and brick kilns) and analyzed the corresponding impacts on regional air quality. First, we estimated the on-road vehicle emissions in the valley using the International Vehicle Emission (IVE) model with local emission factors and the latest available data for vehicle registration. We also identified the locations of the brick kilns in the Kathmandu Valley and developed an emissions inventory for these kilns using emission factors measured during the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) field campaign in April 2015. Our results indicate that the commonly-used global emissions inventory, the Hemispheric Transport of Air Pollution (HTAP_v2.2), underestimates particulate matter emissions from vehicles in the Kathmandu Valley by a factor greater than 100. In addition, brick kilns account for nearly 70% of total sulfur dioxide (SO2) emissions from all sectors considered in HTAP_v2.2. Next, we simulated air quality using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) for April 2015 based on three different emission scenarios: HTAP only, HTAP with updated vehicle emissions, and HTAP with both updated vehicle and brick kilns emissions. Comparisons between simulated results and observations indicate that the model underestimates observed surface elemental carbon (EC) and SO2 concentrations under all emissions scenarios. However, our updated estimates of vehicle emissions significantly reduced model bias for EC, while updated emissions from brick kilns improved model performance in simulating SO2. These results highlight the importance of improving local emissions estimates for air quality modeling. We further find that model overestimation of surface wind leads to underestimated air pollutant concentrations in the Kathmandu Valley. Future work should focus on improving local emissions estimates for other major and underrepresented sources (e.g., crop residue burning and garbage burning) with a high spatial resolution, as well as the model's boundary-layer representation, to capture strong spatial gradients of air pollutant concentrations. [ABSTRACT FROM AUTHOR]

Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere, which can act as precursors to secondary pollutants such as ozone and fine particles. Measurements performed with a proton-transfer-reaction time-of-flight mass spectrometer during the FIREX 2016 laboratory intensive were analyzed with positive matrix factorization (PMF), in order to understand the instantaneous variability in VOC emissions from biomass burning, and to simplify the description of these types of emissions. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles, which are mass spectral representations of the relative abundances of emitted VOCs, explained on average 85% of the VOC emissions across various fuels representative of the western US (including various coniferous and chaparral fuels). In addition, the profiles were remarkably similar across almost all of the fuel types tested. For example, the correlation coefficient r² of each profile between ponderosa pine (coniferous tree) and manzanita (chaparral) is higher than 0.84. The compositional differences between the two VOC profiles appear to be related to differences in pyrolysis processes of fuel biopolymers at high and low temperatures. These pyrolysis processes are thought to be the main source of VOC emissions. "High-temperature" and "low-temperature" pyrolysis processes do not correspond exactly to the commonly used "flaming" and "smoldering" categories as described by modified combustion efficiency (MCE). The average atmospheric properties (e.g., OH reactivity, volatility, etc) of the high- and low-temperature profiles are significantly different. We also found that the two VOC profiles can describe previously reported VOC data for laboratory and field burns. [ABSTRACT FROM AUTHOR]

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen-containing particles impact atmospheric chemistry, air quality, and ecological N deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass-derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98±10% efficiency for 100-600 nm particle diameters. We also show efficient conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a nondispersive infrared (NDIR) CO2 detector. However, the application of this method to the atmosphere presents a challenge due to the small signal above background at high ambient levels of common gas-phase carbon compounds (e.g., CO2). We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single-component, laboratory-generated, Nr-containing particles below 2.5 μm in size. In addition we show agreement with mass measurements of an independently calibrated online particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative-ion mode. We obtain excellent correlations (R2 =0.99) of particle mass measured as Nr with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g., nitrate, sulfate, and chloride). The Nr and PILS-ESI/MS are shown to agree to within ~6% for particle mass loadings of up to 120 μgm-3. Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20% for these single-component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index. [ABSTRACT FROM AUTHOR]

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. On-line 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 on-line aerosol instrumentation included a mini aerosol mass spectrometer (mAMS) and a dual-spot 8-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. Non-refractory organic aerosol (OA) size distributions measured by the mAMS from garbage-burning emissions were observed to have lognormal mode dva values ranging from 145–380 nm. Particle-phase hydrogen chloride (HCl) was observed from the 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 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 a 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 and, 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. on-line photoacoustic extinctiometer (PAX) and off-line filter-based), and existing literature. This work provides critical field measurements of aerosol emissions from important yet under-characterized combustion sources common to South Asia and the developing world. [ABSTRACT FROM AUTHOR]

Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by protontransfer- reaction time-of-flight mass spectrometry (PTRToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) preseparation with electron ionization, H3O+ chemical ionization, and NOC chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90% of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (I- CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R², of > 0.8, including compounds that are not frequently reported by PTRMS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fireintegrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire. [ABSTRACT FROM AUTHOR]

Western wildfires have a major impact on air quality in the US. In the fall of 2016, 107 test fires were burned in the large-scale combustion facility at the US Forest Service Missoula Fire Sciences Laboratory as part of the Fire Influence on Regional and Global Environments Experiment (FIREX). Canopy, litter, duff, dead wood, and other fuel components were burned in combinations that represented realistic fuel complexes for several important western US coniferous and chaparral ecosystems including ponderosa pine, Douglas fir, Engelmann spruce, lodgepole pine, subalpine fir, chamise, and manzanita. In addition, dung, Indonesian peat, and individual coniferous ecosystem fuel components were burned alone to investigate the effects of individual components (e.g., "duff") and fuel chemistry on emissions. The smoke emissions were characterized by a large suite of state-of-the-art instruments. In this study we report emission factor (EF, grams of compound emitted per kilogram of fuel burned) measurements in fresh smoke of a diverse suite of critically important trace gases measured using open-path Fourier transform infrared spectroscopy (OP-FTIR). We also report aerosol optical properties (absorption EF; single-scattering albedo, SSA; and Ångström absorption exponent, AAE) as well as black carbon (BC) EF measured by photoacoustic extinctiometers (PAXs) at 870 and 401 nm. The average trace gas emissions were similar across the coniferous ecosystems tested and most of the variability observed in emissions could be attributed to differences in the consumption of components such as duff and litter, rather than the dominant tree species. Chaparral fuels produced lower EFs than mixed coniferous fuels for most trace gases except for NOx and acetylene. A careful comparison with available field measurements of wildfires confirms that several methods can be used to extract data representative of real wildfires from the FIREX laboratory fire data. This is especially valuable for species rarely or not yet measured in the field. For instance, the OP-FTIR data alone show that ammonia (1.62 g kg-1), acetic acid (2.41 g kg-1), nitrous acid (HONO, 0.61 g kg-1), and other trace gases such as glycolaldehyde (0.90 g kg-1) and formic acid (0.36 g kg-1) are significant emissions that were poorly characterized or not characterized for US wildfires in previous work. The PAX measurements show that the ratio of brown carbon (BrC) absorption to BC absorption is strongly dependent on modified combustion efficiency (MCE) and that BrC absorption is most dominant for combustion of duff (AAE 7.13) and rotten wood (AAE 4.60): fuels that are consumed in greater amounts during wildfires than prescribed fires. Coupling our laboratory data with field data suggests that fresh wildfire smoke typically has an EF for BC near 0.2 g kg-1, an SSA of ~0.91, and an AAE of ~3.50, with the latter implying that about 86 % of the aerosol absorption at 401 nm is due to BrC. [ABSTRACT FROM AUTHOR]

Fine particulate matter (PM2.5) was collected in situ from peat smoke during the 2015 El Niño peat fire episode in Central Kalimantan, Indonesia. Twenty-one PM samples were collected from 18 peat fire plumes that were primarily smoldering with modified combustion efficiency (MCE) values of 0.725-0.833. PM emissions were determined and chemically characterized for elemental carbon (EC), organic carbon (OC), water-soluble OC, water-soluble ions, metals, and organic species. Fuel-based PM2.5 mass emission factors (EFs) ranged from 6.0 to 29.6 g kg-1 with an average of 17.3 ± 6.0 g kg-1. EC was detected only in 15 plumes and comprised ~1% of PM mass. Together, OC (72%), EC (1%), water-soluble ions (1%), and metal oxides (0.1%) comprised 74 ± 11% of gravimetrically measured PM mass. Assuming that the remaining mass is due to elements that form organic matter (OM; i.e., elements O, H, N) an OM-to-OC conversion factor of 1.26 was estimated by linear regression. Overall, chemical speciation revealed the following characteristics of peat-burning emissions: high OC mass fractions (72%), primarily water-insoluble OC (84 ± 11%C), low EC mass fractions (1%), vanillic to syringic acid ratios of 1.9, and relatively high n-alkane contributions to OC (6.2%C) with a carbon preference index of 1.2-1.6. Comparison to laboratory studies of peat combustion revealed similarities in the relative composition of PM but greater differences in the absolute EF values. The EFs developed herein, combined with estimates of the mass of peat burned, are used to estimate that 3.2-11 Tg of PM2.5 was emitted to atmosphere during the 2015 El Niño peatland fire event in Indonesia. Combined with gas-phase measurements of CO2, CO, CH4, and volatile organic carbon from Stockwell et al. (2016), it is determined that OC and EC accounted for 2.1 and 0.04% of total carbon emissions, respectively. These in situ EFs can be used to improve the accuracy of the representation of Indonesian peat burning in emission inventories and receptor-based models. [ABSTRACT FROM AUTHOR]

Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere, which can act as precursors to the formation of secondary pollutants such as ozone and fine particles. Measurements collected with a proton-transfer-reaction time-of-flight mass spectrometer during the FIREX 2016 laboratory intensive were analyzed with Positive Matrix Factorization (PMF), in order to understand the instantaneous variability in VOC emissions from biomass burning, and to simplify the description of these types of emissions. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles, which are mass spectral representations of the relative abundances of emitted VOCs, explained on average 85 % of the VOC emissions across various fuels representative of the western US (including various coniferous and chaparral fuels). In addition, the profiles were remarkably similar across almost all of the fuel types tested. For example, the correlation coefficient r of each profile between Ponderosa pine (coniferous tree) and Manzanita (chaparral) is higher than 0.9. We identified the two VOC profiles as resulting from high-temperature and low-temperature pyrolysis processes known to form VOCs in biomass burning. High-temperature and low-temperature pyrolysis processes do not correspond exactly to the commonly used flaming and smoldering categories as described by modified combustion efficiency (MCE). The average atmospheric properties (e.g. OH reactivity, volatility, etc.) of the high- and low-temperature profiles are significantly different. We also found that the two VOC profiles can describe previously reported VOC data for laboratory and field burns. This indicates that the high- and low-temperature pyrolysis profiles could be widely useful to model VOC emissions from many types of biomass burning in the western US, with a few exceptions such as burns of duff and rotten wood. [ABSTRACT FROM AUTHOR]

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 three-stone 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 emissions. 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. [ABSTRACT FROM AUTHOR]

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical aerosol populations is critical for accurate radiative transfer models, and for correctly interpreting remote sensing data. We deployed a laser imaging nephelometer at the Missoula Fire Sciences Laboratory to sample biomass burning aerosol from controlled fires during the FIREX intensive laboratory study. The laser imaging nephelometer measures the unpolarized scattering phase function of an aerosol ensemble using diode lasers at 375 and 405 nm. Scattered light from the bulk aerosol in the instrument is imaged onto a chargecoupled device (CCD) using a wide-angle field-of-view lens, which allows for measurements at 4–175° scattering angle with ~ 0.5° angular resolution. Along with a suite of other instruments, the laser imaging nephelometer sampled fresh smoke emissions both directly and after removal of volatile components with a thermodenuder at 250 °C. The total integrated aerosol scattering signal agreed with both a cavity ring-down photoacoustic spectrometer system and a traditional integrating nephelometer within instrumental uncertainties. We compare the measured scattering phase functions at 405 nm to theoretical models for spherical (Mie) and fractal (Rayleigh–Debye–Gans) particle morphologies based on the size distribution reported by an optical particle counter. Results from representative fires demonstrate that particle morphology can vary dramatically for different fuel types. In some cases, the measured phase function cannot be described using Mie theory. This study demonstrates the capabilities of the laser imaging nephelometer instrument to provide realtime, in situ information about dominant particle morphology, which is vital for understanding remote sensing data and accurately describing the aerosol population in radiative transfer calculations [ABSTRACT FROM AUTHOR]

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen (N)-containing particles impact atmospheric chemistry, air quality, and ecological N-deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98 ± 10 % efficiency for 100-600 nm particle diameters. We also show conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a non-dispersive infrared (NDIR) CO2 detector. We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single component, laboratory generated, Nr-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated on-line particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative ion mode. We obtain excellent correlations (R² = 0.99) of particle mass measured as Nr with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g. nitrate, sulfate, and chloride). The Nr and PILS-ESI/MS are shown to agree to within ~ 6 % for particle mass loadings up to 120 µg m-3. Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20 % for these single component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index. [ABSTRACT FROM AUTHOR]