Showing papers by "Robert J. Yokelson published in 2020"

Molecular composition and photochemical lifetimes of brown carbon chromophores in biomass burning organic aerosol

Abstract: . To better understand the effects of wildfires on air quality and climate, it is important to assess the occurrence of chromophoric compounds in smoke and characterize their optical properties. This study explores the molecular composition of light-absorbing organic aerosol, or brown carbon (BrC), sampled at the Missoula Fire Sciences laboratory as a part of the FIREX Fall 2016 lab intensive. A total of 12 biomass fuels from different plant types were tested, including gymnosperm (coniferous) and angiosperm (flowering) plants and different ecosystem components such as duff, litter, and canopy. Emitted biomass burning organic aerosol (BBOA) particles were collected onto Teflon filters and analyzed offline using high-performance liquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer (HPLC–PDA–HRMS). Separated BrC chromophores were classified by their retention times, absorption spectra, integrated absorbance in the near-UV and visible spectral range (300–700 nm), and chemical formulas from the accurate m∕z measurements. BrC chromophores were grouped into the following classes and subclasses: lignin-derived products, which include lignin pyrolysis products; distillation products, which include coumarins and flavonoids; nitroaromatics; and polycyclic aromatic hydrocarbons (PAHs). The observed classes and subclasses were common across most fuel types, although specific BrC chromophores varied based on plant type (gymnosperm or angiosperm) and ecosystem component(s) burned. To study the stability of the observed BrC compounds with respect to photodegradation, BBOA particle samples were irradiated directly on filters with near UV (300–400 nm) radiation, followed by extraction and HPLC–PDA–HRMS analysis. Lifetimes of individual BrC chromophores depended on the fuel type and the corresponding combustion condition. Lignin-derived and flavonoid classes of BrC generally had the longest lifetimes with respect to UV photodegradation. Moreover, lifetimes for the same type of BrC chromophores varied depending on biomass fuel and combustion conditions. While individual BrC chromophores disappeared on a timescale of several days, the overall light absorption by the sample persisted longer, presumably because the condensed-phase photochemical processes converted one set of chromophores into another without complete photobleaching or from undetected BrC chromophores that photobleached more slowly. To model the effect of BrC on climate, it is important to understand the change in the overall absorption coefficient with time. We measured the equivalent atmospheric lifetimes of the overall BrC absorption coefficient, which ranged from 10 to 41 d, with subalpine fir having the shortest lifetime and conifer canopies, i.e., juniper, having the longest lifetime. BrC emitted from biomass fuel loads encompassing multiple ecosystem components (litter, shrub, canopy) had absorption lifetimes on the lower end of the range. These results indicate that photobleaching of BBOA by condensed-phase photochemistry is relatively slow. Competing chemical aging mechanisms, such as heterogeneous oxidation by OH, may be more important for controlling the rate of BrC photobleaching in BBOA.

Rapid evolution of aerosol particles and their optical properties downwind of wildfires in the western US

Abstract: . 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 hours 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 transect more than 90 % of aerosol is organic. In freshly emitted smoke aerosol, NH4+ is approximately equivalent to NO3−. After two hours 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 increased in ~ two hours by 56 % and in one fight doubled. Coagulation and material transport from small to large particles are discussed as mechanisms for increasing particle size. 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 one to two hours 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.

Ambient air quality in the Kathmandu Valley, Nepal, during the pre-monsoon: concentrations and sources of particulate matter and trace gases

Abstract: . 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.

The nitrogen budget of laboratory-simulated western US wildfires during the FIREX 2016 Fire Lab study

Abstract: . 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 = CO 2 / ( CO + CO 2 ) , 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) ( ∘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.

Aerosol Mass and Optical Properties, Smoke Influence on O 3 , and High NO 3 Production Rates in a Western U.S. City Impacted by Wildfires

Abstract: Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include both inert tracers to test production and transport and reactive species to ...

Garbage Burning in South Asia: How Important Is It to Regional Air Quality?

Abstract: Increasing air pollution in South Asia has serious consequences for air quality and human/ecosystem health within the region. South Asia, including India and Nepal, suffers from severe air pollutio...