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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]

Light alkane hydrocarbons are present in major quantities in the near-surface atmosphere of Texas, Oklahoma, and Kansas during both autumn and spring seasons. In spring 2002, maximum mixing ratios of ethane [34 parts per 10[SUP9] by volume (ppbv)], propane (20 ppbv), and n-butane (13 ppbv) were observed in north-central Texas. The elevated alkane mixing ratios are attributed to emissions from the oil and natural gas industry. Measured alkyl nitrate mixing ratios were comparable to urban smog values, indicating active photochemistry in the presence of nitrogen oxides, and therefore with abundant formation of tropospheric ozone. We estimate that 4-6 teragrams of methane are released annually within the region and represents a significant fraction of the estimated total U.S. emissions. This result suggests that total U.S. natural gas emissions may have been underestimated. Annual ethane emissions from the study region are estimated to be 0.3-0.5 teragrams. [ABSTRACT FROM AUTHOR]

Abstract: While it is well known that combustion of ethanol as a biofuel will lead to enhanced emissions of methane, ethene (ethylene), acetaldehyde, formaldehyde, and oxides of nitrogen (primarily NO) when compared to gasoline alone, especially during cold starts or if catalytic converters are not operating properly, the impacts of increases in atmospheric ethene levels from combustion of fuels with higher ethanol content has not received much attention. Ethene is a well known and potent plant growth hormone and exposure to agricultural crops and natural vegetation results in yield reductions especially when combined with higher levels of PAN and ozone also expected from the increased use of ethanol/gasoline blends. We report here some baseline measurements of ethene obtained in 2002 in the southwestern and south central United States. These data indicate that current ethene background levels are less than 1 ppb. Anticipated increases in fuel ethanol content of E30 or greater is expected to lead to higher atmospheric levels of ethene on regional scales due to its atmospheric lifetime of 1.5–3 days. These background measurements are discussed in light of the potential enhancement of ethene levels expected from the anticipated increases in ethanol use as a renewable biofuel. [Copyright &y& Elsevier]

We use recent aircraft measurements of a comprehensive suite of anthropogenic halocarbons, carbon monoxide (CO), and related tracers to place new constraints on North American halocarbon emissions and quantify their global warming potential. Using a chemical transport model (GEOS-Chem) we find that the ensemble of observations are consistent with our prior best estimate of the U.S. anthropogenic CO source, but suggest a 30% underestimate of Mexican emissions. We develop an optimized CO emission inventory on this basis and quantify halocarbon emissions from their measured enhancements relative to CO. Emissions continue for many compounds restricted under the Montreal Protocol, and we show that halocarbons make up an important fraction of the total greenhouse gas source for both countries: our best estimate is 9% (uncertainty range 6-12%) and 32% (21-52%) of equivalent CO2 emissions for the U.S. and Mexico, respectively, on a 20 year time scale. Performance of bottom-up emission inventories is variable, with underestimates for some compounds and overestimates for others. Ongoing methylchloroform emissions are significant in the U.S. (2.8 Gg/y in 2004-2006), in contrast to bottom-up estimates (<0.05 Gg), with implications for tropospheric OH calculations. Mexican methylchloroform emissions are minor. [ABSTRACT FROM AUTHOR]

Abstract: As part of the third NASA Aircraft Particle Emissions Experiment (APEX-3, November 2005), whole air samples were collected to determine the emission rates of volatile organic compounds (VOCs) from aircraft equipped with three different gas-turbine engines (an Allison Engine 3007-A1E, a Pratt–Whitney 4158, and a Rolls–Royce RB211-535E4B). Samples were collected 1 m behind the engine exhaust plane of the engines while they were operated at powers ranging from idle up to 30% of maximum rated thrust. Exhaust emission indices (mass emitted per kilogram of fuel used) for CO and non-methane hydrocarbons (NMHCs) were calculated based on enhancements over background relative to CO2. Emissions of all NMHCs were greatest at low power with values decreasing by an order of magnitude with increasing power. Previous studies have shown that scaling idle hydrocarbon emissions to formaldehyde or ethene (which are typically emitted at a ratio of 1-to-1 at idle) reduces variability amongst engine types. NMHC emissions were found to scale at low power, with alkenes contributing over 50% of measured NMHCs. However, as the power increases hydrocarbon emissions no longer scale to ethene, as the aromatics become the dominant species emitted. This may be due in part to a shift in combustion processes from thermal cracking (producing predominantly alkenes) to production of new molecules (producing proportionally more aromatics) as power increases. The formation of these aromatics is an intermediate step in the production of soot, which also increases with increasing power. The increase in aromatics relative to alkenes additionally results in a decrease in the hydroxyl radical reactivity and ozone formation potential of aircraft exhaust. Samples collected 30 m downwind of the engine were also analyzed for NMHCs and carbonyl compounds (acetone, 2-butanone and C1–C9 aldehydes). Formaldehyde was the predominant carbonyl emitted; however, the ratio of ethene-to-formaldehyde varied between the aircraft, possibly due to the sampling of transient emissions such as engine start-up and power changes. A large portion of the measured emissions (27–42% by mass) in the plume samples was made up of hazardous air pollutants (HAPs) with oxygenated compounds being most significant. [Copyright &y& Elsevier]

Abstract: Ground-based surveys of three coal fires and airborne surveys of two of the fires were conducted near Sheridan, Wyoming. The fires occur in natural outcrops and in abandoned mines, all containing Paleocene-age subbituminous coals. Diffuse (carbon dioxide (CO2) only) and vent (CO2, carbon monoxide (CO), methane, hydrogen sulfide (H2S), and elemental mercury) emission estimates were made for each of the fires. Additionally, gas samples were collected for volatile organic compound (VOC) analysis and showed a large range in variation between vents. The fires produce locally dangerous levels of CO, CO2, H2S, and benzene, among other gases. At one fire in an abandoned coal mine, trends in gas and tar composition followed a change in topography. Total CO2 fluxes for the fires from airborne, ground-based, and rate of fire advancement estimates ranged from 0.9 to 780mg/s/m2 and are comparable to other coal fires worldwide. Samples of tar and coal-fire minerals collected from the mouth of vents provided insight into the behavior and formation of the coal fires. [Copyright &y& Elsevier]

Abstract: Between 1999 and 2005 a sampling campaign was conducted to identify and quantify the major species of atmospheric nonmethane hydrocarbons (NMHCs) in United States cities. Whole air canister samples were collected in 28 cities and analyzed for methane, carbon monoxide (CO) and NMHCs. Ambient mixing ratios exhibited high inter- and intra-city variability, often having standard deviations in excess of 50% of the mean value. For this reason, ratios of individual NMHC to CO, a combustion tracer, were examined to facilitate comparison between cities. Ratios were taken from correlation plots between the species of interest and CO, and most NMHCs were found to have correlation coefficients (r 2) greater than 0.6, particularly ethene, ethyne and benzene, highlighting the influence of vehicular emissions on NMHC mixing ratios. Notable exceptions were the short-chain alkanes, which generally had poor correlations with CO. Ratios of NMHC vs. CO were also used to identify those cities with unique NMHC sources. [Copyright &y& Elsevier]

We present a statistical representation of the aggregate effects of deep convection on the chemistry and dynamics of the upper troposphere (UT) based on direct aircraft observations of the chemical composition of the UT over the eastern United States and Canada during summer. These measurements provide unique observational constraints on the chemistry occurring downwind of convection and the rate at which air in the UT is recycled. These results provide quantitative measures that can be used to evaluate global climate and chemistry models. [ABSTRACT FROM AUTHOR]

Oil and gas (O&G) facilities emit air pollutants that are potentially a major health risk for nearby populations. We characterized prenatal through adult health risks for acute (1 h) and chronic (30 year) residential inhalation exposure scenarios to nonmethane hydrocarbons (NMHCs) for these populations. We used ambient air sample results to estimate and compare risks for four residential scenarios. We found that air pollutant concentrations increased with proximity to an O&G facility, as did health risks. Acute hazard indices for neurological (18), hematological (15), and developmental (15) health effects indicate that populations living within 152 m of an O&G facility could experience these health effects from inhalation exposures to benzene and alkanes. Lifetime excess cancer risks exceeded 1 in a million for all scenarios. The cancer risk estimate of 8.3 per 10 000 for populations living within 152 m of an O&G facility exceeded the United States Environmental Protection Agency's 1 in 10 000 upper threshold. These findings indicate that state and federal regulatory policies may not be protective of health for populations residing near O&G facilities. Health risk assessment results can be used for informing policies and studies aimed at reducing and understanding health effects associated with air pollutants emitted from O&G facilities.

During the Deepwater Horizon (DWH) oil spill, a wide range of gas and aerosol species were measured from an aircraft around, downwind, and away from the DWH site. Additional hydrocarbon measurements were made from ships in the vicinity. Aerosol particles of respirable sizes were on occasions a significant air quality issue for populated areas along the Gulf Coast. Yields of organic aerosol particles and emission factors for other atmospheric pollutants were derived for the sources from the spill, recovery, and cleanup efforts. Evaporation and subsequent secondary chemistry produced organic particulate matter with a mass yield of 8 ± 4% of the oil mixture reaching the water surface. Approximately 4% by mass of oil burned on the surface was emitted as soot particles. These yields can be used to estimate the effects on air quality for similar events as well as for this spill at other times without these data. Whereas emission of soot from burning surface oil was large during the episodic burns, the mass flux of secondary organic aerosol to the atmosphere was substantially larger overall. We use a regional air quality model to show that some observed enhancements in organic aerosol concentration along the Gulf Coast were likely due to the DWH spill. In the presence of evaporating hydrocarbons from the oil, NO(x) emissions from the recovery and cleanup operations produced ozone.

Various brands and types of cigarettes were purchased at retail locations in southern California. Volatile gas samples were analyzed using multicolumn/multidetector gas chromatography. Results showed methyl chloride (CH(3)Cl) levels as much as four orders of magnitude higher than typical urban levels, about 30-500 ppmv (1.5-5.3 mg/cigarette), compared with about 500 pptv in urban air. The concentration of CH(3)Cl correlated well with the levels of both CO (r (2) = 0.63) and CO(2) (r (2) = 0.77), showing the link between CH(3)Cl and combustion. In some brands, CH(3)Cl levels were well above the U.S. Environmental Protection Agency's maximum exposure limit of 200 ppmv. Light branded cigarettes tended to have higher CH(3)Cl levels than the heavier and filtered brands, possibly showing the dependence of cigarette packing on CH(3)Cl production. In addition, CH(3)Cl emitted from cigarette smoke may prove to be an important anthropogenic source of CH(3)Cl in the United States, at about 5%.