Browsing by Author "Gouw, J. A. de"
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Item Airborne measurements of the atmospheric emissions from a fuel ethanol refinery(AGU Pubication, 2015-04-08) Gouw, J. A. de; McKeen, S. A.; Aikin, K. C.; Brock, C. A.; Brown, S. S.; Gilman, J. B.; Graus, M.; Hanisco, T.; Holloway, J. S.; Kaiser, J.; Keutsch, F. N.; Lerner, B.M.; Liao, J.; Markovic, M. Z.; Middlebrook, A. M.; Min, K.-E.; Neuman, J. A.; Nowak, J. B.; Peischl, J.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Trainer, M.; Veres, P. R.; Warneke, C.; Welti, A.; Wolfe, G. M.Ethanol made from corn now constitutes approximately 10% of the fuel used in gasoline vehicles in the U.S. The ethanol is produced in over 200 fuel ethanol refineries across the nation. We report airborne measurements downwind from Decatur, Illinois, where the third largest fuel ethanol refinery in the U.S. is located. Estimated emissions are compared with the total point source emissions in Decatur according to the 2011 National Emissions Inventory (NEI‐2011), in which the fuel ethanol refinery represents 68.0% of sulfur dioxide (SO₂), 50.5% of nitrogen oxides (NOₓ = NO + NO₂), 67.2% of volatile organic compounds (VOCs), and 95.9% of ethanol emissions. Emissions of SO₂ and NOₓ from Decatur agreed with NEI‐2011, but emissions of several VOCs were underestimated by factors of 5 (total VOCs) to 30 (ethanol). By combining the NEI‐2011 with fuel ethanol production numbers from the Renewable Fuels Association, we calculate emission intensities, defined as the emissions per ethanol mass produced. Emission intensities of SO₂ and NOₓ are higher for plants that use coal as an energy source, including the refinery in Decatur. By comparing with fuel‐based emission factors, we find that fuel ethanol refineries have lower NOₓ, similar VOC, and higher SO₂ emissions than from the use of this fuel in vehicles. The VOC emissions from refining could be higher than from vehicles, if the underestimated emissions in NEI‐2011 downwind from Decatur extend to other fuel ethanol refineries. Finally, chemical transformations of the emissions from Decatur were observed, including formation of new particles, nitric acid, peroxyacyl nitrates, aldehydes, ozone, and sulfate aerosol.Item Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements(Copernicus Publications, 2015-10-23) Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; Sá, S. S. de; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, Jason; Wertz, G. Isaacman-Van; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; Gouw, J. A. de; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C₅H₆O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC₅H₆O (fC₅H₆O= C₅H₆O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC₅H₆O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC₅H₆O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC₅H₆O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO₂ vs. fC₅H₆O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC₅H₆O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.Item The Chemistry of Atmosphere-Forest Exchange (CAFE) Model – Part 2: Application to BEARPEX-2007 observations(Copernicus, 2011-02-15) Wolfe, G.M.; Thornton, J. A.; Bouvier-Brown, N. C.; Goldstein, A. H.; Park, J. H.; McKay, M.; Matross, D. M.; Mao, J.; Brune, W. H.; LaFranchi, B. W.; Browne, E. C.; Min, K.E.; Wooldridge, P. J.; Cohen, R. C.; Crounse, J.D.; Faloona, I. C.; Gilman, J. B.; Kuster, W. C.; Gouw, J. A. de; Huisman, A.; Keutsch, F. N.In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm (~29 °C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes.Item Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007(Copernicus, 2009-10-12) LaFranchi, B. W.; Wolfe, G. M.; Thornton, J. A.; Harrold, S. A.; Browne, E.C.; Min, K.E.; Wooldridge, P. J.; Gilman, J. B.; Kuster, W. C.; Goldan, P. D.; Gouw, J. A. de; McKay, M.; Goldstein, A. H.; Ren, X.; Mao, J.; Cohen, R. C.Acyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO₂. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of this chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO₂, numerous oVOC, and NO₂. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find that the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, accounting for 26%, 2%, 7%, 20%, and 45%, of the production rate on average during the campaign, respectively. At high temperatures, when upwind isoprene emissions are highest, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate, with methylvinyl ketone being the most important of the isoprene-derived sources. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO₂ rate constant by a factor of 3.Item Emissions of organic carbon and methane from petroleum and dairy operations in California's San Joaquin Valley(Copernicus Publications, 2014-05-21) Gentner, D. R.; Ford, T. B.; Guha, A.; Boulanger, K.; Brioude, J.; Angevine, W. M.; Gouw, J. A. de; Warneke, C.; Gilman, J. B.; Ryerson, T. B.; Peischl, J.; Meinardi, S.; Blake, D. R.; Atlas, E.; Lonneman, W. A.; Kleindienst, T. E.; Beaver, M. R.; St. Clair, Jason; Wennberg, P. O.; VandenBoer, T. C.; Markovic, M. Z.; Murphy, J.G.; Harley, R. A.; Goldstein, A. H.Petroleum and dairy operations are prominent sources of gas-phase organic compounds in California's San Joaquin Valley. It is essential to understand the emissions and air quality impacts of these relatively understudied sources, especially for oil/gas operations in light of increasing US production. Ground site measurements in Bakersfield and regional aircraft measurements of reactive gas-phase organic compounds and methane were part of the CalNex (California Research at the Nexus of Air Quality and Climate Change) project to determine the sources contributing to regional gas-phase organic carbon emissions. Using a combination of near-source and downwind data, we assess the composition and magnitude of emissions, and provide average source profiles. To examine the spatial distribution of emissions in the San Joaquin Valley, we developed a statistical modeling method using ground-based data and the FLEXPART-WRF transport and meteorological model. We present evidence for large sources of paraffinic hydrocarbons from petroleum operations and oxygenated compounds from dairy (and other cattle) operations. In addition to the small straight-chain alkanes typically associated with petroleum operations, we observed a wide range of branched and cyclic alkanes, most of which have limited previous in situ measurements or characterization in petroleum operation emissions. Observed dairy emissions were dominated by ethanol, methanol, acetic acid, and methane. Dairy operations were responsible for the vast majority of methane emissions in the San Joaquin Valley; observations of methane were well correlated with non-vehicular ethanol, and multiple assessments of the spatial distribution of emissions in the San Joaquin Valley highlight the dominance of dairy operations for methane emissions. The petroleum operations source profile was developed using the composition of non-methane hydrocarbons in unrefined natural gas associated with crude oil. The observed source profile is consistent with fugitive emissions of condensate during storage or processing of associated gas following extraction and methane separation. Aircraft observations of concentration hotspots near oil wells and dairies are consistent with the statistical source footprint determined via our FLEXPART-WRF-based modeling method and ground-based data. We quantitatively compared our observations at Bakersfield to the California Air Resources Board emission inventory and find consistency for relative emission rates of reactive organic gases between the aforementioned sources and motor vehicles in the region. We estimate that petroleum and dairy operations each comprised 22% of anthropogenic non-methane organic carbon at Bakersfield and were each responsible for 8–13% of potential precursors to ozone. Yet, their direct impacts as potential secondary organic aerosol (SOA) precursors were estimated to be minor for the source profiles observed in the San Joaquin Valley.Item Formaldehyde production from isoprene oxidation across NOx regimes(Copernicus, 2016-03-02) Wolfe, G. M.; Kaiser, J.; Hanisco, T. F.; Keutsch, F. N.; Gouw, J. A. de; Gilman, J.B.; Graus, M.; Hatch, C. D.; Holloway, J.; Horowitz, L. W.; Lee, B. H.; Lerner, B.M.; Lopez-Hilifiker, F.; Mao, J.; Marvin, M. R.; Peisch, J.; Pollack, I. B.; Robert, J. M.; Ryerson, T. B.; Thornton, J. A.; Veres, P. R.; Warneke, C.The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.Item Hydrocarbon Removal in Power Plant Plumes Shows Nitrogen Oxide Dependence of Hydroxyl Radicals(American Geophysical Union, 2019-07-05) Gouw, J. A. de; Parrish, D. D.; Brown, S. S.; Edwards, P.; Gilman, J. B.; Graus, M.; Hanisco, T. F.; Kaiser, J.; Keutsch, F. N.; Kim, S.‐W.; Lerner, B. M.; Neuman, J. A.; Nowak, J. B.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Veres, P. R.; Warneke, C.; Wolfe, G. M.Abstract During an airborne study in the Southeast United States, measured mixing ratios of biogenic hydrocarbons were systematically lower in air masses containing enhanced nitrogen oxides from power plants, which we attribute to increased concentrations of hydroxyl (OH) radicals within the power plant plumes. Plume transects at successively further downwind distances provide a decreasing gradient of nitrogen oxides (NOx) concentrations, which together with the implied loss rates of isoprene, constrains the OH dependence on NOx. We find that OH concentrations were highest at nitrogen dioxide concentrations near 1–2 ppbv and decreased at higher and at lower concentrations. These findings agree with the dependence of OH on NOx concentrations expected from known chemical reactions but are not consistent with some studies reporting direct OH measurements higher than expected in regions of the atmosphere with low NOx (NO < 0.08 and NO2 < 0.46 ppbv) and high biogenic hydrocarbon emissions. Plain Language Summary Hydroxyl radicals are the main chemical species that removes trace gases from the atmosphere. They determine the atmospheric lifetime of some greenhouse gases and chemicals involved with the destruction of the stratospheric ozone layer. Hydroxyl reactions also play an important role in air pollution chemistry. Measuring hydroxyl radicals is very challenging because of their high reactivity and low concentrations. Some recent measurements have shown unexpectedly high concentrations in relatively clean conditions. In this work, we indirectly estimated the dependence of hydroxyl radicals on the concentration of nitrogen oxides downwind from power plants in the Southeast United States. We observed that mixing ratios of isoprene, a reactive hydrocarbon released from deciduous trees to the atmosphere, were systematically lower in power plant plumes, caused by higher hydroxyl radical concentrations at the elevated nitrogen oxide concentrations. These findings can be explained by known chemical reactions but are not consistent with some studies that found unexpectedly high hydroxyl concentrations in relatively clean conditions.Item Speciation of OH reactivity above the canopy of an isoprene-dominated forest(Copernicus Publications, 2016-07-28) Kaiser, J.; Skog, K. M.; Baumann, K.; Bertman, S. B.; Brown, S.B.; Brune, W. H.; Crounse, J.D.; Gouw, J. A. de; Edgerton, E. S.; Feiner, P. A.; Goldstein, A. H.; Koss, A.; Misztal, P. K.; Nguyen, T. B.; Olson, K. F.; St. Clair, Jason; Teng, A. P.; Toma, S.; Wennberg, P. O.; Wild, R. J.; Zhang, L.; Keutsch, F. N.Measurements of OH reactivity, the inverse lifetime of the OH radical, can provide a top–down estimate of the total amount of reactive carbon in an air mass. Using a comprehensive measurement suite, we examine the measured and modeled OH reactivity above an isoprene-dominated forest in the southeast United States during the 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign. Measured and modeled species account for the vast majority of average daytime reactivity (80–95 %) and a smaller portion of nighttime and early morning reactivity (68–80 %). The largest contribution to total reactivity consistently comes from primary biogenic emissions, with isoprene contributing ∼ 60 % in the afternoon, and ∼ 30–40 % at night and monoterpenes contributing ∼ 15–25 % at night. By comparing total reactivity to the reactivity stemming from isoprene alone, we find that ∼ 20 % of the discrepancy is temporally related to isoprene reactivity, and an additional constant ∼ 1 s⁻¹ offset accounts for the remaining portion. The model typically overestimates measured OVOC concentrations, indicating that unmeasured oxidation products are unlikely to influence measured OH reactivity. Instead, we suggest that unmeasured primary emissions may influence the OH reactivity at this site