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Oil and natural gas (ONG) extraction emits volatile organic compounds (VOCs). Certain VOCs are identified as hazardous air pollutants (HAPS) while others contribute to ozone formation. This study examines the impact of ONG operations on VOC levels during the development of multi-well ONG pads in suburban Broomfield, Colorado. From October 2018 to December 2020, weekly VOC measurements were taken at 18 sites across the area. These included spots near well pads, in adjacent neighborhoods, and at a background site, covering various stages of well pad development including drilling, hydraulic fracturing, flowback, and production. Analysis using Positive Matrix Factorization (PMF) identified six factors, including combustion, background/biogenic sources, light and complex alkanes, drilling activities, and ONG acetylene. Factors linked to local ONG activities exhibited clear temporal and spatial correlations with Broomfield well development. Benzene source analysis revealed distinct contribution gradients, with ONG-related sources notably influencing areas near the well pads, particularly in pre-production. ONG-related weekly benzene contributions varied from 9% to 63% at a community background site and 18% to 89% in a neighborhood close to a well pad.

Biomass burning is a significant source of trace gases and aerosols to the atmosphere, and the evolution of these species depends acutely on where they are injected into the atmosphere. GEOS-Chem is a chemical transport model driven by assimilated meteorological data that is used to probe a variety of scientific questions related to atmospheric composition, including the role of biomass burning. This paper presents the development and implementation of a new global biomass burning emissions injection scheme in the GEOS-Chem model. The new injection scheme is based on monthly gridded Multi-angle Imaging SpectroRadiometer (MISR) global plume-height stereoscopic observations in 2008. To provide specific examples of the impact of the model updates, we compare the output from simulations with and without the new MISR-based injection height scheme to several sets of observations from regions with active fires. Our comparisons with Arctic Research on the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) aircraft observations show that the updated injection height scheme can improve the ability of the model to simulate the vertical distribution of peroxyacetyl nitrate (PAN) and carbon monoxide (CO) over North American boreal regions in summer. We also compare a simulation for October 2010 and 2011 to vertical profiles of CO over the Amazon Basin. When coupled with larger emission factors for CO, a simulation that includes the new injection scheme also better matches selected observations in this region. Finally, the improved injection height improves the simulation of monthly mean surface CO over California during July 2008, a period with large fires.

Peroxyacyl nitrate (PAN) is a critical atmospheric reservoir for nitrogen oxide radicals, and plays a lead role in their redistribution in the troposphere. We analyze new Tropospheric Emission Spectrometer (TES) PAN observations over North America from July 2006 to July 2009. Using aircraft observations from the Colorado Front Range, we demonstrate that TES can be sensitive to elevated PAN in the boundary layer (∼ 750 hPa) even in the presence of clouds. In situ observations have shown that wildfire emissions can rapidly produce PAN, and PAN decomposition is an important component of ozone production in smoke plumes. We identify smoke-impacted TES PAN retrievals by co-location with NOAA Hazard Mapping System (HMS) smoke plumes. Depending on the year, 15–32 % of cases where elevated PAN is identified in TES observations (retrievals with degrees of freedom (DOF) > 0.6) overlap smoke plumes during July. Of all the retrievals attempted in the July 2006 to July 2009 study period, 18 % is associated with smoke . A case study of smoke transport in July 2007 illustrates that PAN enhancements associated with HMS smoke plumes can be connected to fire complexes, providing evidence that TES is sufficiently sensitive to measure elevated PAN several days downwind of major fires. Using a subset of retrievals with TES 510 hPa carbon monoxide (CO) > 150 ppbv, and multiple estimates of background PAN, we calculate enhancement ratios for tropospheric average PAN relative to CO in smoke-impacted retrievals. Most of the TES-based enhancement ratios fall within the range calculated from in situ measurements.

The Sequential Spot Sampler (S3), a newly developed instrument to collect aerosols for time-resolved chemical composition measurements, was evaluated in the laboratory and field for the measurement of particulate sulfate and nitrate. The S3 uses a multi-temperature condensation growth tube to grow individual aerosols to droplets which are then deposited as a ∼ 1 mm diameter dry spot at the end of the growth tube in a 100 µL well of a multi-well plate. The well plate advances automatically to provide a sequence of time-resolved samples. The collected aerosols are subsequently analyzed in the laboratory. The sample is concentrated during the collection process, and the laboratory extraction and analysis steps can be automated. The well plate, as received from the field, is placed onto a needle-based autosampler that adds liquid for sample extraction and injects sample extract from each well onto an ion chromatograph for analysis. Laboratory evaluation for sulfate and nitrate ions showed that poly ether ether ketone (PEEK) used as well plate material does not contribute any artifacts; a 60 min extraction procedure leads to the recovery of sulfate and nitrate from the dry spots at above 95 % extraction efficiency; and samples stored frozen and analyzed up to 23 months later show less than a 10 % change in sulfate and nitrate concentrations. The limit of detection was 0.5 µg m−3 for sulfate and 0.2 µg m−3 for nitrate for a 1 h sampling period. In a month-long field study conducted in southern California, two S3s were deployed alongside a URG denuder–filter-pack and a Particle-Into-Liquid Sampler combined with an Ion Chromatograph (PILS-IC). Collocated S3 sampler concentrations compared by linear regression show good agreement, with r2 = 0.99 and slope = 0.99 (±0.004) µg m−3 for sulfate and r2 = 0.99 and slope = 1.0 (±0.006) µg m−3 for nitrate. When compared to the URG denuder–filter-pack and the PILS-IC, the S3 sulfate and nitrate concentrations yielded correlations above 0.84 for the square of the correlation coefficient and regression slopes close to 1.

The Bakken formation contains billions of barrels of oil and gas trapped in rock and shale. Horizontal drilling and hydraulic fracturing methods have allowed for extraction of these resources, leading to exponential growth of oil production in the region over the past decade. Along with this development has come an increase in associated emissions to the atmosphere. Concern about potential impacts of these emissions on federal lands in the region prompted the National Park Service to sponsor the Bakken Air Quality Study over two winters in 2013–2014. Here we provide an overview of the study and present some initial results aimed at better understanding the impact of local oil and gas emissions on regional air quality. Data from the study, along with long-term monitoring data, suggest that while power plants are still an important emissions source in the region, emissions from oil and gas activities are impacting ambient concentrations of nitrogen oxides and black carbon and may dominate recent observed trends in pollutant concentrations at some of the study sites. Measurements of volatile organic compounds also definitively show that oil and gas emissions were present in almost every air mass sampled over a period of more than 4 months.

During two intensive studies in summer 2010 and spring 2011, measurements of mercury species including gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM), trace chemical species including O3, SO2, CO, NO, NOY, and black carbon, and meteorological parameters were made at an Atmospheric Mercury Network (AMNet) site at the Grand Bay National Estuarine Research Reserve (NERR) in Moss Point, Mississippi. Surface measurements indicate that the mean mercury concentrations were 1.42 ± 0.12 ng∙m−3 for GEM, 5.4 ± 10.2 pg∙m−3 for GOM, and 3.1 ± 1.9 pg∙m−3 for PBM during the summer 2010 intensive and 1.53 ± 0.11 ng∙m−3 for GEM, 5.3 ± 10.2 pg∙m−3 for GOM, and 5.7 ± 6.2 pg∙m−3 for PBM during the spring 2011 intensive. Elevated daytime GOM levels (>20 pg∙m−3) were observed on a few days in each study and were usually associated with either elevated O3 (>50 ppbv), BrO, and solar radiation or elevated SO2 (>a few ppbv) but lower O3 (~20–40 ppbv). This behavior suggests two potential sources of GOM: photochemical oxidation of GEM and direct emissions of GOM from nearby local sources. Lack of correlation between GOM and Beryllium-7 (7Be) suggests little influence on surface GOM from downward mixing of GOM from the upper troposphere. These data were analyzed using the HYSPLIT back trajectory model and principal component analysis in order to develop source-receptor relationships for mercury species in this coastal environment. Trajectory frequency analysis shows that high GOM events were generally associated with high frequencies of the trajectories passing through the areas with high mercury emissions, while low GOM levels were largely associated the trajectories passing through relatively clean areas. Principal component analysis also reveals two main factors: direct emission and photochemical processes that were clustered with high GOM and PBM. This study indicates that the receptor site, which is located in a coastal environment of the Gulf of Mexico, experienced impacts from mercury sources that are both local and regional in nature.

The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50–85° N and 40–130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66–94% by volume), with a water-soluble mass fraction of more than 50%. The aerosol hygroscopicity parameter, κ, ranged between κ = 0.08–0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08 ± 0.01, while the Arctic background had the highest and most variable κ of 0.32 ± 0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18 ± 0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κorg) was parameterized by the volume fraction of water-soluble organic matter (εWSOM), with a κ = 0.12, such that κorg = 0.12εWSOM. Assuming bulk (size-independent) composition and including the κorg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing and therefore may not always be representative of the environments sampled. No correlation was observed between κorg and O : C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5×104 cm−3 and introduced supersaturation depletions of ≥25%. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure up to 25% and inferred κ by up to 50%.

Secondary organic aerosol (SOA) in the southeastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24-h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan < 50 ng m−3), WSOC and sulfate were highly correlated with PM2.5 mass (r2~0.7). Both components comprised a large mass fraction of PM2.5 (13% and 31%, respectively, or ~25% and 50% for WSOM and ammonium sulfate). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly linked to faster photochemistry and/or synoptic meteorology and less due to enhanced biogenic hydrocarbon emissions. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC were associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55 mgC m−2 h−1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the southeastern US, confirming the importance of SOA and the roles of both biogenic and anthropogenic emissions.

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pmol mol−1) under unpolluted conditions (NO−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008.

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska, USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Approximately 500 smoke plumes from biomass burning emissions that varied in age from minutes to days were segregated by fire source region and urban emission influences. The normalized excess mixing ratios (NEMR) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen and ozone) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared. A detailed statistical analysis of the different plume categories for different gaseous and aerosol species is presented in this paper. The comparison of NEMR values showed that CH4 concentrations were higher in air-masses that were influenced by urban emissions. Fresh biomass burning plumes mixed with urban emissions showed a higher degree of oxidative processing in comparison with fresh biomass burning only plumes. This was evident in higher concentrations of inorganic aerosol components such as sulfate, nitrate and ammonium, but not reflected in the organic components. Lower NOx NEMRs combined with high sulfate, nitrate and ammonium NEMRs in aerosols of plumes subject to long-range transport, when comparing all plume categories, provided evidence of advanced processing of these plumes.

Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = −0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr−1 is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

Light absorption of fine particle (PM2.5) aqueous extracts between wavelengths of 200 and 800 nm were investigated from two data sets: 24-h Federal Reference Method (FRM) filter extracts from 15 Southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified: biomass burning, mobile source emissions, and compounds linked to secondary organic aerosol (SOA) formation. Absorption spectra of aerosol solutions from filter extracts were similar for different sources. Angstrom exponents were ~7±1 for biomass burning and non-biomass burning-impacted 24-h filter samples (delineated by a levoglucosan concentration of 50 ng m−3) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370 nm (Abs365, in units m−1) was used as a measure of overall brown carbon light absorption. Biomass-burning-impacted samples were highest during winter months and Abs365 was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs365/WSOC (i.e., mass absorption efficiency) was typically ~3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs365 to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ~10% of the regional yearly average Abs365. Summertime diurnal profiles of Abs365 and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs365/WSOC. After noon, this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis on the 24-h integrated filter data associated ~20 to 30% of Abs365 over 2007 with a secondary source that was highest in summer and also the main source for oxalate, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the Southeastern US in summer.

Archived Federal Reference Method (FRM) Teflon filters used by state regulatory agencies for measuring PM2.5 mass were acquired from 15 sites throughout the southeastern US and analyzed for water-soluble organic carbon (WSOC), water-soluble ions and carbohydrates to investigate biomass burning contributions to fine aerosol mass. Based on over 900 filters that spanned all of 2007, levoglucosan and K+ were studied in conjunction with MODIS Aqua fire count data to compare their performances as biomass burning tracers. Levoglucosan concentrations exhibited a distinct seasonal variation with large enhancement in winter and spring and a minimum in summer, and were well correlated with fire counts, except in winter when residential wood burning contributions were significant. In contrast, K+ concentrations had no apparent seasonal trend and poor correlation with fire counts. Levoglucosan and K+ only correlated well in winter (r2=0.59) when biomass burning emissions were highest, whereas in other seasons they were not correlated due to the presence of other K+ sources. Levoglucosan also exhibited larger spatial variability than K+. Both species were higher in urban than rural sites (mean 44% higher for levoglucosan and 86% for K+). Positive Matrix Factorization (PMF) was applied to analyze PM2.5 sources and four factors were resolved: biomass burning, refractory material, secondary light absorbing WSOC and secondary sulfate/WSOC. The biomass burning source contributed 13% to PM2.5 mass annually, 27% in winter, and less than 2% in summer, consistent with other souce apportionment studies based on levoglucosan, but lower in summer compared to studies based on K+.

Measurements of atmospheric gases and fine particle chemistry were made in the Mexico City Metropolitan Area (MCMA) at a site ~30 km down wind of the city center. Ammonium nitrate (NH4NO3) dominated the inorganic aerosol fraction and showed a distinct diurnal signature characterized by rapid morning production and a rapid mid-day concentration decrease. Between the hours of 08:00–12:45, particulate water-soluble organic carbon (WSOC) concentrations increased and decreased in a manner consistent with that of NO3−, and the two were highly correlated (R2=0.88) during this time. A box model was used to analyze these behaviors and showed that, for both NO3− and WSOC, the concentration increase was caused primarily (~75–85%) by secondary formation, with a smaller contribution (~15–25%) from the entrainment of air from the free troposphere. For NO3−, a majority (~60%) of the midday concentration decrease was caused by dilution from boundary layer expansion, though a significant fraction (~40%) of the NO3− loss was due to particle evaporation. The WSOC concentration decrease was due largely to dilution (~75%), but volatilization did have a meaningful impact (~25%) on the decrease, as well. The results provide an estimate of ambient SOA evaporation losses and suggest that a significant fraction (~35%) of the fresh MCMA secondary organic aerosol (SOA) measured at the surface volatilized.

During the National Aeronautics and Space Administration (NASA) Intercontinental Chemical Transport Experiment, Phase B (INTEX-B), in the spring of 2006, airborne measurements were made in the United States Pacific Northwest of the major inorganic ions and the water-soluble organic carbon (WSOC) of submicron (PM1.0) aerosol. An atmospheric trajectory (HYSPLIT) and a Lagrangian particle dispersion model (Flexpart) quantifying source contributions for carbon monoxide (CO) were used to segregate air masses into those of primarily Asian influence (>75% Asian CO) or North American influence (>75% North American CO). Of the measured compounds, fine particle mass mostly consisted of water-soluble organic carbon and sulfate, with median sulfate and WSOC concentrations in two to four times higher, respectively, in North American air masses versus transported Asian air masses. The fraction of WSOC to sulfate in transported Asian air masses was significantly lower than one at altitudes above 3 km due to depleted organic aerosol, opposite to what has been observed closer to Asia and in the northeastern United States, where organic components were at higher concentrations than sulfate in the free troposphere. The observations could be explained by loss of sulfate and organic aerosol by precipitation scavenging, with reformation of mainly sulfate during advection from Asia to North America. In contrast to free tropospheric measurements, for all air masses below approximately 2 km altitude median WSOC-sulfate ratios were consistently between one and two. WSOC sources were investigated by multivariate linear regression analyses of WSOC and volatile organic compounds (VOCs). In Asian air masses, of the WSOC variability that could be explained (49%), most was related to fossil fuel combustion VOCs, compared to North American air masses, where 75% of the WSOC variability was explained through a nearly equal combination of fossil fuel combustion and biogenic VOCs. Distinct WSOC plumes encountered during the experiment were also studied. A plume observed near the California Central Valley at 0.6 km altitude was related to both fossil fuel combustion and biogenic VOCs. Another Central Valley plume observed over Nevada at 3 to 5 km, in a region of cloud detrainment, was mostly related to biogenic VOCs.

Biomass burning is a significant source of trace gases and aerosols to the atmosphere, and the evolution of these species depends acutely on where they are injected into the atmosphere. GEOS-Chem is a chemical transport model driven by assimilated meteorological data that is used to probe a variety of scientific questions related to atmospheric composition, including the role of biomass burning. This paper presents the development and implementation of a new global biomass burning emissions injection scheme in the GEOS-Chem model. The new injection scheme is based on monthly gridded Multi-angle Imaging SpectroRadiometer (MISR) global plume-height stereoscopic observations in 2008. To provide specific examples of the impact of the model updates, we compare the output from simulations with and without the new MISR-based injection height scheme to several sets of observations from regions with active fires. Our comparisons with Arctic Research on the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) aircraft observations show that the updated injection height scheme can improve the ability of the model to simulate the vertical distribution of peroxyacetyl nitrate (PAN) and carbon monoxide (CO) over North American boreal regions in summer. We also compare a simulation for October 2010 and 2011 to vertical profiles of CO over the Amazon Basin. When coupled with larger emission factors for CO, a simulation that includes the new injection scheme also better matches selected observations in this region. Finally, the improved injection height improves the simulation of monthly mean surface CO over California during July 2008, a period with large fires. [ABSTRACT FROM AUTHOR]

Biomass burning is a significant source of trace gases and aerosols to the atmosphere, and the evolution of these species depends acutely on where they are injected into the atmosphere. GEOS-Chem is a chemical transport model driven by assimilated meteorological data that is used to probe a variety of scientific questions related to atmospheric composition, including the role of biomass burning. This paper presents the development and implementation of a new global biomass burning emissions injection scheme in the GEOS-Chem model. The new injection scheme is based on monthly gridded Multi-Angle Imaging Spectro Radiometer (MISR) global plume-height stereoscopic observations in 2008. To provide specific examples of the impact of the model updates, we compare the output from simulations with and without the new MISR-based injection height scheme to several sets of observations from regions with active fires. Our comparisons with ARCTAS aircraft observations show that the updated injection height scheme improves the ability of the model to simulate the vertical distribution of peroxyacetyl nitrate (PAN) and carbon monoxide (CO) over North American boreal regions in summer. We also compare a simulation for October 2010 and 2011 to vertical profiles of CO over the Amazon Basin. When coupled with larger emission factors for CO, a simulation that includes the new injection scheme also better matches selected observations in this region. Finally the improved injection height also improves the simulation of monthly mean surface CO over California during July 2008, a period with large fires. [ABSTRACT FROM AUTHOR]

Peroxyacyl nitrate (PAN) is a critical atmospheric reservoir for nitrogen oxide radicals, and plays a lead role in their redistribution in the troposphere. We analyze new Tropospheric Emission Spectrometer (TES) PAN observations over North America from July 2006 to July 2009. Using aircraft observations from the Colorado Front Range, we demonstrate that TES can be sensitive to elevated PAN in the boundary layer (~750hPa) even in the presence of clouds. In situ observations have shown that wildfire emissions can rapidly produce PAN, and PAN decomposition is an important component of ozone production in smoke plumes. We identify smoke-impacted TES PAN retrievals by co-location with NOAA Hazard Mapping System (HMS) smoke plumes. Depending on the year, 15-32% of cases where elevated PAN is identified in TES observations (retrievals with degrees of freedom (DOF)>0.6) overlap smoke plumes during July. Of all the retrievals attempted in the July 2006 to July 2009 study period, 18% is associated with smoke . A case study of smoke transport in July 2007 illustrates that PAN enhancements associated with HMS smoke plumes can be connected to fire complexes, providing evidence that TES is sufficiently sensitive to measure elevated PAN several days downwind of major fires. Using a subset of retrievals with TES 510hPa carbon monoxide (CO) >150ppbv, and multiple estimates of background PAN, we calculate enhancement ratios for tropospheric average PAN relative to CO in smoke-impacted retrievals. Most of the TES-based enhancement ratios fall within the range calculated from in situ measurements. [ABSTRACT FROM AUTHOR]

Peroxyacetyl nitrate (PAN) is a critical atmospheric reservoir for nitrogen oxide radicals, and it plays a lead role in their redistribution in the troposphere. We analyze new Tropospheric Emission Spectrometer (TES) PAN observations over North America during July 2006 to 2009. Using aircraft observations from the Colorado Front Range, we demonstrate that TES can be sensitive to elevated PAN in the boundary layer even in the presence of clouds. In situ observations have shown that wildfire emissions can rapidly produce PAN, and PAN decomposition is an important component of ozone production in smoke plumes. We identify smoke-impacted TES PAN retrievals by co-location with NOAA Hazard Mapping System (HMS) smoke plumes. We find that 15-32 % of cases where elevated PAN is identified in TES observations (retrievals with DOF > 0.6) overlap smoke plumes. A case study of smoke transport in July 2007 illustrates that PAN enhancements associated with HMS smoke plumes can be connected to fire complexes, providing evidence that TES is sufficiently sensitive to measure elevated PAN several days downwind of major fires. Using a subset of retrievals with TES 510 hPa carbon monoxide (CO) > 150 ppbv, and multiple estimates of background PAN, we calculate enhancement ratios for tropospheric average PAN relative to CO in smoke-impacted retrievals. Most of the TES-based enhancement ratios fall within the range calculated from in situ measurements. [ABSTRACT FROM AUTHOR]

The Bakken formation contains billions of barrels of oil and gas trapped in rock and shale. Horizontal drilling and hydraulic fracturing methods have allowed for extraction of these resources, leading to exponential growth of oil production in the region over the past decade. Along with this development has come an increase in associated emissions to the atmosphere. Concern about potential impacts of these emissions on federal lands in the region prompted the National Park Service to sponsor the Bakken Air Quality Study over two winters in 2013-2014. Here we provide an overview of the study and present some initial results aimed at better understanding the impact of local oil and gas emissions on regional air quality. Data from the study, along with longterm monitoring data, suggest that while power plants are still an important emissions source in the region, emissions from oil and gas activities are impacting ambient concentrations of nitrogen oxides and black carbon and may dominate recent observed trends in pollutant concentrations at some of the study sites. Measurements of volatile organic compounds also definitively show that oil and gas emissions were present in almost every air mass sampled over a period of more than 4 months. [ABSTRACT FROM AUTHOR]

The Bakken formation contains billions of barrels of oil and gas trapped in rock and shale. Horizontal drilling and hydraulic fracturing methods have allowed for extraction of these resources, leading to exponential growth of oil production in the region over the past decade. Along with this development has come an increase in associated emissions to the atmosphere. Concern about potential impacts of these emissions on federal lands in the region prompted the National Park Service to sponsor the Bakken Air Quality Study over two winters in 2013-2014. Here we provide an overview of the study and present some initial results aimed at better understanding the impact of local oil and gas emissions on regional air quality. Data from the study, along with long term monitoring data, suggest that while power plants are still an important emissions source in the region, emissions from oil and gas activities are impacting ambient concentrations of nitrogen oxides and black carbon and may dominate recent observed trends in pollutant concentrations at some of the study sites. Measurements of volatile organic compounds also definitively show that oil and gas emissions were present in almost every air mass sampled over a period of more than four months. [ABSTRACT FROM AUTHOR]

The Sequential Spot Sampler (S3), a newly developed instrument to collect aerosols for time resolved chemical composition measurements, was evaluated in the laboratory and field for the measurement of particulate sulfate and nitrate. The S3 uses a multi-temperature condensation growth tube to grow individual aerosols to droplets which are then deposited as a ~ 1 mm diameter dry spot at the end of the growth tube on a 100 µL well of a multi-well plate. The well plate advances automatically to provide a sequence of time-resolved samples. The collected aerosols are subsequently analyzed in the laboratory. The sample is concentrated during the collection process and the laboratory extraction and analysis steps can be automated. The well plate, as received from the field, is placed onto a needle-based autosampler that adds liquid for sample extraction and injects sample extract from each well onto an ion chromatograph for analysis. Laboratory evaluation for sulfate and nitrate ions showed that PEEK used as well plate material does not contribute any artifacts; a 60 min extraction procedure leads to the recovery of sulfate and nitrate from the dry spots at above 95% extraction efficiency; and samples stored frozen and analyzed up to 23 months later show less than a 10% change in sulfate and nitrate concentrations. In a month long field study conducted in Southern California, two S3s were deployed alongside a URG denuder/filter-pack and a Particle-Into-Liquid Sampler combined with an Ion Chromatograph (PILS-IC). Collocated S3 sampler concentrations compared by linear regression show good agreement with r² = 0.99 and slope = 0.99 (±0.004) µg m-3 for sulfate and r² = 0.99 and slope =1.0 (±0.006) µg m-3 for nitrate. When compared to the URG denuder/filter-pack and the PILS-IC, the S3 sulfate and nitrate concentrations yielded correlations above 0.84 for the square of the correlation coefficient and regression slopes close to one. [ABSTRACT FROM AUTHOR]

The article presents results from two intensive studies during the summer of 2010 and spring of 2011 on measurements of mercury species including gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM) at an Atmospheric Mercury Network (AMNet) site at the Grand Bay National Estuarine Research Reserve (NERR) in Moss Point, Mississippi, in the northern Gulf of Mexico region.

The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50-85° N and 40-130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66-94%by volume), with a water-soluble mass fraction of more than 50 %. The aerosol hygroscopicity parameter, k, ranged between k =0.08-0.32 for all air mass types. Industrial pollution had the lowest k of 0.08±0.01, while the Arctic background had the highest and most variable k of 0.32±0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar k (0.18±0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (korg) was parameterized by the volume fraction of water-soluble organic matter (εWSOM), with a k =0.12, such that korg = 0.12εWSOM. Assuming bulk (size-independent) composition and including the korg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing and therefore may not always be representative of the environments sampled. No correlation was observed between korg and O: C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5×104 cm-3 and introduced supersaturation depletions of ≥25 %. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure up to 25% and inferred k by up to 50 %. [ABSTRACT FROM AUTHOR]

The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and 5 aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50-85° N and 40-130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66-94% by volume), more than half of which was water-soluble. The aerosol hygroscopicity parameter, κ, ranged between κ =0.1-0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08±0.01, while the Arctic background had the highest and most variable κ of 0.32±0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18±0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κ org) was parameterized by the volume fraction of water-soluble organic matter (εWSOM), with a κ =0.12, such that κorg=0.12εWSOM. Assuming bulk (size-independent) composition and including the κorg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only 20 exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing. No correlation was observed between κorg and O:C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5x104 cm-3 and introduced supersaturation depletions of ≥25 %. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure and inferred κ by up to 50 %. [ABSTRACT FROM AUTHOR]

Secondary organic aerosol (SOA) in the south-eastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24-h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan <50 ngm-3), WSOC and sulfate were highly correlated with PM2.5 mass (r² ∼ 0.7). Both components comprised a large mass fraction of PM2.5 (13% and 31%, respectively, or ∼25% and 50% for WSOM and ammonium sulfate). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly linked to faster photochemistry and/or synoptic meteorology and less due to enhanced biogenic hydrocarbon emissions. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC were associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55mgCm-2 h-1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the south-eastern US, confirming the importance of SOA and the roles of both biogenic and anthropogenic emissions. [ABSTRACT FROM AUTHOR]

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska, USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTASCARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Approximately 500 smoke plumes from biomass burning emissions that varied in age from minutes to days were segregated by fire source region and urban emission influences. The normalized excess mixing ratios (NEMR) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen and ozone) and fine aerosol particulate components (nitrate, sulfate. ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared. A detailed statistical analysis of the different plume categories for different gaseous and aerosol species is presented in this paper. The comparison of NEMR values showed that CHa concentrations were higher in air-masses that were influenced by urban emissions. Fresh biomass burning plumes mixed with urban emissions showed a higher degree of oxidative processing in comparison with fresh biomass burning only plumes. This was evident in higher concentrations of inorganic aerosol components such as sulfate, nitrate and ammonium. but not reflected in the organic components. Lower NOx NEMRs combined with high sulfate, nitrate and ammonium NEMRs in aerosols of plumes subject to long-range transport, when comparing all plume categories, provided evidence of advanced processing of these plumes. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60 ~0.3%±0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) =-0.01 to ~0.05, with a mean ΔOA/POA ~19 %. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8±7 Tg OA yr-1 is estimated, of the order of 5% of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden. [ABSTRACT FROM AUTHOR]