Organic aerosol formation downwind from the Deepwater Horizon oil spill.

A large fraction of atmospheric aerosols are derived from organic compounds with various volatilities. A National Oceanic and Atmospheric Administration (NOAA) WP-3D research aircraft made airborne measurements of the gaseous and aerosol composition of air over the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico that occurred from April to August 2010. A narrow plume of hydrocarbons was observed downwind of DWH that is attributed to the evaporation of fresh oil on the sea surface. A much wider plume with high concentrations of organic aerosol (>25 micrograms per cubic meter) was attributed to the formation of secondary organic aerosol (SOA) from unmeasured, less volatile hydrocarbons that were emitted from a wider area around DWH. These observations provide direct and compelling evidence for the importance of formation of SOA from less volatile hydrocarbons.

Airborne measurements of ethene from industrial sources using laser photo-acoustic spectroscopy.

A laser photoacoustic spectroscopy (LPAS) instrument was developed and used for aircraft measurements of ethene from industrial sources near Houston, Texas. The instrument provided 20 s measurements with a detection limit of less than 0.7 ppbv. Data from this instrument and from the GC-FID analysis of air samples collected in flight agreed within 15% on average. Ethene fluxes from the Mt. Belvieu chemical complex to the northeast of Houston were quantified during 10 different flights. The average flux was 520 +/- 140 kg h(-1) in agreement with independent results from solar occultation flux (SOF) measurements, and roughly an order of magnitude higher than regulatory emission inventories indicate. This study shows that ethene emissions are routinely at levels that qualify as emission upsets, which need to be reported to regional air quality managers.

Comparison of ultraviolet absorbance, chemiluminescence, and DOAS instruments for ambient ozone monitoring.

This paper evaluates the accuracy of ozone measurements made by monitors that determine ozone concentrations in ambient air by UV absorption. These monitors are typically used to measure ozone for the purpose of establishing local compliance to air-quality standards. The study was predicated by the concern that commercially available UV absorbance O3 monitors may be subject to interference from volatile organic carbon (VOC) species that absorb light at 254 nm. To test for these and other effects, we compared simultaneous O3 measurements made by a commercial UV O3 monitor with an O3-NO chemiluminescence instrument, which is not subject to interference by VOC compounds. The comparisons were carried out in the summers of 1999 and 2000 at urban/industrial sites in Nashville and Houston, and in 2004 aboard a ship in the Gulf of Maine. In the two urban areas, we also compared the 03 measurements from these two methods with O3 measurements made by a long-path differential optical absorption spectrometer (DOAS). Our tests indicate that, with well-maintained monitors, there are no significant interferences even in areas with significant ambient concentrations of potentially interfering VOCs.

Variability in nocturnal nitrogen oxide processing and its role in regional air quality.

Nitrogen oxides in the lower troposphere catalyze the photochemical production of ozone (O3) pollution during the day but react to form nitric acid, oxidize hydrocarbons, and remove O3 at night. A key nocturnal reaction is the heterogeneous hydrolysis of dinitrogen pentoxide, N2O5. We report aircraft measurements of NO3 and N2O5, which show that the N2O5 uptake coefficient, g(N2O5), on aerosol particles is highly variable and depends strongly on aerosol composition, particularly sulfate content. The results have implications for the quantification of regional-scale O3 production and suggest a stronger interaction between anthropogenic sulfur and nitrogen oxide emissions than previously recognized.

Intercomparison of volatile organic carbon measurement techniques and data at La Porte during the TexAQS2000 Air Quality Study.

The Texas Air Quality Study 2000 (TexAQS2000) investigated the photochemical production of ozone and the chemistry of related precursors and reaction products in the vicinity of Houston, TX. The colocation of four instruments for the measurement of volatile organic carbon compounds (VOCs) allowed a unique opportunity for the intercomparison of the different in-situ measuring techniques. The instruments included three gas chromatographs, each with a different type of detector, and a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) with each system designed to measure a different suite of VOCs. Correlation plots and correlation statistics are presented for species measured by more than one of these instruments. The GC instruments were all in agreement to within 10-20% (slope) with coefficients of variation (r2) of > or = 0.85. The PTR-MS agreement with other instruments was more dependent on species with some very good agreements (r2 values of approximately 0.95 for some aromatics), but isoprene, acetaldehyde and propene were substantially less highly correlated (0.55 < r2 < 0.80). At least part of these differences were undoubtedly due to the timing of sample acquisition in an environment in which VOC levels changed very rapidly on both quantitative and temporal scales.

Fossil-fueled power plants as a source of atmospheric carbon monoxide.

Elevated carbon monoxide (CO) mixing ratios in excess of those derived from emissions inventories have been observed in plumes from one gas- and coal-fired power plant and three of four lignite coal-fired electric utility power plants observed in east and central Texas. Observations of elevated CO on days characterized by differing wind directions show that CO emissions from the lignite plants were relatively constant over time and cannot be ascribed to separate sources adjacent to the power plants. These three plants were found to be emitting CO at rates 22 to 34 times those tabulated in State and Federal emissions inventories. Elevated CO emissions from the gas- and coal-fired plant were highly variable on time scales of hours to days, in one case changing by a factor of 8 within an hour. Three other fossil-fueled power plants, including one lignite-fired plant observed during this study, did not emit substantial amounts of CO, suggesting that a combination of plant operating conditions and the use of lignite coal may contribute to the enhanced emissions. Observed elevated CO emissions from the three lignite plants, if representative of average operating conditions, represent an additional 30% of the annual total CO emissions from point sources for the state of Texas.

Observations of ozone formation in power plant plumes and implications for ozone control strategies.

Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NO(x) (NO plus NO(2)) concentration, which is determined by plant NO(x) emission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NO(x) and volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NO(x) emission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NO(x) reductions from these sources.

Export of north american ozone pollution to the north atlantic ocean.

Measurement of the levels of ozone and carbon monoxide (a tracer of anthropogenic pollution) at three surface sites on the Atlantic coast of Canada allow the estimation of the amount of ozone photochemically produced from anthropogenic precursors over North America and transported to the lower troposphere over the temperate North Atlantic Ocean. This amount is greater than that injected from the stratosphere, the primary natural source of ozone. This conclusion supports the contention that ozone derived from anthropogenic pollution has a hemisphere-wide effect at northern temperate latitudes.

Natural vegetation as a source or sink for atmospheric ammonia: a case study.

Measurements of gaseous ammonia above a montane-subalpine forest in the Colorado mountains show that the role of the forest as a source or sink depends on the atmospheric concentrations. The canopy appeared to be an ammonia source when exposed to air containing low concentrations, but a sink when exposed to air enriched by nearby agricultural sources. The forest-averaged compensation point was 0.8 part per billion by volume at 20 degrees C. The net burden of ammonia and other nitrogen species of anthropogenic origin at this site was much less than at forest sites in the eastern United States and Europe and may provide a valuable resource for this nitrogen-limited ecosystem.

Instrumental requirements for global atmospheric chemistry.

The field of atmospheric chemistry is data-limited, primarily because of the challenge of measuring the key chemical constituents in the global environment. Several recent advances, however, in rugged, portable, remotesensing, ground-based instrumentation and accurate, fast-response airborne instrumentation have provided powerful tools for the understanding of stratospheric ozone, particularly in polar regions. Current discoveries of the role of heterogeneous chemical processes point to the need for better techniques for characterization of stratospheric aerosols. In the troposphere, advances in in situ, sensitive methods for detecting reactive nitrogen compounds have demonstrated the role that these compounds have in controlling global oxidation processes, but better measurements of the reservoir species by which the long-ranged transport of pollutant-reactive nitrogen compounds is thought to occur are urgently needed. The role of hydrocarbons, particularly those of natural origin, in ozone formation in rural areas has focused attention on the requirement for better speciation of these ubiquitous compounds. Lastly, rigorous instrument intercomparison experiments have provided unbiased estimates of measurement capabilities.