Donna Sueper

Evolution of Organic Aerosols in the Atmosphere

Framework for Change Organic aerosols make up 20 to 90% of the particulate mass of the troposphere and are important factors in both climate and human heath. However, their sources and removal pathways are very uncertain, and their atmospheric evolution is poorly characterized. Jimenez et al. (p. 1525; see the Perspective by Andreae) present an integrated framework of organic aerosol compositional evolution in the atmosphere, based on model results and field and laboratory data that simulate the dynamic aging behavior of organic aerosols. Particles become more oxidized, more hygroscopic, and less volatile with age, as they become oxygenated organic aerosols. These results should lead to better predictions of climate and air quality. Organic aerosols are not compositionally static, but they evolve dramatically within hours to days of their formation. Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high–time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

An Aerosol Chemical Speciation Monitor (ACSM) for Routine Monitoring of the Composition and Mass Concentrations of Ambient Aerosol

We present a new instrument, the Aerosol Chemical Speciation Monitor (ACSM), which routinely characterizes and monitors the mass and chemical composition of non-refractory submicron particulate matter in real time. Under ambient conditions, mass concentrations of particulate organics, sulfate, nitrate, ammonium, and chloride are obtained with a detection limit <0.2 μg/m3 for 30 min of signal averaging. The ACSM is built upon the same technology as the widely used Aerodyne Aerosol Mass Spectrometer (AMS), in which an aerodynamic particle focusing lens is combined with high vacuum thermal particle vaporization, electron impact ionization, and mass spectrometry. Modifications in the ACSM design, however, allow it to be smaller, lower cost, and simpler to operate than the AMS. The ACSM is also capable of routine stable operation for long periods of time (months). Results from a field measurement campaign in Queens, NY where the ACSM operated unattended and continuously for 8 weeks, are presented. ACSM data is analyzed with the same well-developed techniques that are used for the AMS. Trends in the ACSM mass concentrations observed during the Queens, NY study compare well with those from co-located instruments. Positive Matrix Factorization (PMF) of the ACSM organic aerosol spectra extracts two components: hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA). The mass spectra and time trends of both components correlate well with PMF results obtained from a co-located high resolution time-of-flight AMS instrument.

Emissions lifetimes and ozone formation in power plant plumes

The concept of ozone production efficiency (OPE) per unit NOx is based on photochemical models and provides a tool with which to assess potential regional tropospheric ozone control strategies involving NOx emissions reductions. An aircraft study provided data from which power plant emissions removal rates and measurement-based estimates of OPE are estimated. This study was performed as part of the Southern Oxidants Study-1995 Nashville intensive and focuses on the evolution of NOx, SO2, and ozone concentrations in power plant plumes during transport. Two approaches are examined. A mass balance approach accounts for mixing effects within the boundary layer and is used to calculate effective boundary layer removal rates for NOx and SO2 and to estimate net OPE. Net OPE is more directly comparable to photochemical model results than previous measurement-based estimates. Derived net production efficiencies from mass balance range from 1 to 3 molecules of ozone produced per molecule of NOx emitted. A concentration ratio approach provides an estimate of removal rates of primary emissions relative to a tracer species. This approach can be combined with emissions ratio information to provide upper limit estimates of OPE that range from 2 to 7. Both approaches illustrate the dependence of ozone production on NOx source strength in these large point source plumes. The dependence of total ozone production, ozone production efficiency, and the rate of ozone production on NOx source strength is examined. These results are interpreted in light of potential ozone control strategies for the region.

Design and initial characterization of an inlet for gas‐phase NOy measurements from aircraft

An understanding of gas-phase HNO3 transmission through an inlet is necessary to evaluate the quality of NOy measurements from an aircraft platform. A simple, inexpensive, low-volume Teflon inlet is described and its suitability as an aircraft inlet for gas-phase NOy is assessed. Aerosol transmission is not characterized, but inlet design and orientation probably discriminates against the majority of aerosol by mass. Laboratory data, in-flight HNO3 standard addition calibrations, and ambient NOy measurements from the 1997 North Atlantic Regional Experiment aircraft mission are used to characterize inlet transmission efficiencies and time constants. Laboratory tests show high transmission efficiencies for HNO3 which are relatively independent of ambient temperature and humidity. In-flight standard addition calibrations were carried out at ambient temperatures ranging from −20° to +8°C and relative humidities from 3% to 71%. These data suggest that nearly all the sampled air contacts an inlet surface, with 90% of added HNO3 being transmitted in ∼1.5 s. Ambient data are presented to demonstrate negligible hysteresis in 1-Hz NOy measurements, relative to variability observed in ozone data, from an air mass where HNO3 is expected to be a large fraction of the total NOy. Power spectra of ambient NOy (at temperatures from −35° to +35°C and relative humidities from 3% to 100%) and ozone measurements suggest an effective NOy instrument time constant of ∼2 s.

Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 Southern Oxidants Study

Isoprene (ISOP) and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK), were measured at an urban forested site in Nashville, Tennessee, as part of the 1999 Southern Oxidants Study (SOS). Hourly observations were performed at Cornelia Fort Airpark for a 4 week period between June 13 and July 14. At the midday photochemical peak (1200 local standard time, LST), average mixing ratios of isoprene, MACR, and MVK were 410 parts per trillion by volume (pptv), 240 pptv, and 430 pptv, respectively. Median isoprene, MACR, and MVK mixing ratios were 400 pptv, 200 pptv, and 360 pptv, respectively, at 1200 LST. An emissions inventory calculation for Davidson County, encompassing Nashville, suggests that MACR and MVK were produced predominately from isoprene oxidation rather than direct combustion emissions. The observations are compared with results from two chemical models: a simple sequential reaction scheme and a one-dimensional (1-D) numerical box model. The daytime ratios of MVK/ISOP and MACR/ISOP varied in a systematic manner and can be reproduced by the analytical solution of the sequential reaction scheme. Air masses with more photochemically aged isoprene were observed during SOS 1999 at Cornelia Fort (0.3-1.6 hours) compared to the SOS 1990 canopy study at Kinterbish (0.1-0.6 hours). This is consistent with the proximity of the tower inlets to the forest canopies during both campaigns. Isoprene had a chemical lifetime of 20 min at the average observed midday HO mixing ratio of 8 x 10 6 molecules/cm 3 . As a result, significant conversion of isoprene to its oxidation products was observed on the timescale of transport from the dense forest canopies surrounding Nashville. The systematic diurnal behavior in the MVK/MACR ratio can also be simulated with a 1-D photochemical box model. General agreement between the observations of MACR and MVK during SOS 1999 with the two chemical models suggests we have a comprehensive understanding of the first few stages of isoprene oxidation in this urban forested environment.

Measurement of peroxycarboxylic nitric anhydrides (PANs) during the ITCT 2K2 aircraft intensive experiment

[1] Measurements of peroxycarboxylic nitric anhydrides (PANs), peroxyacetic nitric anhydride (CH3C(O)OONO2; PAN), and peroxypropionic nitric anhydride (CH3CH2C(O)OONO2; PPN) were made in the spring of 2002, off the west coast of North America, as part of the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) project. Long-range transport of Asian emissions was observed in which PAN and PPN mixing ratios were as high as 650 pptv and 90 pptv, respectively. Moreover, these two species constituted as much as 80% of the odd nitrogen (NOy) in those air masses, and median PAN/NOy was more than 60% at altitudes of 4 km and above. Systematic differences in the ratio of PPN to PAN were observed in air masses that had been impacted by Asian urban emissions relative to those impacted by biomass burning. Mixing ratios of PAN and PPN were also elevated in the marine boundary layer close to the west coast of California, possibly because of photochemical production driven by maritime NOx emissions. INDEX TERMS: 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); KEYWORDS: peroxyacetic nitric anhydride, Asian pollution, eastern Pacific

Airborne measurements of isoprene, CO, and anthropogenic hydrocarbons and their implications

Measurements of the mixing ratios of light hydrocarbons (≥C6) were made aboard the National Oceanic and Atmospheric Administration Lockheed Orion WP-3 aircraft during June and July of 1994 and 1995 during a series of flights over the region around Nashville, Tennessee. The measurements were carried out as part of the Nashville/Middle Tennessee Study of the Southern Oxidant Study (SOS) whose purpose was to describe the sources, variation, and distribution of ozone and its precursors in the southeastern United States during the summer season. The spatial (altitude and latitude) distribution of isoprene and anthropogenic nonmethane hydrocarbons (NMHCs) is described. The isoprene distribution measured within the planetary boundary layer over the region is compared to the recent inventories. The correlations between the various anthropogenic hydrocarbons are used to demonstrate the combined influence of OH photochemistry and dilution on their concentrations. Finally, the distributions of those NMHCs that were measured are compared to those of CO and methane and discussed in terms their implications for odd hydrogen photochemistry and our understanding of regional ozone production. In the boundary layer, OH reactions are dominated by isoprene in the southern part of the region explored and by CO and methane in the northern part. The other measured NMHCs are seen to play only a minor role in ozone production in the nonurban atmosphere.

Trace gas and aerosol measurements using aircraft data from the North Atlantic Regional Experiment (NARE 1993)

Measurements of the concentrations of O3, CO, NO, NOy, condensation nuclei, and aerosols in 12 size bins ranging from 0.1 to 3.1 μm as well as a variety of meteorological parameters were collected aboard the NCAR King Air in August 1993 during 16 flights over or near the Gulf of Maine. The purpose of this measurement campaign was to describe the sources and variation of ozone and its precursors in the western NARE region during the summer season. Correlations between O3 and CO, O3 and NOy, and other chemical and aerosol measurements are examined. Several features in the altitude profiles are investigated using principal component analysis. The results of the trace gas analyses indicate that anthropogenically influenced ozone production dominated ozone throughout the experimental region at altitudes below 1500 m. Other factors identified include a distinct signature from fresh emissions below 1500 m. Above 1500 m the sources of ozone were determined by transport from a variety of sources.

Ground-based intercomparison of nitric acid measurement techniques

An informal intercomparison of gas-phase nitric acid (HNO3) measuring techniques was carried out. The intercomparison involved two new chemical ionization mass spectrometers (CIMSs) that have been developed for the measurement of HNO3 along with an older, more established filter pack (FP) technique. The filter pack was composed of a teflon prefilter which collected aerosols followed by a nylon filter which collected the gas-phase HNO3. The study was carried out during the late winter and early spring of 1996 at a site located on the western edge of the Denver metropolitan area. Throughout the study the two CIMS techniques were in general agreement. However, under certain conditions the HNO3 levels obtained from the nylon filter of the FP gave values for the gas-phase concentration of HNO3 that were somewhat higher than that recorded by the two CIMS systems. The formation of ammonium nitrate (NH4NO3) containing aerosols is common during the colder months in this area. An analysis of these results suggests that the HNO3 collected by the nylon filter in the FP suffers an interference associated with the disproportionation of NH4NO3 from aerosols containing that compound that were initially collected on the teflon prefilter. This problem with the FP technique has been suggested from results obtained in previous intercomparisons.

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.