NERL Research Abstract

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APM #442

Significant Research Findings

Role of Anthropogenic Nitrogen Oxides and
Volatile Organic Compounds as Ozone Precursors

Scientific
Problem and
Policy Issues

In the 1991 National Research Council (NRC) Report Rethinking the Ozone
Problem in Regional and Urban Pollution, a panel of national experts
concluded that the previous U.S. emission control efforts may have focused too
heavily on control of volatile organic compounds (VOCs) for reducing ozone
pollution. The reviewers recommended that more research and control
attention be directed to nitrogen oxides (NOx) as an ozone precursor. The
atmospheric chemistry by which VOCs and NOx form ozone is complex,
especially since VOCs and NOx may both create and destroy ozone in the air.
In response to the NRC Report, EPA funded the Southern Oxidants Study
(SOS) to explore the scientific issues underpinning the roles of VOCs and NOx
as ozone precursors. The SOS was been designed to investigate such issues in
urban and regional atmospheres within southern environments.

Research The recent focus of the SOS research has compared the use of Observation-
Approach Based Models (OBM) to the traditionally used Emissions-Based Model (EBM)
methods. OBMs use real-world observations to estimate the relative influence
of VOCs versus NOx in creating ozone, whereas EBMs use emission
inventories and air quality models to estimate the relative roles of the two
classes of precursors. As a part of the SOS efforts, observational data have
been collected in extensive ambient monitoring networks covering the
southeastern region of the country, as well as in specially designed urban and
regional field campaigns. The observational data are used to develop OBMs
and also to test and refine EBMs. Critical technical issues are explored through
combined use of OBM and EBM methods.

Results	A number of OBM methods were developed for comparison with traditional

and _ _ EBMs. Some of these OBM methods are empirical in nature, while others were
Implications developed with the help of modeling derivations. This research used OBM

methods to investigate the relative effectiveness of VOC and NOx controls for
reducing ozone in urban and rural areas in the southeast, as well as the relative

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effectiveness of controls of NOx emissions from different source types (e.g.,
autos, power plants, biogenic). Based upon data obtained in a variety of urban
and rural areas, a general trend was detected: center-city sections of an urban
area were usually VOC-limited—that is, control of VOCs would be more
effective in reducing ozone than would control of NOx. Farther downwind
away from the center-city sections, the ozone formation process becomes less
VOC-limited and more NOx-limited. In rural areas, and also in those urban
areas where the biogenic VOC emissions are dominant, ozone formation is
clearly NOx-limited. These findings are significant because they provide
invaluable guidance about the most effective emission control efforts. The data
suggest that in most urban areas both VOCs and NOx should be controlled,
whereas in rural areas control of the NOx emission sources would be more
effective.

The report meets the requirement of Annual Performance Measure (APM) 442
under GPRA Annual Performance Goal (APG) 01 (Recommend methods for
measuring NOx [nitrogen oxides and their products]). Results of the report are
directly relevant to the improvement of instrumentation for national monitoring
networks including the Photochemical Assessment Monitoring Stations
(PAMS) and regulatory networks associated with the National Ambient Air
Quality Standards.

Research The Southern Oxidant Study is been a collaborative effort involving EPA,
Collaboration Georgia Institute of Technology, North Carolina State University, the
Publications University of Alabama at Huntsville, the University Corporation for

Atmospheric Research (UCAR), the National Center for Atmospheric Research
(NCAR), the Brookhaven National Laboratory, and the Tennessee Valley
Authority. Examples of recent publications from this study follow.

Meagher, J.F., Cowling, E.B., Fehsenfeld, F.C., Parkhurst, W.J. Ozone formation and transport
in southeastern United States: Overview of the SOS Nashville/Middle Tennessee
Ozone Study. Journal of Geophysical Research D: Atmospheres 103: 22,213-22,223,
1998.

Tonnesen, G.S., Dennis, R.L. Analysis of radical propagation efficiency to assess ozone

sensitivity to hydrocarbons and NOx. Part 1. Local indicators of instantaneous odd
oxygen production sensitivity. Journal of Geophysical Research D: Atmospheres 105:
9213-9225.

Tonnesen, G.S., Dennis, R.L. Analysis of radical propagation efficiency to assess ozone

sensitivity to hydrocarbons and NOx. Part 2. Long-lived species as indicators of ozone
concentration sensitivity. Journal of Geophysical Research D: Atmospheres 105:
9227-9241.

Daum, P.H., Kleinman, L.I., Imre, D., Nunnermacker, L.J., Lee, Y.-N., Springston, S.R.,

Newman, L., Weinstein-Lloyd, J., Valente, R.J., Imhoff, R.E., Tanner, R.L., Meagher,
J.R. Analysis of 03 formation during a stagnation episode in central Tennessee in
summer 1995. Journal of Geophysical Research D: Atmospheres 105: 9107-9119,
2000.

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The SOS Study is nearing the end of its second 5-year period (1991-1196 and
1996-2001). A third 5-year phase of the effort is being considered. Such a
future effort, if funded, will focus on completing the analysis of the field
programs mounted through 2001, including an expanded collaborative effort
with the State of Texas, the TEXAS2000 Study, conducted in Houston and its
surrounding area.

Inquiries concerning this project should be directed to:

Dr. Paul Solomon

U.S. Environmental Protection Agency
National Exposure Research Laboratory
P.O. Box 93478

Las Vegas, Nevada 89193-3478
Phone: (702)798-2280
E-mail: solomon.paul@epa.gov

Federal funding for this research was administered under EPA cooperative
agreements CR824839 with the North Carolina State University, CR824840
with the University of Alabama at Huntsville, CR824843 and CR824849 with
the Georgia Institute of Technology, CR824833 with UCAR/NCAR, and
interagency agreements DW89938059 with DOE's Brookhaven National
Laboratory, and DW64938057 with the Tennessee Valley Authority.

Future
Research

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