June 1983
        OZONE PLUMES ?ROM SMALL CITIES
   AND OZONE IN HIGH PRESSURE WEATHER SYSTEMS
 ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U. S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA   27711

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        OZONE PLUMES FROM SMALL CITIES
   AND OZONE IN HIGH PRESSURE WEATHER SYSTEMS
                       BY
     Chester W. Spicer, Darrell W. Joseph,
    Philip R. Sticksel, George M. Sverdrup,
               and Gerald F. Ward
        Battelle, Columbus Laboratories
              Columbus, Ohio  43201
            Contract No. 68-02-2439
               Project Officer
               William Lonneman
 Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina   27711
 ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U. S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA   27711

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                      NOTICE

This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication.  Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
                           ii

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                                 ABSTRACT
     This report presents the results of a field investigation of ozone
distribution and transports.  The program focuses on the formation and transport
of ozone in urban plumes of small cities and the behavior of ozone in a high
pressure weather system traversing the eastern half of the United States.
The field experiments were conducted in July - August 1977.  Both ground
level and airborne monitoring were conducted.  The study was a collaborative
effort involving Battelle-Colum&us, the EPA Environmental Sciences Research
Laboratory (ESRL), and Washington State University (WSU).  This report
concerns the aircraft and ground level measurements obtained by Battelle-
Columbus, although some aircraft results by WSU and detailed hydrocarbon
measurements by ESRL are presented.  The report builds upon earlier
investigations of ozone transport in the Ohio Valley and New England,
                                   iii

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                               CONTENTS



Abstract	iii
Figures	   yi
Tables	xii
Acknowledgement	xiii

   1.  Introduction and Background 	     1

   2.  Summary and Conclusions 	     3

   3.  Sampling Sites	     5:

   4.  Experimental Methods	     7

   5.  Results	   13

   6.  Analysis and Interpretation	   19-

References	100
Appendices

   A.  Ground Station Data from 1977 Midwest Field Program .  .  .   102
   B.  Flight Maps and Vertical Profiles from the 1977 Midwest
       Field Program	127

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                                FIGURES

Number                                                            Page
  1    St. Louis area showing Civic Memorial Airport where
         mobile labs were located.	     6

  2    Battelle Mobile Air Quality  Laboratory	     8

  3    Aircraft Sampling Platform	    11

  4    Ozone concentrations along upwind and downwind
         traverses of St. Louis on  July 9,  1977	    21

  5    Distribution of 03 downwind  of St. Louis,
         July 28, 1977	    22

  6    Cross section of Phoenix plume, October 14,  1977	    23

  7    Cross section of Phoenix plume, Flight 21  	    24

  8    Ozone distribution in southern New England on
         July 23, 1975	    25

  9    Ozone concentration for cross section from the
         Massachusetts-Connecticut  border to south shore of
         Long Island — approximately 73° 10' longitude,
         August 10, 1975	    26

 10    Ozone (in ppb) and other pollutant results for after-
         noon flight conducted on August 10, 1975	    28

 11    Ozone concentrations upwind  and downwind of
         Springfield, Illinois, on  July 12, 1977  (afternoon) .  .    29

 12    Ozone concentrations upwind  and downwind of
         Springfield, Illinois, on  August 1, 1977 (afternoon).  .    31

 13    Ozone concentrations along upwind and downwind
         traverses of Springfield,  Illinois, on
         August 3, 1977  (afternoon)	    34
 14    Ozone isopleths downwind of  Springfield, Illinois,
         on August 3, 1977	    36

 15    Ozone concentrations (ppb) along the paths of the
         Washington State University and Battelle's
         Columbus Laboratories cross-country flights
         between July 22 and July 24	    41

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                           FIGURES (continued)

Number

 16    Daily weather map for July 18, 1977	      43
 17    Daily weather map for July 19, 1977	      44
 18    Daily weather map for July 20, 1977	      45

 19    Daily weather map for July 21, 1977	      46
 20    Daily weather map for July 22, 1977	      47
 21    Daily weather map for July 23, 1977	      48
 22    Daily weather map for July 24, 1977	      49

 23    Temperature, dewpoint and ozone concentration variations
         with height in central Illinois on the morning of
         July 21, 1977, before the cold front passed.  The (a)
         diagram is a plot of temperature in degrees C (solid
         line) and dewpoint (dashed line) for NOAA's Salem,
         Illinois station at 07:00 CDT.  The (b) diagram
         is a plot of ozone mixing  ratio (ppmm)  measured  over
         East Alton, Illinois between 06:05 and 07:23 CDT.  See
         text for description of the (a) skew T, log p
         diagram and the (b) ozonagram	      56

 24    Information from central Illinois obtained from upper-
         air soundings made on the morning of Friday,
         July 22.  (a) temperature (solid line) and Dewpoint
         (dashed line) measured by Battelle aircraft at 10:30
         CDT above Springfield, Illinois, (b) ozone mixing
         ratio (ppmm) measured by Battelle aircraft at 10:30
         CDT, (c) Peoria, Illinois, potential vorticity
         (solid line) and water vapor mixing ratio (dashed
         line) measured by NOAA Rawinsonde network at 07:00
         CDT	      60
 25    Isentropic trajectory traced backward in 13-hour steps
         on 8 = 30°C surface from Peoria, Illinois, at 1200
         GMT (07:00 CDT)  on July 22 to 1200 GMT on July 20 ..      63
 26    Isentropic trajectory traced backward in 12-hour steps
         on the 0 = 39°C  surface from Peoria,  Illinois,
         1200 GMT (07:00  CDT)  on July 22 to 0000 GMT on
         July 20 (19:00 CDT on July 19)	      64
 27    Information from central Wisconsin obtained from upper-
         air soundings made on the afternoon/evening of
         Friday,  July 22,  1977,  (a)  temperature (solid line)
         and dewpoint (dashed  line)  measured by the Battelle
         aircraft at 15:00  CDT near Fond du Lac,  Wisconsin;
         (b) ozone mixing ratio (ppmm measured by Battelle air-
         craft at 1500 CDT; (c)  Green Bay,  Wisconsin, potential
         vorticity (solid line)  and water vapor mixing ratio
         (dashed line) measured by NOAA rawinsonde network at
         1900 CDT	      66
                                    vii

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                         FIGURES (continued)

Number                                                           Page

 28   Isentropic trajectory traced backward in 12-hour steps
        on the 0 = 44 °C surface from Green Bay,  Wisconsin,
        at 0000 GMT on July 23 (19:00 CDT on July 22) to
        1200 GMT (07:00 CDT) on July 20	   67

 29   Three temperature soundings made along the 0 = 44°C
        isentropic trajectory of Figure 28 showing the descent
        of the stable layer from the stratosphere to the
        middle troposphere.  Green Bay, Wisconsin, at 0000
        GMT on July 23 (dashed line).  International Falls,
        Minnesota, at 0000 GMT on July 22 (dash-dot line).
        The Pas, Manitoba, at 1200 GMT on July 20 (solid line).   69

 30   Information from central Michigan obtained from upper
        air soundings made on the afternoon/evening of
        Saturday, July 23, 1977.  (a) Temperature (solid
        line) and dewpoint (dashed line) measured by
        Battelle aircraft at 15:00 EDT east of Muskegon,
        Michigan; (b) ozone mixing ratio (ppmm)  measured
        by Battelle aircraft at 15:00 EDT; (c) Flint,
        Michigan, potential vorticity and water vapor mixing
        ratio measured by the NOAA rawinsonde network at
        20:00 EDT	   71
 31   Information from western New York obtained from upper-
        air soundings made on the evening of Saturday, July 23,
        1977.  (a) Temperature (solid line) and dewpoint
        (dashed line) measured by Battelle aircraft at 19:00
        EDT northeast of Erie, Pennsylvania, (b) ozone
        mixing ratio (ppmm) measured by Battelle aircraft
        at 19:00 EDT, (c) Buffalo, New York potential
        vorticity and water vapor mixing ratio measured by
        the NOAA rawinsonde network at 20:00 EDT	   73

 32   Isentropic trajectories traced in 12-hour steps on the
        0 = 30°C surface from Toronto, Ontario,  at 0000
        GMT on July 24 (20:00 EDT on July 23) to Prince
        George, British Columbia, at 0000 GMT on July 17 (20:00
        EDT on July 16).  Pressures at each 12-hour step are
        given in millibars.  The 0 = 44°C trajectory from
        Figure 28 is also shown	   76
 33   Measurements made during the Battelle aircraft sounding
        south of Toledo, Ohio, at 10:00 EDT,  (2) temperature
        (solid line) and dewpoint (dashed line); (b) ozone
        mixing ratio (ppmm) 	   77
 34   Path of Battelle cross-country flight showing location of
        spiral soundings, NOAA rawinsonde stations, and the
        Washington State University monitoring site at
        Robinson, Illinois	   80
                                 viii

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                         FIGURES (continued)

Number                                                           Pagt

 35   Information from southeastern Illinois obtained from
        upper-air soundings made on the morning of Saturday,
        July 23, 1977, (a) temperature measured by Washington
        State University aircraft at 10:00 CDT above
        Robinson, Illinois, (b) ozone mixing ratio (ppmm)
        measured by Washington State aircraft at 10:00 CDT,
        (c) temperature (solid line) and dewpoint (dashed
        line) measured during NOAA rawinsonde sounding at
        Salem, Illinois, at 07:00 CDT	    81

 36   Horizontal extent of moist and dry portions of the
        stable layer with potential temperature between 0  =
        25°C and Q = 30°C on Wednesday, July 20, 1977 at
        1200 GMT.  Dry portions (water vapor mixing ratio
        <1.5 gm/kgm) are indicative of air with a strato-
        spheric origin.  Surface positions of front and high
        pressure center (H) are shown.  Median pressure of
        the potential temperature surface at the rawinsonde
        stations is given in millibars	    84
 37   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between 0 = 25°C
        and 0 = 30°C on Friday, July 22, 1977 at 1200 GMT.
        Dry portions (water vapor mixing ratio <1.5 gm/kgm) are
        indicative of air with a stratospheric origin.  Surface
        positions of front and high pressure center (H) are
        shown.  Median pressures of the potential temperature
        surface at the rawinsonde stations is given in
        millibars	    85
 38   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between Q = 25°C
        and 6 = 30°C on Saturday, July 23, 1977 at 1200 GMT.
        Dry portions (water vapor mixing ratio <1.5 gm/kgm)
        are indicative of air with a stratospheric origin.
        Surface positions of fronts and high pressure center
        (H) are shown.  Median pressure of the potential
        temperature surface at the rawinsonde stations is  given
        in millibars	    86
 39   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between 9 = 35°C and
        G = 40°C on Wednesday,  July 20, 1977 at 1200 GMT.
        Surface positions of front and high pressure center (H)
        are shown.  Median pressure of the potential temperature
        surface at the rawinsonde stations is given in
        millibars	    87

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                         FIGURES (continued)

Number                                                           Page

 40   Horizontal extent of moist and dry portions of the
        stable layer with potential temperature between 0 =
        35°C and 0 = 40°C on Friday, July 22,  1977 at 1200
        GMT.  Surface positions of the front and high pressure
        center (H) are shown.  Median pressure of the
        potential temperature surface at the rawinsonde
        stations is given in millibars	    88
 41   Horizontal extent of dry portion of the stable layer
        with potential temperatures between 0 = 35°C and 0 =
        40°C on Saturday, July 23, 1977 at 1200 GMT.  There
        was no moist stable layer at this time.  Surface
        positions of the fronts and high pressure center (H)
        are shown.  Median pressure of the potential tempera-
        ture surface at the rawinsonde stations is given in
        millibars	    89
 42   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between 0 = 40°C and
        9 = 45°C on Wednesday, July 20, 1977 at 1200 GMT.
        Surface positions of front and high pressure center
        (H) are shown.  Median pressure of the potential
        temperature surface at the rawinsonde stations is
        given in millibars	    90
 43   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between 0 = 40°C and
        0 = 45°C on Friday, July 22, 1977 at 1200 GMT.
        Surface positions of front and high pressure center
        (H) are shown. ,Median pressure of the potential
        temperature surface at the rawinsonde stations is
        given in millibars	    91
 44   Horizontal extent of moist and dry portions of the stable
        layer with potential temperatures between 0 = 40°C and
        0 = 45°C on Saturday, July 23, 1977 at 1200 GMT.
        Surface positions of front and high pressure center
        (H) are shown.  Median pressure of the potential
        temperature surface at the rawinsonde stations is
        given in millibars.  .	    92
 45   Weather maps for Sunday, July 17, 1977.  Top map is the
        surface map for 7:00 a.m. EST (08:00 EDT).  Lower left
        map is the 500 millibar map for the same time.  The
        right center map displays the maximum and minimum
        surface temperatures for the previous day.  Map in
        the lower right corner depicts areas and amounts of
        precipitation (in inches) for the previous day	    95
                                    x

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                          FIGURES (continued)

Number                                                           Pagj

 46   Weather maps for Saturday, July 16, 1977.  Top map is
        the surface map for 7:00 a.m. EST (08:00 EDT).   Lower
        left map is the 500 millibar map for the same time.
        The right center map displays the maximum and minimum
        surface temperatures for the previous day.  Map in the
        lower right corner depicts areas and amounts of
        precipitation (in inches) for the previous day	   96

 A7   Temperature (solid line) and dewpoint (dashed line)
        soundings made at the Annette Island, British Columbia,
        rawinsonde station at 1200 GMT (07:00 CDT) on
        July 17, 1977.  The potential temperature of 30°C is
        found at the base of the stratosphere at 345 mb . . . .   97
                                  .xi..

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                                TABLES

Numb er                                                           Page
1
2
3
4
5
6
7
St. Louis Ground Station Measurements .. 	

Summary of Air Quality Data - Bethalto, Illinois. . . .
3
Aerosol Results from Bethalto, Illinois (yg/m ) . . . .
Fluorocarbon 11 Results From Aircraft Bags (ppt) ....

Upwind and Downwind Precursor Concentration From
Q
j
i n
J.U
14
15
17
18

         Flight 20, August 1,  1977	     32
       Upwind and Downwind Precursor Concentrations From
         Flight 23	     35
       Battelle Aircraft Spiral Soundings Made During
         High Pressure Area Study — 1977	     42
                                   xii

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                            ACKNOWLEDGMENT

          We are pleased to acknowledge several dedicated scientists
who assisted us during this program.  Joseph Pietrowicz provided daily
meteorological forecasts which were valuable in mission planning.
William Lonneman, Sarah Weeks and Richard Kuntz performed the detailed
hydrocarbon analyses for all aircraft samples.
                                    rxiii

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                               SECTION 1
                      INTRODUCTION AND BACKGROUND

          This report presents the results of a field investigation of
ozone (0») distribution and transport conducted by Battelle,  Columbus
Laboratories under the sponsorship of the Environmental Protection Agency
(EPA).  The program focuses on the formation and transport of ozone in
urban plumes of large and small cities,  and the behavior of ozone in a
high pressure weather system traversing  the eastern half of the country.
The program has involved detailed ground level and aircraft monitoring
studies and the analysis and interpretation of the resulting data.  This
study builds upon earlier investigations of ozone transport in the Ohio
Valley and New England.
          The issue of ozone/precursor transport has caused a great deal  of
controversy, and this program was directed at providing additional infor-
mation on various aspects of the controversy.  Specifically,  we have
investigated the contribution of smaller cities to the downwind ozone
burden and the long range transport of ozone associated with a high pressure
system.

OBJECTIVES
          The overall objective of the program is to determine the propen-
sity of air masses to generate and transport ozone over long  distances.
Specific goals of the project are itemized below:
       •  to investigate the transport of ozone and precursors
          from urban areas,  and especially to determine whether
          smaller cities contribute measurably to the downwind
          ozone burden
       •  to study the behavior of ozone associated with high
          pressure weather systems

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          to improve current understanding of ozone variations  with
          altitude, with emphasis on obtaining more data ac nigher
          altitudes (up to 20,000 feet MSL).
PROJECT DESCRIPTION
          The field measurements obtained as part of this study are a signi-
ficant contribution to the currently available data on atmospheric ozone
distribution and transport.  The measurements are crucial to the success
of the program since they provide the data which will be used to address
the program's objectives.  The field experiments were conducted in July-
August, 1977 in the midwestern U.S.  Both ground level and airborne
monitoring were conducted during the field experiments.  Measurements were
made from a single ground site and a twin engine research plane.  The
study was a collaborative effort involving Battelle-Columbus, EPA-ESRL,
who provided a second ground monitoring station near St. Louis and detailed
hydrocarbon analyses of our aircraft samples, and Washington State
University (WSU), with whom we coordinated a number of aircraft operations.
A comparison of the ozone monitors aboard the two aircraft (BCL and WSU)
showed agreement within 2.5 percent.
          The data from the field experiments are contained in appendices
to this report.  Much of the data is also summarized within the report
itself.

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                               SECTION 2

                        SUMMARY AND CONCLUSIONS


          This report presents the results of a field investigation of

atmospheric ozone distribution and transport conducted by Battelle's

Columbus Laboratories under the sponsorship of the Environmental Protection

Agency (EPA).  The program focuses on the formation and transport of ozone

in urban plumes of large and small cities, and the behavior of ozone in a

high pressure weather system traversing the eastern half of the country.

          The field experiments were conducted in July and August, 1977

in the midwestern U.S.  Both ground level and airborne monitoring were

employed.

          This report describes the experimental aspects of the field

program and an interpretation of the data as they relate to the program

objectives.  The study findings are summarized succinctly below.

       •  The St. Louis urban area generates an ozone plume with 0
          concentrations approaching 300 ppb under appropriate
          conditions.

       •  Smaller cities (populations £100,000) generate a measurable
          ozone plume under photochemically reactive conditions.  The
          additional 03 in the plumes is related to the cities'
          precursor emissions.

       •  During studies of ozone and precursors in a high pressure
          system traversing the eastern U.S., several layers rich in
          ozone were observed in vertical profiles.  The upper layer of
          ozone, which was found between 10,000 and 15,000 feet MSL,
          was observed to cover nearly the entire eastern half of the
          U.S. (from Wisconsin to Virginia).  Such a pervasive
          tropospheric O-j layer has not been reported previously.
          The source of this ozone layer was demonstrated to be
          the stratosphere.

       •  Analysis of our vertical profile results and rawindsonde
          data during the high pressure system study suggests that
          the pervasive 03 layer observed over the eastern U.S. at
          10,000-15,000 feet MSL resulted from an injection of
          stratospheric air into the troposphere during cyclogenesis

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in northern Canada several days before our observations
over the U.S.  If this is the case, then the persistence
of 0- in this elevated layer must be at least 3-4 days.

During the high pressure system study, ozone concentrations
near the surface increased steadily over the three days  that
it took the high to cross the eastern U.S.  During flights
over rural areas, concentrations of 30-40 ppb were observed
on the first day over Wisconsin, 70-90 ppb on the second
day over Ohio, and >100 ppb on the third day over Pennsylvania.

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                                SECTION 3
                             SAMPLING SITES

          Chemical and meteorological monitoring during the field
program made use of two mobile laboratories situated at Civic Memorial
Airport in Bethalto, Illinois.  The location of Civic Airport is noted in
Figure 1.   The site is approximately 36 km northeast of downtown St.  Louis.
Civic Airport is far enough removed from St. Louis proper that the density
of air traffic is tolerable for an airborne study such as this.   Neverthe-
less, air traffic occasionally caused deviations in our flight patterns
and frequently dictated the location of the 20,000' vertical atmospheric
profiles which were planned as an integral part of the study.
          The mobile laboratories were positioned next to the hanger used
for the research plane.  This greatly facilitated communications and pro-
vided for rapid sample bag transfer and analysis in the mobile labs.
However, local airport emissions from taxiing planes and other sources
precluded collection of meaningful ground level hydrocarbon data at this
site.  Detailed ground level hydrocarbon data representative of the area
were obtained by EPA-ESRL scientists at a location approximately 13 km
southeast of Civic Airport.

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Figure 1.  St. Louis area showing  Civic Memorial Airport
           where mobile labs  were  located.

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                               SECTION 4
                          EXPERIMENTAL METHODS

          The field experiments made use of the Battelle mobile lab,
shown in Figure 2, as well as a smaller mobile laboratory and an instru-
mented aircraft.  The two mobile laboratories were located side by side
at Civic Memorial Airport in Bethalto, Illinois.  The mobile labs served
both as continuous ground monitoring stations and as support laboratories
for the airborne operations.  Ground-level monitoring data were collected
continuously, 24 hours a day at the mobile labs.
          The variables measured at the mobile laboratories are listed in
Table 1.  The measurement techniques and instruments are also tabulated.
Details of the operation and calibration of  the instruments have been
                   (1 2)
presented elsewhere   '   .  The ground-level NMHC and CH  measurements at
the airport were so influenced by local airport emissions that these data
have been deleted from  the report.

Aircraft Measurements
          The airborne sampling platform utilized during this study was
the Battelle Cessna 411 research aircraft pictured in Figure 3.  This twin-
engine all-weather aircraft was equipped at the start of the study for
measurements listed in Table 2.  Most flights were conducted at 1000 feet
AGL (above ground level).  Power was supplied to the instruments listed
in Table 2, as well as recorders and data acquisition system, from a 1.0
KVA power inverter supplied from two 100-amp 28-volt alternators.  The
instruments were operated 24 hours a day on ground power and instantaneously
switched to aircraft power just prior to takeoff.

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FIGURE 2.  BATTELLE MOBILE AIR QUALITY LABORATORY

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            TABLE  1.    ST LOUIS  GROUND STATION MEASUREMENTS
Measured Variable Technique
°3
NO
NO
X
PAN
HONO
Chemiluminescence
Chemiluminescence
Chemiluminescence
Electron Capture G.C.
Coulometry
Fluorocarbon-11 Electron Capture G.C.
NMHC
CH4
CO

FID Gas Chroma tography

Mass Loading HiVol/weighing
NO"
SO,
<4
NH,
4
C,H,N
HiVol/Ion Chroma tography
HiVol/Ion Chromatography
HiVol/Gas Sensing Electrode
HiVol /Combustion- Thermal
Instrument
Bendix 8002
Bendix 8101-B
Bendix 8101-B
Varian 1200
Battelle Modified
Mast
Varian 1200

Beckman Model 6800

Cahn Microbalance
D-ion-x Model 10
D-ion-x Model 10
Orion NH-
Perkin-Eliner 240
Temperature
Relative Humidity
Wind Speed
Wind Direction
Global Radiation Intensity
  Conductivity
Automated Weather Station
Automated Weather Station
Automated Weather Station
Automated Ueather Station
180° pyrheliometer
MRI Model  802
MRI Model  907
MRI Model  1074-2
MRI Model  1074-2
Eppley

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-------
          The gas monitoring instruments obtained their samples from excess
ram air which entered the plane through a stainless-steel sampling probe.
Each instrument was connected to the sample manifold by Teflon tubing.
Tedlar sampling bags were filled through Teflon tubing containing a variable
stainless steel orifice.  Ram pressure was used to fill the bags.  Each bag
was evacuated, tested for leaks, backfilled with zero nitrogen and evacuated
twice more in the mobile lab prior to loading aboard the aircraft.  Each bag
was evacuated again on board the plane just prior to sample collection.  The
final evacuation aboard the aircraft used the TECO 14-D vacuum pump.  This
procedure ensures negligible contamination or carry-over in the sample bags,
at least for the compounds of interest in this study.
          Quartz filters (61 mm diameter) were used for aerosol sampling
aboard the aircraft.  The high volume sampler on the plane used a separate
stainless steel probe extending out the roof of the cockpit with a gentle
bend.  This probe can be seen in Figure 3.  The aircraft samples were
                                 3
collected at a flow rate of 0.3 m /min.  Several filters were preloaded in
individual filter holders specially designed for this application.  The
preloaded filters could be changed easily during a flight, permitting
separate aerosol collections over different portions of  the flight path.
After each flight,  the filters were stored in individual glassine envelopes
and sealed in separate plastic bags.
          The aircraft filters were analyzed and the gas monitoring instru-
ments were calibrated in  the same manner as described earlier.  The chemi-
luminescent nitric  acid monitor used on  the plane has been described
elsewhere    .
          Signals from the 0.,, NO , HONO-, and  temperature monitors were
continuously recorded by  two dual-pen strip chart recorders.  These signals,
as well as time and dew point, were also recorded on a Pertec magnetic
tape data acquisition system.
                                    12

-------
                               SECTION 5
                                RESULTS

GROUND MONITORING RESULTS
          Daily air quality and meteorology are summarized in Table 3 for
each day of  the St. Louis area study.  Both 24-hour averages and 1-hour
maxima are tabulated for several key pollutants.  Total suspended particu-
late (TSP) results are also presented.  These data were collected from two
mobile laboratories located in Bethalto, Illinois at Civic Memorial Airport
approximately 36 km northeast of downtown St. Louis.
          A daily tabulation of the detailed air quality and meteorology
data is included in Appendix A of this report.  The symbol -1.00 in these
and other tables indicates no data for the specified time period.  Hourly
averages are reported in central daylight time (CDT).   Data were collected
24 hours a day and are tabulated starting with the 1000 CDT average each
day to correspond with the start of the daily high volume aerosol collection.
Thus the daily averages have been computed over the same times as the high
volume collections.
          Some short-term high concentrations of primary pollutants appear
periodically throughout the daily data tables.  These values frequently
were caused by planes warming up or taxiing near the mobile laboratories.
As mentioned earlier, the continuous hydrocarbon data were so influenced by
this and other local airport emission sources that the data have been
deleted from the tables,  so as not to mislead the reader.  Since the study
was designed almost exclusively around the aircraft results, the objectives
are in no way compromised  by the missing ground level hydrocarbon data.
          Twenty-four hour high volume sampling was conducted at the mobile
laboratory site at Civic Airport using quartz fiber filters as the collection
medium.  The TSP data and results of inorganic analyses of the filters are
shown in Table 4.   The filters were analyzed for ammonium, nitrate and
                                    13

-------An error occurred while trying to OCR this image.

-------
   TABLE 4.  AEROSOL RESULTS FROM BETHALTO,  ILLINOIS
             (yg/m3*)
Date
7/8/77
7/9/77
7/11/77
7/12/77
7/13/77
7/14/77
7/15/77
7/16/77
7/17/77**
7/13/77
7/20/77
7/22/77
7/25/77
7/26/77
7/27/77
7/28/77**
7/29/77
7/30/77**
8/1/77
8/3/77
Avg.
Total Mass
48.6
31.4
49.1
49.8
70.8
72.5
104.3
118'. 9
•85.1
86.5
47.5
38.9
25.2
20.6
46.1
87.7
60.0
46.6
43.6
62.1
63.6
NH4+
0.64
1.15
1.12
0.82
1.17
2.10
7.45
11.73
9.07
5.95
1.70
2.55
2.47
0.96
—
7.64
3.23
3.60
2.53
3.02
3.91
N03~
0.50
0.30
2.86
0.29
0.27
0.14
0.13
0.07
0.05
0.06
0.07
0.06
0.05
0.15
0.14
0.12
0.26
0.07
0.27
0.45
0.36
S04=
5.30
5.94
9.45
6.58
10.29
13.11
32.61
40.19
39.68
19.57
11.30
10.00
6.98
2.05
13.12
29.72
10.34
8.90
5.00
10.24
14.41
*   Minimum Detectable Limits
    Total - 0.1   yg/m3
    NH4+  - 0.01  yg/m3

    N03~  - 0.03  yg/m3

    S04=  - 0.01  yg/m3

**  Partial sampling day
                           15

-------
sulfate.  Episodes of high sulfate concentration are evident from the data.
Ammonium generally followed the same trend as the sulfate concentration.
                                                                     3
The amount of nitrate present at Civic Airport was less than 0.5  yg/m
on all days but two.
Aircraft Results
          Twenty-seven aircraft sampling flights were conducted during the
study.  Flight patterns for each of the sampling missions are mapped in
Appendix B.  Ozone and 3!0  were monitored continuously during the flights.
                         X
Two maps for each flight are included in Appendix B,  one showing 0. con-
centrations and one representing NO .  Sampling was at 1000 feet AGL unless
                                   X
noted otherwise.  Locations of spirals and bag sample collection points are
marked on the maps.
          Vertical profiles of 0«,  temperature and dew point are also
included in Appendix B and are keyed to the flight maps.  The vertical 0
profiles have been corrected for atmospheric density.  Results of fluoro-
carbon 11 determinations from the bag samples from each flight are shown in
Table 5.  Detailed €„-€..„ hydrocarbon analyses were performed on each
aircraft bag by EPA scientists at the EPA mobile laboratory located approxi-
mately 13 km southwest of our site.  The results of these analyses are
available elsewhere.(4)  Pertinent portions of the hydrocarbon data
will be presented and discussed later in this report.
          Results of ion chromatographic analysis of the high volume filters
collected aboard the aircraft are listed in Table 6.  The concentrations
reported for filters collected over short times should be used with caution
since the amounts of NO- and SO, collected on the filters were only
slightly greater than the filter blanks.
                                    16

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TABLE 6.  AIRCRAFT HIGH VOLUME FILTER RESULTS

Flight
10
12
14



15
16

18
19
22


23

27


Date
7-2A-77
7-27-77
7-28-77



7-29-77
7-29-77

7-30-77
7-30-77
8-03-77


8-03-77

8-04-77


Filter No.
2
1
1
2
3
4
1
1
2
1
1
1
2
3
1
2
1
2
3
Volume,
(m3)
21.6
6.9
3.3
5.2
5.2
5.7
51.9
50.3
25
16.5
25.6
8.1
7.2
8.6
6.8
7.4
11.4
14.4
5.7
NO^,
yg/m3
<0.2
3.2
2.1
1.3
0.9
<0.9
0.4
1.1
0.8
0.6
<0.2
6.3
2.1
2.1
1.5
1.6
1.4
<0.3
1.0
S04>
Pg/m3
29.1
8.1
29.7
18.1
16.1
15.4
2.4
1.7
2.1
4.4
8.7
17.0
5.0
5.9
3.4
2.6
9.3
6.9
12.1
                       18

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                                  SECTION 6
                         ANALYSIS AND INTERPRETATION

          The two major goals of this study are:
          (1)  to determine the contribution of cities of
               moderate population (
-------
experiments will be described shortly.  First, however, a review of the
characteristics of urban ozone plumes is in order.

Ozone Plumes from Major Metropolitan Areas
          Clearly defined ozone plumes are frequently observed downwind of
major centers of population and industry on photochemically active days.
Such a plume has been observed downwind of St. Louis    and was mapped by
a few flights during the present study for comparison with the plumes of
smaller urban areas.  On July 9, 1977, upwind and downwind patterns were
flown around St. Louis to search for the city's plume.  The results from
this flight are presented in Figure 4.  The A0_ is  unmistakable, with
upwind concentrations averaging 70 ppb and downwind levels reaching 130 ppb.
Another example of the St. Louis CL plume observed  during this program is
shown in Figure 5.  Data from the afternoon flight  of July 28, 1977 have
been used to draw contours representing CL concentrations downwind of St.
Louis at 1000'  AGL.   Various shadings represent the 03 levels  within the con-
tour areas.  The plume character of the downwind concentrations is obvious.
          Urban C-  plumes from a number of major cities have been observed
and characterized in recent years.  Examples of ozone plumes from other
major cities will give perspective to this discussion.  Two examples of
downwind traverses of the Phoenix, Arizona, plume    are shown in Figures 6
and 7.  These- traverses were carried out over the desert, where sources of
interfering emissions are minimal.  In both cases the plume 0_ can be
clearly distinguished from ambient background ozone concentrations.
          The New York metropolitan area generates  an ozone plume which was
mapped on several days in the summer of 1975.  Figure 8 shows the New York
plume at two different times on July 24, 1975^  .  Winds on 24 July were
from the southwest, and trajectories show that the location of the high
ozone concentrations over central Connecticut coincided with the position
of the morning precursor emissions from New York after the corresponding
transport time.  The shape of the plume in the horizontal plane is clear
from Figure 8.   A vertical outline was obtained on 10  August, 1975,  by
making both vertical and horizontal 0« measurements downwind of New York
perpendicular to the wind direction.  This cross-sectional pattern
resulted in the 03 distribution depicted in Figure 9.  The darkly shaded

                                     20

-------
 .150

 .140

 .130

 J20

 .110

 JOO

 090

.080

.070

.060

.050
Upwind
Downwind
      15   10   5   0    5    10   15     20  15   10   5   0
                   Distance From Wind Axis Through S». Louis, mites
                                              10  15  20
     Figure 4.  Ozone concentrations  along upwind and downwind
                 traverses of St.  Louis  on July 9, 1977.
                                   21

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                                                        July 28,1977
                                                       1436-1640 COT
                                        SPRINGFIELD
                     JACKSONVILLE
          ST LOUS.

Wind Direction
     COLLINSVILLE

E. ST. LOUIS

  ^BELLEVILLE
                                                          o
                                       DECATUR
            EFFINGHAM
                   0
 Concentration
     <  100 ppb
     100-150 ppb
     150-200 ppb

     200-250 ppb
     250-300 ppb

OCENTRAL1A
                                                        *IOOO'AGL
     Figure  5.   Distribution  of 03  downwind  of St.  Louis,
                 July  28, 1977.
                                   22

-------
   200
 "7? 100
 O
                                  Distance
Figure 6.  Cross section of Phoenix, AZ  plume,  October 14,  1977,
                                 23

-------
  200
   100
                                 Distance-
Figure 7.  Cross section  of  Phoenix,  AZ plume, October 18, 1977
                                24

-------
                                                                  Density
                                                                  D 0-90ppb
                                                                  E3 50-100 ppb
                                                                  Q3 lOO-ISOppb
                                                                  G I50-200ppb
                                                                  S 20O-25Oppb
                                                                  Q 2SO-3OOppb
                                                                  • >30Oppb
Figure  8.   Ozone distribution in southern New England on July 23, 1975.
                                     25

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                                                               6000
.a
a.
a




en
2
                                                          c/l
Figure 9.  Ozone concentration for  cross  section  from the Massachusetts-
           Connecticut border to south  shore  of Long  Island—approxi-
           mately 73° 10' longitude, August 10, 1975.
                                  26

-------
lower right corner of the figure represents the New York plume.  The wind
direction and the location of the flight path relative to the city are
shown in Figure 10.
          It is clear from the preceding figures and discussion that large
cities generate well defined CL plumes which extend downwind of the urban
center.  The shape of the plume and the concentration of 0. in the plume
are dependent on meteorological and emissions factors.  It seems logical
that emissions from smaller cities should result in the same plume
phenomenon, only on a smaller scale.  The question to be addressed is
whether the 0  concentrations formed in the plumes of smaller cities
are high enough to be detected unambiguously above the regional CU concen-
trations characteristic of the Midwest.  To answer this question, three
flights around Springfield, Illinois, will be discussed.
          Springfield is the capital of Illinois and is located near the
center of the state.  The census lists the population as 87,000.  The area
to the west and northwest of Springfield is farmland, and there are no
cities of significant size for nearly 100 miles (Quincy, Illinois being
the largest) in these directions.  Consequently, winds from these directions
are expected to exhibit the relatively low and uniform ozone concentrations
necessary for this experiment.  Flights around Springfield were conducted on
July 12, August 1, and August 3, 1977.

Ozone Plumes from Small Cities
July 12, 1977—
          Winds on July 12 were out of the southwest to west-southwest
averaging 7 mph.  The path of the monitoring flight around Springfield is
shown in Appendix B (page B-3, Flight 2).  Figure 11 displays ozone results
from the flight legs perpendicular to the wind direction 10 miles upwind
and 11 and 44 miles downwind of the city.  Comparison of the downwind 0_
concentrations with those upwind fails to reveal a A0_.  The concentration
is uniform between .03-.04 ppm on both sides of the city.
          The lack of an ozone plume from Springfield on July 12 could be
due to insufficient precursor emissions from the city or it may be that the
meteorological conditions were not conducive to 0, formation on this day.
In fact, the morning of July 12 was rather overcast until 12:00-13:00 CDT,

                                     27

-------
    /i  I  .      {£    NEW        X-«J         I
"*r »J^  / VERMONT (-  HAMPSHIRE    /"'  I         |
                      ' VERMONT;__HAMPS
                  *   I"   '   [J
                     '
Figure 10.   Ozone (in ppb) and other pollutant  results for
             afternoon flight  conducted on August  10, 1975.
                              28

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   .08

   .07

   .06

   .05

   .04

   .03

   .02

   .01

    0

   .07

   .06

   .05
£
ex .04'

cT
   .03

   .02

   .01

    0

   .07

   .06

   .05

   .04

   .03

   .02

   .01
                       Upwind (10miles)
                       Downwind (I) mites)
                       Downwind (44miles)
                   I
I
I
          10       5        0        5        10        15
           Distance on Either Side of Wind Axis Through Springfield, mites
  Figure 11.  Ozone  concentrations upwind and downwind of  Springfield,
               Illinois, on July 12,  1977 (afternoon).
                                     29

-------
and the lack of a discernable plume may well be related to the relatively
low photochemical activity during the morning hours.   Ozone levels at the
mobile laboratory downwind of St. Louis (at Bethalto  Airport)  only reached
.072 ppm, suggesting that meteorological conditions were not conducive to
formation of high concentrations of ozone.
August 1, 1977—
          August 1, 1977 was a clear sunny  day in central Illinois.   Winds
were from the north-northwest at 6-10 mph during the morning.   Monitoring
flights perpendicular to the wind direction were undertaken 9  miles  upwind
and 12, 33, and 65 miles downwind of Springfield.   All flights were  at 1000'
AGL during the early afternoon.  The flight pattern may be found in  Appendix
B (page B-25).  A vertical profile upwind of the city (also shown in
Appendix B (page B-58)  revealed nearly uniform ozone  concentrations  of
40 ppb up to an altitude of 6500 feet.  The 0  data from the upwind  and
downwind traverses are  plotted in Figure 12.  The  concentration upwind of
the city was almost constant at 39 ppb, while the  downwind levels outside
the path of the Springfield plume were 34-38 ppb.
          A power plant plume from a plant south of Springfield shows up
clearly in the second and third downwind profiles.  All three  downwind
profiles show a slight indication of increased 0  directly downwind  of the
city, but in no case is the 0. in the center of the plume more than 6 ppb
above the concentration to the side of the plume.   A A0_ of 6  ppb is barely
discernable in the data and is rather small compared to the 100-300 ppb A0»
observed in the plumes of major cities.  Nevertheless, the data do suggest
that a city the size of Springfield contributes to the downwind ozone burden.
The final case study, to be discussed shortly, makes an even more convincing
case for such a contribution.
          A comparison of the upwind and downwind ozone precursor concentra-
tions may be found in Table 7.  Only traces of reactive olefins such as
propylene were observed.  Aromatic hydrocarbons are not included in the
comparison because data are not available for two of the traverses.
Precursor concentrations are greater downwind of the city, but only
marginally so.  With increases in precursor concentrations downwind of the
city barely detectable, it is not surprising that AO- is so small.  A case
in which Springfield's ozone plume is more apparent is discussed next.

                                     30

-------
    .06




    .05




    .04




    .03




    .02




    .01




      0




    .05




    .04




    .03




    .02




    .01




   :   o
   r>



    .05




    .04




    .03




    .02




    .01




      0




    .05




    .04




    .03




    .02




    .01




      0
                                   Upwind (Smites)
                                   Downwind (12 miles)
                                   Downwind (33 miles)
                  Industrial Plume
                  I     I     I    I
                                   Downwind (65 miles)
           Industrial Plume
         Springfield
>     I    I     I    [
               20   15   10    5    0   5    10   IS   20

              Distance  on Ether Side of Wind Axis Through Springfield, miles
Figure 12.   Ozone concentrations upwind and downwind  of Springfield,

              Illinois,  on August 1, 1977 (afternoon).
                                       31

-------
  TABLE 7.   UPWIND AND DOWNWIND  PRECURSOR  CONCENTRATION FROM
            FLIGHT 20, AUGUST 1, 1977  [Concentrations  in  ppb
            (NO )  or ppbC]
               A

NO
X
ethylene
acetylene
n-butane
isobutane
Isopentane
n-pentane
Upwind
9 Miles
4

.5
.3
1.6
3.5
.9
.5
Downwind
12 Miles
5

.9
.3
2.5
4.7
1.4
.7
33 Miles
6*

.6
.3
1.9
3.5
1.4
.6
65 Miles
7*

.5
.4
1.7
3.1
1.0
.6
* Estimate required subtraction of power plant plume
  contribution
                            32

-------
August 3, 1977—
          Clear sunny weather prevails;: en August 3, with winds from the
northwest at about 5 mph during most of the day.  Meteorological conditions
were conducive to 0_ formation since 0_ concentrations in excess of 110 ppb
were observed at the mobile lab when a wind shift late in the evening trans-
ported polluted air from St. Louis to the mobile lab site in Bethalto.
          The flight pattern for  the afternoon of August 3 consisted pf up-
wind and downwind traverses around Springfield.  The path of Flight 23 is
mapped in Appendix B (page B-30).  Preflight predictions indicated westerly
winds for Springfield, so north-south traverses were performed.  Since the
actual wind direction was northwest, the traverses cut the Springfield
plume at an angle less than the desired perpendicular.  This resulted in
some of the traverses yielding only partial profiles of the city's plume.
Results from the flight are plotted in Figure 13 for traverses 14 miles
upwind and 10, 27, and 45 miles downwind of the city.  The final traverse
of the Springfield plume occurred on the flight back to Bethalto and is,
fortuitously, perpendicular to the wind direction.  All three downwind pro-
files show a significant increase in 0., over upwind values, with the greatest
AO- observed 27 miles downwind.  With an average wind speed of 5 mph this
represents a reaction time of 5 hours.  The AO  at this point was nearly 30
ppb.
          All downwind traverses  from Flight 23 clearly show the Springfield
ozone plume, and the AO, values are highly significant.  It is obvious from
this flight that under appropriate conditions Springfield contributes
significantly to the downwind ozone burden.  Comparison of upwind and down-
wind precursor concentrations from Table 8 suggests that the increased ozone
results from precursor emissions  in Springfield.
          A clearer depiction of  the Springfield urban plume on August 3,
1977 is shown in Figure 14.  Ozone isopleths have been drawn from the
afternoon flight data.  Various shading densities represent ozone con-
centrations, as indicated in the  legend.  Afternoon winds were from the
northwest.  Plotted in this manner, the shape and dimensions of the
Springfield plume are easier to distinguish.  The ozone concentration in the
center of the plume is in the 70-80 ppb range.  While this is below the
Federal standard, it is nonetheless significantly above the surrounding
background levels.  When one considers all the small cities and towns
                                     33

-------
  .06
  .06
  .04
  .02
                                                       Upwind (14 miles)
  .06
  .04
Q.
                                                       Downwind (10 miles)
  .06
  .04
  .02
                                                       Downwind (27 miles)
  .06
  .04
  .02
                   I
                                                       Downwind  (45 miles)
         15       10       5        05         10       15
                      Distance on Either Side of Wind Axis Through Springfield, mites

  Figure 13.   Ozone  concentrations  along upwind and  downwind traverses
               of Springfield, Illinois, on August  3,  1977 (afternoon).
                                     34

-------
            TABLE 8.   UPWIND AND DOWNWIND  PRECURSOR  CONCENTRATIONS
                      FROM FLIGHT 23  [Concentrations in ppb  (N0x)
                      or ppbC]
                           Upwind       	Downwind	
                          14 Miles      10 Miles     22 Miles     45 Miles
NO                            7             15           12             7
  x
acetylene                    .4            .8           .4             .5
isopentane                  1.6           4.0          1.6           2.3
n-pentane                    .9           1.9           .9           1.1
toluene                     3.1           5.6          3.5           3.5
o-xylene                    3.3           7.3          4.6           4.7
                                    35

-------
                                                                  en
                                                                  C
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                                                                  "O
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                                                                  •H
36

-------
which contribute ozone and ozone precursors to the boundary layer, it is
easier to understand why large regions of the country are occasionally
blanketed by high ozone.
          The conclusion to be drawn from the three Springfield plume
experiments is that under conditions conducive to photochemical ozone
formation, emissions from moderate size cities (populations -100,000) lead
to a definable ozone plume.  These experiments demonstrate that smaller
cities contribute measurably to the downwind ozone burden.

THE HIGH-PRESSURE AREA STUDY
Introduction and Summary
           One objective of the program was to investigate the ozone concen-
trations in the air within a high pressure weather system.  The methodology
of the investigation was to make aircraft traverses across the high pressure
system at 1000 feet above ground level with occasional spiral soundings to
measure conditions at higher altitudes.  The high pressure center chosen for
the study moved across the eastern United States more rapidly than was antici-
pated.  Nevertheless, the data that was gathered provided some interesting
insights into the ozone concentrations above 1000 feet in relation to the
position of the high pressure center and the location of urban areas.  The
observation of relatively high ozone concentrations at altitudes above the
boundary layer led to an inquiry into the source of this ozone.  Resolution
of this question involved the use of three-dimensional trajectories and
two tracer parameters—water vapor mixing ratio and potential vorticity.   The
objective of this inquiry was to learn whether this mid-tropospheric ozone
had originated in the stratosphere or at the ground.
           From the horizontal aircraft traverses at 1000 feet the following
observations were made:
      (1)   At this altitude ozone concentrations within the high pressure
           area can be 30-40 ppb  higher at the western (back) side of the
           high pressure area than on the eastern (leading)  side.
      (2)   The ozone plume from urban areas is distinct on both sides of  the
           high pressure area.   It may reach concentrations  as high as 40-50
           ppb  above background levels  on  the  first or second day  of  the  high
           pressure  center's  occupation of an  area.   However,  by  the  third
           day higher concentrations  pervade the  entire region and the ozone
           concentration  in  the urban plume  at 1000 feet may  be only  15
           ppb  above background levels.
                                     37

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          In the analysis of conditions above 1000 feet the information
from the aircraft spiral sounding was supplemented by data from
rawinsonde soundings of temperature, humidity and winds made every 12 hours
by the upper air networks of the United States and Canada.  These rawinsonde
soundings do not measure ozone, but their measurements of other properties
were used to identify layers where ozone may exist.
          One source of ozone in the middle troposphere is the stratosphere.
A parcel of stratospheric air entering into the troposphere through a discon-
tinuity in the tropopause can be distinguished by its low water vapor mixing:
ratio  (dryness) and its high potential vorticity (tendency to be both hydro-
dynamically stable and to move in a counterclockwise direction).  The
stratospheric air will move into the troposphere along an  adiabatic  layer
and consequently can be tagged by a specific potential temperature (see
definition, page 53) .  Using this identifier,  the parcel within  this
layer  can be checked at different places along its tropospheric  path  to
examine  the ozone content,  the water vapor mixing ratio value, and the
potential vorticity  (see explanation, page 52).
          In the middle troposphere ozone study  the aircraft spiral
soundings of ozone,  temperature and humidity were matched with concurrent
vertical variations of water vapor mixing ratio  and potential vorticity
obtained from the rawinsonde network.  All these vertical data were
displayed on special diagrams to aid in distinguishing the air parcels
which  were injected  from the stratosphere.
          Results of several sets of soundings were examined to  gain  an
understanding of the ozone maxima which appeared in the middle troposphere.
Some of  this ozone is introduced by injections from the stratosphere  and
a cycle  related to the progress of the high pressure area across the
country  could be hypothesized.  On the soundings, ozone maxima were also
observed in the lower troposphere just beneath the subsidence inversion
which  overlay the surface high pressure area.  This ozone was traced  back
to the ground and apparently was generated from  anthropogenic emissions.
          The cold frontal surface which preceded the high pressure area
was a  stable layer which could be traced back  to the stratosphere where an
                                    38

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injection of ozone could possibly have occurred above the coast of British
Columbia or southern Alaska.  Any ozone in this injection disappeared during
a seven-day trip from the tropopause along the Pacific Coast at about 25,000
feet to the ground in central Illinois where the Battelle aircraft conducted
its initial sounding.
          The injection of stratospheric air into this stable layer coin-
cided with the time when a transient low pressure center at 500 millibars
(about 18000 feet) moved into the position of the semi-permanent low
pressure trough located above the northwestern United States at this
altitude.  The juxtaposition of the two low pressure areas coincided with
the occurrence of a minimum tropopause height.  As the transient low
pressure moved on across southern Canada, several other injections of
stratospheric air occurred at heights higher than the original injection
on the coast.  These injections could be traced as dry stable layers
descending in the atmosphere.  They were measured by the spiral soundings
in the middle troposphere and contained high concentrations of ozone.
As these stable layers moved eastward within the high pressure area,
they lost their dryness and became less stable.  It seems probable that
in the air above the backside of the high, the layers containing elevated
ozone still are contiguous, but they no longer have the identifying
characteristic of stratospheric air—low water vapor mixing ratios and
high potential vorticities.  It is also possible that this ozone can be
mixed uniformly within the middle troposphere and that eventually, some
of this well-mixed ozone could descend to the ground at a concentration
considerably less than that which it had when it left the stratosphere.
The Study
          On Thursday July 21, 1977, a cold front passed across Illinois
from northwest to southeast and by Friday a large high pressure area was
moving across the Great Lakes region on its way to the Atlantic Ocean where
the center of the high crossed the Maryland-Virginia coast between Saturday
and Sunday.   During the period of Friday July 22 to Sunday July 24 measure-
ments by both the Battelle and Washington State University aircraft were
                                  39

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devoted to the study of conditions in the high pressure area.  Measurements
of ozone, ozone precursors, and meteorological parameters at about 1COO feet
AGL were made on cross country flights covering the mideastern United States
(Figure 15).  Several bag samples were collected for later analysis and
spiral soundings were made at nine locations along the route.  Additional
descriptive material regarding the flights and soundings is  presented
in Table 9.
Findings
Meteorological Situation—
          Figures 16 through 22 are the seven daily weather maps prepared
by the National Oceanic and Atmospheric Administration ,for the period July
18-24, 1977.  This series depicts the sequence of weather system movements
at the surface and also in the upper air during the time of the cross-
country flights.  One day's maps consists of (1) the surface weather map
(top) for 7:00 a.m. EST (08:00 EDT and 07:00 CDT), (2) the 500-millibar
chart (lower left hand map) with height contours in feet and temperatures
in degrees  Celsius for 7:00 a.m. EST, (3) the highest and lowest tempera-
tures in degrees Fahrenheit for the previous day (lower right center map)
and  (4) the areas  (black) where precipitation was recorded during the
previous day (lower right hand map).
          From the surface weather map one can determine such pertinent
information as locations of high pressure centers, locations of fronts,
and winds at the weather stations.  A station with a circle  around it
denotes calm conditions for the 07:00 CDT weather observation.  Interest
in the 500 mb chart is centered on the location of low centers and troughs
(areas where contours dip southward).  Large areas devoid of precipita-
tion on the precipitation map will frequently match areas covered by high
pressure centers on the previous day's 07:00 surface weather map.
          From July 18 to July 20 the surface pressure pattern over the
seven states bordering the lower Great Lakes did not change.  The region
was  in the  rear of a high pressure area.  Winds were southwesterly or  calm
on the 07:00 CDT map, maximum temperatures were in the 90's, and precipita-
tation was  scattered.  Haze or fog was reported at many of the stations at
                                    40

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WSU Flights;

Sat.  7/23
Sun.  7/24

BCL Flights:

Fri.  7/22
Sat.  7/23
Sun.  7/24
Robinson to Richmond
Richmond to Robinson
Bethalto to Muskegon
Muskegon to Columbus
Columbus to Bethalto
1130 CDT to 1700 CDT
1130 EDT to 1740 EDT
1000 CDT to 1608 CDT
1400 EDT to 2040 EDT
0845 EDT to 1415 EDT
   Figure 15.  Ozone concentrations (ppb) along the paths of the Washington
               State University and Battelle's Columbus Laboratories cross-
               country flights between July 22 and July 24.   (Sites of spiral
               soundings are shown.)

                                      41

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MONIUT, JULY It 19TT
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         Figure 16.   Daily weather map for July 18,  1977.
                             43

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                                                   TOZSDAY. JULY 11. LJT7

Figure  17.  Daily  weather map for July  19, 1977,
                         44

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WDNBDAT. JOLT «. MTT
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          Figure 18.  Daily weather map for July  20, 1977.
                              45

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                                                        THUBSDAY, XJLf a. 1717
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          Figure 19.   Daily weather map for  July 21, 1977.
                                 46

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reiDAT. JUIT a. am
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         Figure 20.  Daily weather map for July 22, 1977,
                             47

-------
                                 * * f t  s  «_ * * * a * %f
                                   * V^-an * «  ****"%
Figure 21.  Daily weather map  for  July 23, 1977.
                      48

-------
SUNDAY. AJLT M. UTT
      p|g^^ v~ ^ ^'!^f f!
        Figure 22.  Daily weather map for July 24, 1977,
                         49

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07:00 CDT.  A front across the northwestern United States showed little
movement; however, a distinct high pressure area did develop behind it by
Wednesday July 20.
          At 500 mb a small trough moved from the large semi-permanent
trough in the Pacific Ocean eastward from British Columbia, across Alberta,
and into northern Saskatchewan.  During the next three days this 500
millibar trough continued moving eastward and on July 23 it had helped
produce a deep trough along the North Atlantic coast.  Between July 20
and July 24 the cold front and the high pressure area behind it moved
quickly across the eastern United States.  The high pressure center moved
from southern Alberta on July 20, to northern Minnesota on July 21, to
northern Wisconsin on  July  22 and to West Virginia on July 23.  By July
24 it was off the Virginia coast and another cold front was entering the
Great Lakes region.
          Measurements of wind direction, temperature, and humidity at
Battelle's Bethalto, Illinois station and at the St. Louis airport indicate
that the front which was across northern Illinois on the morning of July 21,
passed through the St. Louis region at about 18:00 CDT.  Thunderstorms occurred
in the area at this time.  At Bethalto the ozone concentration, which had
reached its daily maximum of 116 ppb at 15:00 CDT, dropped from 93 ppb to 75
ppb between 17:00 and 18:00 and continued to fall until midnight.

Cross Country Flights—
          Between Friday morning and Sunday evening, both the Battelle and
Washington State University airplanes made cross country flights across the
high pressure area from west  to east and back.  Battelle's aircraft flew
from Bethalto to Muskegon, Michigan, on July 22, then to Columbus, Ohio, on
July 23, and returned to Bethalto on July 24.  The Washington State cross
country flights were from Robinson, Illinois to Richmond, Virginia, along
a southern route on July 23 with a return to Robinson by a more northerly
route the following day.
          Ozone concentrations measured at about 1000  ft AGL  along these
flight paths are shown in Figure 15.  On Friday, July 22, no  concentrations
above 100 ppb were observed on the Battelle flight which traversed a path
slightly to the rear of the high pressure center.

                                   50

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          During its Saturday afternoon flight, the Washington State air-
craft's highest measured ozone concentration was 102 ppb on the Ohio-
Kentucky border.  Later that day, the Battelle flight traversed areas of
greater than 100 ppb concentrations northeast of Detroit, northeast of
Cleveland—Erie, and northeast of Columbus, directions which were downwind of
these cities since they were on the northwest side of the high pressure center.
          By the following day, the movement of the high pressure center
had slowed considerably.  The Battelle flight on this day began at 08:45
EDT at Columbus and ended at about 16:00 EDT at Bethalto.  During the
flight, only two areas of plus 100 ppb concentrations were observed—in the
morning over northwestern Ohio and in the afternoon northeast of St. Louis.
The morning ozone must have been preserved from the preceding day; however,
the afternoon maximum can be attributed to transport from St. Louis along
the trailing edge of the high pressure area.
          The Washington State flight on this date was almost entirely in
the afternoon.  After this aircraft entered western Pennsylvania, ozone
measurements at 1000 feet never dropped below 100 ppb for the remainder of
the flight across central Ohio and Indiana.  Taking into consideration the
concentrations observed in the pre-noon portions of both flights on this
date, it is reasonable to assume that the entire area from Washington, D.C.
to St. Louis, on the rear of the high pressure area, was submerged in ozone
concentrations between 100 and 150 ppb with the maximum concentrations
lying above eastern Ohio.  There were some indications of city plume
effects downwind of the larger cities, but the plus 100 ppb concentrations
pervaded rural as well as urban areas.
Atmospheric Soundings—
          Air with high ozone concentrations has been observed to occur
in contiguous volumes or clouds within that part of the troposphere lying
between the boundary layer (approximately 3000-5000 feet above mean sea
level) and the tropopause (approximately 25,000-35,000 feet above mean
sea level in mid latitudes).   Singh,  Johnson, Ludwig, and Viezee (8,9,10)
have reported on several field investigations of upper - tropospheric ozone.
They concluded that the stratosphere is the major source for this
trospheric ozone.  Their work suggests that 03 of stratospheric origin

                                   51

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descends into the troposphere and is found at altitudes as low as 8000
feet.  When cyclones form or intensify intermittently in an upper tropo-
spheric trough, an injection of stratospheric air into the troposphere
occurs.  The point of injection is at a break in the tropopause below
and to the north of the jet stream.  From this point the stratospheric
air proceeds generally downward and southward.  This contiguous volume of
                                                                       (9)
air is 100-300 km wide and several hundred km long.   Johnson and Viezee
state  that  this stratospheric ozone may reside in the  troposphere for up
to four months during which time it is dissipated by tropospheric mixing,
surface-based mixing, precipitation scavenging,  and   deposition to  the
ground.
          In an investigation of unusually high  ozone concentrations at a
surface station, Lamb(H) employed two meteorological parameters frequently
used in stratospheric/tropospheric exchange studies—water vapor mixing ratio
and potential vorticity—to demonstrate that the ozone had originated in
the stratosphere.   Low values of water vapor mixing  ratio and high values
of potential vorticity are typical of stratospheric  air that is residing
in the troposphere.
          It is easy to understand that low values of water vapor mixing
ratio indicate dry air and that air from the relatively moisture-free
stratosphere would be dry in comparison with typical tropospheric air.
Potential vorticity, however, is not a familiar parameter.  A few
paragraphs will be provided here for those who are interested in a
discussion of potential vorticity and why high values of this parameter are
found in stratospheric air which has been injected into the troposphere.
Potential Vorticity—
          Vorticity is a measure of rotation in fluid flow.  Absolute
vorticity is the sum of the vorticity relative to the earth (V = relative
vorticity) and the vorticity of the earth itself as  it rotates on its axis
(f = Coriolis parameter).  Relative vorticity can be written as
                           _ 5v   3u
                             8x " 3y
in x-y coordinates where v is velocity in the y direction and u is velocity
in the x direction.  In a coordinate system based on the direction of flow
of an air parcel,  the relative vorticity  can  be expressed as
                                    52

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                         v _         _
                             3n ~C Ss
where s is the direction along the flow, n is the direction perpendicular
to the flow  (positive to the right of the flow), c is the speed of the flow,
and a is the  angle  (positive in a  clockwise direction) between  the
direction of flow at an initial point and at a point downstream.
          Positive vorticity in the northern hemisphere is counterclockwise
rotation (cyclonic flow).  In the x-y coordinate system, increasing southern-
                                      3v
ly winds as one proceeds to the east (-T— positive) would cause a parcel of
air to be rotated counterclockwise.  Similarly,  counterclockwise rotation
along the y axis (northward direction) would occur with a decrease in
easterly winds along this axis (-r— decreasing or - -r— increasing) .
                                dy                 dy
          The jet stream blows from west to east in the northern hemisphere.
An air parcel just north of the jet stream is subjected to a strong counter-
clockwise rotation.  Injections of air from the stratosphere into the
troposphere occur at the tropopause-break area which coincides with the
jet stream position.  The injected air originates north of the jet stream
in the stratosphere and passes beneath it into the troposphere.   This air
retains its high positive vorticity.
          In hydrodynamic theory potential vorticity is defined as the
product of the absolute vorticity and the stability
          The term - •— is a measure of stability.
                     9P                          *
In a stable atmosphere the potential temperature,  9, as measured from a
rising balloon would increase with height.  In other terms, it increases
with decreasing atmospheric pressure, p, as one goes upward in the
atmosphere.
*  In meteorology potential temperature (denoted by 0) is the temperature a
   parcel of dry air would have if brought adiabatically from its initial
   pressure to the standard pressure of 1000 millibars.  Thus the potential
   temperature measured within a parcel of air would remain constant if the
   parcel ascends or descends in the atmosphere without heat transfer and
   without condensation of the water vapor in the parcel.
                                    53

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Thus, in a stable atmosphere, -T~, would be positive.  There is a high
rate of increase of 6 with height above the tropopause, thus, the value
     30
of - — is positive and relatively large.
          From hydrodynamic  theory it can also be shown that in dry
adiabatic motion the potential vorticity of an air parcel remains constant
(conservation of potential vorticity).  In meteorology, dry adiabatic motion
is considered to be isentropic motion, that is, motion in which the
potential temperature remains constant.   For many purposes motion in the
free atmosphere over periods of two days or less is assumed to be adiabatic.
The conservation of potential vorticity on an isentropic (constant
potential temperature) surface is written mathematically as
                      P      96
                       9 = - T~ U s+ On = constant
                             dp   9    o
                              J} ^
In practice,  the stability (	) of the parcel is an average of the
                              9 P
stability in a layer extending about 0.5 km on either side of the surface.
          Air injected from the stratosphere into the troposphere would
                                                     ^ ft
have relatively high positive values of  stability (- — and absolute
vorticity (L + f) and thus, the product  of these two terms (potential
vorticity)  would be higher within the encroaching stratospheric air than
within the surrounding tropospheric air.  As long as the dry adiabatic
motion of the stratospheric air is not disturbed, the difference in
potential vorticity between the injected stratospheric air and the ambient
tropospheric air is quite marked.  Over  longer periods of time (e.g. more
than two days) the potential vorticity  of  the  injected air can be expected
to decrease as mixing with the tropospheric air takes place.   However,
the potential vorticity values of the air which originated in the strat-
osphere may still be sufficiently greater than those in the ambient air
to still identify it as stratospheric air.
Measurement and Data Display Methods—
          Upper atmospheric  temperatures, humidities, and winds as measured
by balloon-borne rawinsondes are used routinely in the preparation of
weather forecasts.  A single sounding reveals  considerable detail about
the structure of the atmosphere  above a station, specifically, the height
of temperature inversions  and  other stable layers and whether these layers
                                    54

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are moist or dry.  By considering the soundings made concurrently at
several nearby stations one can discern  the horizontal extent of  these
stable layers and whether they slope from one point to another.  When
consecutive soundings at one station or at a network of stations are
compared, the movement of the stable layers can be determined.  The slope
and movement of a frontal surface, one type of stable layer, can be
ascertained by inspecting the plots of temperature versus height from
several rawinsonde stations.  Plotting the soundings on special adiabatic
diagrams can aid in the analysis of the data by displaying stabilities,
          Measurements of ozone variation with height by balloon-borne or
aircraft-borne instruments have disclosed that there is considerable ozone
structure in the atmosphere.  Variations in ozone structure are frequently
found to coincide with variations in the temperature-humidity structure.
By noting this coincidence and observing the movement and continuity of a
specific structural detail, such as a temperature inversion which has a
specific potential temperature, one can surmise the movement and horizontal
extent of the accompanying layer of ozone.
          Example Diagram—Figure 23 (a and b) presents two diagrams used
to depict the variations of ozone, temperature and dew point with height.
It shows ozone, temperature and dew point conditions which prevailed before
the front passed.  The bottom diagram presents a plot of the ozone sounding
made during an airplane spiral near East Alton, 111. on July 21 between
06:05 and 07:23 CDT (Appendix B, page B-40).  The top diagram is a plot
of the results of a balloon sounding of temperature-humidity made by the
NOAA weather station at Salem, Illinois, for the 1200 GMT (Greenwich
Meridian Time equivalent to 07:00 CDT)  regularly scheduled sounding.
Salem ±s 60 miles east of the Bethalto-East Alton area.
          Figure 23 (a)  is a portion of an Air Force Skew T, log p type
adiabatic diagram.   Isotherms in degrees Celsius slope upward from left
to right.  Three dry adiabats (lines of constant potential temperature)
for 20, 30, and 40 C are shown as curved lines sloping from lower right
to upper left.  Water vapor mixing ratios (in grams of water vapor per
kilogram of dry air) are the dashed lines sloping upward from lower left
to upper right.  Horizontal lines are isobars (lines of constant pres-
                                    55

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                                 t ff , C
   400
   490
    HO
    •90
    TOO

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    •00
 =  «00
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IOOO
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               /  /  /  X  ;
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   /   /   /   /:  7
 /   /   /  /7/   /  >'/
                                                        XX   /   X
                                                            /  /
        ///;////.'/
/    /        /   /   /:   /        /
^^^^^^^^^^^^^^~^^^^"^^^^       "^^"^"^^^^^
                                                      /
                                                      ^
 /   /
                      /    /.«
                                 /»   /
   Y   /   / r
                   /;//•'/
                                                 /   /
   /    / / /   /   : /    /.   /
                                                    /
       Solid Unw • Ttmecrattm, C     OoWW« Lm«t • *af«r Vapor Mixing Rqtia,
                                      (a)
490
900
990
«OO
(90
TOO
790
•00
•40
»OO
• 90
\\\ \
\ \ \
\ \ \
\ \ \
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\
\ \
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\ X j
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\ \ X
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*r^ — V-' \ \ _
TV \ «>^-
                                                                 It

                                                                 to
 Cur*«d Lino* • 0,
                         gram* por millton from* of atr
                                     (b)
Figure 23.   Temperature, dewpoint and  ozone concentration variations with
             height in central Illinois on the morning of July  21,  1977,
             before the cold front passed.  The (a) diagram is  a  plot of
             temperature in degrees C  (solid line) and dewpoint (dashed line)
             for  NOAA's Salem, Illinois station at 07:00 CDT.   The  (b) diagram
             is a plot of ozone mixing  ratio (ppmm) measured over East Alton,
             Illinois between 06:05 and 07:23 CDT.  See text for  description
             of the (a) skew T, log p diagram and the (b) ozonagram.
                                      56

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sure). Atmospheric pressures are indicated on the left-hand ordinate with
heights in thousands of feet on the right-hand ordinate.  The pressure-
height relationship on the diagram is that of the U.S. Standard Atmosphere,
so for most soundings either the pressure or the height of a temperature
feature will be slightly incorrect.
          Figure 23b shows the results from Flight 6 converted to the form
               (12)
of an ozonagram     to portray the variations of ozone from the surface
to the upper stratosphere.  The diagram here has been designed so that
the isobars and height lines are identical with those on the Skew T,
log p diagram.  The lines curving upward to the left are ozone mixing
ratio lines.  An ozonagram depicts mixing ratio as parts per million by
mass (ppmm) rather than parts per million by volume (ppmv),   The aircraft
sounding measurements of ozone in parts per million by volume were multi-
plied by 1.65 to convert to parts per million by mass.  Ozone mixing
ratio is a conservative property of an air parcel and will not change
during vertical movements unless turbulent mixing occurs.
          The temperature lapse rate on the morning of July 21 was generally
uniform and slightly stable up to 460 mb (20,000 feet) where there was a
stable layer (temperature inversion).  The layer from the surface to 400 mb
(23,000 feet) was quite moist as shown by the dew point sounding (dashed
line) which parallels the temperature plot.  The relative humidity for the
layer from the surface to 400 mb varied between 60 and 95 percent.
Temperatures were also measured during the airplane sounding, but humidity
was not; thus, the Salem sounding is plotted here so that both parameters
can be shown.
                (13)
          Reiter    has stated that the ozone which appears in moist upper-
air layers of the troposphere is of surface origin as compared with very
dry layers which are indicative of stratospheric air.  Thus the ozone which
reached a concentration of 0.109 ppmm (.066 ppmv) at 3000 feet over East
Alton was part of a deep layer of surface-generated ozone on the backside
portion of the high pressure area which dominated the southeastern section
of the United States.  Ozone concentrations of 0.1 ppmm may have extended
                                 57

-------
even higher than the 10,000-foot limit of the airplane sounding.   No barrier
is found in the temperature sounding until the stable layer at 16,000 feet.
          Analysis Techniques—While no conspicuous  ozone peak and stable
layer combinations appeared on the July 21 sounding,  made before  passage of
the cold front, there were numerous examples on the  cross-country flight
soundings made behind the front.  Several techniques were used to investigate
these ozone peaks and to explain their origin.
          The initial step was to identify the magnitude of the ozone peak
in relation to the ozone concentrations above and below it.  An isolated
maximum would suggest that ozone had been transported adiabatically into
an area.  Uniform ozone mixing ratios through a considerable depth, such
as in Figure 23(b) would indicate that the ozone originated at the surface
and was mixed upward.
          Further investigation of this aspect involved comparison of the
ozone sounding,details with those of the temperature sounding. Ozone spikes
appearing at the same height as temperature inversions were likely to have
moved with this stable layer.  They could be tagged  with the potential temper-
ature range of the stable layer and other soundings  could be examined for
evidence of this same stable layer.  Occasionally, a part of the  ozone peak
might extend below or above the inversion layer.  In these cases  it was
assumed that the lag time of one of the instruments  was the cause for the
misalignment and that the ozone peak actually coincided with the  stable
layer.
          As previously mentioned, water vapor mixing ratio and potential
vorticity value can distinguish air of stratospheric origin within the
troposphere.  Values of both these parameters were determined during the
analyses of the soundings made during the cross-country flight.  Data
acquired during the aircraft sounding were insufficient for calculating
potential vorticity so information gathered from NOAA soundings in the
vicinity was used to plot the value of this parameter versus height.
Vertical profiles of water vapor mixing ratios for the NOAA sounding closest
in time and distance to the aircraft sounding were also prepared.
                                                                  (14)
          As identifiers  of stratospheric air, Reiter  and Mahlman
have recommended water vapor mixing ratio values less than 1.4 grams/
kilogram and potential vorticity values greater than 10 x 10~^ cm sec deg
                                    58

-------
gm   .  Potential vorticity is conserved during dry adiabatic descent and
is thus an.indication cf stratospheric air which has entered the
troposphere.  In the present study there were several distinct potential
                                                   -9              -1
vorticity maxima which had values less than 10 x 10   cm sec deg gm
These smaller maxima probably indicate stratospheric air which has been
partially mixed with tropospheric air.
          Another technique used in this investigation of the high altitude
ozone concentrations was to trace the air accompanying an ozone maximum
backward in time along an isentropic surface.  It was anticipated that
this isentropic trajectory would show the path of adiabatic descent
followed by stratospheric air from the tropopause to the point of the
aircraft sounding.  The choice of an isentropic surface was determined by
the potential temperature of the subsidence inversion layer associated
with the ozone maximum.   The trajectory was constructed in 12-hour steps
using the wind and pressure data from the NOAA sounding network.   Movement
along an isentropic trajectory assumes that no turbulent mixing occurs and
that the route is dry.   If there was a stable layer on a sounding in the
vicinity of each 12-hour end point of the trajectory, its appearance was
taken as confirmation of the continued adiabatic movement of the parcel.
Sounding Results From the Battelle Cross-Country Flights—
          Springfield,  Illinois—10;30 CDT, July 22—-Shortly after the
initial leg of the Battelle cross-country flight began,  the first spiral
sounding was made between 3,000 and 12,000 feet above a location near
Springfield, Illinois (Appendix B,  pages B-10, B-43) .  Results of this
sounding are plotted in parts a and b of Figure 24.   Plots of the variation
with height of potential vorticity and water vapor mixing ratio are pre-
sented in Figure 24c.  These are based on data collected during the
regularly-scheduled NOAA rawinsonde sounding at Peoria,  Illinois, made
about 3-1/2 hours earlier (07:00 CDT).  Peoria is 70 miles north of Spring-
field.   NOAA records indicate that the cold front passed both Peoria and
Springfield during the previous afternoon.  On the morning of July 22
the frontal surface (appearing as an inversion layer) would have overlain
both cities.  As a consequence of the aircraft sounding being later than
the NOAA sounding,  it is expected that the frontal surface would appear at
a higher elevation above Springfield.
                                   59

-------An error occurred while trying to OCR this image.

-------
          Temperature measurements (solid line on the right of Figure 24a)
depict a temperature inversion between 5,000 and 7,000 feet with a potential
temperature range of 32 to 36C.  The dewpoint (dashed line in Figure 24a)
in this inversion layer decreased to a temperature where the water vapor
mixing ratio was less than 0.6 gm/kgm at 6500 feet.   The corresponding
feature on the earlier Peoria sounding is water vapor mixing ratio of
17 gm/kgm at 5000 feet (dashed line on Figure 24c).
          Variation of potential vorticity (P) with height is shown by
                                                       -9       -1
the solid line in Figure 24c.  A maximum of P (7.8 x 10   deg gm  cm sec)
is located between 4,000 and 6,000 feet.  It coincides with the dry layer
there; thus one may conclude that the P maximum is associated with the
frontal layer.  The maximum value of P does not meet the Reiter criterion
        -9       -1
(10 x 10   deg gm  cm sec) for stratospheric air; however, the water vapor
mixing ratios on the aircraft sounding indicate that the air is dry enough
(less than 1.4 grams/kgm) to be of stratospheric origin.  Our conclusion
is that the portion of the stable layer observed above Peoria contains
stratospheric air that has been diluted by tropospheric air.
          Ozone measurements made during the aircraft sounding are plotted
in Figure 24b.  Two distinct maxima were observed, one between 4,000 and
5,000 feet and the other at 10,000 feet.  However, there is a minimum at
7,000 feet which is the height of the dry inversion layer over Springfield.
Thus the frontal zone contains little ozone and it can be assumed that no
ozone was supplied to the surface at the time of the frontal passage.  As
noted previously, the ozone concentration at the Bethalto station dropped
at the time of the frontal passage and continued to decrease.
          Still to be explained are the ozone maxima at 4500 feet and
10,000 feet.   Temperature structure, moisture content, and potential
vorticity of the air at these levels all indicate that this air is not of
recent stratospheric origin.  However, the heights of these ozone maxima
are high enough that there is some question as to whether they are of
surface origin.  To investigate the origin of these ozone maxima, isentropic
trajectories were constructed tracing the air backwards from the Peoria-
Springfield area.  Isentropic trajectories show three dimensional motion.
However, their construction requires adiabatic motion and an assumption
of adiabatic movement may not be true in this instance.
                                   61

-------
          The lower layer trajectory (potential temperature of  30C)  is shown
in Figure 25.  The air parcel was carried backward for two days in four
12-hour steps.   During this period the parcel was behind the front moving
in a clockwise direction from southern Wisconsin to central Illinois.   It
ascended from 950 mb (about 2000 feet) to 845 mb (about 5000 feet).
Apparently ozone generated at the surface was transported upward within
the boundary layer and accumulated at the top of this layer.  Destruction
of the ozone in the lower portion of the layer left an ozone maximum
(0.135 ppmm or about 80 ppbv) at the top of the layer.  Potential urban
sources for this ozone are the medium-sized cities of Des Moines, Iowa
(population 194,000), Madison Wisconsin (173,000) and Rockford, Illinois
(141,000).  It is noteworthy that this ozone maximum of about 80 ppbv
(130 ppbm) appeared at the top of the boundary layer above central
Illinois less than one day after the frontal passage and without the air
passing over a major city.
          Figure 26 displays the isentropic trajectory for the upper ozone
maxima  (0 a 39C) carried backward 2-1/2 days.  There was little vertical
motion indicated during this time; the parcel remained at about 700 mb.
This parcel was always in the high pressure area that existed over eastern
United States preceding the arrival of the new front  (refer to Figure 23
for the concentrations measured at 10,000 feet 24 hours earlier).  At
Springfield on July 22, this air with relatively high ozone still existed
above the wedge of the new cold front.  The trajectory indicates a meandering
around the backside of the old high pressure area.  As stated previously,
the mixing ratios at 10,000 feet indicate that the air at this height had
been mixed with surface air.  Even if the ozone had been of stratospheric
origin at one time, there is no way of identifying it as such by July 21 or
22.

          Fond  du Lac, Wisconsin—15:00  CDT,  July  22—A  second  spiral
sounding  on  the flight of  July  22 was made  in the  afternoon over  Fond  du
Lac, Wisconsin,  50 miles  northeast of Milwaukee  (see  Appendix  B,  pages
B-10, B-44) .  The cold front had passed  over  this  area  2 days  earlier  on
July  20.  By the  time of  the sounding  the front  was  two  states  away  to
                                   62

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the south and southeast and the high pressure center was over Michigan.
Surface winds over Wisconsin were from the southern quadrant.
          Figures 27 a and 27b are plots of the aircraft sounding of
temperature, dewpoint, and ozone while Figure 27c displays water vapor
mixing ratio and potential vorticity as measured and calculated for the
rawinsonde sounding at Green Bay, Wisconsin, 4 hours later and 50 miles
north northeast of the Fond du Lac aircraft sounding.
          An isothermal layer extends from 4000 feet to 6000 feet (Figure
27a) and has a potential temperature range from about 27 C to 34 C.  It is
the remains of the cold frontal layer that passed through on July 20.   This
layer coincides with a potential vorticity maximum at 5000 feet (Figure 27c)
and has very low values of water vapor mixing ratio on both the Fond du Lac
and Green Bay soundings.  In contrast to the morning sounding at Springfield,
the Fond du Lac sounding measured a relative maximum of ozone in the frontal
layer (Figure 27b).   The low water vapor mixing ratio and the relatively
high potential vorticity of the layer suggest that this ozone had a strato-
spheric origin.
          Examination of the water vapor mixing ratios throughout the depth
of the two soundings reveals that the air from 5000 feet to 24,000 feet was
dry enough to meet the criterion for stratospheric air.  However, the plot
of potential vorticity suggests that only the layer between 14,000 and 15,000
feet is actually the result of a stratospheric injection.  The potential
                             -9       -1
temperature meets the 10 x 10   deg gm   cm sec criterion for stratospheric
air.  There is a slightly stable layer at this height on the aircraft
temperature sounding  (Figure 27a).  Furthermore, there is an ozone maximum
of about 0.165 ppmm (0.100 ppmv) in the layer.
          To investigate the origin of the ozone measured during this
sounding, an isentropic trajectory was traced backward along the © = 44C
surface from the Green Bay-Fond du Lac area at 14,000 feet (595 mb) on
July 23 at 0000 GMT (19:00 CDT).  Figure 28 depicts the 2-1/2 day trajectory
of this ozone-rich parcel.  At 1200 GMT (07:00 CDT) on July 20 the parcel
was in the stratosphere at 300 mb (about 30,000 feet) above western
Saskatchewan.
                                   65

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          Figure 29 is a temperature-pressure plot of soundings made at
three ravinsonde stations which were along the 9 = 44C air parcel trajectory
during the 3 days.  The Green Bay sounding (a) was made at 19:00 CDT on
July 22.  Twenty four hours earlier the closest sounding to the air parcel
was the one at International Falls, Minnesota.  When the parcel was at its
minimum atmospheric pressure, 60 hours before it arrived over Fond du Lac,
the nearest rawinsonde sounding was the one at The Pas, Manitoba.
          Although the potential temperatures for the stable layer are not
identical on the Fond du Lac, Green Bay, and International Falls soundings,
they are close enough to confirm that they all represent the same air parcel.
At The Pas the pressure of the 6 = 44C surface places it above the tropo-
pause (the temperature inversion which begins at 325 mb).
          Examination of the 500 mb map portions of Figures 17 and 18 indi-
cates that the injection of the ozone-bearing stratospheric air along the
0 » 44C layer was associated with the low-pressure trough which moved across
Canada.  On July 20 at 1200 GMT (07:00 EST) the low center at 500 mb was at
60° north latitude and 90° west longitude.  The trough at 500 mb at this
time was oriented in a southwest direction from the low center.  At 300 mb
(about 10,000 feet higher up) this trough would have been displaced to the
west.  The stratospheric air injection over western Saskatchewan associated
with this 300 mb trough resulted in a stable layer in the middle troposphere.
This layer was not a frontal layer and did not extend to the surface.  Thus
the ozone within it would not be transported directly to low elevations, but
would remain in the middle troposphere until dissipated by mixing which
occurred there.
          The three temperature soundings in Figure 29 also indicate the
presence of a stable layer at lower elevations.  This stable layer has a
potential temperature in the vicinity of 30C and thus corresponds to the
frontal layer observed on the Springfield and Fond du Lac aircraft soundings.
The temperature inversions denoting this  stable layer on  Figure 29  are at
5000 feet above Green Bay, 6000 feet above International Falls,  and 10,000
feet above The Pas.  The layer would have to  rise to  considerably higher
elevations to reach the stratosphere.  Thus,  the tropopause injection  point
of the ozone found in tthis layer at Fond du Lac must  have been  further west
than western Saskatchewan, the injection point for the air on  the
G = 44C surface.
                                     68

-------
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Figure 29.  Three temperature soundings made along the 0 = 44°C isentropic
            trajectory of Figure 28 showing the descent of the stable layer
            from the stratosphere to the middle troposphere.  Green Bay,
            Wisconsin, at 0000 GMT on July 23 (dashed line).  International
            Falls, Minnesota, at 0000 GMT on July 22 (dash-dot line).  The
            Pas, Manitoba, at 1200 GMT on July 20 (solid line).
                                    69

-------
          Muskegon. Michigan—15;00 CDT.  July 23—The second leg of the
cross country flight was made from Muskegon,  Michigan, eastward to  Buffalo,
New York, and then southwestward to Columbus, Ohio,  covering the period from
14:00 EDT to 20:40 EDT on Saturday, July  23.   The first spiral sounding on
this flight was made about 50 miles east  of Muskegon.  At the surface this
location was well back of the high pressure center and winds were from the
south or southwest (refer to Figures 21 and 22).  At 500 mb  the low pressure
trough was also east of Michigan and the  upper level winds over the state
were west northwest.
          Results of the airplane soundings are displayed in Figures 30a
and 30b while Figure 30c is a plot of the potential  vorticity and mixing
ratio from the Flint, Michigan, rawinsonde sounding  made at  20:00 EDT on
July 23, 5 hours later than the aircraft  sounding.  Flint is about  80 miles
east of the point where the aircraft sounding was made.
          During the aircraft sounding which covered the layer between 2000
feet and 12,000 feet, several ozone peaks were measured.  The highest ozone
was found just below the upper extent of  the sounding.  A smaller peak was
found between 5000 and 6000 feet while between 5000  feet and 2000 feet the
ozone never dropped below 0.125 ppmro (0.075 ppmv).
          Both the aircraft sounding and  the rawinsonde sounding reported
very low water vapor mixing ratios between 6000 and  12,000 feet (dashed
lines in Figures 30a and c).  The potential vorticity curve  (solid  line in
Figure 30c) leads one to conclude that within this dry air there were two
layers of air which still had traces of their stratospheric  origin.  One of
these is at about 10,000 to 12,000 feet while the other lies between 5000
and 6000 feet.
          The potential vorticity plot from the Flint sounding (solid line
                                                   -9       -1
on Figure 30c) contains a maximum of nearly 10 x 10    deg gm   cm sec at
about 10,500 feet.  It is hypothesized that this layer is associated with
the temperature inversion and ozone maximum which appeared at about 11,500
feet (Figures 30a and c) on the aircraft sounding.  The potential tempera-
ture of this inversion layer on the aircraft sounding was 42C.  Thus this
is apparently part of the same injection (0 = 44C) that was traced back
to the stratosphere in Figure 28.
                                     70

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-------
          Between 5000 and 6000 feet there is a potential vorticity maximum
and a marked temperature inversion with a potential temperature of 30C, but
no distinct ozone maximum.  This is the layer that was identified as the
frontal layer observed on the two aircraft soundings of the previous day.
Ozone content on this central Michigan sounding is uniform at 0.10 ppmm
(0.06 ppmv) between 6000 and 10,000 feet.   This concentration is similar to
the concentrations associated with the frontal layer on the earlier soundings,
          At about 22,000 feet (425 mb) on the Flint sounding (Figure 30c)
there are indications of a layer of air which has stronger stratospheric
characteristics than any of the previously noted injections.  The high ele-
vation, the low mixing ratio (0.5 gm/kgm)  and the high potential vorticity
          -9       -1
(12.5 x 10   deg gm   cm sec) all suggest  air that was recently in the
stratosphere.  Unfortunately, the aircraft sounding was not high enough to
measure the ozone in this layer.
          Between 2000 and 5000 feet the ozone concentration varies between
0.10 and 0.145 ppmm  (0.06 to 0.09 ppmv).  The temperature lapse rate and
the relatively high moisture content in this layer lead to the assessment
that this is ozone generated at the surface.  It has been mixed upward until
stopped by the barrier of the temperature inversion at 5000 feet.

          Erie, Pennsylvania—19:00 EDT, July 23—A spiral sounding was
made midway between Buffalo, New York, and Erie, Pennsylvania, late in the
second leg of the cross country flight (see Appendix B, pages B-10, B-46).
This sounding explored the layer between 2000 and 20,000 feet.  Results of
the aircraft sounding are shown in Figures 31a and 31b.  This sounding was
made within 50 miles of the Buffalo rawinsonde station and within one hour
of the regular Buffalo 0000 GMT (20:00 EDT) sounding.  Water vapor mixing
ratio and potential vorticity for Buffalo  are displayed in Figure 31c.
Comparison of the observations from the two soundings provided an estimate
of the accuracy range for the instruments  and data reduction methods used.
For instance, the water vapor mixing ratios on the aircraft sounding were
lower than those on the balloon; but the aircraft sounding picked up mixing
ratio variations between 9000 and 13,000 feet that the rawinsonde did not
record.
                                     72

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Figure 31. Information from western New York obtained  from  upper-air
           soundings  made on the evening of Saturday,  July 23,  1977.
           (a) Temperature (solid line) and dewpoint  (dashed line)
           measured by Battelle aircraft at 19:00 EDT  northeast of Erie,
           Pennsylvania,  (b) ozone mixing ratio (ppmm)  measured by
           Battelle aircraft at 19:00 EDT,  (c) Buffalo,  New York
           potential  vorticity and water vapor mixing  ratio measured
           by  the  NOAA rawinsonde network at 20:00 EDT

                                         73

-------
          Examination of Figure 31 shows that two  stable temperature layers
are present as they were on previous soundings.   The dry layer with a poten-
tial temperature of 42C is located at a height of  about 13,000 feet while
the dry layer with a potential temperature of 31C  is at 7000 feet.   There
are dual maxima of potential vorticity (Figure 31c)  as appeared in  the mid
troposphere on earlier soundings,  but their values are lower than previously
observed.  Moreover, while the upper potential vorticity maximum coincides
with the dry inversion layer, the lower potential vorticity maximum is
associated with a stable layer slightly above the 0 = 30 C surface.  The
9 = 30 C surface actually coincides with a potential vorticity minimum.
          There is another stable layer (3 = 35  C) at a height of about
9000 feet.  It contains an ozone maximum of 0.14 ppmm, which is about
twice as large as the ozone maximum contained in the frontal layer (0 =
31 C) on earlier soundings.  The ozone maximum within the 0 = 42 C layer
is about the same (0.155 ppmm) as on earlier soundings.
          Earlier, Figure 25 presented the backwards isentropic trajectory
of an air parcel which was found just below the  frontal surface above
Peoria, Illinois.  This trajectory was performed on the 0 = 30C surface.
It was found on later soundings that frequently  the potential temperature
of 30C was within the frontal layer instead of beneath it as was true on the
Peoria sounding.
          Another backwards isentropic trajectory was constructed on the
0 • 30C surface beginning at a point north of Buffalo at the time of the
Erie aircraft sounding.  For this trajectory the 0 - 30C surface represented
the path that an air parcel would take along the cold front layer.   Figure
32 displays the path of this trajectory.  The backwards trajectory from
Green Bay along the 0 » 44C surface (Figure 28)  is also shown to point out
similarities between the paths of the two trajectories.  Both parcels
descended; however, the upper air parcel (0 = 44C) descended more rapidly.
It went from within the stratosphere at 300 mb to 595 mb, a height differen-
tial of about 15,000 feet in 60 hours.  During the same time period (1200
GMT on July 21 to 0000 GMT on July 23) the parcel on the 0 - 30C surface
descended from 630 mb to 780 mb, a height differential of about 5000 feet.
                                     74

-------
          An attempt was made to trace the parcel on the 0 = 30C surface
back  to a point where the  parcel was within the stratosphere.   This goal
was not achieved.  For about 2-1/2 days prior to July 20 the pressure level
remained constant and no descent was shown in the trajectory.  However, as
is shown in Figure 32,  there were rawinscnde stations in British Columbia
July  17 and 18 at which the 0 = 30C surface was in the stratosphere.  It is
concluded that the frontal layer air and the relatively high ozone concen-
trations did actually originate in the stratosphere; however, the isentropic
trajectory method used in this analysis was not refined enough to precisely
trace the parcel backward for the 4-5 day period needed to get from the
tropopause to the lower troposphere.
          An examination of the 500 mb chart for 07:00 EST (1200 GMT)
shown in Figure 16 shows that the low-pressure trough was above British
Columbia at the time of the presumed injection of stratospheric air onto
the 0 - 30C surface.  This injection along the frontal surface supplied
stratospheric air to the lower troposphere.  Injections associated with this
same  trough (e.g., along the 0 * 44C surface) occurred at the later times
and at locations further to the east (c.f. Figure 32).  These later
injections did not descend as deeply into the troposphere,  at least
while they were contiguous within the encompassing stable layer.

          Toledo, Ohio—10;00 EDT, July 24—On Sunday, July 24, during the
early part of the third leg of the cross-country flight, the Battelle
aircraft made a sounding about 25 miles south of Toledo, Ohio.   It was 3
days  since the cold front had passed through this area and the region had
been  at the rear of the high pressure system for 2 days.  Surface winds in
the area were light and predominantly southerly or southwesterly (refer to
Figure 22).  Flow at 500 mb was primarily westerly.   Above Toledo there were
no longer any vestiges of the trough at SCO mb.
          Figure 33 presents plots of the temperature,  dew point,  and
ozone measurements made during this  aircraft sounding (see  Appendix B,
pages B-10,  B-47).   In the lower part of the sounding,  the  3000 to 5000
foot layer is  neutrally stable (i.e.,  its temperature lapse rate follows
                                     75

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the adiabatic temperature line).   Between 5000 and  10,000  feet  the  air  is
quite dry;  however, the layer has two different temperature  lapse rates.
Between 5000 and 7000 feet the lapse rate is isothermal, while  from 7000
to 10,000 feet the layer is slightly stable.
          Ozone concentrations in the lower part of the dry  layer between
5000 and 10,000 feet are uniform at 0.11 ppmm (0.067  ppmv);  however in  the
less stable upper portion of the dry layer there is an ozone maximum of
0.175 ppmm (0.106 ppmv).  The potential temperature associated  with this
ozone maximum is 40C which places it about midway between  the potential
temperatures of the two ozone maxima observed the previous evening  over
western New York (Figure 31).  It is not clear whether the ozone maximum of
0.175 ppmm at 9000 feet above Toledo is part of either of  the two ozone
maxima above Erie or whether it represents still another stratospheric-air
injection.   The slightly stable lapse rate of the layer in which it is  con-
tained is similar to the lapse rate of the lower ozone layer at Erie but its
ozone concentration is more nearly like the concentration  of the upper  ozone
maximum at Erie.
          Concentrations in the lowest layer (below the subsidence  inversion
base at 5000 feet) are higher than for any other sounding  during this series.
The uniformity of the ozone mixing ratio values (in ppmm or  ppmv) with  no
gradient from lower to higher altitudes demonstrates  that  the tropospheric
ozone (relatively high water vapor mixing ratio) in this layer  has  been
uniformly mixed up to the base of the subsidence inversion at 5000  feet.
This well-mixed layer with its relatively high ozone concentrations (0.155
ppmm or 0.095 ppmv) is  indicative of aged air with  ozone that was  generated at
the surface.  The photochemical processes acting upon the  precursor emissions
from the states south of the Great Lakes has produced a massive ozone layer
beneath the subsidence inversion.  It can be expected to move across the
eastern portion of the United States as the next cold front  pushes  the large
high pressure area eastward.  The high ozone concentrations  within  this layer
have the potential to be mixed downward toward the  surface on any  afternoon
when the temperature lapse rate is neutrally stable or unstable through the
layer.  If there is an ozone gradient from the upper portion of this layer
to the surface, this mixing will add to the surface ozone  concentrations.
                                     78

-------
          Robinson. Illinois—10;00 CDT. July 23—As noted earlier,
Washington State University, in their part of the study, also made a cross-
country flight during this period to investigate the nitrogen oxides and
oxidants within the'high pressure area.  One of their aircraft soundings
was made above Robinson, Illinois, on Saturday morning July 23, at 10:00
CDT.  Robinson is near  the Illinois-Indiana border 75 miles north of
Evansville, Indiana, and 150 miles east of St. Louis.  A map showing the
location of Robinson relative to the Battelle cross-country flight path
is given in Figure  34.
          At  the time of the sounding, Robinson was in the southwestern
portion of the large high pressure system with surface winds from the east.
Six hours later, when the Battelle airplane made its sounding above Grand
Rapids, Michigan, the winds in central Michigan were from the southwest
and had traversed the Chicago area.  Both sounding sites were in the north-
west flow (see the  500  mb map in Figure 21).
          Two temperature soundings and an ozone sounding are displayed in
Figure 35.  Figure 35a  is the temperature sounding from the Washington
State flight while Figure 35c is the temperature-humidity sounding made by
NOAA at Salem, Illinois (75 miles southwest of Robinson) at 07:00 CDT that
same morning.  Within the dry layer of the atmosphere located above 5000
feet both soundings measured several stable layers.   Only one layer of high
ozone was within the dry layer — a maximum of about 0.21 ppmm (0.13 ppmv)
at 14,000 feet.  The potential temperature associated with this maximum
(0 - 51C) is larger than any that were encountered on the other soundings.
This suggests that this ozone entered the troposphere as part of another
stratospheric injection during the movement of the low-pressure trough
across Canada.
          Mixing from the surface upward is limited by the base of the
subsidence inversion (G » 32 C)  which is the trailing portion of the frontal
layer.   The base of the inversion is located at a height of about 5000 feet
which is nearly identical to its height above Springfield 24 hours earlier
(Figure 24).   It was concluded in the discussion of  the Springfield sounding
that the ozone maximum  (0.13 ppmm)  below the subsidence inversion had resulted
                                    79

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from transport from a level near the surface.   The ozone concentration at
5000 feet on the Springfield sounding was  greater  than  the ozone  concentra-
tions below it, a situation which implies  that there  was no mixing  upward
from the surface to 5000 feet.
          On the Robinson sounding of 10:00 CDT on July 23, there is  a
gradient of ozone concentrations from high levels  at  4000 feet  to lower
levels at 5000 feet.   There is  a nearly adiabatic  lapse rate between  these
heights which would also support the mixing hypothesis.  Below  2000 feet
the ozone decrease is probably  related to  nocturnal surface-based destruction
processes .

Horizontal Extent of  the Ozone  Layers—
          The aircraft spiral sounding measures the ozone concentrations
above a single location at a single time.   The question arises  as to  the
extent of the ozone layer that  is sensed during the sounding.   One  can
hypothesize that the horizontal extent of  a stratospheric injection of ozone
into the troposphere  can be estimated by using a single ozone sounding in
combination with the routine temperature-humidity  soundings made  by the
National Weather Service (NWS).  The ozone sounding identifies  one or more
dry stable layers which contain ozone of stratospheric  origin.  An  average
potential temperature for each  layer can be determined  from this  sounding.
Using this information one can  analyze the NWS soundings from surrounding
stations and pick out those which have dry stable layers with similar
potential temperatures.
          This concept of a contiguous layer of stratospheric ozone moving
within the troposphere has been studied using the aircraft spiral sounding
data.
          Several days of rawinsonde soundings made in  the United States
and Canada during the period of the cross-country flight were examined.  Dry
stable layers were sought in three potential temperature ranges (a) 9 = 25-
30C,  (b) 0 - 35-40C,  and (c) 9  - 40-45C.  The results of this investigation
for the 1200 GMT  (08:00 EDT) soundings on  July 20, 22,  and 23 are shown in
Figures 36-44.  These figures present a median atmospheric pressure for each
of the three potential temperature categories and identify whether  (1) a dry
stable layer,  (2) a wet stable layer, or  (3) an unstable layer  was  recorded
                                     82

-------
at this pressure.  A wet stable layer is one which did not meet the 1.5 gm/
kgm criterion for dryness.  These data are displayed on a map which pictures
the surface positions of the fronts and the high pressure center at 1200 GMT
on the date in question.
          Figures 36-38 exhibit the pressure, stability, and dryness of the
layer which had potential temperatures (9) in the range 25-30C on the 3 days.
The horizontal area designated as the dry stable layer is hypothesized to
contain the stratospheric ozone.  This dry layer included only the central
portion of the entire stable layer.  It generally lagged behind the position
of the surface front by about 200 miles and did not descend below a pressure
of 850 millibars.  Between July 20 and 23, the dry area moved in a south-
easterly direction, descended (as shown by the increasing pressures) and
contracted in horizontal extent.
          Examination of the three maps that depict the position of the
dry stable layer which has potential temperatures in the range 35-40C
(Figures 39-41) shows both similarities and differences between this stable
layer and the previous one.  It moves in a southeasterly direction, but it
increases in size and there is no obvious tendency to descend.  However,
12 hours later at 0000 GMT on July 24 (map not shown) this stable area did
continue its movement to the southeast with descent.  The size had
decreased — the dry layer covered only Ohio, Pennsylvania, West Virginia
and New York.
          These characteristics of the dry stable layer were also evident
in the behavior of the 0 «• 40-45C layer (Figures 42-44).  It moved to the
southeast following the front, and it descended toward high pressures.  On
the 23rd the layer had split in two.  Twelve hours later (not illustrated)
the layer was still in two parts but they had diminished in size.
          Two airplane soundings through these layers were made by the
Battelle aircraft on both July 22 and July 23.  Positions of the soundings
(Figures 24, 27, 30, 31) are denoted on the maps (Figures 37,  38, 40,  41,  43,
44).   The aircraft soundings were made several hours after the NWS sounding
times, consequently the dry stable layers  are expected to be displaced
southeastward of their illustration position by the time of the aircraft
spirals.
                                    83

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          From the airplane temperature, humidity, and ozone profiles, one
can deduce that most of the soundings penetrated into a portion of the dry
stable layer and found ozone there.  The one exception was the sounding over
central Illinois on the morning of July 22.  The dry stable layer on this
sounding (Q • 35C) had no ozone maximum.  It did have moist layers below and
above it with relative maxima of ozone.  As mentioned previously, these ozone
maxima are respectively surface generated and air which probably has been
modified since its entrance into the troposphere.  Figures 37 and 40 indicate
that this area of Illinois was in the moist stable layer both at 9 = 25-30C
and 9 = 30-35C.
          Upon inspection of the dry stable layers on the maps of July 22
and 23, one can deduce that they generally overlay the position of the
surface high pressure center,  moving with it as it crossed the country.
          Based on the upper tropospheric trajectory (0 = 44C in Figure 32)
it appears that after about 4  days the ozone injected from the stratosphere
into the upper troposphere lost its identity.   The ozone maximum may have
persisted,  but the air containing it is moist.   This result would be similar
to the ozone maximum which appeared at 10,000  feet in Figure 24b.   The ozone
could then be dispersed to become middle-tropospheric background ozone.

Upper Level  Cyclogensis and Ozone
Injection  from  the Stratosphere
           As was shown in Figure 28,  the ozone maximum  that was associated
with a potential  temperature of 44C could be traced backwards from 595
millibars  above Green  Bay, Wisconsin, at 07:00 CDT on July  23,  to a pressure
of  300 mb  above northern  Saskatchewan at 06:00 MDT on July  20.  At this
latter time  the 300 mb level above  Saskatchewan was in the stratosphere.
Thus the ozone maximum associated with the 0 = 44C stable layer, and identi-
fied as stratospheric ozone by its low water vapor mixing ratio and its high
potential  vorticity, was  confirmed as stratospheric by the isentropic
trajectory analysis.
                                    93

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          Each of the aircraft soundings made in the region behind the cold
front observed a second stable layer which generally contained an ozone
maximum.  This layer was the frontal layer and had a potential temperature in
the range of 0 = 25-35C.  Isentropic trajectories along the 9 = 30C surface,
such as the trajectory shown in Figure 32, paralleled the path of the 0 =
44C trajectory.   However,  they were well below the tropopause at the
time of the stratospheric  injection at 0 = 44C (see Figure 29).   If
the air within the 9 » 30C stable layer originated in the stratosphere, the
injection must have occurred at an earlier time and further to the west.
During its long trajectory the ozone content and the potential vorticity of
this layer dissipated until the parcel could no longer be identified as
stratospheric when it had reached the mid United States.
         Previous investigators      5-18) of stratospheric injections have
shown that the injection occurs during high-level cyclogenesis.   In a
sequence of 500 mb maps, the time of cyclogenesis can be identified as the
time when the trough first contains a low pressure center with the flow
around  it shown by a closed circle.
          By looking at the 500 mb charts for times that are earlier than
those shown in Figures 16-22,  one can identify the period of cyclogenesis
associated with the trough that provided the ozone to the 0 = 30C stable
layer.  A closed low at 500 mb (17,900 feet) appears above British Columbia
on the map for 07:00 EST on July 17 (Figure 45) but is absent on the previous
day  (Figure 46) and the succeeding day  (Figure 16).  Confirmation that this
period of cyclogenesis is the probable time of injection of the ozone at
0 = 30C is shown in Figure 47, a plot of the rawinsonde sounding temperatures
and dewpoints from the ground to 300 mb above Annette Island.  Annette Island
is off northwestern British Columbia near the southeastern tip of Alaska.
On this sounding, made at 07:00 EST on July 17 in the area where cyclogenesis
                                  94

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  SUXDAV. JtJLY 17, IfTT
Figure 45.  Weather maps for Sunday, July 17,  1977.   Top map is the
            surface map for 7:00 a.m. EST (08:00  EDT).   Lower left map
            is the 500 millibar map for  the  same  time.   The right center
            map displays the maximum and minimum  surface temperatures
            for the previous day.  Map in the  lower  right corner depicts
            areas and amounts of precipitation (in inches)  for the previous
            day.
                                     95

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                                                 SATUSDAY, JULY 16, an
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Figure 46.  Weather maps  for Saturday, July 16, 1977.   Top map is  the surface
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           Map in the lower right corner depicts areas and amounts of preci-
           pitation (in  inches) for the previous day.
                                 96

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-------
was occurring, the tropopause was at a height just above the 350 mb level.
On the plot it is clear that the 0 = 30C surface is within the stratosphere
at this place and time.  Thus, the ozone appearing in the troposphere within
the 0 » 30C stable layer (the frontal layer) was of stratospheric origin,
even though the potential vorticity maxima did not meet the criterion of
       -9       -1
10 x 10   deg gm   cm sec in the Great Lakes region.
          As mentioned earlier, the trajectory plotting method would have
to be refined in order to trace the parcel from the midwest back to Alaska.
It would be informative to make calculations of potential vorticity and water
vapor mixing ratios at points along the trajectory to see whether their
values in western North America met the criteria for stratospheric air.  It
can be hypothesized that the potential vorticity of the air parcel decreased
during the long journey from the Alaskan stratosphere to the Midwest tropos-
phere as a consequence of nonadiabatic processes.
          In his study of stratospheric ozone which reached ground level in
November, 1972, Lamb     showed that the air in a stable layer at about 8000
feet  (corresponding to 750 mb) met the potential vorticity and water vapor
mixing ratio criteria for stratospheric air.  However, the horizontal
distance covered by Lamb's stable layer between the stratosphere and 750 mb
was considerably less than the horizontal distances discussed here.  It is
likely that the potential vorticity, water vapor mixing ratio, and ozone
characteristics of the 1977 0 = 30C layer, if measured in the northwest U.S.
on July 17 or 18, would be stronger indicators of stratospheric air than
was the case for this layer when it reached the Midwest.

Summary of the Spiral Sounding Investigation—
          Based upon the sounding results and the associated analyses for
this July, 1977, high pressure area investigation, there are several points
to be emphasized.
          (1)  Ozone was injected from the stratosphere into the the
troposphere along a stable frontal layer at the time of upper air cyclo-
genesis when the height of the tropopause was a minimum.
          (2)  The injection along the frontal layer took place over
northwest Canada-southeast Alaska.  The injection was limited in time so
                                     98

-------
that the ozone remained as a finite layer when it later appeared above the
surface high pressure area in the Midwest.
          (3)  The ozone in the frontal layer did not extend to the ground
in the Midwest and thus there was no rise in ozone at the surface marking
the frontal passage.
          (4)  The frontal stable layer was also the subsidence inversion
overlying the high pressure area.  On the backside of the high pressure
area the stratospheric ozone within this inversion layer could be distin-
guished from the anthropogenic ozone which filled the layer from the ground
to the base of the inversion.
          (5)  As a new front passes, it may have stratospheric ozone
within its stable layer wedging a path beneath a deep layer of aged anthro-
pogenic ozone.
          (6)  In addition to the ozone in the frontal stable layer,  there
were ozone layers above the frontal/subsidence inversion.   These upper ozone
maxima were  the result of injections from the stratosphere at higher alti-
tudes and at later times than the frontal layer injection.   All of these
layers were originally created when a finite amount of ozone was injected
from the stratosphere.  These ozone areas retained their finite extent as
they subsided through the troposphere.   These upper ozone layers, like the
ozone in the frontal layer, were loosely centered above the surface high
pressure area as it moved across the country.
          (7)  Each finite area of high ozone concentration within its
stable layer retained its downward slope from northwest to southeast  as
it progressed across the Midwest from west to east.
          Observations made during the cross-country traverse of this
July high pressure area lead to the conclusion that layers of stratospheric
ozone with concentrations in excess of the surface ambient standard can be
found in the troposphere above a high pressure area, but that the ozone
in these layers has no direct effect on the surface concentrations in the
Midwest during the summer.
                                    99

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                               REFERENCES
 1.   Spicer,  C.  W.,  "The Fate of  Nitrogen Oxides  in  the Atmosphere",  in
     Adv.  Environ.  Sci.  and Tech.,  Vol.  7,  163-261 (1977).
 2.   Spicer,  C.  W.,  Joseph, D.  W.,  and Ward,  G. F.,  The Transport of
     Oxidant Beyond Urban Areas—Compilation  of Data, Battelle-Columbus
     report to EPA,  EPA-600/3-76-109  (1976).
 3.   Joseph,  D.  W.  and Spicer,  C. W., Anal. Chem., 50, 1400  (1978).

 4.   Lonneman, W.  A.,  U. S. Environmental Protection Agency,  1977 Midwest
     Field Study (unpublished data).  Computer printout of data  collected
     in the study  are  available on  request, Research Triangle Park, NC.
 5.   White, W. H.,  Anderson, J. A., Blumenthal, D. L., Husar, R. B.,  Gillani,
     N. V., Husar,  J.  D., and Wilson, W.  E.,  Jr., Science, 194,  187  (1976).

 6.   Spicer,  C.  W.,  Joseph, D.  W. and Ward, G. F., "Investigations of
     Nitrogen Oxides Within the Plume of  an Isolated City",  Battelle-Columbus
     report to CRC (CAPA-9-77)  July,  1978.
 7.   Spicer,  C.  W.,  Gemma, J. L., and Sticksel, P. R., "The  Transport of
     Oxidant Beyond Urban Areas—Data Analysis and Predictive Models  for
     Southern New  England Study", EPA-600/3-77-041 (1977).
 8.   Singh, H. B.,  Ludwig, F. L., and Johnson, W. B., Atmos.  Environ.,
     12, 2185 (1978).

 9.   Johnson, W. B.  and Viezee, W., "Stratosphere Ozone in the Lower  Tropo-
     sphere:   Presentation and Interpretation of  Aircraft Measurements",
     proceedings of Ozone/Oxidants—Interactions  with the Total  Environment
     II Specialty  Conference",  Air  Pollution  Control Association, October,
     1979, p 451.
10.   Singh, H. B.,  Viezee, W.,  Johnson,  W.  B., and Ludwig, F. L., J.  Air
     Poll. Control Assoc., _30,  1009 (1980)..
11.   Lamb, R. G.,  J. Applied Meteor., 16, 780 (1977).

12.   Godson,  W.  L.,  Quart. J. Roy.  Meteor.  Soc.,  88, 220  (1962).
13.   Reiter,  E.  R.,  Proceed. Int. Conf.  on Photochem. Oxidant Pollution and
     Control, EPA  600/2-17-001A (1977).

14.   Reiter,  E.  R.  and Mahlman, J.  D., J. Geophys. Res..  70_  (18), 4501 (1965)
15.   Reed, R. J.,  J. Meteor., 12, 226-237 (1955).

16.   Staley,  D.  W.,  J. Meteor., 1]_, 541-620 (1960).
                                   100

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17.  Danielsen, E.  F.,  and Hipskind,  R. S., J. Geophys_. Res.. 85 (Cl) ,
     393 (1980).

18.  Haagenson, P.  L.,  Shapiro, M.  A., and Middleton, P., J. Geophys. Res.,
     86 (C6), 5231  (1981).
                                    101

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                              APPENDIX A
          GROUND STATION DATA FROM 1977 MIDWEST FIELD PROGRAM
          The data in Appendix A are hourly averages from the Bethalto,
Illinois ground site covering the period July 7 to August 3,  1977.   Study
averages are given on page A-24.  The symbol -1.0 indicates missing data.
A negative sign for any other value indicates an interpolated value.
                                   1Q2

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-------
                              APPENDIX B
              FLIGHT MAPS AND VERTICAL PROFILES FROM THE
                      1977 MIDWEST FIELD PROGRAM
          Appendix B provides aircraft flight maps and vertical profiles
for the airborne monitoring portion of the 1977 Midwest Field Program.
Two maps are shown for each flight; one contains 03 data,  the other shows
NOX results.  The vertical profiles are grouped together at the end of the
Appendix and are keyed to the flight maps by flight number and date.
                                  127

-------
Vf)    ^nV
-iw^,  p^w
Flight 1
Saturday    7-9-77
Afternoon   12:25 -
                                    14:02
                                   4KJHTUC
                              I •LOOMINGTO"
                  . SMINOf ICLO
                          > ClNTKAJ.lt
                              ^ HT. VCIINOH
                                   MATTOON •   fCHMLUTOII
       Spiral
PT. A  	> 12,000  ft.
                        Bag
                   PT.  A @ 5,000 ft.
                     128

-------
                       03, ppb
                       Flight 1
                       Saturday
                                               Afternoon
                                               12:25	»• 14:02
                                            7-9-77
                                MATTOOK «»
                           ^ UT. VMNON
 Spiral
Ft. A —
12,000 ft
PT. A at 12,000 Ft.
                129

-------
                             03, ppb
                             Flight 2
                             Tuesday, July  12,  1977
                             Afternoon  12:45 —> 16:20
                                                 • ST«E*TO«
  rorr
  IUDISON
                                      reoout
                                                             »CMML£»TOI.
                                            t CENTUM, i*
                                                ^ MT VCRNON
No.  1
No.  2
No.  3
Filters
A —*•  B
C —*  D
E —*  F
       Bags
No.  1   A —> B
No.  2   C —* D
No.  3   E —»• F
           Spiral
PT. G  2,000 —* 20,000  Ft
                                     130

-------
                         NOX, ppb
                         Flight 2
                         Tuesday  7-12-77
                         Afternoon  12:45
                  16:20
     Filters

No. 1.  A —  B
No. 2.  C —  D
No. 3.  E —  F
No. 1.  A —  B
No. 2.  C —  D
No. 3.  E —  F
      Spiral

FT. G  2,000 — 20,000 ft.
                                  131

-------
                    Flight  4
                    Friday  7-15-77
                    Afternoon  12:45
                              15:42 PM
                                             (OCttTUft
                                                 MATTOON B
Spiral
Pt. B -
20,000 Ft
No. 1.
No. 2.
No. 3.
No. 4.
No. 5.
No. 6.
No. 7.
No. 8.
  Bags
PT. B -
PT. B -
PT.
PT.
PT.
                                                      B
                                                      B
                                                      B
                                                  PT.
                                                  C -
                                                  E -
                                           B -
                                          *  D
                                          »  F
20,000 ft.
15,000 ft.
10,000 ft.
 6,000 ft.
 3,000 ft.
 1,000 ft
                                   132

-------
                             NOX, ppb
                             Flight 4
                             Friday  7-15-7:
                             Afternoon   12:45
15:42 PM
                       UlESKM*
                                                 «JT»E»TO«
                                                                  lUMUXCC
                                                    HATTOON *
                                                      f CFF
Filter          Spiral
A -»• F      PT. B •> 20,000 ft.
No.
No.
No.
No.
No.
No.
No.
No.
1.
2.
3.
4.
5.
6.
7.
8.
PT
PT
PT
PT
PT
PT
C
E
. B -
. B -
. B -
. B -
. B -
. B -
-»• D
-*• F
20,
15,
10,
6,
3,
1,


000
000
000
000
000
000


ft
ft
ft
ft
ft
ft


                                   133

-------
                                   Flight 5  -   Spiral
                                   Wednesday -   7-20-77
                                   Night  -  10:00 —» 10:55 p.m.
                           JACKSONVILLE
                                   COWAROSVILLC



                                 ^COLUNSVtLLE

                              E ST LOUIS
       Spiral
2,000  —*  10,000 ft
No.  1.   10,000 ft.
No.  2.    6,000 ft.
No.  3.    5,000 ft
No. 4.   4,000 ft.
No. 5.   3,000 ft.
No. 6.   2,000 ft.

-------
                      Flight  6  - Spiral
                      Thursday  7-21-77
                      Early Morning 6:05 *  7:2.3
                   JACKSON VU.C
                         ^| EOWASOSVILLE
                          COCLINSVILLC

                      C ST LOUIS
     Spiral
1600 * 10,000  ft
No.
No.
No.
No.
No.
1.
2.
3.
4.
5.
10,000 ft.
 6,000 ft.
 4,000 ft.
 2,000 ft.
 1,600 ft.
                                335

-------
                  NOX>  ppb
                  Flight  7
                  Thursday   7-21-77
                  Afternoon   15:05 -
18:10 PM
                                          mtmcmtf
          Spirals                Filter
No. 1.  PT.  B 1500 —* 6000 ft   PT. A —>
No. 2.  PT.  C 1800 —> 3500 ft
              Bags
       No. 1. PT. B -  6000  ft
       No. 2. PT. B -  3000  ft
       No. 3. PT. C -  3500  ft
                                  136

-------
    031 ppb
    Flight 8
    Friday  7-22-77
    10:00 AM -* 1608
03, ppb
Flight 9
Saturday  7-23-77
2:00 -+  20:40
03, ppb
Flight 10
Sunday  7-24-77
8:45 AM -*• 14:15
Flight  3  A
     Flight  9 F
Filter
No. 1. B -> F
Spirals
No. 1. PT. C 3,000 •* 12,000'
No. 2. PT. D 3,000 -> 20,000'
Bags
No. 1. PT. C - 6,500'
No. 2. PT. D - 20,000'
No. 3. PT. E - 1,000' AGL






Filters
No.
No.
1.
2.
F -
J -
*• J
Spiral
No.
No.
Bagi
No.
No.
No.
No.
No.
No.
No.
No.
1.
2.
s.
1.
2.
3.
4.
5.
6.
7.
8.
PT.
PT.

PT.
PT.
PT.
PT.
PT.
PT.
PT.
PT.
G
J

G
G
H
I
J
J
J
K
2,000
2,000

- 11,
- 4,
- 1,
- 1,
- 20,
- 14,
- 2,
- 1,
i _^
' •»

250'
500'
000'
000'
000'
000'
000'
000'
20,000'
20,000'


AGL
AGL



AGL
Filters
No.
No.
1
2
. N ~
- Q
-* T
Spiral
No.
Bag
No.
No.
No.
No.





1
3
1
2
3
4





PT.

. PT.
. PT.
. PT.
. PT.





0 3,000* 12,OOD

0 2,000'
P 1,000' AGL
R 1,000' AGL
S 1,000' AGL





                                  137

-------
     Nox, ppb
     Flight 8
     Friday  7-22-77
     10:00 AM -»•  16:08
Nox,  ppb
Flight 9
Saturday 7-23-77
14:00 —*20:40
         TT
NOX, ppb
Flight 10
Sunday 7-24-77
8:45 AM —* 14:15
Filter
No. 1 B
 Filter
 No. 1. F
 No. 2. J
           Flight 10 M - A
     Filter
     No. 1. N -»Q
     No. 2. Q -» T
No. 1 PT. C 3,000 -» 12,000
No. 2 PT. D 3,000 -» 20,000
Bags
No. 1. PT C - 6,500'
No. 2. PT D -20,000'
No. 3. PT E - 1,000' AGL






jy j.j
No.
No.
taxs
1 PT. G 2,000
2 PT. J 2,000'
•* 20,000
-» 20,000
Bags
No.
No.
No.
No.
No.
No.
No.
No.
1.
2.
3.
4.
5.
6.
7.
8.
PT.
PT.
PT.
PT.
PT.
PT.
PT.
PT.
G -
G -
H -
I -
J -
J -
J -
K -
11,
4,
1,
1,
20,
W.
2,
1,
250'
500'
000' AGL
000' AGL
000'
000
000'
000' AGL
jjj n,a.j.
No. L PT. 0 3,000 -* 12,000
Bags
No. LPT. 0 2,000'
No. 2. PT. P 1,000' AGL
No. 3. PT. R 1,000' AGL
No. 4. PT. S 1,000' AGL





                                            1 18

-------
                      NCX,  ppb
                      Flight  12
                      Wednesday   7-27-77
                      Afternoon  16:18 * 18:43
Filters
No. 1.  C * D
No. 2.  E * I
No. 1. A * B
No. 2. C * D
No. 3. E * H
No. 4. F * G
No. 5. PT. J 8,500 ft.
No. 6. PT. J 6,300 ft.
No. 7. PT. L 3,400 ft.
J
K
Altitudes
K   6,300 ft.
M   3,400 ft.
                                                        Spiral
                                                  PT. J. 1,500 * 8,500 ft.
                                  139

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Flight 13
Thursday   7-28-77
Morning  7:08 	>  9: 29 AM
No. 1.
No. 2.
No. 3.
No. 4.
No. 5.
No. 6.
Bags

20,000 ft.
15,000 ft.
10,000 ft.
 6,000 ft.
 3,000 ft.
 1,500 ft.
          140

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                   03, ppb
                   Flight  14
                   Thursday  7-28-77
                   Afternoon 14:35 —
                                     16:40
              JACKSONVILLE
                                I SWIN6F1ELO
                                                        oecATun
                    •41 EDWAROSVILLE



                   ^COCLINSVIU-E

                E.ST LOUIS


                   J  seurvitLE
                                            CENTRALIA
     Filters
No.
No.
No.
B
1. A
2. C — »H
3. I — *L
No.  4. M
     Bags

No.  1. A
No.  2. D
No.  3. E
No.  4. J
No.  5. N
No.  6. Q
                                        B
                                        G
                                        F
                                        K
                                        0
                                        R
                           141

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               NOX,  ppb
               Flight 14
               Thursday    7-28-77
               Afternoon   14:35 —
16:40
           JACKSONVILLE
                                                    I DCCATUR
                 •^| EDWAftOSVILLE



                ^COLUNSVILLE

              E.ST LOUIS



                J   BELLEVILLE
                                                          EFFINGHAM ff
      CENTRAL!*
     Filters

No.  1. A —» B
No.  2. C —> E
No.  3. I —» L
No.  4. M —»• P
 No. 1.  A —>• B
 No. 2.  D —* G
 No. 3.  E —* F
 No. 4.  J —» K
 No. 5.  N —* 0
 No. 6.  Q —> R
                          142

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03,  ppb
   Flight 15
   Friday 7-29-77
   10:50 AM -» 13:52 PM
               Flight 16
               Friday 7-29-77
               15:10 -»•  18:21 PM
 Flight 15

  A * F

 Flight 16

  F * A
   Filter

   B -•• E

   Filter

No. 1. G •* I
No. 2. J * M
  Bag
 PT. C

  Bag

No. 1 PT. H
No. 2 PT. K
       Spiral
PT. D  2,500' * 12,000

       Spiral
PT. L  1,800' *  8,000'
                                 143

-------
       ppb        Flight 15
                  Friday 7-29-77
                  10:50 * 13:52 PM
                                           Flight  16
                                           Friday  7-29-77
                                           15:10 •* 18:21 PM
Flight 15

 A * F
                Filter

                B * E
Flight 16       Filters
 F -» A
           No. 1. G - I
           No. 2. J * M
                              PT. C

                               Bags
                            No. 1. PT. H
                            No. 2. PT. K
          Spiral
PT. D.  2,500 -»• 12,000'

          Spiral
PT. L.  1,800 *  8,000'

-------
             03, ppb
             Flight 17
             Saturday  7-30-77
             Morning 10:10	»• 11:09
                  ENUOWU.C
   Baas
No. 1.  B
No. 2.  D
• C
• E
       Spiral

PT. A. 1,500 * 3,500 ft.
                       145

-------
                  NOX,  ppb
                  Flight  17
                  Saturday   7-30-77
                  Morning 10:10 —»  11:09
                  MCltSOMVIXC
            Spiral
PT. A 1,500	»  3,500 ft.
No. 1.  -
No. 2.  -
                               146

-------
  jj, ppb
Flight 18
Saturday   7-30-77
Afternoon   14:41
                          16:05
4ICIOOKVU.C
                                    Bag
        147

-------
                   03, ppb
                   Flight 18
                   Saturday  7-30-77
                   Afternoon   14:41
                     16:05
            > JACKSONVILLE
                                I SPRINGFIELD
                                                       I OECATUft
                  •^1 EDW4ROSVIU.E



                  ^COU-WSVILLE

               E ST LOUIS



                 & BELLEVILLE
                                                             EFFINSHAU f
                          CENTRALIA
Filter
    Spiral

B —*   8,000 ft
                         148

-------
               03,  ppb
               Flight 19
               Saturday   7-30-77
               Afternoon   16:36 -
                       19:03
Filter
         Spirals

No. 1.  PT. A - 6,000 ft.
No. 2.  PT. C - 6,500 ft.
No. 3.  PT. F - 6,500 ft.
No. 4.  PT. G - 6,500 ft.
                                          No. 1. D 	J> E
                                          No. 2. PT. F. 5,000—>3,000
                                          No. 3. H —* I
                        149

-------
15Q

-------
                 NOX, ppb
                 Flight 19
                 Saturday  7-30-77
                 Afternoon  16:36 -
                 19:03
 Filters
B
          Spirals
No. 1.  PT. A - 6,000 ft.
No. 2.  PT. C - 6,500 ft.
No. 3.  PT. F - 6,500 ft.
No. 4.  PT. G - 6.500 ft.
No. 1.  D —* E
No. 2.  PT. F
 5,000 —>  3,000 ft
No. 3.  H —» I
                           151

-------
03,  ppb
Flight 20
Monday  8-1-77
Early Afternoon 11:37
13:54
      BELLEVILLE
                                           EFFINGHAU
                                 CENTRAL!*
Spiral
PT. A 	 >• 6,500 ft.




No.
No.
No.
No.
Bags
1. B — » C
2. D — * E
3. F — » G
4. H — > I
             152

-------
          NOX,  ppb
          Flight  20
          Monday  8-1-77
          Early Afternoon   11:37
  13:54
    Spiral

PT. A —  6,500 ft.
      Bags
No. 1.
No. 2.
No. 3.
No. 4.
B
D
F
H
C
E
G
I
                          153

-------
Night
Flight 21
Monday   8-1-77
20:08  —*  22:09
                                                   I OCCATUR
     1 JACKSONVILLE
                                                         EFFINGHAU f
        ALTON


            •^1 EDW4ROSVILLE



           ^COLLINSVILLE

        E. ST. LOO1S



           J@ SEU.EV1V.LE
                            Spiral
                             6
No
No
No
No
No
No
•
*
•
•
•
•
1.
2.
3.
4.
5.
6.
20
15
10
6
3
1
»
»
»
>
>
>
000
000
000
000
000
600
ft
ft
ft
ft
ft
ft
                  154

-------
Late Morning
   03, ppb
   Flight 22
   Wednesday  8-3-77
   10:54 —  12:48
       Filters
  No. 1.  A
  No. 2.  D
  No. 3.  K
B
H
L
No. 1.  C
No. 2.  F
No. 3.  I
E
G
J
                      155

-------
      Late Morning
              NOX, ppb
              Flight  22
              Wednesday 8-3-77
              10:54 —» 12:48
                                               A H t   It   Ji
                                                           _J?
                                                              EFFINGHAM f
                      ^COLLINSVtLLE

                   ' E ST LOUIS



                        SELLEVILtf
                                        0CENTRALIA
         Filters
No.  1.
No.  2.
No.  3.
A
D
K
B
H
L
No.  1.  C
No.  2.  F
No.  3.  I
E
G
J
                           156

-------
              03,  ppb
              Flight 23
              Wednesday   8-3-77
              15:44 	> 17:36
    Filters
No. 1.  A —
No. 2.  D —
No. 1.
No. 2.
No. 3.
No. 4.
B
D
F
H
C
E
G
I
                   157

-------
                 NOX,  ppb
                 Flight 23
                 Wednesday   8-3-77
                 15:44 —»  17:36
                                                  If'11 _• /7/J4
                 ^COLLINSVILLE

              'E.ST LOUIS
                                                        EFFINGHAM ff
     Filters
No.  1.   A —»  C
No.  2.   D —*  G
   Bags
No.  1.   B
No.  2.   D
No.  3.   F
No.  4.   H
C
E
G
I
                          158

-------
      Flight   24
      Thursday    8-4-77
      Earling Morning 5:22
                       6:52
                                         lOCCATUK
                  I SPftlNGflELD
JACKSONVILLE
                                              EFHNGHAM
  ALTON


     •41EOWAflOSVILLE



     ^COLLINSVILLE

  E.ST LOUIS



     |  BELLEVILLE
                Spiral
                        CENTRAL!*
 No.  1.
 No.  2.
 No.  3.
 No.  4.
 No.  5.
12,000 ft.
 5,500 ft.
 3,000 ft.
    600 ft.
 PT. A - 1,600 ft.
             159

-------
       Flight 25
       Thursday   8-4-77
       Morning 8:08 —* 9:36
                   SPRINGFIELD
JACKSONVILLE
                                          lOeCATUR
  ALTON


      •^| EOWAROSVILLE




     ^COUUNSVILLE

  E. ST. LOUIS



     ^BELLEVILLE
                                               EFFIN6HAM f
Spiral
        CENTR&UA
   No.  1.   12,000 ft.
   No.  2.    5,000 ft.
   No.  3.   PT. A - 1,600  ft.
              160

-------
Flight  26
Thursday  8-4-77
Late Morning  10:43
 12:07
                                          I OECATUR
                   I SPRINGFIELD
JACKSONVILLE
  ALTON


      •H EDWAROSVILLE



     j^COLLINSVILLE

  E.ST LOUIS



     ^ BELLEVILLE
                                               EFFINQHAM
Spiral
      CENTRAL!*
             Baj
   No. 1.    12,000  ft.
   No. 2.      5,000  —> 4,000  ft.
   No. 3.      1,599   ft.
            161

-------
03, ppb
Flight 27
Friday  8-5-77
10:45 -»  13:00
     Filters
   No. 1,  A
   No. 2.  C
   No. 3.  E
B
D
F
       162

-------
                                  Altitude , feet x 10  (MSU
                                          
                                                                               (V)
 O
u
•O
    (\3
    O
                                               163

-------
     'fc
     : i
     !>-
     ', N-
                                                  CJ
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                                                                         8
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                                                                           o

                                                                         g


                                                                         3
O
CJ
              ut>
                        (1SW)
                                    164

-------
    20
     18
     16
    14
3  '2
w
S  10

-s

0
•o
     2  —
      -10
J	L

 10          20


   Temp ,*C
30
40
                                  165

-------
                                                         Flight 5      7-20-77
    10
 en

 5
 
-------
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                                                                                                                       Q.
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«-«
-H
u.
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                           8
CM
   169

-------
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                                 170

-------
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                                171

-------
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                                                                    r
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                                                                   Q.

                                                                   Q.
                                                                S
                                                                O
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                                    172

-------
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175

-------
.176

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                              173.—

-------
                                               Flight 18
                                                               7-30-77
to
0>
•o
              J	L

               40         50
                 03, ppb
K>          20

    TempfC
30
                                  180

-------
                                             Flight 19-1
                                                             7-30-77
                      I
                                          I
40
50        60
  03,ppb
10         20
  Temp,°C
30
                               181

-------

                                                               m
                                                               O
(0

                      182

-------
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                                                Q.


                                                10

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184

-------
                                           Flight 20
                                                          8-1-77
x
~z

-------
186

-------
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           187

-------
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                           "189

-------
                                   TECHNICAL REPORT DATA
                                   /nrtnicao"r n^ the re\'?r?
-------