EPA-450/3-77-022b
October 1977
RELATIOIN
OF OXIDANT LEVELS
TO PRECURSOR EMISSIONS
AND METEOROLOGICAL
FEATURES -
VOLUME II: REVIEW
OF AVAILABLE
RESEARCH RESULTS
AND MONITORING DATA
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
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EPA-450/3-77-022b
Final Report September 1977
(Originally published
as an Interim Report November 1975)
THE RELATION OF OXIDANT LEVELS TO
PRECURSOR EMISSIONS AND
METEOROLOGICAL FEATURES
Volume II: Review of Available Research Results
and Monitoring Data
(As of November 1975)
By: H. B. SINGH and W. B. JOHNSON
SRI Internationa/
E. REITER
Colorado State University
Prepared for:
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF AIR QUALITY PLANNING AND STANDARDS
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
Attention: MR. PHILLIP L. YOUNGBLOOD
CONTRACT 68-02-2084
SRI Project 4432
Approved by:
R.T.H. COLLIS, Director
Atmospheric Sciences Laboratory
RAY L. LEADABRAND, Executive Director
Electronics and Radio Sciences Division
!) SRI International
Menlo Park, California 94025 - U.S.A.
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CONTENTS
I BACKGROUND, OBJECTIVES, AND
LIMITATIONS OF THIS REVIEW 1
II REVIEW OF THE CURRENT STATE OF KNOWLEDGE ON THE RELATION
OF OXIDANT LEVELS TO METEOROLOGICAL FEATURES 3
A. Historical Overview 3
B. The Stratosphere as a Source
of Tropospheric Ozone 7
C. Natural Sources and Sinks of
Ozone in the Troposphere 22
D. Long-Range Transport and the Nonurban Oxidant Problem . . 23
E. Summary of. Significant Scientific Findings 31
III DESCRIPTION OF SELECTED RESEARCH STUDIES 35
IV SUMMARY OF AVAILABLE SOURCES OF OXIDANT/OZONE DATA 67
V REFERENCES AND COMPREHENSIVE BIBLIOGRAPHY 107
111
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I BACKGROUND, OBJECTIVES, AND LIMITATIONS OF THIS REVIEW
This review is a part of a research study being conducted for the
U.S. Environmental Protection Agency (EPA). The overall study aims to
answer the following questions:
• What causes the high oxidant values that are frequently
observed in rural areas well removed from emission
sources?
• What are the effects of synoptic and smaller-scale
meteorological variables on ground-level oxidant
concentrations?
• How much does ozone of stratospheric origin contri-
bute to ground-level oxidant concentrations?
• Is it possible on the basis of relationships between
oxidant concentrations and synoptic-scale meteorological
conditions to identify geographic regions for
uniform oxidant control strategies? If so, how?
As a logical first step in this effort, a relatively comprehensive survey
of the relevant available literature and data has been carried out and
is presented here. The objectives of this review are to:
• Develop a clear picture of the current scientific
consensus on the oxidant problem in the eastern
United States, with particular emphasis on the
relation of nonurban oxidant to meteorological
processes.
• Provide a compilation of appropriate available data
as a basis for selection of the most available data
from specific sites for further detailed analysis.
Accordingly, Sections II, III, and IV of this report provide an over-
view of the current state of knowledge on the oxidant problem, a
descriptive listing of selected research studies, and a summary of
available data sources, respectively.
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Since the oxidant problem in the eastern United States is the
topic of this investigation, studies and data dealing specifically with
the West Coast oxidant problem have generally not been included in this
report.
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II REVIEW OF THE CURRENT STATE OF KNOWLEDGE ON THE
RELATION OF OXIDANT LEVELS TO METEOROLOGICAL FEATURES
A. Historical Overview
In the early part of this century it was discovered that ozone is
synthesized in the stratosphere by chemical processes that involve photo-
dissociation of molecular oxygen. It was found that Oo has a unique
vertical distribution with a maximum concentration of about 5-10 ppm
(10 v/v) occurring at about 25 km (Junge, 1963). Thus the largest
natural source of ozone was discovered and found to be extremely impor-
tant in providing a protective (UV) shield against ultraviolet radiation
for the earth.
In the early 1940s ozone was also found to be a tropospheric
constituent, and the primary source was proposed to be the stratosphere.
In the intervening years, it has been postulated that the downward
transport of stratospheric ozone is controlled by air exchange mechanisms
across the tropopause or through tropopause gaps, particularly in the
vicinity of the jet stream and weather frontal zones (EPA, 1970) .
Ozone took on a new role in the 1950s when it was discovered that
ozone could be synthesized in the polluted air of cities by photochemical
processes involving reactions between hydrocarbons and oxides of nitrogen
(Leighton, 1961). Bell (1959) showed that ozone or ozone precursors
could persist overnight and appear at high concentrations the next
In this report, the terms "ozone" and "oxidant" are used inter-
changeably for convenience, since the models predict ozone and the
standards apply to oxidants, and the difference between the two is
not important in our discussion.
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morning at distances as far as 100 miles away from their apparent
sources in southern California. At this time it was still believed that
the principal source of world-wide tropospheric ozone was the stratos-
phere, since ozone produced in polluted urban areas was considered to
be only a localized problem, not contributing significantly to the
global budget.
Based upon observed 0-j concentrations and diffusion theory,
Frenkiel (1960) and Paetzold (1961) concluded that there must be a
large tropospheric source of ozone. McK.ee (1961), from the vertical
distribution of 03 measured over Greenland, concluded that there must
be local Oo synthesis.
Went (1960) became the first to propose that natural ozone synthe-
sis could take place in the troposphere in a manner similar to ozone
synthesis in polluted air, with "terpenoid" compounds emitted by vege-
tation replacing the simpler olefins of the polluted air. Based on
subsequent measurements, it was confirmed that both natural terpenes
and N02 (as NO) are emitted in great enough quantities to influence 0,
concentrations in the troposphere (Rasmussen and Went, 1965; Lodge and
Pate, 1963; Worth et al., 1967).
During the 1960s ozone began to draw serious attention as a pollu-
tant in urban areas with a potential for both health and plant damage.
The primary precursors were identified as hydrocarbons and oxides of
nitrogen emitted by both mobile and stationary sources. The focus of
photochemical pollution problems became Los Angeles, because of large
numbers of automobiles, intense sunlight, and meteorological features
leading to stagnation of air and trapping of pollutants. The diurnal
variation of Oo was recognized, with ground-level ozone values starting
near zero in the early morning, building to a maximum in the late after-
noon, and then decreasing to low levels again by late evening. Limited
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measurements in other urban areas demonstrated by the late 1960s that
photochemical pollution, while most severe in Los Angeles, was to be
found in almost all urban locations (NAS, 1974; Rubino, 1975; Jacobson
and Salotollo, 1975; Hawke, 1974).
By 1970 the EPA promulgated National Ambient Air Quality Standards
(NAAQS) for oxidants at 0.08 ppm, not to be exceeded more than once a
year (EPA, 1970). To achieve this standard, abatement programs were
undertaken and further steps proposed to limit hydrocarbon and NO,,
X
emissions as a means of controlling oxidants. EPA has published procedures
for determining the necessary precursor reductions (Federal Register,
1971) to be applied in local areas in which a measurable oxidant problem
exists. At this time, it was still believed that ozone was a local
urban problem only and that diffusive and destructive processes limited
the oxidant concentrations in rural areas to insignificant levels.
Therefore, control strategies (Federal Register, 1971) were based
primarily on emission controls at locations in which a photochemical
oxidant problem was observed.
However, in a study conducted by EPA in 1970 in a rural area of
western Maryland and eastern West Virginia, oxidant values exceeding the
NAAQS were frequently measured. This finding was responsible for the
subsequent initiation of a number of intensive field studies covering
a broad area east of the Mississippi River. It was discovered that
high oxidant concentration was not limited to any given rural location
but was a widespread phenomenon.
While there is no doubt that high oxidant values can be measured
in rural and remote locations, the sources have become a matter of
considerable controversy. It is agreed qualitatively that stratosphere
and natural ozone precursors contribute to the tropospheric background.
The possibility of other tropospheric sources (Chemides and Walker, 1973)
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cannot be ruled out. It is also becoming more evident that processes
that destroy ozone or ozone precursors are not as effective as initially
believed, and large-scale transport from urban to rural areas may be a
key aspect of the oxidant problem. On the basis of several recent
studies, it has become clear that sources of nonurban ozone must be
identified before effective control strategies can be developed.
The implications of these findings may be significant for control
strategies at the national level, as discussed by Altshuller (1975).
For example, regional-scale control strategies may be required to achieve
the NAAQS if long-range transport of ozone is found to be important.
If the "natural" ozone concentration is in excess of the current standards,
the standards are too stringent.
In subsequent sections we will review the available scientific
literature that deals with the following major questions:
• How much of the tropospheric oxidant can be attri-
buted to stratospheric exchange processes, and
how do these processes occur?
• What are the natural tropospheric sources and
sinks of oxidant, and what is their significance
to the oxidant budget?
• What is the geographical extent of the transport
of oxidant or oxidant precursors, and what is its
effect on air quality control strategies?
Considerable overlap between these questions occurs in the avail-
able research papers. This is to be expected since the ultimate explana-
tion of oxidant behavior is likely to involve a number of different
mechanisms.
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B. The Stratosphere as a Source of Tropospheric Ozone
1. Mass Exchange Mechanisms
The exchange of air masses between stratosphere and troposphere
is accomplished by various mechanisms of different efficiency. These
mechanisms are summarized below.
a. Seasonal Adjustments in the Height
of the Mean Tropopause Level
In spite of some ambiguities in the definition, and there-
fore in the exact location, of the tropopause level, it is evident from
statistical studies that this level in each hemisphere undergoes seasonal
fluctuations, becoming lower during fall and higher during spring.
Staley (1962) pointed out that his seasonal variation contributes towards
a net flux of air between stratosphere and troposphere, upward or down-
ward, depending on the season. The lowering and rising of the tropopause
should not be envisioned as a continuous process, however. It comes
about by an imbalance between the vertical mass fluxes produced by the
mean Hadley circulation in low latitudes and by the eddy transport
processes mainly in the jet-stream region of middle latitudes. There
also is a compensatory horizontal mass flux within the stratosphere,
directed from the summer to the winter hemisphere.
Table 1 (Reiter, 1975a) provides an estimate of changes
in the median tropopause pressure over North America between January 1963
and July 1963. Since the total mass of stratospheric air above the
winter tropopause is approximately 4260 x 10 g, the seasonal variation
of tropopause heights over North America—when applied to the whole
northern hemisphere--amounts to approximately 10 percent of the mass
equivalent to one hemispheric stratosphere.
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Table 1
SEASONAL VARIATION OF MEDIAN TROPOPAUSE PRESSURES
(IN MILLIBARS) OVER NORTH AMERICA
(Reiter, 1975a)
Latitude
(deg)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
Tropopause
Pressures (mb)
Winter
95
100
160
200
220
250
250
240
225
230
240
Summer
120
120
120
120
120
140
200
210
225
230
240
Ap
+ (25)
+(25)
+(25)
+ (25)
+25
+20
-40
-80
-100
-110
-50
-30
0
0
0
Mass Change
(1017 g)
+28.4
+56.7
+55.6
+55.0
+53.3
+41.3
-78.9
-148.8
-174.6
-177.1
-72.6
-38.8
0
0
0
-400.5
b. Transport by the Mean Meridional
Circulation Across the Tropopause
Figure 1 (from Louis, in Reiter et al., 1975) shows the distri-
bution for the four seasons of the integrated mean meridional mass flux,
ty , i.e., the mass-weighted stream function defined by
v =
(1)
2rr Rp dz
w =
2
2TTR p
(2)
where v is the northward component
w is the vertical component
R is radius of the earth
p is air density
i is latitude
8
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90 «0 70 60 30 40 30 20
10 20 30 40 50 60 70 80 90
(a) DECEMBER-FEBRUARY
60 50 40 30 20 10 0 10 20 30 40 50 60 70
(b) MARCH-MAY
SA-4432-2
FIGURE 1
MEAN MERIDIONAL CIRCULATION (MASS FLOW IN UNITS OF 1012 g s'1)
FOR THE FOUR SEASONS (From Louis)
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80 '0
(c) JUNE-AUGUST
50 40
°No.rh
(d) SEPTEMBER-NOVEMBER
SA-4432-3
FIGURE 1
MEAN MERIDIONAL CIRCULATION (MASS FLOW IN UNITS OF 1012
FOR THE FOUR SEASONS (From Louis) (Concluded)
gs-1)
10
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The upward fluxes from the troposphere into the stratosphere
and consequently, for reasons of continuity, the downward fluxes into
the troposphere accomplished by the Hadley circulation, can be obtained
from Figure 1 as follows:
Total Flux in Contribution to
Season Mass Flow 3 Months Northern Hemisphere
Dec. - Feb. 10 x 1012 g/s 788 x 1017 g 622 x 1017 g
March - May 4 x 1012 g/s 311 x 1017 g 272 x 1017 g
June - August 7.5 x 1012 g/s 583 x 1017 g 389 x 1017 g
Sept. - Nov. 7 x 1012 g/s 544 x 1017 g 560 x 1017 g
Annual total flux to northern hemisphere: 1843 x 10 ' g
This flux corresponds to 43 percent of the mass equivalent to one
hemispheric stratosphere.
c. Transport by the Mean Meridional Circulation
into the Other Hemisphere
From Figure 1 we can also estimate the interhemispheric
exchange of mass within the stratosphere as a function of season. We
arrive at the following numbers:
Total flux in 3 months
Season Mass Flow into Northern Hemisphere (+)
Dec. - Feb. 6.5 x 1012 g/s 505 x 1017 g
March - May 2.0 x 1012 g/s 156 x 1017 g
June - August -6.5 x 1012 g/s -505 x 1017 g
Sept. - Nov. -2.0 x 1012 g/s -156 x 1017 g
The mass flux between the stratospheres of the two hemis-
pheres, thus, replaces 661 x 10 g of mass from one hemisphere within
one year. This is equivalent to 16 percent of the mass of one hemis-
pheric stratosphere.
11
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d. Transport by Large-Scale Eddy Exchange, Mainly
in the Mid-Latitude Jet-Stream Region
Intrusion of stratospheric air into the troposphere by
large-scale eddy exchange occurs mainly within the jet-stream front
during the tropopause-folding process, i.e., during periods of active
cyclogenesis. A number of case studies illustrating this mass-transfer
process are available in the literature (e.g., Danielsen, 1960, 1961,
1964, 1968; Danielsen et al., 1970; Mahlman, 1964a, b, 1965a, b, 1966;
Reiter, 1963b, c, 1964, 1968; Reiter et al., 1969; Reiter and Mahlman,
1964, 1965a, b, c, d; Staley, 1960, 1962). The return flow of tropos-
pheric air into the stratosphere occurs at levels above the jet-stream
fronts and at potential temperatures characteristic of the core of the
jet-stream itself (Reiter et al., 1969).
Only very few studies are available that give quantitative
estimates of this eddy flux across the tropopause level (Danielsen,
1960; Reiter and Mahlman, 1965; Reiter et al., 1969). Our best guesses
indicate that 22 to 23 cyclogenetic events occur per year in the polar-
front jet-stream region of the North American longitude sector, with an
average mass transport contribution of about 6 x lO*7 g each, providing
an annual mass flux out of the stratosphere of approximately 135 x 10 ' g
in the sector 70° to 180° W, and of approximately 405 x 10 ' g around
the hemisphere. This number includes only the latitude belt 40° to 60° N.
If one were to allow for the effects of the subtropical and artic-front
jet streams of winter, and of the tropical easterly jet stream of summer,
one might estimate the total eddy mass flux from the stratosphere to the
troposphere to be 800 x 10 g. For reasons of mass continuity, an
equal amount of tropospheric air will have to enter the stratosphere in
eddy exchange processes. This flux corresponds to roughly 20 percent
of the mass equivalent to one hemispheric stratosphere.
12
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e. Meso- and Small-Scale Eddy Transport Processes
Thunderstorms penetrating the tropopause level, as well as
small-scale turbulence continuously present in the atmosphere, will
contribute in a minor way towards the mass exchange between troposphere
and stratosphere. Since these processes are either very slow-acting
(due to the relatively small vertical eddy exchange coefficients normally
effective at tropopause level), or are present with significant magni-
tude only sporadically (e.g., clear-air turbulence at tropopause level,
or thunderstorms penetrating the tropopause), the total contribution
towards the mass flux from the stratosphere to the troposphere from
meso- and small-scale eddy processes most likely lies near 1 percent of
the mass equivalent to one hemispheric stratosphere.
2. Implications on Ozone Transport from the Stratosphere
From the foregoing discussion the annual mass budget of the
stratosphere of the northern hemisphere appears as follows:
Seasonal adjustments of tropopause level 10%
Mean meridional circulation 437=.
Stratospheric exchange between hemispheres 167°
Large-scale eddies 207»
Small-scale eddies negligible
Total: 897o
These transport processes would act on an atmospheric tracer
that has been introduced into the northern hemisphere stratosphere and
disperses from there into the northern hemisphere troposphere and into
the southern hemisphere stratosphere. A typical tracer of this sort is
9^Sr, injected in large quantities into the northern hemisphere lower
and middle stratosphere during the US and USSR atmospheric tests before
the Test Ban Treaty went into effect in 1963. Figure 2 illustrates a
90
typical Sr distribution in the stratosphere.
13
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Km 20 -.
120.000
- 100.000
- 80,000
- 60,000
- 40,000
- 20,000
90* 6O» 30
NORTH
30*
SOUTH
60*90*
SA-4432-4
FIGURE 2 90Sr CONCENTRATIONS DURING MARCH-MAY 1965 IN UNITS
OF DISINTEGRATIONS PER MINUTE PER 1000 STANDARD FT3
Decay corrected to time of sampling. Dots show location of mean
aircraft data; crosses indicate mean balloon samples. (From List
and Telegadas, 1969)
14
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Figure 3 shows the northern and southern hemispheric burdens of
" Sr, as well as the total stratospheric burden, as functions of time.
The e-folding residence time of "^Sr in the northern hemisphere appears
to be 14 months (before the effects of the French and Chinese tests) .
If we assume that concentrations of radioactive debris, N , diminish
according to
where T is the e-folding residence time, N is taken to be 100 percent,
AN is 89 percent and At is one year, we arrive at T = 1 . 12 years or
13.4 months.
According to Figure 3, the e-folding residence time in the southern
hemisphere stratosphere appears to be of the order of 21 months.
Assuming that the mean meridional and eddy exchange processes between
stratosphere and troposphere are as effective in the southern as in the
northern hemisphere, we have to blame the discrepancy in e-folding resi-
dence times between the two hemispheres on the following fact: inter-
hemispheric exchange processes within the stratosphere tend to reduce
the radioactive burden of the northern hemisphere where the original
source was located. At the same time this transport process increases
the southern hemisphere burden. Therefore, in approximation we can write
where S (= 16 percent, the stratospheric mass exchange between hemis-
pheres) is the "source" of stratospheric debris for the southern hemis-
phere in the form of transport from the northern hemisphere. This
16 percent contribution towards the mass budget of the stratosphere now
appears as a "source" of debris and has to be removed from the "sink"
effects of the mass budget. Therefore, for the southern hemisphere, we
15
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«*-!
A TOTAL STRATOSPHERE
• NORTHERN HEMISPHERE
o SOUTHERN HEMISPHERE
' 9 LARGE ATMOSPHERIC TESTS IN
RESPECTIVE HEMISPHERE
1963 I96« 1965 1966 1967 1968 1969
1970 I97i 1972
SA-4432-5
FIGURE 3 STRATOSPHERIC INVENTORY OF 9°Sr (From Krey et al. 1974)
16
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have to assume a value of 73 percent for AN (89% - 16%). For N = 100
percent and At = 1 year , we thus arrive at T = 1.75 years or 21
months, which is exactly what Figure 3 indicates.
E-folding residence times for other radioactive tracers introduced
into the lower and middle stratosphere under similar conditions yield
similar residence times (for references see Reiter, 1975b).
The above discussion leads us to the following preliminary conclu-
sions:
• The estimate of an annual exchange of 16 percent of the mass
equivalent to one hemispheric stratosphere appears to be
accurate when applied to tracers in the lower and middle
stratosphere.
• The total effects of other transport processes listed
above have been estimated with similar reliability.
The mixing ratios of ozone, as reported by Newell (1964) (see
Figure 4), show a distribution with respect to latitude and height that
is similar to that for ^Sr. ^he axis of maximum ozone mixing ratios
dips downward from the equator to high latitudes, similar to the axis
of maximum ^Sr concentrations (see Figure 5 for similar evidence from
additional other tracers).
Since the photochemical life-time of Oo is relatively long at levels
below 25 km (for references see Reiter, 1971 and Reiter et al., 1975) we
can regard it almost as an inert tracer when comparing it, for instance,
90
with Sr. However, the following exception applies: in contrast to
9^Sr, o^ is produced in both hemispheres. Interhemispheric transport
processes within the stratosphere, therefore, will have no profound
effect on the mean residence time of 0-j. To calculate the mass budget
of one hemisphere, as it applies to ozone, we thus use Equation (3),
with a value AN = 73 that includes all effects except the one from
interhemispheric exchange. The e-folding residence time of 0-j in the
17
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30mb
50mb
100 mb
10 20 3O 40 5O 6O 70 80
LATITUDE (°N)
SA-4432-6
FIGURE 4 SLOPES OF SURFACES OF PREFERRED MIXING
(SHORT LINE SEGMENTS) FOR WINTER SEASON
AS DERIVED FROM HEAT FLUX DATA
Solid lines represent mean potential temperature (°A)
and dashed lines mean ozone mixing ratio (/jgm/gm)
after Newell (1964). (From Reed and German, 1965)
18
-------
o
90* N
FIGURE 5 OBSERVED LEVELS OF MAXIMUM CONCENTRATION AND MEAN ANNUAL
ISENTROPES
Numbers in parentheses are months from injection into the stratosphere to
observation (From Machta et a/., 1970)
19
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lower and middle stratosphere, therefore, should be of the order of
1.4 years or approximately 16 months (similar to the e-folding residence
QO
time of Sr in the total stratosphere as shown in Figure 3).
It is not surprising that estimates of the 0_ residence time in the
stratosphere made from the phase lag between the maximum in total Oo and
that in surface Oo concentrations are much larger than this estimate of
16 months. Junge (1962, 1963) and Fabian and Junge (1970) arrive at a
stratospheric residence time of three to five years, a tropospheric
residence time of 3.3 months, and a tropospheric vertical flux of
approximately 0.5 x 10"' g/nr/sec (equivalent to 0.804 x 10^ tons of
Q
Oo per year over the entire globe). A vertical flux of 1.3 x 10 tons
of Oo per year over the globe was estimated by Regener and Aldaz (1969).
Since Oo is continuously generated photochemically in the stratosphere,
Equation (3) is inapplicable, even for a crude estimate of residence
time. Influx of Oo, from higher levels and from lower latitudes also
provides a source for the atmospheric "box" that comprises the northern
hemisphere stratosphere between the tropopause and approximately 30 km.
From satellite data, Lovill (1972) estimates the average global
value of total ozone to be 303.3 Dobson units (or milli-atmospheric-
o
centimeters, i.e., the height of the layer in units of 10 cm if all
ozone were compressed to normal temperature and pressure). To convert
these units into mass of ozone we apply the gas law
^t
P = ^- P T , (5)
O o
where p = 1013.25 x 10J dynes/car , the universal gas constant
R* = 8.31436 x 10^ erg mole -1 deg K~ , the molecular weight of ozone,
m = 47.998, T = 273.16 deg K. We arrive at a density for ozone of
~ 3
p = 2.14138 x 10"J g/cm , at normal temperature and pressure. The
weight of the average ozone column, therefore, is 6.4948 x 10 g/cm .
20
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On a hemispheric basis (area = 2.55 x 10 km^) this amounts to
1.6565 x 1015 g, or 1.6565 x 109 tons.
9
The annual downward flux in one hemisphere (0.402 x 10 tons) thus
corresponds to approximately one-quarter of the total atmospheric burden.
Dividing the latter by the former to arrive at a crude measure of resi-
dence time (Ehhalt, 1973) one obtains a value of about four years, which
falls within the range given by Junge.
Since the average tropospheric ozone mixing ratio of the troposphere
is « 0.1 M
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ground. In the further investigation of the impact of stratospheric
ozone concentrations on ground-level ozone concentrations, we will there-
fore concentrate our attention almost exclusively on this transport
mechanism.
C. Natural Sources and Sinks of Ozone in the Troposphere
In the 1950s (Leighton, 1961; Wayne, 1962), it was shown that ozone
synthesis was possible in polluted atmospheres. In 44 out of 251 cases,
Bering and Borden (1967) found ozone concentration below 5 km to be
greater than above 5 km. In seven of these cases, the 0^ concentration
was greater at or below 2.5 km than at the tropopause. As argued by
Kroening and Nye (1962) , tropospheric layers of 0-j concentration near
the tropopause can be explained by stratospheric intrusion, but high
values near the ground can be more easily explained in terms of in-situ
synthesis than in terms of subsidence, through half the troposphere, of
a layer of high Oo content.
As previously mentioned in Section I-A, Went (1960) suggested a
photochemical mechanism for tropospheric ozone synthesis using natural
terpenes and NC^. Ripperton et al. (1971) tested this hypothesis under
controlled conditions and confirmed that this process can result in
ozone formation similar to that occurring in polluted atmospheres.
Rasmussen and Went (1965) found an average of 1 pphm (maximum of 5 pphm)
of atmospheric terpenoid compounds in the Appalachian and Ozark Mountains.
Lodge and Pate (1963) measured an average of 0.09 pphm NOo (maximum of
0.5 pphm) in Panama, and Worth et al., (1967) measured an average of
0.4 pphm NOo (maximum of 2.6 pphm) in the southern Appalachians. Thus
it is clear that both natural terpenes and natural N0£ are emitted in
quantities significant enough to influence 0-j behavior.
Crutzen (1973) pointed out that the methane oxidation chain, which
ultimately leads to the production of CO, represents a large source of
22
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ozone. Chemides and Walker (1973) presented a photochemical theory of
tropospheric ozone synthesis from the methane oxidation chain. Calcu-
lations indicate that this mechanism can support an ozone production
rate of 5 x 10" cnrVs . Their calculations yield a photochemical life-
time of Oo ranging from about one day at 5 km to about 10 days at 10 km.
Since the mixing time due to the presence of eddies in the troposphere
is about 30 days (Junge, 1962), this result suggests that 0^ is in photo-
chemical equilibrium in the troposphere, contradicting the usual view of
Oo as a relatively inert constituent of tropospheric air.
The model of Chemides and Walker (1973) was found to satisfactorily
explain the general variation of Oo with season as well as its depen-
dence on altitude. Indeed there is agreement that earlier assumptions
that ozone is destroyed on heterogeneous surfaces only were incorrect
and that gas phase ozone destruction is an effective sink for ozone
(Ripperton and Vukovich, 1971). Lightning from thunderstorms may also
cause local increases in ozone, but by itself this mechanism constitutes
an insignificant ozone source in remote areas (Shalanta and Moore, 1972).
D. Long-Range Transport and the Nonurban Oxidant Problem
Most of the nonurban data taken before the mid-1960s consistently
reports low ozone values all over the world. McKee (1961) reports a
maximum ozone concentration of 0.013 ppm based on his measurements in
Greenland. Junge (1963) summarizes a number of observations prior to
1961, with most of the concentrations being below 0.045 ppm (see Table
2). Only one location reports 0^ values as high as 0.06 ppm. In the
Antarctic region, the mean surface ozone values ranged from 0.01 to
0.034 ppm, based on data from April 1957 to May 1958. At the Admundsen
Scott Station located at the geographical South Pole monthly average
mean values of 0.01 to 0.04 were obtained (Aldaz, 1967). During other
studies conducted by the University of North Carolina during 1964 and
23
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Table 2
COMPILATION OF REPRESENTATIVE OZONE CONCENTRATION NEAR THE
GROUND AND AT HIGHER LEVELS WITHIN THE TROPOSPHERE (Junge, 1963)
OZONE CONCENTRATION ug/m3 C
OBSERVER
Gotz & Volz
(1951)
Ehmert (1952)
Kay (1953)
Regener (1954)
Regener (1954)
Teichert (1955)
Brewer (1955)
Teichert &
Warmbt (1956)
Price & Pales
(1959, 1961)
Wexler et al .
(1960)
Ramanathan
et al. (1961)
Dave (1961)
LOCATION ,
TIME AND RESULTS
Arosa, Switzerland,
1950-51, high valley,
daily maxima value
Ueissenau, Bodensee,
Germany, 1952
Farnborough , England ,
1952-53
Mt. Capillo and
Albuquerque, New
Mexico, USA,
1951-52
O'Neil, Nebraska,
USA, 1953
Lindenberg Observ.,
Germany, 1953-54
Tromso, Norway, 1954
Fichtelberg, Central
Germany, 1954-55
Brocken, Central
Germany, 1955
Ka 1 t ennordhe im ,
Central Germany,
1955
Wahnsdorf, near
Dresden, East
Germany, 1954-55
Mauna Loa, Hawaii,
1958
Little America
Antarctica, 1958
Srinagar, North
India, 1957-1960
Ahmedebad, 1954-55
a Influence of ozone destruction near
To sooe extent
this applies also to
ALTITUDE
(Meters)
1860 m above
sea level
20 m above
ground
0-12000 m
above ground
3100 and 1600 m
above sea level
12 m above
ground
80 m above
ground
0-10000 m
above ground
1215 m above
sea level
1152 m above
sea level
494 m above
sea level
257 m above
sea level
3000 m above
sea level
50 m above sea
level, near
the ground
1700 m above
sea level
50 m above sea
1 eve 1 , near the
ground
RANGE AVERAGE
APPROXIMATE APPROXIMATE
19-90
daily maximum
values
0-90
all values
26-50
a few aircraft
soundings
3-120 .
all data
0-90
all data
0-50
all data
60-70
a few air-
craft sound-
ings
20-67
month ly average
values of
hourly observa-
tions
26-52
monthly average
values
15-25
monthly average
values
2-26
monthly average
values of hourly
observations
20-80
daily maxi-
mum values
10-70
all values
26-59
monthly average
values of daily
maxima
24-50
monthly average
values of daily
maxima
the ground not eliminated in these average
other sets of data, exce
pt for those which
50
353
38b
36a
35"
30a
65
40
40
20"
123
50
50
50
40
values.
refer
to dailv maximum values.
b Values likely
c To convert ug/
too low due to ozone destruction in the intake
m^ to pphffl, divide by
20.
tube.
24
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1967 in rural North Carolina, high ozone values were not observed
(RTI, 1975).
However, as mentioned earlier, a study sponsored by EPA in 1970 in
a rural area of western Maryland and eastern West Virginia, oxidant values
well in excess of the NAAQS (0.08 ppm) were frequently measured (EPA,
1970; Richter, 1970)^ which led to a number of studies on the rural oxi-
dant problem. In the summer of 1972, the EPA sponsored a special study
for ozone measurements in Garret County, Maryland, and Preston County,
West Virginia (EPA, 1972). Approximately 11 percent of the 1043 hourly
measurements measured by the gas-phase chemiluminescent method exceeded
0.08 ppm. The maximum Oo value during the study period (4 August to
25 September 1972) was 0.12 ppm. Simultaneous measurements of NC> and
X
nonmethane hydrocarbons (NMHC) concentrations yielded values that were
at or near geochemical levels. Neither natural nor anthropogenic sources
in the study area appeared capable of producing the required precursor
species (HC and NOX) in sufficient quantities for synthesis of ozone at
the levels observed.
A more extensive study was conducted in the summer of 1973, when
ground-level ozone was measured at McHenry, Maryland, Kane, Pennsylvania,
Coshocton, Ohio, and Lewisburgh, West Virginia between 26 June and 30
September 1973. The measurement period at Kane extended through October.
A C-45 aircraft equipped with a solid-phase chemiluminescent ozone meter
was used to measure 0^ aloft. Hourly 0^ concentrations exceeded the
NAAQS for oxidants 37, 30, 20 and 15 percent of the hours for which data
were available at McHenry, Kane, Coshocton, and Lewisburgh, respectively.
The aircraft data further indicated that the source of high Oz was
located at the surface, because vertical Oz profiles showed a distinct
concentration decrease with altitude. Maximum hourly ozone concentra-
tions were 0.16 ppm at McHenry, 0.14 ppm at Kane, 0.17 ppm at Coshocton,
and 0.13 ppm at Lewisburgh.
25
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Miller et al. (1972) measured ozone at several rural and urban
locations near Fresno, California during the period 17-27 August 1970,
and found the NAAQS was widely exceeded. In the rural locations the
11-day average for each of the hours between 11 a.m. and 6 p.m. was in
excess of 0.08 ppm, with the lowest hourly average about 0.05 ppm. High
03 concentrations in rural areas were attributed to transport from the
Fresno urban area; however, the authors were unable to explain why the
Oo concentration remained high when the prevailing wind was not from the
direction of the city.
Since 1973, a great deal of emphasis has been placed on the non-
urban problem. The oxidant conditions that had been typically observed
in California were found to be quite widespread. Based on limited 1973
oxidant data in New York state, Stasiuk and Coffey (1974) concluded
that, since average daily rural ozone concentrations at widely separated
sites correlated well with the daily maximum urban ozone concentrations,
a common source was implied. They discounted transport as the primary
source of high nonurban oxidant values.
In another study, Cleveland et al. (1975) conducted an analysis of
data from the New Jersey/Pennsylvania area and concluded that the
oxidant problem in rural Ancora was caused by regional oxidant transport
from the Philadelphia-Camden urban complex. These authors also observed
that Sundays, with typically lower emissions, were overrepresented among
the days that exceeded the NAAQS in New Jersey.
Wolff (1974), in a preliminary investigation of the tri-state (New
York-New Jersey-Connecticut) photochemical oxidant problem, concluded
that the NAAQS is widely exceeded in the tri-state region and suggested
that this may be due to precursor transport from the Philadelphia-Camden
area, especially with west or southwest winds. No correlation was found
between the early morning (6 to 9 a.m.) hydrocarbons and the afternoon
26
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ozone at any given station. High afternoon temperatures (> 86°F) and a
mixing depth of less than 500 m resulted in high 0 concentrations.
Wolff also observed high Oo concentrations associated with the sea-breeze
cycle, and proposed a hypothesis similar to the one suggested by Lyons
and Cole (1974).
Lyons and Cole observed very high oxidant values in 1973 in southern
Wisconsin rural areas and along the shoreline of Lake Michigan. Rural
hourly ozone values as high as 0.2-0.3 ppm were measured several times.
The results of this study indicated that significant mesoscale and even
synoptic-scale transport of ozone into this particular area might occur.
Several other studies conducted in California (Cavanagh and Smith,
1973; Blumenthal et al., 1974) confirmed large-scale transport of ozone
and ozone precursors. In Los Angeles.it was found that the urban plume
may extend as much as 70 to 100 miles downwind of the city. Studies at
Houston and Phoenix (Rasmussen et al., 1974) and Philadelphia (Cleveland,
1975) confirmed that transport from urban centers as far as 30-50 miles
downwind is quite widespread.
Extensive oxidant monitoring in rural areas was conducted in 1974.
Perhaps the most comprehensive single study to date on urban/nonurban
oxidant interrelationships was conducted in the Ohio Valley in the
summer of 1974. It was concluded that oxidant values in the rural areas
clearly exceeded the NAAQS. After about 30 to 50 miles, a single urban
plume was found to lose its identity (RTI, 1975). It was also found
that a distinct and nearly identical diurnal ozone variation at widely
separated locations indicated that area-wide mixing processes were impor-
tant. Specific air trajectories could not be consistently associated
with the arrival of air containing high or low oxidant values. It was
found that high oxidant values persisted with the incoming movement of
high pressure systems. Martinez (1975), in reviewing the relation of
27
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oxidant values with meteorological features, found that high rural
oxidant values appear to be related to the influence of high pressure
cells, maximum temperatures above 60 F, abundant sunshine, low wind
velocities, and low-level atmospheric instability.
On the basis of the Ohio studies, Ripperton et al. (1974) support the
surface origin of high oxidant values and discount the possibility of
significant stratospheric transport. Rasmussen and Robinson (1975)
present a qualitative surface ozone model which describes the approxi-
mate oxidant contributions to be expected in rural and urban locations
from both natural and anthropogenic sources.
Other studies in the New York-New Jersey-Connecticut area have
attempted to relate the high east coast rural oxidant values to various
meteorological factors (Graedel et al., 1974). Bruntz et al. (1974)
have attempted to obtain an empirical correlation between Oo, solar
radiation, wind speed, and air temperature by using statistical curve-
fitting methods. Cleveland et al. (1975) explain that the high night-
time ozone values in Massachusetts are indicative of transport from
the New York-Connecticut area. Coffey and Stasiuk (1975) propose that
the high nonurban ozone concentrations would result in a reverse trans-
port to urban areas, making any urban oxidant controls ineffective.
Rubino et al. (1975) report high urban and nonurban 0- values in
Connecticut, and attribute this to transport from New York City.
In the Houston area, the Goober III study (Fowler et al. 1975)
confirmed that oxidant was transported from Houston to a nonurban site
in Prairie View (40 miles northwest of Houston). However, during the
Yellow Pine study conducted during April-June 1974 in eastern Texas,
no evidence of transport could be found. The measured ozone concentra-
tions showed a diurnal profile, with peak Oo concentrations in the early
afternoon. The NAAQS was exceeded only twice during the monitoring period.
28
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Becker (1974) analyzed data from the Wisconsin area, where 0., was
monitored at seven urban and four nonurban locations. The rural sites
in southern Wisconsin were found to experience more hours of alert
levels (400 ppb) than the four urban Milwaukee sites.
Based on his ozone measurements in Miami, Florida, Nagler (1974)
confirmed the high 63 levels on an area-wide basis, with indications of
long-range transport from the Chicago-Pittsburgh urban complex (Fank-
hauser, 1975).
In Beulah, North Dakota, a relatively remote location, it was found
that 23 percent of all one-hourly average concentrations exceeded the
NAAQS, based on a brief sampling study in July 1974. Values as high as
0.12 ppm were measured and no evidence of transport was found. It was
suggested that scarcity of foliage in the area with which 0-, might
react could account in part for the high ozone values (Browning, 1975) .
In a modeling study based on measurements from the Ohio Valley and
Los Angeles, Johnson and Singh (1975) examined the significance of 0.,
in the upper inversion layer in terms of its effects on concentrations
at the surface level. They found that high night time ozone values
and the "weekend effect" could be explained by ozone layers aloft
dispersing downwards during turbulent conditions. This phenomenon is
expected to be significant in both urban and rural locations. It may
be especially significant in nonurban areas because of the lack of
primary ozone-destroying precursors.
Among the locations that showed low oxidant values were monitoring
sites in Wyoming and Montana. At the Powder River Plant in northwest
Wyoming, ozone data taken from 1 January to 30 June 1974 yielded values
that were typically between 0.03 and 0.05 ppm (Ancell, 1975). The
maximum hourly concentration measured was 0.071 ppm. At McRae, Montana
(Tsao, 1974) 0-j was monitored from December 1973 to June 1974 with a
29
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total of 3820 hourly values obtained over a period of 184 days. At no
time did the maximum 0- value exceed the NAAQS. A vast majority of the
data was below 0.06 ppm.
It is obvious, therefore, that effective control strategies cannot
be formulated until there is general agreement on some of the basic
questions. Altshuller (1975) has attempted to delineate some of the
important questions that must be answered. He concludes that the
effects of downwind transport and the growth of suburban cities must be
isolated. He also points to a scenario that may apply on the east coast
area, in which urban plumes constantly intermix with naturally emitted
precursors as well as with other plumes.
The question of what is a natural ozone background is also a
confusing one, since recent data seem inconsistent with measurements
made a few years ago. While it is not possible to completely define
the accuracy of data taken before the mid-1960s, it is difficult to
make a strong argument that the earlier data are wrong (RTI, 1975).
However, even today there is considerable controversy about ozone
measurement methods, and the possibility that all EPA measurements are
22 percent too high (Demore et al., 1975) would imply that the nonurban
problem is probably less serious than hitherto believed.
Vertical ozone profiles showing a characteristic decline with
height have been used as the primary argument in favor of the surface
origin of ozone in rural areas (RTI, 1975). However, high concentra-r
tions of ozone aloft at these same rural areas are found trapped within
inversion layers (Johnson and Singh, 1975).
As more data become available it should be possible to develop a
consensus on what is a typical background ozone level, what is the
nature and extent of urban transport, and what strategies must be used
to control the oxidant problem. If trajectory analyses cannot define
30
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consistent source-receptor relationships, and if area-wide effects are
shown to be prevelant, regional strategies will have to be developed.
E. Summary of Significant Scientific Findings
As has been discussed in this section, a number of intensive studies
have been made on the urban/nonurban oxidant relationship, and a wealth
of data are at hand. In addition, a number of monitoring stations over
the continental United States have helped generate an extensive data
base for both urban and nonurban locations. Although considerable
disagreement still persists on various points, a number of findings
have been generally confirmed by these efforts, and are summarized
below:
• Urban oxidants are directly attributable to precursor
emissions and their relationships (HC, NOX, HC/NOX)
in urban areas.
• Oxidant levels are generally higher in those suburban areas
that are located directly downwind from central urban locations.
• In the absence of NO, the sinks for oxidant such as
N02, olefins, particulate matter, and surface features
scavenge ozone slowly. However, urban plumes can affect
oxidant levels at a range exceeding 50 miles.
• Oxidant aloft may be effectively isolated from destructive
precursors and can be entrapped within stable inversion
layers. This oxidant can diffuse downward either during
the following day or at night if turbulent conditions
persist. The persistence of oxidant in layers aloft
and its downward diffusion occurs in nonurban as well
as urban locations.
• While short-range horizontal transport of oxidant and
oxidant precursors has been generally invoked as the
cause of high oxidant levels, recent investigations
indicate mesoscale and even synoptic-scale transport
of oxidant over the United States. Distances of travel,
persistence of oxidant and oxidant precursors, and the
contributions of large and small sources superimposed
on large-scale transport have prevented the identifica-
tion of clear cut source-receptor relationships by
31
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trajectory analysis. An analysis of nonurban hydro-
carbon data, even though limited, suggests that
nonurban hydrocarbons are composed of the same
complex mixtures that characterize urban areas.
Similar oxidant diurnal variations are also observed
in both urban and nonurban areas.
Lightning from thunderstorms may cause brief local
increases in ozone but by itself constitutes an
insignificant source of ozone.
Ozone contributions from natural precursors and
stratospheric ozone injections are likely to be
between 0.04 and 0.05 ppm. Ozone from natural hydro-
carbons may increase the ambient ozone by 0.02 to
0.05 ppm, however the atmospheric conditions that
are conducive to ozone production from photochemical
processes are usually different from conditions that
favor transport from the stratosphere.
Typically, high temperatures (> 60°F), abundant solar
flux, low wind speeds, high pressure cells and low-
level instability present favorable conditions for
elevated oxidant levels. A fairly good statistical
correlation exists between oxidant levels and tempera-
ture, relative humidity, and inverse mixing height.
Synoptic-scale weather patterns with migratory anti-
cyclones achieve a widespread mass of air contamination.
High pressure cells often have the highest oxidant
concentrations near the center of the cell in an area
of about 100 to 200 miles in diameter, where conditions
are apparently conducive to high oxidant formation.
More recent results favor the area-wide mixing hypothesis,
in which natural precursors constantly intermix with
urban plumes. So far, trajectory analysis has not been
useful to relate high or low rural oxidant concentra-
tions to any specific sources. A significant possi-
bility is the transport of hydrocarbon precursors of
lower reactivities from urban locations over long
distances, which then intermix with NOX from both
natural and anthropogenic sources to form high oxidant
concentrations in rural areas.
For a long time the belief has been that oxidants were
formed from reactive hydrocarbons such as olefins, some
aromatics and aldehydes only, and nonreactive hydrocarbons
32
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which were a significant portion of the hydrocarbons
emitted, did not contribute to oxidant formation, it
has now become clear that all hydrocarbons (even
methane) are capable of forming oxidants and the only
real difference is the relative time of irradiation.
Thus very low reactivity hydrocarbons (say alkanes)
will eventually lead to ozone formation but the
chemical processes may take several days. Such
occurrences will lead to a higher background of ozone,
and long-range transport of hydrocarbons and thereby
of oxidants.
33
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Ill DESCRIPTION OF SELECTED RESEARCH STUDIES
In this section we present brief summaries of the results of a
selected number of research studies that are judged to be significant in
terms of the relation of oxidant levels to meteorological features.
Both theoretical studies and observational studies that contain analyses
of data are included. With regard to observational studies, the emphasis
in this review has been placed on the results of analyses of oxidant or
ozone data collected in the United States east of a line from the
western border of the Dakotas southward to El Paso, Texas. However, a
few studies elsewhere that contain results of apparent general signifi-
cance have also been included. The summaries are presented in alpha-
betical order, by author.
35
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(1) Flux Measurements of Atmospheric Ozone over Land and Water
(Aldaz, 1969)
Based on experimental measurements, it is estimated that ozone
-1 3 -2 -1
destruction rates are 0.60 cm s (cm cm s ) over land, 0.04 cm/s
over fresh water, and 0.02 cm/s over the ocean. Assuming a destruction
rate of ozone by tropical vegetation that may vary from 0.06 cm/s to
3.0 cm/s, it is estimated that global sinks for ozone vary from 5.4 to
29 -1 9
8.6 x 10 molecules s (or 1.3 to 2.1 x 10 tons of ozone per year).
Because of the land-sea distributions of the northern and southern
hemisphere, the southern hemisphere is estimated to account for 1.5 to
29 -1
3.1 x 10 molecules s . The ozone density is taken to vary from
3
35 to 55 |o,g/m , depending on latitude.
36
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(2) Evaluation of Oxidant Results at CAMP sites in the United States
(Altshuller. 1975)
Oxidant measurements available between 1964 and 1973 at six CAMP
sites (Chicago, Cincinnati, Denver, Philadelphia, St. Louis, and
Washington, D.C.) were evaluated. Elevated oxidant concentrations
were characterized by season, hour of the day, Sundays compared to
weekdays, sampling site, and long-term trend. With the exception of
Chicago, downward oxidant trends are reported at all CAMP sites. These
and other studies indicate that proportional declines in suburban
locations have not been achieved. It is concluded that effects of
downwind urban transport cannot be isolated from the growth of suburban
cities. The paper points to the significance of urban plumes that
extend 50 to 100 miles downwind, constantly intermixing with natural
emissions as well as with other urban plumes. If long-range transport
is indeed important, regional scale strategies will be required. It
has been generally observed at CAMP sites that a general downwind shift
in HC/NOX ratios is occurring. This could also explain the greater
linear decrease in oxidants, compared with the nonmethane hydrocarbons.
37
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(3) Mesoscale Flows and Ozone Levels in a Rural California
Coastal Valley (Baboolal. 1975)
The mesoscale flow over a rural California coastal valley is
characterized using year-long data collected by a network of field sites
made up of surface winds, acoustic radar, sigma meter, and temperature
soundings. With the additional support of the historical meteorological
data the air pollution is defined. The presence of well-developed
drainage flows with noticeable turbulence appears on the acoustic radar
record; this is supported by the sigma meter turbulence measurements.
Three times daily, temperature profiles, taken at increasingly greater
distances from the Pacific Coast, were used to characterize the
inversion climatology of the marine layer. Simultaneous ozone soundings
reveal unusually high levels aloft, suggesting the rural valley itself
to be the unlikely source. This suggestion is supported by the results
of a limited modeling effort.
38
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(4) Three-Dimensional Pollutant Gradient Study—1972-1973 Program
(Blumenthal et al.. 1974)
Two years of data on the 3-D distribution and transport of
aerosols and gaseous pollutants in the South Coast (Los Angeles),
San Joaquin Valley, and San Francisco Bay air basins were obtained
and analyzed. Two hundred forty sampling flights on 59 different
days were made by two aircraft in conjunction with ground-level sampling.
Extensive meteorological data were obtained along with the scattering
coefficient, condensation nuclei, 0~, NO , CO, turbulence, temperature,
•J X.
and humidity data obtained by the aircraft.
The data present a detailed picture of the mixing layer structure
and ventilation processes in the Los Angeles Basin and point out the
modifications to the normal mixing and ventilation processes that lead
to episode conditions. The air pollution problem in Los Angeles and
other air basins is shown to be a regional problem exemplified by the
accumulation of pollutants in a stagnant air mass and subsequent
transport to downwind areas. Various statistical and other analyses
were performed on the data, which demonstrated the changes in the aerosol
and gaseous pollutants as they aged and indicated certain factors
contributing to aerosol formation and growth.
Other special studies were performed, which documented in some
detail the structure of a few point source plumes and demonstrated
the possible buoyant effect of roadways. A 24-hour sampling program
in the eastern Los Angeles Basin documented the overnight stability
of ozone at high concentrations in aged polluted air.
39
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(5) Some Large-Scale Features of the Vertical Distribution of
Atmospheric Ozone Associated with the Thermal Structure
of the Atmosphere (Breiland. 1968)
Ten-case running means of the vertical distributions of hydro-
static stability and of the vertical fractional gradient of the partial
pressure of ozone computed from ozone and temperature soundings
arranged according to tropopause height are presented for four stations
located in different latitudes. It is shown that the characteristic
large-scale features of the vertical distributions of the vertical
ozone gradient correspond closely to similar characteristic large-
scale features of the thermal structure of the atmosphere depicted by
the vertical distributions of the hydrostatic stability. The layer
structure of the ozone gradient and of the hydrostatic stability both
show characteristic features that vary significantly with latitude and
with the height of the tropopause.
40
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(6) The Dependence of Ambient Ozone on Solar Radiation, Wind
Temperature, and Mixing Heigh (Bruntz et al.. 1974)
Based on physical theory and "weathervane plots" of data collected
from New York metropolitan area, the authors conclude that 0., concentra-
tions are statistically related to wind speed, solar radiations, and air
temperature. They obtain the following equation using statistical curve-
fitting methods, and claim a correlation coefficient of 0.84 between the
observations and the predicted values:
Ot = 3.29 (±0.70) +0.21 (±0.04) log S - 0.61 (±0.11) log V
+ 2.65 (±0.36) Iog1() T
where
[03(PPb) +5]
S = solar radiation (Langleys)
V = wind speed (mi hr )
T = air temperature (deg F)
41
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(7) The Transport of Photochemical Air Pollution From the
Camden-Philadelphia Urban Complex (Cleveland and Kleiner. 1975)
This paper reports the results of an analysis of ground-level
hourly chemiluminescent ozone measurements obtained from 1 May 1973
to 30 September 1973 and from 1 May 1974 to 13 September 1974 from
four stations surrounding the Fhiladelphia-Camden urban complex.
With the aid of a graphical-statistical technique, it is shown that at
each of four sites in New Jersey and Pennsylvania, ranging from 27 km
to 49 km away from the center of the Camden-Philadelphia urban area,
ozone concentrations are higher when the air is flowing from the urban
area to the site. It is judged by the authors that this accounts for
some of the ozone previously observed in the nonindustrial, low-traffic-
density area of Ancora, New Jersey, where concentrations of primary
pollutants are low, but where ozone daily maxima frequently exceed the
federal standard. It is thus concluded that photochemical air pollution
in this area is a regional rather than a local phenomenon, and ozone
resulting from emissions from the urban area is widespread and not
confined to the urban area itself.
42
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(8) The Analysis of Ground-Level Ozone Data from New Jersey, New York.
Connecticut, and Massachusetts: Data Quality Assessment and
Temporal and Geographical Properties (Cleveland et al., 1975)
Hourly ground-level ozone measurements from 41 sites in eastern
New York, northern New Jersey, Connecticut, and Massachusetts from
1 May 1974 to 30 September 1974 were analyzed. Various techniques for
assessing data quality and uniform calibrations show the data to be of
high reliability for yielding information on the ozone problem in the
region. Nighttime concentrations, relative to those during the day, are
highest in Massachusetts; more specifically, the ratio of the upper
quartile of hourly average ozone concentrations at 1500 hours EST to
the upper quartile at 0100 hours EST decreases with increasing distance
from New York City, which is in the center of the tri-state urban
complex (northern New Jersey, southwestern Connecticut and New York
City). The site distributions of daily maximum concentrations are high-
est in the Stamford-Greenwich region of Connecticut and next highest in
a region to the east and northeast of Stamford-Greenwich. The lowest
0,, concentrations were found in Boston, Waltham, Springfield, Newark
and Elizabeth; however, all five stations were located next to automobile
emission sources and the NO emissions could account for the low oxidant
levels measured at these poorly located sites.
43
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(9) Long-Range Transport of Photochemical Ozone in Northwestern
Europe (Cox et al., 1975)
Measurements of the concentrations of ozone and trichlorofluoromethane
in the atmosphere were obtained in 1973 at three locations in the
southern British Isles. The U.S. Air Quality Standard for photochemical
oxidants was exceeded on a number of days at all three sampling sites,
including one situated in southern Ireland. The authors conclude that
in suitable meteorological conditions, measurable amounts of photochemical
pollution of anthropogenic origin are transported over distances up to at
least 1,000 km in northwestern Europe, and that occasionally continental
emissions provide a major contribution to photochemical pollution in the
United Kingdom. During such periods photochemical pollution is essentially
a regional rather than a local problem, with uniformly elevated concentra-
tions of photochemical ozone being observed simultaneously over different
parts of the United Kingdom. It follows that, should controls on the
emission of the pollutant precursors (hydrocarbons and nitrogen oxides)
be considered necessary to reduce future levels of photochemical oxidants
in the United Kingdom, then such controls are unlikely to be effective in
the absence of similar controls elsewhere in Europe.
44
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(10) Vertical Distribution of Photochemical Smog in Los Angeles
Basin (Edinger. 1973)
Aircraft soundings of oxidant concentration and temperature in
the vertical section from the Santa Monica coastline inland to the
San Bernardino area were analyzed. In addition to the polluted layer
confined beneath the temperature inversion, laminae of pollution were
detected within the inversion layer with concentrations of oxidant as
high as those observed in the ground-based smog layer. It is hypoth-
esized that the upper layers of pollution are formed when a portion of
the smog moving up the heated mountain slopes that bound the basin on
the north moves out horizontally from the slopes at elevations between
the top and bottom of the inversion.
(11) Penetration and Duration of Oxidant Air Pollution in the
South Coast Air Basin of California (Edinger et al., 1972)
On June 18, 19, and 20, 1970, two aircraft, a rawinsonde, two
pibal stations, and four ground stations provided simultaneous samples
of total oxidant, temperature, and winds up to 8000 ft in an area extend-
ing from Santa Monica, Calif., east to Redlands and north across the
San Bernardino Mountains. It was shown that photochemical oxidant
formed in the marine layer is vented up the slopes and over the crest
of the San Bernardino Mountains during the day. Layers of high oxidant
concentrations were detected above the inversion base, suggesting that
some pollution is vented up the slopes and subsequently advected back
to the south. The diurnal changes in the temperature inversion also
contribute to the high concentration found above the inversion base.
These processes result in multi-layers of pollution. The study suggests
that oxidant air pollution is transported up to 80 mi to forested
mountains, where severe damage to conifer species has been documented.
45
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(12) Control of Photochemical Oxidants—Technical Basis and Implications
of Recent Findings (EPA. 1975)
To insure the technical accuracy of the oxidant control strategy
and to refine that strategy where necessary, EPA has conducted a continuing
program of research studies and data analysis. New findings based on
laboratory and field studies accomplished over the last several years
generally support the control measures currently being taken and further
indicate that additional measures may be necessary to meet the oxidant
standard nationwide. These recent studies have documented frequent
violations of the oxidant standard in both urban and rural areas although,
in some urban areas, both the maximum concentrations of oxidants and the
frequency of violations have decreased over the past several years. At
rural locations, the number of violations of the standard and the maximum
concentrations are sometimes as high and even higher than in nearby urban
areas. It is thus apparent that oxidants are a rural as well as an urban
problem.
The recent studies show that: (1) man-made emissions are the
predominant source of high levels of oxidants, even in remote rural areas;
(2) the contribution of natural sources of oxidants is usually not more
than 0.05 ppm, compared with the oxidant standard of 0.08 ppm; and (3)
transport of oxidants and their precursor compounds has been demonstrated
to about 50 miles downwind of urban areas and it is likely that transport
over longer distances occurs. It also has been shown that the highest
oxidant concentrations in the Midwest in both rural and urban areas occur
during periods of stagnant conditions associated with high pressure
weather systems.
In both urban areas and in many nonurban areas, there appear to
be sufficient emissions of man-made precursors to account for the high
oxidant levels observed. While transport of oxidants and their precursors
may occur, most urban areas probably are responsible for their own
46
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oxidant problem. The high oxidant levels in nonurban areas appear to be
the result of both locally produced precursors and precursors transported
from urban and other nonurban sources. As a result, control strategies
for nonurban areas will need to be directed at measures which reduce
emissions from both nonurban sources as well as urban sources and which
meet the specific needs of each of these areas.
The following implications of the new findings are suggested:
• Because of the high precursor emission densities and the
large numbers of people exposed to oxidants, continued
emphasis on intensive control measures within cities will
be necessary to meet the oxidant standard in major urban
areas.
• It may be necessary to extend some measures under present
state implementation plans to include nonurban areas
as well as cities.
• Although mobile source controls (including transportation
control plans) will continue to be a major part of the
oxidant control program, there is a need for more stringent
control of precursor emissions from stationary sources.
• Both under conditions of transport and under persistence
of stagnant air masses there can be sufficient time for
less reactive hydrocarbons to contribute to oxidant
formation. This indicates the importance of controlling
all organic compounds that can form oxidants.
• Nitrogen oxides emissions may be transported into rural
areas and contribute to oxidant formation by reaction
with locally emitted organic compounds. It may eventually
become necessary to consider control of nitrogen oxides,
coordinated with the control of hydrocarbons, as a part
of the oxidant control strategy.
• Oxidant concentrations that can be attributed to natural
sources are usually less than 0.55 parts per million
compared with the oxidant standard of 0.08 parts per
million. Because of emissions from natural sources, more
stringent reductions of man-made emissions may be necessary
in some areas.
47
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(13) A Theoretical Investigation of Tropospheric Ozone and Stratospherlc-
Tropospheric Exchange Processess (Fabian. 1973)
Based on the global distribution of various surface types the mean
tropospheric residence time of ozone is estimated as a function of
latitude. Due to the land-sea distribution t varies from 50 days in the
northern hemisphere to 190 days in the southern hemisphere. For the
stratospheric-tropospheric exchange a sinusoidal variation with season
is assumed. The annual variation of tropospheric ozone thus gets a
sine function from mean, amplitude* and phase from which the injection
function for the particular latitude can be determined. Ozone and strontium-
90 fallout data show similar behavior between 25° south and 65° north
latitudes.
(14) Qzone.spn.de Observations over North America, Vols. 1-4 (Hering and
Borden. 1964a. 1964b. 1965b. 1967)
An experimental program for the measurement of the vertical ozone
distribution was established by the Air Force Cambridge Research Labora-
tories (AFCRL) in Janyary 1963. Observations from eleven network stations
spread throughout North America have been published in this series of four
reports. Ozonagrams for individual ozonesonde ascents made during the
period January 1963 to January 1966 are included.
The fourth volume also presents a statistical summary of the ozone-
sonde data for the three-year period ending December 1965. Seasonal mean
ozone profiles and the standard deviations from the average distributions
are given for each station. Correlations of the ozone concentration at
specific levels with temperatrue, pressure, and total ozone are also
summarized.
48
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(15) Mean Distribution of Ozone Density over North America, 1963-1964
(Bering and Borden. 1965)
An interim summary of the ozone climate over North America was pre-
pared from AFCRL ozonesonde network observations made during 1963 and
1964. Mean bimonthly distributions of ozone density computed for individual
network stations depict the average ozone structure as a function of
altitude and season for the first two years of network operation. Data
are also presented on the standard deviation of ozone density and the
mean seasonal distributions along a meridional cross section extending
from the Canal Zone to Greenland. A brief statistical analysis indicates
that approximately 35 to 50 percent of the variance in the total ozone
amount at middle and high latitudes is given by the fluctuations in ozone
density in the 11- to 13-km or 13- to 15-km layers.
49
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(16) Photochemical Oxldants in the New York-New Jersey Metropolitan
Area (Jacobson and Salottola. 1975)
Atmospheric oxidant concentrations measured at seven locations
during the years 1970-1972 were compared to explore the nature of the
photochemical oxidant problem in the New York-New Jersey metropolitan
area. The results indicate that oxidants occurred in highest concentrations
during the months of May-September; a diurnal pattern existed during the
spring and summer seasons with concentrations usually rising to a maximum
between 12:00 and 17:00h Eastern Standard Time; the federal ambient air
quality standard of 0.08 ppm was exceeded each year with a frequency
varying with location; maximum hourly average concentrations for the region
were in the range of 0.2-0.3 ppm; sites located in heavily trafficked
areas generally reported lower oxidant concentrations than sites in sub-
urban areas.
Comparisons between oxidants at Yonkers, a suburban location north
of the metropolitan area, and meteorological measurements indicated that
elevated concentrations occurred more frequently with wind directions
from the southeast through southwest sectors, wind speeds between 6 and
11 miles h , solar radiation intensities above 400 Langleys, temperatures
greater than 75°F, and with early morning mixing depths less than 1000 m.
Concentrations of oxidants in Yonkers rarely exceeded 0.05 ppm during the
winter or on days with low solar radiation.
It is concluded that during the spring and summer in the metropolitan
area oxidant concentrations exceed federal standards more frequently than
any other pollutant, that oxidants are formed largely by photochemical
reactions as polluted air is transported from urban to suburban areas,
that elevated oxidant concentrations occur more frequently at less urbanized
locations downwind of major sources of emissions, and that concentrations
which reach or exceed the ambient air quality standard arise mainly from
50
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pollutant emissions occurring in the heavily urbanized portion of the
metropolitan area while natural sources of oxidants and their precursors
make less significant contributions to the photochemical oxidant problem
in this region.
The oxidant measurement methods employed either colorometric
(Beckman or Technicon) or coulometric (Mast) analyzers. The standard
calibration method (neutral buffered KI) was used throughout. At the
Yonkers station during the summer of 1973, chemiluminescent measurements
of ozone and coulometric oxidant measurements gave comparable results.
51
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(17) Surface Ozone in the Arctic Atmosphere (Kelly. 1973)
Near-surface atmospheric ozone measurements were carried out at
Barrow, Alaska (71° 19'N, 156°W), from January 1965 to September 1967.
Ozone was continuously monitored by microcoulombmetric analysis at a
level 2 m above the ground. Daily ozone concentrations near the ground
varied from 7 to less than 1 pphm by volume. Highest concentrations
occurred in the spring and showed sharp increases lasting from several
hours to a few days. These sudden rises in ozone concentration correlated
with storm front passages. The concentration of surface ozone from late
spring through the summer and fall showed less variability from day to day
than in the spring. The lowest ozone concentrations occurred from late
May to early June.
(18) The Vertical Distribution of Ozone Over the San Francisco
Bay Area (Lovill and Miller. 1968)
Observations of the vertical distribution of ozone were made during
February 1967 in the San Francisco Bay Area with the carbon-iodine (Komhyr)
ozonesonde. Horizontal and vertical velocity components were obtained by
simultaneous tracking with an M33 radar. In the lower troposphere, two
peaks of ozone were found near 1 and 1.5 km within the west coast sub-
sidence inversion; the lower maximum coincides in position with a wind
jet. In the middle and upper troposphere there are significant time
variations of ozone, believed to be caused by intrusions of stratospheric
air. Undulations in the ozone, temperature, and wind profiles in the
stratosphere suggest laminas of air masses. The mean profile of ozone
suggests that there are several distinct zones that are related to ozone
production and vertical mixing.
52
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(19) The Use of Monitoring Network and ERTS-1 Data to Study Interregional
Pollution Transport of Ozone in the Gary-Chicago-Milwaukee Corridor
(Lyons and Cole, 1974)
Limited ozone monitoring conducted by EPA in Milwaukee during the
summer of 1971 revealed surprisingly high values (5 episode alert levels
in 99 days). In the summer of 1973, the Wisconsin Department of Natural
Resources began installation of nine air quality monitoring stations in
southeast Wisconsin, and one in rural Poynette (32 km north of Madison).
The southeastern sites again revealed high values, two or more sites
exceeding 8 pphm on 27 days over a 47-day period, with alert levels (40 pphm)
being reached 9 times. Peak values between 20-30 pphm were recorded several
times, especially at Racine, Wisconsin. Poynette also frequently
exceeded 8 pphm.
An analysis of the data revealed several interesting facts. The
winds were from the southwest through east-southeast fully 92 percent
of the days during which the primary oxidant standard was exceeded. The
data show that 0« levels are comparatively low within 1 km of the shore-
line and reach their highest values 1-4 km inland. This is confirmed by
extensive bioindicator monitoring conducted in Milwaukee in 1972. A
mechanism is proposed that illustrates how the complex wind and thermal
structures in lake breezes could lead to continuous fumigation of stored
oxidants to the surface in a narrow band parallel to the shore. Simply
stated, oxidants are conserved over the lake area (in the absence of NO
fluxes) and returned to the shore during the lake-breeze cycle in the
morning.
In addition, the unexpectedly high values found both along the
shoreline and at rural Poynette suggest that oxidants can be subjected
to significant mesoscale and even synoptic scale transport. An ERTS
image of the Lake Michigan area strongly supports a theory that much of
the oxidants and/or its predecessor HC and NO originates in the Chicago-
X
Gary area and is funneled northwards in the lake-breeze convergence zone.
53
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It even seems conceivable that the high Poynette readings are the result
of transport from such areas as St. Louis, Kansas City, Dallas, etc.
The low level nocturnal jet stream of the Great Plains is suggested as a
plausible mechanism.
54
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(20) Temporal-Spatial Variations of Nonurban Ozone Concentrations and
Related Meteorological Factors (Martinez, 1975)
This paper provides a history of the nonurban ozone problem and
summarizes the results of various studies that have been conducted since
1970. The primary information for the paper came from EPA-sponsored
studies the eastern U.S. in 1972-1973 (Figure 6) and the summer of 1974
(Figure 7). These studies have revealed considerable temporal and spatial
variations in ozone concentrations, with levels sometimes exceeding the
3
national one-hour average ambient standard of 160 M-g/m (0.08 ppm).
Both local and synoptic scale meteorological factors, including
the role of transport from urban areas, have been examined and apparent
relationships with ozone concentrations are described. A consistent
statistical correlation was found between air temperatures in excess of
60°F and ozone concentrations in excess of the NAAQS. Trajectory analyses
were inconclusive and showed no direct urban/nonurban pathway pattern.
However, high 0 values were associated with slower air movement.
Further, synoptic weather features were found to correlate with ozone
variations. Some high-pressure cells have maximum ozone concentrations
at the center of the high. A slow-moving high pressure system is expected
to be particularly conducive to high ozone values.
55
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SCALE
7 •
(km X 100)
No.
Town
Me Henry
Kane
Coshocton
Lmlsburg
County
Gorrftt
McKean
Coshocton
SA-4432-8
FIGURE 6 NONURBAN OZONE GROUND SAMPLING STATIONS. 1972-73 ERA-SPONSORED
STUDIES (McHENRY ONLY 1972 SITE)
56
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0
Indianapolis
Cleveland
(Wooster)
I
(DuBois)
Dayton
Cincinnati
—' .
BSI Canton {'
I -
Columbus / Pittsburgh
(McConnelsville) j
s I
(Wilmington) <~ ^ (McHenry)
t /
x
/
rJ
Louisville
\ Charleston
City Stations
(6)
Rural Sites
(5)
SA-4432-9
FIGURE 7 OZONE GROUND SAMPLING STATIONS, 1974 EPA-SPONSORED STUDY
57
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(21) Ozone Within and Below the West Coast Temperature Inversion
(Miller and Ahrens. 1970)
The oxidant concentration in the air over the San Francisco Bay
Area and the Pacific Ocean was measured up to an altitude of 2500 m and
the observed distribution in the vertical and horizontal has been related
to the characteristics and behavior of the west coast temperature inversion.
Vertical time sections at fixed points and vertical cross sections were
constructed of oxidant concentration, temperature, humidity, and winds
measured from aircraft and radar.
The oxidant concentration in polluted air is strongly dependent
on the destruction rate. The mean destruction rate within the surface
layer depends directly on the intensity of eddy mixing and inversely on
the square of the depth of the vertical mixing. Thus, the existence of
a temperature inversion does not necessarily lead to a high concentration
of oxidants, since the destruction rate may be high in a shallow mixing
layer. The highest oxidant concentration was observed almost invariably
at the edges of the west coast marine inversion, where pollutants are
available for ozone production and the mixing layer is deep. Explanations
are offered for the maxima of ozone that often occur above the inversion
base. Distribution patterns of oxidants clearly depict the waving of
the inversion layer.
58
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(22) Oxidant Air Pollution in the Central Valley, Sierra Nevada Foothills,
and Mineral King Valley of California (Miller et al.. 1972)
Total oxidant air pollution, temperature, and winds were measured
in the Central Valley, the Sierra Nevada foothills, and Mineral King
Valley from 17-28 August 1970. Vertical profiles of total oxidant and
temperature were determined by aircraft (at Fresno, Visalia, Three Rivers
and Mineral King) several times daily during a 2-day period. Evidence
was recorded of the transport of photochemical smog from the Central
Valley to Mineral King. In situ formation of oxidant and diurnal changes
in the temperature profile in Mineral King Valley were observed.
59
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(23) The Average Tropospheric Ozone Content and Its Variation with
Season and Latitude as a Result of the Global Ozone Circulation
(Pruchniewicz. 1973)
Evaluations of radiosonde soundings over North America and Europe,
measurements aboard commercial airlines, and permanent ozone registrations
at nineteen ground-based stations between Tromso, Norway, and Hermanus,
South Africa, yield three belts of higher ozone intrusion from the strato-
sphere and maximum values of the annual means at about 30 N, and between
40°-45°N and at about 60°N. A marked decrease of the annual mean values
of the tropospheric ozone is detected towards the equator and the pole,
respectively.
In the northern hemisphere the maximum of the annual cycle of the
tropospheric ozone concentration occurs in spring at high latitudes and
in summer at mid-latitudes.
For the tropical region from 30 S to 30 N a strong asymmetry of
the northern and southern hemisphere occurs. This fact is discussed in
detail. The higher troposphere of the tropics seems to be a well-mixed
reservoir and mainly supplied with ozone from the tropopause gap region
in the northern hemisphere. The ozone distribution in the lower tropo-
sphere of the whole tropics seems to be controlled by the up and down move-
ments of the Hadley cell. The features of large-scale and seasonal
variation of tropospheric ozone are discussed in connection with the
ozone circulation in the stratosphere, the dynamic processes near the
tropopause and the destruction rate at the earth's surface.
60
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(24) The Role of Trace Atmospheric Constituents in a Surface Ozone Model
(Rasmussen and Robinson, 1975)
The authors present a description of a qualitative model of ground
level ozone concentrations obtained by the chemiluminescent methods during
several field studies conducted during 1973 and 1974. The model considers
a typical rural site upwind and downwind of an urban site. The following
features characterize model:
• Stratospheric ozone transport contributes about 30 to 50 ppb to
the ozone concentration at ground level.
• Natural photochemical reactions (between terpenes and biogenic
NO) contribute about 20 ppb to the natural background.
• Out of this total of 50 to 70 ppb of natural ozone, at least
10 ppb is lost due to reactions involving surface 0 background
level is about 40 to 60 ppb.
• As this air enters an urban location, the 0 value quickly
approaches zero because of reactions with urban NO and aerosols.
The urban precursors (HC and NOX) can photolyze to produce as
much as 50 ppb of photochemical ozone.
• Urban ozone is then advected to downwind rural sites, while
slow dispersive and destructive processes reduce this ozone
level to near background concentrations.
The authors believe that the high rural ozone levels are primarily due to
the transport of pollutants from a number of closely located urban sources,
which cannot always be clearly identified.
61
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(25) Stratospheric-Tropospheric Exchange Processes (Reiter. 1975a)
Qualitative descriptions and quantitative estimates are presented
of various transport processes between stratosphere and troposphere. The
seasonal changes of tropopause heights account for a flux of about 10
percent of the mass of the stratosphere in one hemisphere during the
course of 1 year. This flux is balanced approximately by the seasonal
shift of stratospheric air masses between the northern and southern
hemispheres. Vertical transport through the Hadley cell transfers
approximately 38 percent of the mass equivalent to one hemispheric
stratosphere through the tropopause per year. This appears to be the
most effective of all transport mechanisms. Large-scale eddies of the
scale of cyclones and anticyclones transfer about 20 percent of strato-
spheric air through the tropopause per year. Small-scale and mesoscale
diffusion processes at tropopause level probably account for the transfer
of only 1 percent of stratospheric air. These mass flux estimates are in
reasonable agreement with observed residence times of stratospheric
pollutants.
62
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(26) High Ozone Concentrations in Nonurban Atmospheres (Ripperton et al..
1974)
In the summer of 1973, ozone concentrations were measured at several
rural locations in West Virginia, Pennsylvania, and Ohio. Chemiluminescent
techniques were used and calibrations were performed using the standard
method (neutral buffered KI) . A C-45 aircraft was used to make 0., measure-
ments aloft, between and over the fixed field stations. Mean wind data
at 900 mb from NOAA were used for trajectory analysis. Some of the
results from the field program are as follows (see Figure 6 for station
locations):
Station No. of Hours Percentage of Hours Highest One-Hour
Location of Data Exceeding 0 Standard 0 Concentration (ppm;
McHenry, Md. 1652 37 0.16
Kane, Pa. 2131 30 0.14
Coshocton, Ohio 1785 20 0.17
Lewisburgh, W.V. 1663 15 0.13
The aircraft data, some of which show lower concentrations aloft
than at ground level, are used to exclude the possibility of significant
stratospheric air intrusions. Collection of air samples in outdoor smog
chambers indicates that local air is sufficiently contaminated to permit
significant local ozone synthesis. It is contended that ozone in nonurban
areas is not due to any given urban source but is a result of area-wide
mixing. The interdispersed urban sources add to an air mix that already
has natural as well as anthropogenic precursors, thereby making it
impossible to identify precursor sources by trajectory analysis. The
authors agree with the now well-accepted notion that ozone can be generated
in a "spent photochemical system." They conclude that rural ozone is of
surface origin.
63
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(27) Investigation of Rural Oxidant Levels as Related to Urban Hydrocarbon
Control Strategies (RTI, 1975)
A network of ground stations was established to document the occur-
rence of high ozone values in the rural areas of the eastern United States
and their interrelationships with urban contaminants. A total of 11
stations (6 urban and 5 rural) were operational during the study period
of 14 June to 31 August, 1974. Aircraft measurements were taken to obtain
vertical ozone profiles and to determine the extent of urban plumes. In
addition to meteorological parameters, THC, CHi , 0,, N02, and selected
hydrocarbons were measured.
It was found that the NAAQS for photochemical oxidants was exceeded
twice as frequently at rural as at urban stations. Area-wide contamination
of air masses was observed. It was not possible to track an urban plume
for more than 30-50 miles downwind of Columbus, Ohio. High ozone concen-
trations were observed when a synoptic high pressure system moved over a
given station, and high ozone levels persisted as long as the high pressure
system remained in the vicinity.
Although no specific air trajectory terminating at the nonurban
stations could be consistently associated with either high or low ozone
concentrations, the results of the field measurement program still provide
support for transport of ozone precursors from urban areas to rural stations
under appropriate meteorological conditions. These results also imply
that the control of hydrocarbon in any individual city will not necessarily
prevent the occurrence of high rural ozone concentrations in excess of the
NAAQS at any given nonurban site. The implication is that the release
of hydrocarbons and oxides of nitrogen from anthropogenic or biogenic
sources, located in either an urbanor rural area, all combine to generate
appreciable quantities of ozone over wide areas.
64
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(28) Rural and Urban Ozone Relationships in New York State (Stasiuk
and Coffey. 1974)
Ozone data from a number of air monitoring stations in New York
State were analyzed. The rural monitoring stations were set up in Delaware
(Mt. Utsayantha--elevation 3200 ft) and in the Northern Adirondacks
(White Face Mountain--elevation 4980 ft). The urban sites were at Welfare
Island (New York City); Kingston, Renesslaer> and Glen Falls in the
Hudson River Valley; Syracuse in mid-state; and Buffalo in western New York.
All 0, data were measured using gas phase chemiluminescent analyzers and
the federal calibration method.
High 03 concentrations, often in excess of the NAAQS, were measured
both at urban and nonurban locations. Average daily 0- concentrations in
rural areas--typically 30 to 100 ppb--were found to correlate well with
the daily maximum ozone concentrations in the urban locations. The authors
state that because of the high correlation between 0^ levels at widely
separated urban and rural sites a common source for 0 is suggested.
Additionally, rough calculations of atmospheric 0- overburden within the
mixing layer show that the flux of 0^ into New York state can be an
order of magnitude greater than that which might be generated by complete
photochemical reactions of hydrocarbons emissions from New York state.
On the basis of these rough estimates the authors question the likely
effectiveness of oxidant abatement strategies.
65
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IV SUMMARY OF AVAILABLE SOURCES OF OXIDANT/OZONE DATA
In this section descriptions are presented of sources of oxidant
(or ozone) data believed to be suitable for studying the relation of
oxidant levels to meteorological features. In searching for these data,
we have carefully surveyed the EPA National Aerometric Data Bank (NADB),
and have obtained information and data from various EPA central and
regional offices, various state agencies, and a number of private organi-
zations who have conducted or sponsored routine oxidant monitoring or
special research studies.
Since the nonurban oxidant problem and its relation to meteorological
processes is currently of considerable interest, we have excluded all
urban and near-urban data. Hence this listing includes only those data
that are believed to be relatively free from short-range urban contam-
ination.
Particular efforts have been made to identify and include here
sources of nonurban data in the eastern United States since this is a
geographical region of much interest at the present time. Accordingly,
data from the far western states have not been included in this compila-
tion.
The two-year period 1973-1974 has been selected as optimum for the
purposes of our later data analysis, and thus our review of the data has
been restricted to this period. Any stations reporting less than 300
hours of data during this period have been excluded from this compilation.
The locations of the selected stations are shown in Figure 8.
Following this, the data source descriptions are presented in alpha-
betical order by station name.
67
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68
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Data Source Number:
Station Name: Ancora (SAROAD Code 310740Q01F01)
Location: Camden County, New Jersey (39 41' N. 74° 51' 45" W)
Responsible Organization: New Jersey Bureau of Air Pollution Control
Cognizant Individual/Organization: EPA Region II
Telephone: 212-264-2525
Type of Site: Rural-Agricultural
0
Type of Pollutant Measured: £
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 3,368 observations reported during 1973-1974
69
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Data Source Number:
Station Name: Badger (SAROAD Code 513160999F05)
Location: Sauk County, Wisconsin
Responsible Organization: Wis. Dept. of Nat. Resources, Air Pollution Control Section
Cognizant Individual/Organization: EPA Region V
Telephone: 302-353-5250
Type of Site: Rural - Agricultural
0
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 827 observations reported during 1973-1974.
70
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Data Source Number:
Station Name: Berlin (SAROAD Code 300040007FQ1)
Location: Coos County, New Hampshire (44 27' N. 71° 11' 05" W)
Responsible Organization: New Hampshire Air Poll. Control Agency
Cognizant Individual/Organization: New Hampshire Air Poll. Control Agency
Telephone:
Type of Site: Suburban - industrial
Type of Pollutant Measured:
Measurement Technique: Chemiluminsescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 4,547 observations reported during this period.
71
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Data Source Number:
Station Name: Beulah
Location: 7 miles north of Beulah. North Dakota (47° 22' N, 101° 49' W)
Responsible Organization: American Natural Gas Service Company, Detroit, Michigan
Cognizant Individual/Organization: Albert Browning
Telephone: 313-965-1616
Type of Site: Rural-nonurban
Type of Pollutant Measured:
Measurement Technique: Chemiluminescence (Bendix 8002)
(Bendix Model 8002 Ozone Monitor)
Period of Record Examined: 15 June - 31 July 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: Approximately 237, of all 1-hour average concentrations exceeded 0.08 ppm.
Values as high as 0.12 ppm were measured. The ozone values could not be attributed
to transport from urban sources. Lack of foliage, which would otherwise destroy
0 , was postulated as one reason for the high 0^ values.
72
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Data Source Number:
Station Name: Bondurant (SAROAD Code 163120024G02)
Location: Polk County, Iowa (41° 41' 59" N, 93° 28' 00" W)
Responsible Organization: Des Moines-Polk Co. Health Dept.
Cognizant Individual/Organization; EPA Region VII
Telephone: 816-374-5493
Type of Site: Rural - Agricultural
0
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 2,324 observations reported during 1973-1974.
73
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Data Source Number: 6
Station Name: Colstrip
Location: Rosebud County, Montana (45 55'N. 106° 38' W)
Responsible Organization: Department of Natural Resources & Conservations,
Helena, Montana
Cognizant Individual/Organization: James Gelhaus
Telephone: 406-449-3454
Type of Site: Remote
Type of Pollutant Measured:
Measurement Technique: Chemiluminescence
Period of Record Examined: December 1973 - May 1975
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: Data are missing for August and September 1974. Excellent remote location
with very low ^3 values (< 0.06 ppm) and a virtual absence of diurnal variations.
At no time did the ^3 level exceed 0.08 ppm, although a number of observations
were above 0.06 ppm.
74
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Data Source Number:
Station Name: Coschocton
Location: Coschocton, Ohio (40° 15' N, 81° 54' W)
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalini (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
0,
Type of Pollutant Measured: £_
Measurement Technique: Chemiluminescence (Bendix #8002)
Period of Record Examined: 26 June - 30 September 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: High 0 concentrations were recorded. Limited 0 data aloft were
also obtained.
75
-------
Data Source Number:
Station Name: Darien (SARQAD Code 513680099F05)
Location: Walworth County, Wisconsin (42° 38' N, 88° 40' W)
Responsible Organization: Wisconsin Department of Natural Resources
Cognizant Individual/Organization: Ronald W. Becker
Telephone: 608-266-7588
Type of Site: Rural - Agricultural
Type of Pollutant Measured:
Measurement Technique: Chemiluminescence (REM) and/or ultraviolet
Period of Record Examined: June-September 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 1,545 observations reported during this period. Monitoring in this
area is continuing in 1975.
76
-------
Data Source Number:
Station Name: Douglas
Loc at ion: Converse County, near Douglas. Wyoming (42° 55* N, 105 18* W)
Responsible Organization: Panhandle Eastern Pipeline Company
Cognizant Individual/Organization: Kenneth L. Ancell
Telephone:
Type of Site: Rural-remote
0
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: January - June 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: All 0 data recorded during this period were generally below 0.06 ppm.
A maximum of 0.076 ppm was measured on 21 June 1974
77
-------
Data Source Number: 10
Station Name: DuBois
Location: DuBois. Pennsylvania (41 ...10.' N. 78 44' W>
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalini (EPA/EBRD
Telephone: 919-549-8411
Type of Site: Rural
0
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: 14 June - 31 August 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: In addition to 00, other species such as hydrocarbons, NO . etc.. were
-* x.
measured. Some aircraft data on vertical 0 distributions were also obtained.
78
-------
Data Source Number: 11
Station Name: Ft. Lauderdale (SAROAD Code 101260100G03)
Location- Ft> Lauderdale, Florida (26° 07'N, 80° 09' W)
Responsible Organization: EPA Region IV
Cognizant Individual/Organization: Louis Nagler
Telephone: 3Q5-621-p561
Type of Site: Nonurban
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: January - June 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks:
79
-------
Data Source Number: 12
Station Name: Glendale (SAROAD Code 030320Q01G01)
Location: Glendale, Arizona (33° 33' 45". 112° 11' 15" W)
Responsible Organization: Maricopa County Health Dept.
Cognizant Individual/Organization: EPA Region IX
Telephone: 415-556-2320
Type of Site: Rural - near urban
0,
Type of Pollutant Measured: £_
Measurement Technique: Dasibi Ultraviolet
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, Tape, or Printout
Remarks: 1,808 observations reported during 1973-1974
80
-------
Data Source Number: 13
Station Name: Greenwich (SAROAD Code 070330004F01)
Location: Greenwich, Connecticut (41° 4' 37" N, 73° 41' 56 W
Responsible Organization: Conn. Dept. Envir. Protection
Cognizant Individual/Organization: EPA Region I
Telephone: 617-223-7210
Type of Site: Remote
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 5315 observations reported during 1973-1974
81
-------
Data Source Number:
Station Name: Kane
Location:
14
Kane, Pennsylvania (41° 40' N, 78° 47' W)
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalini (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured:
Measurement Technique:
Chemiluminescence (Bendix #8002)
Period of Record Examined: 26 June - 30 October 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: High 0-j concentrations were recorded. Limited 03 data aloft were
also obtained.
82
-------
Data Source Number: 15
Station Name: Lake Kabetogema
Location: Lake Kabetogema, Minnesota (48° 27* N, 93° 02' W)
Responsible Organization:
Cognizant Individual/Organization: Ned Meyers (EPA/OAQPS)
Telephone: 919-688-8146
Type of Site: Rural-Near Urban
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (MEG 1100)
Period of Record Examined: 18 July - 21 August 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: The measurements yielded low ozone values, with an hourly maximum
of 0.055 ppm. -
83
-------
Data Source Number: 16
Station Name: Las Cruces (SAROAD Code 320340010F01)
Location: Dona Ana County, New Mexico (32° 20' 20" N. 106° 49' 00" W)
Responsible Organization: State of New Mexico Envir. Improvement Agency
Cognizant Individual/Organization: EPA Region VI
Telephone: 214-749-1962
Type of Site: Rural-agricultural
Type of Pollutant Measured:
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 3,755 observations reported during 1973-1974
84
-------
Data Source Number: 17
Station Name: La Union (SAROAD Code 320340008F02)
Location: Dona Ana County, New Mexico (31° 55' 50" N. 106° 37' 50" W)
Responsible Organization: State of New Mexico Envir. Improvement Agency
Cognizant Individual/Organization: EPA Region VI
Telephone: 214-749-1962
Type of Site: Rural-agricultural
0,
Type of Pollutant Measured: f
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 7,616 observations reported during 1973-1974
85
-------
Data Source Number: 18
Station Name: Lewisburg
Location: Lewisburg, West Virginia (37 50' N. 80° 22' W\
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalinl (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix #8002)
Period of Record Examined: 26 June - 30 September 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: High near-ground °3 concentrations were recorded. Limited
data aloft were also obtained.
86
-------
Data Source Number: 19
Station Name: MacKenzie Environmental Center (SAROAD Code 510600001F03)
Location: Columbia County, Wisconsin
Responsible Organization: Wisconsin Department of Natural Resources. Air Pollution
Control Section
Cognizant Individual/Organization: EPA Region V
Telephone: 302-353-5250
Type of Site: Rural-industrial
0.
Type of Pollutant Measured: f_
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 12,665 observations reported during 1973-1974
87
-------
Data Source Number:
20
Station Name: Manitowish Waters
Location:
Vilas County. Wisconsin (46° N. 89° 54' w)
(6 miles south of Manitowish Waters on County K)
Responsible Organization: Wisconsin Dept. of Natural Resources
Cognizant Individual/Organization: Ronald W. Becker
Telephone: 608-266-7588
Type of Site: Rural
Type of Pollutant Measured: 3_
Measurement Technique:
Chemiluminescence (REM) and/or Dasibi Ultraviolet
Period of Record Examined: June - September 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: Monitoring in this area is continuing in 1975.
88
-------
Data Source Number:
Station Name: McConnelsville
Location: McConnelsville. Ohj.o (39° 57' M, Rl° p?' u)
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalini (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: 14 June - 31 August 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: In addition to 3, other species such as hydrocarbons, NOX, etc.
were also measured. Some aircraft data on vertical ^3 distributions were
also obtained.
89
-------
Data Source Number:
Station Name: McHenry
Location:
22
McHenry, Maryland (39° 36'N. 79° 16' W)
Responsible Organization:
Research Triangle Institute
Cognizant Individual/Organization: J. J. Bufaline (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured:
Measurement Technique:
Chemiluminescence (Bendix 8002)
Period of Record Examined: 26 June - 30 September 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: High near-ground °3 concentrations were recorded. Limitec^
data aloft were also obtained.
90
-------
Data Source Number:
Station Name: McHenry
Location:
23
McHenry, Maryland (39° 36' N. 79° 16' W)
Responsible Organization:
Research Triangle Institute
Cognizant Individual/Organization: J.J. Bufalini (EPA/ESRL)
Telephone: 919-549-841,1
Type of Site.: Rural
Type of Pollutant Measured: 03
Measurement Technique:
Period of Record Examined:
Chemiluminescence (Bendix 8002)
14 June - 31 August 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: In addition to 3, other species such as hydrocarbons. NO. etc, were
x
measured. Some aircraft data on vertical °3 distributions were also obtained.
91
-------
Data Source Number: 24
Station Name: McRae (SARQAD Code 271360028F03)
Location: Rosebud County, Montana (45° 45' 47" N, 106° 23' 09" W)
Responsible Organization: Montana State Air Quality Bureau
Cognizant Individual/Organization: EPA Region VIII
Telephone: 303-837-3895
Type of Site: Rural - Agricultural
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: _j Cards, tape, or printout
Remarks: 3570 observations reported during 1973-1974.
92
-------
Data Source Number:
Station Name: Miami Jetport (SAROAD Code 100860008P02)
Location: Pade County, Florida (25° 51 50" N, 80° 52' 10" W)
Responsible Organization: EPA Region IV
Cognizant Individual/Organization: EPA Region IV
Telephone: A04-526-5727
Remote
Type of Site:
0
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 4,187 observations reported during 1973-1974.
93
-------
Data Source Number: 26
Station Name: Miami West (SAROAD Code 10270009P05)
Location: Miami. FlorjLda (25° 50' 06/' Nr 80° 14' Q?" W>
(AT&T transmission station Hwy. 27 east of Tamiami Trial)
Responsible Organization: EPA Region IV
Cognizant Individual/Organization: Louis Naeler/EPA Region IV
Telephone: 305-621-0561
Type of Site: Rural - Near Urban
0
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or ptintout
Remarks: 3,176 Observations reported during 1973-1974.
94
-------
Data Source Number:
27
Station Name: Mt. Utsayantha
Location:
Mt. Utsayantha, New York (74° 37' W, 42° 24' N)
Responsible Organization: N.Y. State Dept. of Env. Conservation
Cognizant Individual/Organization: William N. Stasiuk
Telephone: 518-457-5276
Type of Site: Remote
Type of Pollutant Measured:
Measurement Technique:
Period of Record Examined:
Frequency of Observations:
Chemiluminescence
1 August - 17 August 1973
Hourly
Physical Form of Data Record: Printout
Remarks: High altitude location (3200 ft MSL)
95
-------
Data Source Number: 28
Station Name: Naples (SAROAD Code 102880001PQ5)
Location: Naples. Florida (26° 01' 31"N, 81° 43' 50" W) (on Rookery Bay)
Responsible Organization: EPA Region IV
Cognizant Individual/Organization: Louis Nagler
Telephone: 305-621-0561
Type of Site: Rural - Near Urban
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence (Bendix 8002)
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 3342 observations reported during 1973-1974.
96
-------
Data Source Number: 29
Station Name: Old Hickory (SAROAD Code 443320007F01)
Location: Sumner County, Tennessee (36° 17* 53" N, 86° 39* ll"W)
(10 miles northeast of Nashville)
Responsible Organization: Tenn. Dept. of Public Health, Div. of Air Pollution
Control
Cognizant Individual/Organization: EPA Region IV
Telephone: 404-526-5727
Type of Site: Rural-Industrial
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 13,104 observations reported during 1973-1974.
97
-------
Data Source Number: 30
Station Name: Poynette
Location:
Columbia County. Wisconsin (43° 24' N. 89° 28' W)
Responsible Organization:
Wisconsin Dept. of Natural Resources
Cognizant Individual/Organization: Ronald W. Becker
Telephone: 608-266-7588
Type of Site: Rural
Type of Pollutant Measured: 3
Measurement Technique;
Chemiluminescence (REM) and/or Dasibi Ultraviolet
Period of Record Examined: June - September 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: Monitoring in this area is continuing in 1975.
98
-------
Data Source Number: 31
Station Name: Prairie View
Location: Prairie View, Texas (30° 18' N, 95° 26' W)
Responsible Organization: Texas Air Quality Control Board
Cognizant Individual/Organization: Duane J. Johnson
Telephone: 512-451-5711
Type of Site: Suburban - Rural
0
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminexcence (MEG #1100)
Period of Record Examined: 1 May - 1 September 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: This site is located 40 miles north of Houston, Texas. Transport
from Houston was believed responsible for the high ozone values observed
at Prairie View. These measurements were part of the Goober III Study.
99
-------
Data Source Number: 32
Station Name: Queeny (Oxidant) (SARQAD Code 264300006G01)
Location: St. Louis County, Missouri (38° 59' 58" N, 91° 45' 46" W)
Responsible Organization: St. louis Co. Health Dept., Air Pollution Control Div.
Cognizant Individual/Organization: EPA Region VII
Telephone: 816-374-5493
Type of Site: Rural - Near Urban
0
Type of Pollutant Measured:
Measurement Technique: Neutral KI
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 14,683 observations reported during 1973-1974.
100
-------
Data Source Number:
Station Name: Queeny (Ozone) (SARQAD Code 2643QOQ06GQ1>
Location: St. Louis County. Missouri (38° 59' ,58" Hr 91° 4S' 46" w)
Responsible Organization: St. Louis Co. Health Dept. APCD
Cognizant Individual/Organization: EPA Region VII
Telephone: 816-374-549?
Type of Site: Rural - Near Urban
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence
Period of Record Examined: 1973-1974
Frequency of Observations: Hourly
Physical Form of Data Record: Cards, tape, or printout
Remarks: 1,823 observations reported during 1973-1974.
101
-------
Data Source Number:
34
Station Name: White Face Mountain
Location: White Face Mountain, New York (44° 20' N, 74° 05' W)
Responsible Organization; N.Y. State Dept. of Env. Conservation
Cognizant Individual/Organization: William N. Stasiuk
Telephone: 518-457-5276
Type of Site: Remote
Type of Pollutant Measured: 3
Measurement Technique: Chemilumineacence
Period of Record Examined: 1 August - 17 August 1973
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: Additional data have been obtained and will be made available shortly.
This is a high altitude location (4980 ft MSL).
102
-------
Data Source Number: 35
Station Name: Wilmington
Location: Wilmington Industrial Air Park, Ohio (39° 20' N, 83° 48' W)
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J. J. Bufalini (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured: 3
Measurement Technique: Chemiluminescence (Bendix8002)
Period of Record Examined: 14 June - 31 August 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: In addition to 3. other specj.es such as hydrocarbons. N0x. etc.
were measured. Some aircraft data on vertical ^3 distributions were also
obtained.
103
-------
Data Source Number:
Station Name: Wooster
Location: Wooster, Ohio (40 ° 50' N. 81° 56' W)
Responsible Organization: Research Triangle Institute
Cognizant Individual/Organization: J. J. Bufalini (EPA/ESRL)
Telephone: 919-549-8411
Type of Site: Rural
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (Bendix 8p02)
Period of Record Examined: 14 June - 31 August 1974
Frequency of Observations: Hourly _
Physical Form of Data Record: Printout
Remarks: In addition to 3, other species such as hydrocarbons. ^°x. etc. ,
were measured. Some aircraft data on vertical °3 distributions were also
obtained.
104
-------
Data Source Number: 37
Station Name: Yellow Pine
Location: Sabine National Forest. Texas (31 20' N, 94° 00' w)
Responsible Organization: Texas Air Quality Control Board
Cognizant Individual/Organization: Duane J. Johnson
Telephone: 512-451-5711 __
Type of Site: Rural - Remote
Type of Pollutant Measured: 3_
Measurement Technique: Chemiluminescence (MEG #1100)
Period of Record Examined: April - June 1974
Frequency of Observations: Hourly
Physical Form of Data Record: Printout
Remarks: This location is 85 miles north of Beaumont and 135 miles northeast
of Houston. "3 values exceeded 0.08 ppm only twice during this period.
Transport from urban sources was not responsible for high ^3 values.
Local synthesis was predominant.
105
-------
Data Source Number: 3J5
Station Name: Yellowstone Lake (SAROAD Code 511720001F05)
Location: Lafayette County, Wisconsin (42° 46' N, 89° 54' W)
Responsible Organization: Wisconsin Dept. of Natural Resources
Cognizant Individual/Organization: Ronald W. Becker
Telephone: 608-266-7588
Type of Site:
Rural
Type of Pollutant Measured:
Measurement Technique:
Period of Record Examined:
Frequency of Observations:
Chemiluminescence (REM) and/or Dasibi Ultraviolet
June - September 1974
Hourly
Physical Form of Data Record: Cards, tapes, or printout
Remarks: 3,205 observations were reported during this period. Monitoring in
this area is continuing in 1975.
106
-------
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Alley, F. C., and L. A. Ripperton, 1961: The effect of temperature on
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Cleveland, W. S., et. al., 1974: Sunday and workday variations in photo-
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/3-77-022b
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
The Relation of Oxidant Levels to Precursor Emissions
and Meteorological Features. Volume II: Review of
Available Research Results and Monitoring Data (as of
November 1975).
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
H.B. Singh, W.B. Johnson and E. Reiter
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
SRI International
Menlo Park, CA 94025
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-2084
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report was originally published as an Interim Report in November 1975.
Literature available at that time was reviewed and a summary was prepared describing
the processes affecting ozone concentrations in remote areas. The topics discussed
include ozone of stratospheric origin, natural tropospheric sources and sinks, and
long range transport in the troposphere. Selected research studies are abstracted
and 38 sources of ozone or oxidant data taken at remote locations are discussed. A
bibliography is included.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Tropospheric Ozone
Data Sources
Bibliography
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
128
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
125
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