EPA
United States
Environmental Protection
Agency
Office of Environmental Sciences Research
Research add Laboratory
Development Research Triangle Park, North Carolina 27711
EPA-600/7-77-056
June 1977
HYDROCARBON AND OXIDANT
CHEMISTRY OBSERVED AT A
SITE NEAR ST. LOUIS
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en*
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4, Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
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mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-77-056
June 1977
HYDROCARBON AND OXIDANT CHEMISTRY
OBSERVED AT A SITE NEAR ST. LOUIS
by
R.A. Rasmussen, R. Chatfield and M. Holdren
Washington State University
Pullman, Washington 99163
Contract No. 68-02-2254
Project Officer
Jack L. Durham
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
11
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ABSTRACT
Integrated quantitative gas chromatographic measurements of the nearly
one hundred individual hydrocarbons present in ambient air were made to deter-
mine the total non-methane organic burden at a midwest rural site in coordi-
nation with halocarbon, oxidant and local meteorological variables in July
and August 1975. Although the sample location was clearly rural, it was only
100 km north of St. Louis, Missouri. Consequently, four situations could be
distinguished at this site: clean rural air, transport from near urban
areas, transport from distant urban areas, and air-mass stagnation. In the
latter situation, the rural air was well mixed on a regional scale with
natural and anthropogenic ozone precursors. Fluorocarbon-11 and meteorologi-
cal data were used to identify and describe the four situations and to inter-
pret the observed concentrations of hydrocarbons and oxidant resulting from
local photochemistry and transport.
This report was submitted in fulfillment of Contract No. 68-02-2254 by
Washington State University under the sponsorship of the U.S. Environmental
Protection Agency. The data analysis of this project was funded through
Purchase Order No. DA-6-99-1993J. This report covers a period from June
30, 1975 to June 30, 1976, and work was completed as of June 30, 1976.
iii
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CONTENTS
Abstract iii
Figures v
1. Introduction 1
Sampling Site ; 2
2. Methods 4
Hydrocarbon Analysis 4
Halocarbon Analysis 5
Other Analyses 6
Field Data Summary 6
3. Overview and Air Chemistry Observations 8
4. A Clean Rural Situation: August 1 and 2, 1975 ... 13
Air Mass History 13
Hydrocarbon Composition 13
Oxidant Chemistry 14
5. The Urban Plume of St. Louis: August 8 through 10 . 18
Air Mass History 18
Hydrocarbon Composition 20
Oxidant Chemistry 21
6. The Urban Plume of a More Distant City:
August 6, 1975 23
Air Mass History 23
Hydrocarbon Composition 23
Oxidant History 26
7. Regional Air Chemistry During a Stagnation Situation:
August 12, 1975 28
Air Mass History 28
Hydrocarbon Composition 30
Oxidant Chemistry 30
8. Conclusions 34
Bibliography 35
Appendices
A. Hydrocarbon Data Tables for Sampling at Glasgow, IL 36
B. Halocarbon, Ozone and Wind Data and Graphs for
Sampling at Glasgow, IL 65
C, Urban-Tracer Compounds—Time-Series Plots for
Glasgow, IL Sampling 105
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FIGURES
Number
1
2
3
4
5
6
7
Hydrocarbon and Flurocarbon-11 measurements made at
Urban plume of St. Louis as perceived by ambient air
Passage of a high pressure system across the Midwest . .
Model of different transport regimes prevailing in
Page
3
9
15
19
24
25
different sectors of a slowly migratory anticyclone . 31
High oxidant observations during a period of apparent
regional buildup of fluorcarbons and oxidant precursors 32
TABLE
Light and Heavy Hydrocarbons
VI
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SECTION 1
INTRODUCTION
In July and August of 1975, Washington State University (WSU) carried
out an intensive measurement program to determine the species of hydrocarbons
and their concentrations in a clearly rural location that was often influenced
by emissions from the St. Louis urban area as well as other more distant pol-
lutant sources. The intent was to discriminate natural from anthropogenic
hydrocarbons and to apply this understanding to the involved chemistry that
results in hydrocarbon oxidation products such as ozone and aerosols. This
paper will concentrate on the general character of the hydrocarbons measured
at the rural site and on the oxidant behavior in the air masses that passed
over the study site. From the data at this one site, we extract four situa-
tions. These four serve as distinct examples of the interplay of meteorology
and chemistry in the photolysis of urban and rural hydrocarbons, and the
consequent production of elevated rural ozone levels.
The paper begins with a description of the Glasgow site near St. Louis,
Missouri, and the instrumentation WSU used to measure ozone, halocarbon and
hydrocarbon compounds, the latter species being present at concentrations
of just a few micrograms per cubic meter for individual components. The data
are summarized and incorporated into correlations that characterize the
entire sampling period. The halocarbon data also are compared with acetylene
data. Acetylene was used as a secondary tracer. The halocarbon and acetylene,
coupled with available weather information, implicate several different
cities as sources of the polluted air reaching Glasgow. This tracer and
meteorological information suggests that meteorological transport and hydro-
carbon photochemistry may interact in several distinct ways. For this reason,
we present case studies to describe four situations, which are classified as
follows:
-------
1) Remote: unambiguously clean and therefore accepted as character-
istic of air unaffected by any discernable urban contamination;
2) Near plumes: urban pollutant plumes with easily measurable levels
of primary pollutants still reacting in transit over the rural
study site;
3) Distant plumes: clearly marked fluorocarbon plumes, with most
of the reactive hydrocarbons consumed;
4) Regionally pollute'd: no plumes noticeable, but clear evidence of
photochemical oxidation of hydrocarbons and elevated oxidant.
Sampling Site
Washington State University operated its mobile unit at Glasgow, Illinois
from July 17 through August 14, 1975. The actual site was located 1/2 km
west of Glasgow (population 100) and 104 km from the Gateway Arch in St. Louis,
at a bearing of 345° (NNW of the Arch). The site area was rural farmland
primarily used for growing corn and soybeans (See map, Figure 1).
-------
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SCALE
Fieure 1. Map of the site area.
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SECTION 2
METHODS
HYDROCARBON ANALYSIS
Hydrocarbon analyses were performed using three Perkin-Elmer flame ioni-
zation gas chromatographs. Instrument one (PE model 990) analyzed hydrocarbons
from butane through decane (C, to C ). The column used was a 200-ft SCOT
OV-101, phase ratio a = 65, programmed from 0° to 100°C at 6°C/min. Helium
flow rate measured about 7 ml/min. Instrument two (PE Model 3920) quantified
hydrocarbons from ethane through hexane. A 20-ft by 1/16-in. outer diameter
(o.d.) stainless steel column packed with Durapak (n-octane/Porasil C) was
used. Separation was accomplished when programming from -70° to 65°C at
16°C/min with a flow rate of 7 ml/min of helium. The overlap in carbon
number between the two instruments provided a check in determining actual
concentrations of individual compounds. Total non-methane hydrocarbons then
were determined by summing the C~ through C, compounds on instrument two with
the C- through C.,,. compounds on instrument one. Instrument three (PE Model
3920) analyzed specifically for ethane, ethylene and acetylene and provided
another check on the precision between instruments. The column used was 5
ft by 1/8 in. o.d., filled with Porapak N, operated isothermally (55°C) with
a carrier flow rate of 30 ml/min helium.
Calibration was accomplished using neohexane as an external standard.
Response factors for all hydrocarbons were considered to be one. For example,
32 ng of neohexane has an area response of 1.00 on the PEP-1 computer. This
ratio, 32 ng/area of 1.00, is then multiplied by the individual peak areas.
The result for each peak is in nanograms per 1000 ml of sampled air, or the
equivalent of micrograms per cubic meter of sampled air. Summing the indi-
vidual hydrocarbons peaks gives a good indication of the total non-methane
hydrocarbon burden.
-------
Identification of the hydrocarbons was accomplished by periodically
injecting a set of standard compounds and then matching their retention times
with those from an actual sample. Those peaks with similar retention times
were named accordingly. Occasionally an actual sample was "spiked" with a
standard to further support identification.
The air samples (500 to 1000 ml) were obtained from the sampling manifold
with 100-ml ground-glass syringes. The air was passed through an enrichment
trap that was located in front of the head of the column. The liquid oxygen
Dewar flask used to facilitate the freezeout was replaced with one of hot
water (90°C) to assist the transfer of the contents of the traps onto the
analytical column.
HALOCARBON ANALYSIS
Halocarbon analyses were performed employing a Perkin-Elmer 3920 electron
capture (Ni 63) gas chromatograph. The column was fabricated with a 10-ft
by 1/4-in. o.d. stainless steel tubing packed with 10% SF-96 on Chromosorb W
(100-120 mesh). The column oven was operated isothermally at 45°C. Carrier
flow (95% Ar-5% CH4) was 50 ml/min.
Calibration was accomplished by preparing known concentrations in static
chambers in the home laboratory. Dilution of the appropriate amount of pure
halocarbon species into the chambers gave concentrations simulating ambient
air levels to a precision of + 10%. Reference canisters were then calibrated
and shipped to the field site for daily calibration of the instruments.
The ambient air sample was drawn through the sample loop (5-ml volume)
with a metal bellows pump (MB-41) hooked in line to the sampling manifold.
Automatic analyses of Freon-12, Freon-11, methyl chloroform and carbon tetra-
chloride were conducted every 20 minutes. Halocarbon identification was
accomplished by matching retention times with standards. Periodically, samples
were obtained outside the field laboratory to check against possible contami-
nation due to leakage in the gas sampling system.
OTHER ANALYSES
Continuous ozone measurements were also conducted to supplement the
hydrocarbon and halocarbon detection. The instrument used was a Meloy Model
OA 350-2. Zero and calibration checks were performed daily with a MacMillan
-------
Model 1000 ozone generator, which was calibrated in the laboratory by the
standard KI method prior to the field sampling period.
Various meteorological parameters were also recorded. These include
wind speed and direction, solar radiation, temperature, and dew point.
FIELD DATA SUMMARY
A summary table (Table 1) was constructed showing all the ambient
analyses of hydrocarbons during the entire study. In each square, the day,
the time, the C?-to-C, hydrocarbon concentration, and the C_-to-C^_ hydro-
carbon concentration totals are presented. The difference in the number of
analyses made in July versus August is due to a single 8-hour work shift
operated in July and three 8-hour shifts operated in August.
-------
TABLE 1. LIGHT AND HEAVY HYDROCARBONS SAMPLED AT
GLASGOW, IL; TIMES ARE CENTRAL DAYLIGHT TIME
GLASGOW
JULY 1975
, ILL.
AUGUST 1975
in ,ig/m
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-------
SECTION 3
OVERVIEW AND AIR CHEMISTRY OBSERVATIONS
Before we investigate the air chemistry of specific days, let us look
at the correlations that appeared to run through all the data. The halocarbon
and total non-methane hydrocarbon data are shown in Figure 2. Our expectations
were that the changes in the atmospheric concentration distribution of the
halocarbons would reflect their origins mainly for the cities. Thus, they
would be ideal tracers of the relative degree of urban contribution to the
air's composition measured at the rural site at Glasgow. The data were easily
interpreted by this view. Correspondinglyj the minimum concentrations ob-
served were interpreted to be indicative of clean background rural air. The
data show that the lowest Fluorocarbon-11 (CFC1-) concentrations were a mini-
mum of about 115-120 ppt, a magnitude characteristic of the northern hemi-
sphere background for this time period. Positive excursions from this base-
line occurred almost daily, sometimes only 5 or 10 ppt, sometimes 100 ppt or
more when the sampling site was obviously directly downwind of the urban area
of St. Louis. A distinguishing feature of the F-ll profile was its spiky
character, which seemed to indicate that pollutants were not being rapidly
dispersed by vigorous vertical stirring or horizontal transport. The ina-
bility of the fluorocarbon levels to fall to the minimum background level
after major excursions to elevated concentrations indicates that incomplete
dispersion resulted in the buildup of a fluorocarbon residuum level charac-
teristic of area-wide air-mass stagnation. The frequent occurrence of low
levels of fluorocarbons approaching the geographical background level of 115
ppt of that time suggests that Glasgow and St. Louis were generally upwind of
the major Midwest and Northeast urban source areas. Indeed, when the wind
persisted out of the east for two days (August 7 and 8), the minimum levels
of Fluorocarbon-11 were nearer 130 to 135 ppt. Under these latter conditions,
we believe we were observing halocarbon levels representative of a regionally
mixed residue of air of urban origin spread over the area.
-------
GLASGOW, ILL 1975
250
200-
Q.
Q.
O
L±J
IE
O
I
250
-200
MINIMUM BACKGROUND
15
, Figure 2. .Hydrocarbon and Fluorocarbon-11 measurements made at Glas-gow, IL.
Note fluorocarbon peak concentrations indicative of urban plumes.
-------
For hydrocarbons, the situation was more complex. Instead of measurinfa
a few chemical species as for the halocarbons, the hydrocarbon analysis con-
sisted of as many as 50 to 100 hydrocarbon species whose individual concen-
_3
trations were very low, but gave integrated totals of 50 ug m or more.
All of the non-methane hydrocarbon species are expected to be removed
by atmospheric oxidation processes. Thus, even ignoring dilution due to
diffusion or dispersion, the hydrocarbon loading of an air parcel will
decrease downwind from the city of origin. Individual hydrocarbons will
decrease at different rates, determined by their relative rates of reaction
and the oxidizing properties of their environment. This latter phenomenon is
controlled not only by the supply of sunlight, nitrogen oxides, ozone and
hydroxyl radical, but also by the combined effect of the hydrocarbons for
heterogeneous reactions with aerosols and the radicals formed in the atmos-
pheric photolysis.
In general throughout the entire study period, the total hydrocarbon
levels showed considerable variation under conditions that were not merely a
reflection of urban contamination. That is, they did not always correlate
well with the fluorocarbons. This suggests that rural sources may have had
a considerable source strength effect on the atmospheric burden as well as a
geographical or temporal variability. Lower values for total non-methane
_3
hydrocarbons (TNMHC) were around 30 yg m , with typical concentrations more
_3
in the range of 40 to 50 yg m . When the fluorocarbon trace showed clear
urban influence, the TNMHC loading could rise to 150-175 yg m~ . More
difficult to appreciate is the fact that sometimes the TNMHC values would
not rise at all in synchrony with conditions of significant increases in the
fluorocarbon values. Overall, the coincidence between Fluorocarbon-11 and
TNMHC spikes is good, although the relationship does not allow us to predict
peak hydrocarbon levels from the peak fluorocarbon levels.
For certain individual hydrocarbons, the relationship is much clearer.
Acetylene, for example, showed minimum concentrations of 0.2 to 0.5 yg m~^
when fluorocarbons were at baseline levels, and reached peak values of up to
_o
3 yg m simultaneously with the elevated fluorocarbon levels. Of course
as acetylene was measured only every two hours, the detail inherent in the
fluorocarbon record of three analyses per hour could not be reproduced in the
10
-------
hydrocarbon data. Additionally, there was more scatter in the lower acetylene
measurements because the sensitivity limits of the flame ionization detector
were being pushed to make the lowest acetylene measurements.
The data for the other light hydrocarbons (CL and C,) also correlated
fairly well with the fluorocarbon data. The hydrocarbons from C« through C^
were measured separately from the total hydrocarbon burden (TNMHC). This
fraction of the hydrocarbon burden correlated better with the Fluorocarbon-11
data than did the TNMHC. Ethane, propane and i-butane, along with acetylene,
seemed to contribute most to this correlation; propene and the butenes did
not correlate well. These observations concur with the fact that the latter
species display higher reactivity with oxidizing compounds or radicals and
therefore would react earlier and be removed from the air mass before it
reached the Glasgow site if hydrocarbons from distant sources were being
intercepted. Alternately, if the more reactive species (i.e., olefins)
measured at the rural site were of a local natural origin, they would not be
expected to correlate with the fluorocarbons.
The remainder of this report will be concerned with two related questions:
1) the origin of contaminated air reaching the interurban sampling
site at Glasgow, and
2) the nature of the hydrocarbon-oxidant chemistry that modulated
the concentrations of the trace substances observed.
We will address these questions through a series of case studies of the dif-
ferent sampling situations that were observed at the Glasgow site. The
limited weather information available makes the identification of sources of
the compounds measured ambiguous on the basis of the meteorology alone. Some
of the ambiguity is removed by using the halocarbon compounds to trace air
trajectories back to cities. The objective of these case studies is to recon-
struct the air movements and relate these to the oxidant chemistry. The
approach does not provide absolute certainty; however, the fact that similar
conclusions can be reached based on the oxidant profiles, weather information,
and the hydrocarbon data separately encourage the approach.
Rarely does a single day at the site appear to be completely clean or
constantly influenced by recent urban emissions. Thus the case studies must
use information from various days to construct a coherent picture of the
11
-------
pollution episodes that occurred at the Glasgow site. The spiky character
of the fluorocarbon records suggests that plume boundaries are well defined
in the data. The following chemical regimes identified describe most of the
situations intercepted at the rural site.
12
-------
SECTION 4
A CLEAN RURAL SITUATION: AUGUST 1 AND 2, 1975
AIR MASS HISTORY
Geostrophic winds on the surface charts for August 1 and the preceding
days indicate that the air moved in from the southeast, probably missing
urban areas. This is supported by the fluorocarbon trace shown in Figure 3.
The early hours of the day, from 0300 to 0800 CDT, showed CFC1- concentrations
of 130 to 140 ppt, noticea.bly higher than 115 ppt, the northern hemispheric
background at that time. However, from 0900 CDT on, fluorocarbon concentrations
dropped to values below 120 ppt, which indicated that very clean air was
moving over the station. Later in the day, showers in the unstable Gulf air
affected the area, blocking sunlight to the area, washing out the atmosphere,
and mixing in cleaner air from above. The very low fluorocarbon levels (<120
ppt) associated with this air did not persist for more than several hours.
By the next morning (August 3) the fluorocarbon levels had again begun to
increase from 125 to 140 ppt, and the clean episode had ended.
HYDROCARBON COMPOSITION
Total non-methane hydrocarbon was relatively low for August 1, especially
in the afternoon during a period of shower activity. The TNMHC ranged from
30 to 50 yg m . The low 30 yg m readings in the afternoon may well have
been due to rainout experienced at or upwind of the site. A more typical
range for hydrocarbon concentrations under clean conditions is from 30 to 70
_3
yg m . (These estimates are based on analyses of clean situations occurring
on other days at the Glasgow site, and on data from Elkton, Missouri, obtained
a few weeks later by the same instrumentation and field crew.) All of the
hydrocarbon measurements made during the August 1 and early August 2 time
frame seemed to be in the lower portions of their ranges in this weather
situation. During this same period the light hydrocarbon (C« to C,) concen-
13
-------
_0
trations ranged from 5 to 8 yg m , while the higher hydrocarbons (C^ to
r\
C12) totaled 25 to 50 yg in . All values decreased in the afternoon, possibly
due to rainout, as already mentioned, or due to the influx of hydrocarbon-
poor air from above the boundary layer to the surface. In addition, the dimi-
nution of the natural hydrocarbons source strength, with cooling temperatures
and subsequent reactions in the oxidant chcmis^y of the area that would
diminish the measurable hydrocarbon burden at the Glasgow site, is equally
possible.
OXIDANT CHEMISTRY
As Figure 3 illustrates, ozone concentrations were also relatively low
all day August 1, ranging from 13 ppb at 0700 CDT to 40 ppb by 1300 CDT.
Shortly after noon, clouds cut out the radiation, and the ozone declined to
20 ppb by late afternoon and early evening. A minimum of 5 ppb occurred at
_3
0800 CDT on August 2, while hydrocarbons were quite high at 78 yg m . Ozone
levels climbed rapidly to 24 ppb by noon, when F-ll was still only 129 ppt.
After this, ozone continued to rise, but higher fluorocarbon levels indicated
that the situation was no longer identifiable as "clean." By 1700 CDT,
fluorocarbons spiked to 150 ppt; ozone showed a corresponding spike and then
declined rapidly to a minimal value, only to increase briefly coincident with
another fluorocarbon spike just before midnight.
How characteristic are these ozone concentrations of a remote rural
situation? The data for August 1 and 2 suggest that the ozone studies under
clean conditions may or may not be controlled by an oxidant photochemistry—
that is, conditions which allow for both ozone creation as well as destruc-
tion. The clean situation of August 1 typifies the diurnal ozone profile.
However, the less clean situation of August 2 suggests that the afternoon
ozone may have declined because of a decline in vertical mixing related to
the cooling trend instituted by the shower activity, rather than a reduced
intensity of photochemically significant solar radiation. During midday
and into the afternoon, vertical mixing normally brings down ozone from the
free atmosphere above the boundary layer to ground level. This source can
significantly replenish surface ozone. Since the wind on August 2 fell after
1500 CDT, possibly due to the lesser radiative heating of the surface this
source was shut off. The ozone present then further decayed by reactions
14
-------
250
225
200
175
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GLASGOW, ILL.
8/2
MINIMUM BACKGROUND
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* RADIATION
16 20 0 4 8
HOURS
200
150
Q.
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M
O
100
I 15
50
ro
o
12 16 20 0
Figure 3. A clean rural situation: note the very low fluorocarbon-11
concentrations until noon on August 2.
15
-------
with surfaces and airborne trace substances, including hydrocarbons.
The rapid decrease in the August 2 afternoon ozone profile is consistent
with these conditions. The late evening rise with the sharp increase in F-ll
suggests that a residual urban plume intercepted the study site. This inter-
pretation is further supported by examining the events of August 1 that pre-
ceded the increase in the pollution burden observed on August 2.
On August 1, ozone decreased slowly to about 18 ppb at midnight, when the
wind dropped further and the hydrocarbons increased. The ozone continued to
decline to a minimum of 8 ppb at 0800 CDT on the next morning, while the hydro-
_3
carbon level continued to increase to 80 yg m . The fluorocarbon levels
during this same time had very gradually increased from 120 ppt to 125 ppt.
Not until later in the day (1700 CDT) did any significant spiking to 150 ppt
of the fluorocarbons occur. It is tempting to draw a connection; as the
naturally emitted hydrocarbons accumulated in rural air within an increasingly
shallow nocturnal surface layer inversion, the amount of ozone destroyed
correspondingly increased, reducing the ozone level to a minimum until it
could be replenished the next day by onset of the movement of increased
levels of anthropogenic oxidant or oxidant precursors into the study area.
Other typical rural clean nighttime regimes do not show as sharp a de-
crease as do the August 1 data. Generally, the ozone level does not decrease
below 25 or 30 ppb at night, as observed in Elkton, Missouri in 1974 and
1975. At observatories above the surface boundary layer, many nighttime
situations show a temporary increase in the ozone. These latter observations
of increased nighttime ozone are due to the cutoff of surface ozone scavengers
from below; i.e., natural and man-made emissions. This is quite typical of
the Whiteface Mountain Observatory in upstate New York. Data obtained at
Elkton, Missouri (to be reported separately; Rasmussen et al., 1976) show
the same order of variation in the ozone and hydrocarbons, however, with a
much greater stability in the fluorocarbon levels. The nighttime rise in
ozone under conditions that the fluorocarbon levels described as "clean" has
been observed by WSU at several widely different field sites. At Glasgow, a
rise of this kind was observed on July 19. The current explanation for
these nighttime rises in ozone observed below the nighttime inversion layer
are turbulent breakups of the overhead inversion layer. Such a break need
16
-------
not last long; if so, the replenishment needed to sustain the increased
surface level of ozone is soon cut off. When the source is cut off, the
ozone level is observed to decrease gradually to an early morning minimum
through further ozone-scavenging reactions. During persistent windy and
stormy periods, however, the surface ozone traces observed in rural areas
may give no sign of diurnal variability. Under these conditions, vertical
mixing is not controlled by surface heating, and there is not sufficient
short-wavelength radiation to augment the background ozone burden through
the natural photochemical production of ozone.
17
-------
SECTION 5
THE URBAN PLUME OF ST. LOUIS: AUGUST 8 THROUGH 10
AIR MASS HISTORY
From August 5 to 10, a large high-pressure system had settled slowly
over the Midwest from central Canada. The air pollution data for this period
is shown in part in Figure 4. Winds turned slowly from the northeast to east
to south as the high-pressure system continued to move to the southeast. Fig-
ure 7 shows the situation schematically following the migration pattern of
the slowly moving high-pressure system during this period. The daily minimum
fluorocarbon readings, which we may take as a relative index of the general
pollution level of the regional air mass, rose slowly. The rise began on
August 3, and was not significantly disturbed even by the passage of a very
weak cold front. The increase of the daily minima was from about 120 ppt on
August 3, to 130 ppt on the 9th, and 140 ppt on the 10th (Figure 4). This
increase in the minimal background level was gradual. A look at the surface
winds affecting the area leaves little doubt that the air samples intercepted
on August 8,9 and 10 originated from St., Louis.
The distinction between the pollutant plumes in Figure 4 is no doubt due
to specific features of the synoptic weather situation. The high-pressure
system just described was threatened on the 9th by an approaching cold front.
The front weakened steadily and dissolved, and it is doubtful any fresh air
mass was brought into the area. There was no decrease below the lowest
observed level of 130 ppt of the fluorocarbons during this period. As the
cold front approached, however, winds picked up and changed direction several
times, and each time the urban plume of St. Louis blew over the field
laboratory afresh.
The following are the details of the weather as taken from weekly weather
summaries. As the wind swung to the south, the fluorocarbon spike signalled
the presence of the plume observed at 1600 CDT on the 8th. An approaching
18
-------
250
225
GLASGOW, ILL.
200
FREONS
H.C.
. OZONE
A RADIATION
8 12 16 20
HOURS
Figure 4. Urban plume of St. Louis as perceived by ambient air measurements .at
Glasgow. Note the differing behavior of ozone during night and day plume episodes.
-------
squall line propagating ahead of the cold front of the 9th produced a meso-
scale shift in the wind which allowed a second strong influx of city air
seen to be intercepted at the Glasgow site at about 0600 CDT on the 9th. In
this case, fog reported at synoptic stations indicated (for the area around
the Glasgow site) that the transport had taken place beneath a fairly strong
inversion. (Further support for this inteipret^tion may be available in the
acoustic sounder data obtained at the rite for EPA.) A further wind shift
brought the fluorocarbon concentrations down to about 130 ppt for several
hours. As the high-pressure system slowly arched back into the area that
evening, the winds shifted again to the south and slowed. By 0100 CDT on the
10th, the pollutant plume of St. Louis over the Glasgow site had become
increasingly strong, as indicated by its multiple character of several plumes
of different intensity. Once again fog developed at the weather stations in
the area, indicating a strengthening nocturnal inversion.
HYDROCARBON COMPOSITION
The similarity of the hydrocarbon (TNMHC) and halocarbon traces in
Figure 4 helps to confirm an urban origin of the oxidant observed at the
rural site for the three days of August 8, 9 and 10. Notice the fluorocarbon
spikes occurred at the same time as spikes in the TNMHC. There does not seem
to be a one-to-one correspondence, for the relative heights of the TNMHC peaks
_3
of 70, 150 and 80 yg m varied considerably, while fluorocarbon peaks were
of almost equal magnitude, 201, 215, to 225 ppt. There are enough expected
differences in the diurnal emission patterns of the hydrocarbons and halocarbons
released in the St. Louis area that the correlation should not be one to one.
Differing diurnal and spatial variations in the source strengths of the gases
exist; however, another explanation also is suggested by the data. If we
assume that the ratio of halocarbon and hydrocarbon started out from St. Louis
in about equivalent amounts, then the reaction of the hydrocarbon during the
transit time might be reflected in the data. This second explanation is also
supported by some of the hydrocarbon information itself, namely the acetylene
concentrations. Peak acetylene concentrations at Glasgow on August 8, 9 and
10 were almost equal—just as were the peak fluorocarbon levels. We assume
that no significant photolysis occurred to acetylene in transit from St. Louis.
Also, from sampling evidence, the proportion of acetylene in urban emissions
20
-------
was roughly constant. If we assume that auto exhaust emissions were the
prime hydrocarbon source, the acetylene tracer quantity would support the
contention that original hydrocarbon burdens of the plume air were equivalent.
The radiation conditions that affected the plume in transit to the Glasgow
site complete the story. The two hydrocarbon plumes with the lower TNMHC
_3
burden, 70 and 80 yg m , were sampled in Glasgow in the late afternoons and
evenings of August 8 and 10. However, the plume with the maximum hydrocarbon
burden was intercepted in the very early morning hours (0100 to 0700 CDT) on
August 9. Obviously the nighttime transit of the August 9 plume would
preserve its hydrocarbon burden from any appreciable photochemistry. There-
fore, we believe that the equivalent fluorocarbon and acetylene concentrations
observed for all three plumes and the greatly divergent hydrocarbon burden
observed only for the nighttime plume strongly support the approximate 50%
loss in the hydrocarbon through subsequent atmospheric reactions in the two
plumes intercepted after a day's irradiation. The above proof is not rigorous
but does have a consistency with the observed facts.
In summary, due to varying chemical and physical conditions, the three
plume samples detected on these three days had lost differing amounts of hydro-
carbon en route to Glasgow. Under these conditions the dominant variation is
no doubt the amount of solar radiation necessary for photolysis and the time
for reaction that the plume constituents experience en route.
OXIDANT CHEMISTRY
A more subtle, more suggestive feature of the concentrations observed
during the study at Glasgow is that if we add the magnitudes in the units
_3
given for the hydrocarbon (yg m ) and ozone (ppb v/v), the sum has a trace
almost identical in shape to the fluorocarbon trace. This can be construed
_3
to mean that 1 yg m of carbon oxidized produces 1 ppb of ozone. In other
words, about 1.6N carbon atoms in various hydrocarbon compounds oxidize in a
process that gives N molecules of ozone. This formula is, of course, not
very rigorous. We believe it works in this case because essentially the same
hydrocarbon-NO mixture is sampled after approximately a constant time lag
X
from the point of emission. Since N0« is an oxidized species that photo-
dissociates extensively to produce ozone in daylight, it should be added into
the model. We did not measure N0? because the expected low concentrations at
21
-------
the Glasgow site are extremely difficult to measure accurately and routinely
under field conditions.
Ozone during the plume intercept situations acted very much like man-
made ozone observed within a city. When the St. Louis urban plume passed
over Glasgow on the afternoon of the 8th, the early morning St. Louis city
emissions had, by mid-afternoon, reacted (and diluted) to produce a 130-ppb
ozone concentration over the Glasgow farmland. The St. Louis ozone plume
then wandered and was not measured at the site for several hours. But early
in the morning of the 9th (0600 CDT) the ozone level in the plume over the
site had dropped to 12 ppb. The evening of the 10th shows a similar process
of maxima and minima ozone levels associated with the day versus nighttime
interceptions of the St. Louis plume. Presumably, Glasgow on the 10th was
not yet under the plume centerline, as identified by the fluorocarbons, but
ozone concentrations had reached 95 ppb by 2000 CDT. We believe this illus-
trates that in the plume downwind of a city, the surface concentrations of
the pollutants are consistent with the major diurnal features acknowledged
for urban smog-type chemistry. That is, at night the hydrocarbons and other
oxidant scavengers build up, and ozone diminishes rapidly as the photochemical
mechanisms are extenguished. Counter to this is the persistence of the
ozone levels observed in city plumes above the nighttime surface inversion.
22
-------
SECTION 6
THE URBAN PLUME OF A MORE DISTANT CITY: AUGUST 6, 1975
AIR MASS HISTORY
As the high-pressure system previously considered settled into the Mid-
west between August 8 and 10, with the multiple interception of the St. Louis
plume, so did the Glasgow site also experience afi earlier set of air pollu-
tion episodes of a more general nature. On August 5 and 6, the urban plume
from a more distant city that St. Louis was intercepted. This is shown by
the very large increase in the Fluorocarbon-11 level to 207 ppt observed at
0200 CDT (Figure 5). In this case, the wind had been persistently blowing
toward St. Louis. Geostrophic winds on the southeast side of the high-pressure
center—Figure 6 shows that the high was then centered over the upper peninsula
of Michigan—had been blowing from the northeast, and the surface winds
naturally had a more northerly component. The origin of this air mass with
its high fluorocarbon level cannot be absolutely proved; however, we suspect
that it came from Chicago, 270 km to the northeast. Trajectories based on
surface winds certainly allow this origin. Surface winds are more appropriate
for transport within a nocturnal inversion. The geostrophic winds consistently
implicate both near and distant cities. In addition, the intensity of the
elevated fluorocarbon episode suggests that the source's strength was rela-
tively large or relatively near. However, the hydrocarbon and oxidant
information suggest that the city was not near.
HYDROCARBON COMPOSITION
Hydrocarbon concentrations in aggregate showed hardly any change during
the intercept of the urban plume on August 6. TNMHC data showed variations
similar to the variations observed for many relatively clean days. Specifi-
_3
cally, it increased from about 40 to about 66 yg m and then fell again to
_3
50 yg m during the course of the highly elevated fluorocarbon epidose.
23
-------
250
225
200
GLASGOW, luL.
175
o.
Q.
- 150
i
O
125
I 15
100
75
o I
<
tr
a:
8/5
8/6
FREONS
H.C.
OZONE
RADIATION
12
16
20 0 4
HOURS
12
16 20
200
150
a.
D.
z
o
N
O
100
I 15
Figure 5. Urban plume of a more distant city. Note the sharp oxidant
increase at 2 CDT as the plume, signaled by a fluorocarbon-11 spike,
passes over the field laboratory.
24
-------
Figure 6. Passage of a high pressure system across the Midwest from August
6 through 12, 1975. The 1012 mb isobar and center of the high (H) are plotted
to give a general impression of the circulation for that period. Winds
generally blew parallel to the isobars in the directions shown.
25
-------
Previous day concentrations as high as 69 yg m had occurred on August D,
when the fluorocarbon levels were at very low levels (around 125 ppt)• On
the other hand, light hydrocarbons, with the exception of propene, increased
-3
during this period. Acetylene showed peak values of 1.6 yg m at the time
of the fluorocarbon spike. This would suggest a more distant transport. Iso-
prene showed a clear decline during this period. It reached its lowest
values an hour or so after maximum urban fluorocarbon exposure. This is con-
sistent with its diurnal pattern for minimum values early in the morning.
OXIDANT HISTORY
Ozone showed a clearly related increase during this nighttime urban-air
exposure, identified by the rapid rise in the fluorocarbon levels. Ozone
increased from 9 ppb to 28 ppb in parallel with fluorocarbon increase, with
coincident rapid rise in the fluorocarbon levels in the middle of the night.
This behavior contradicts the oxidant behavior observed in the St. Louis
plume. In the latter situation, urban plumes sampled in the early morning
hours showed anomolously low ozone concentrations compared to nighttime clean-
air situations. In other words, the close-in urban plumes show an ozone
pattern similar to the city ozone pattern. Counter to the St. Louis plume
situation, the interception of the Chicago plume shows an increase of ozone
through the nighttime hours with a gradual rise in the hydrocarbons. The
anomalies are explainable in terms of transport from a relatively distant
city. Presumably, the hydrocarbon emissions from Chicago have already under-
gone one day of photochemical oxidation. The photochemically reactive hydro-
carbons, have already been oxidized; e.g., propene, which explains why the
chromatogram showed essentially paraffinic materials. Isoprene entrained from
natural sources in the rural air mass has been similarly consumed by the pre-
sence of high concentrations of ozone and other oxidants in the plume. Un-
j
reactive compounds, e.g., acetylene, remain and are observed to increase with
the increasing fluorocarbon levels. By the second day, photochemical produc-
tion of ozone has slowed for lack of further injection of high levels of
reactive hydrocarbons and/or other requisite species such as NO . Similarly
X
in the evening, ozone consumption has decreased, and the nocturnal values
remain relatively high. Toward the sides of the plume where greater penetration
26
-------
of outside air has occurred, reaction with natural or local anthropogenic
hydrocarbons may have reduced the ozone.
This model is quite consistent with our 1974 observations at Whiteface
Mountain in northern New York state, where high nighttime ozone concentrations,
up to 60 ppb, were observed moving through the Adirondak sampling site in the
early morning, in the company of distinct increases in the fluorocarbon level.
27
-------
SECTION 7
REGIONAL AIR CHEMISTRY DURING A STAGNATION SITUATION: AUGUST 12, 1975
Up to this point, we have considered the rural situation as it experi-
enced the influence of an urban plume, or was remote from such influence.
Monitoring the Fluorocarbon-11 as a tracer of urban activity has allowed
this discrimination to be well defined. Previous oxidant chemistry studies
have had 'to identify these patterns of the interception of "dirty" or "clean"
air masses with less precise data. However, the occurrence of dirty vs.
clean air-mass conditions is not limited to the distinct interception of
local or distant urban plumes. Rather, during periods of stagnation—charac-
teristic of certain periods in the life of a slowly migratory anticyclone—
there may be widespread buildup of oxidant precursors within the boundary
layer of the lower atmosphere that extends over both the urban and rural
area. Nitrogen oxides and hydrocarbons from natural, industrial and urban
sources may accumulate sufficiently to elevate the ozone levels through
smog-type photochemistry that would cover large areas. In addition, some
discrete ozone concentrations will be found in the path of the plume that
continues to emanate from cities. The influence of anthropogenic oxidant
precursor emissions in rural areas by its nature must be complex.
In this section, we present data for a situation of this type which is
best described by the mix of emissions from various sources, and which
exhibits its own local photochemistry that is reflected in area-wide oxidant
i
levels that are not solely of natural origin.
AIR MASS HISTORY
In the overview section of this paper, we described a rise in the fluoro-
carbon baseline from 115 ppt on August 1 to 130 ppt by the 12th of August
1975. This gradual rise in the baseline was suggested by the lowest F-ll
value for each day in Figure 2. In general the lower concentration of these
28
-------
observed fluorocarbon levels did not vary much except for periods of one to
several hours duration when the fluorocarbon level significantly spiked. These
dramatic increases were interpreted as the interception of urban plumes. Under
conditions of shifting winds, the minimum levels used to construct the fluoro-
carbon baseline are characteristic of the extent of the influence of dispersal
of urban emissions in the air mass moving over the sampling station. The
extent of this influence is the air within one or two days journey of the
station. The increased levels of the halocarbon measurements do not represent
an increase of F-ll in global background level. Neither was the analyzer
experiencing a drift in sensitivity—for the reproducibility of the Fluoro-
carbon-11 analyses was 2-3 ppt. The conclusion is that increase in F-ll
minimal levels above the global background baseline and the related increases
by all other species in the Illinois-Missouri region was due to regional
accumulation of anthropogenic and natural emissions during the study period.
The meteorological description of the situation also concurs with these
interpretations of the air-chemistry data. The last distinct influx of clean
air was on August 2, with the advance of the leading edge of a high-pressure
system cutting into the area from the north, introduced by an active, rainy
cold front. This same anticyclone drifted southeastward, as shown previously
in Figure 6. The air trajectories for the pressure system circulated through
or from the eastern United States during this period. The high-pressure system
was slow to leave the area, and a new, threatening cold front to the north
affected winds in the area with south winds as described in the discussion of
August 8 and 9. These later days were associated with the St. Louis plume
situations. However, throughout this period from August 1 to 12, the air mass
as a whole had not been washed by rain or diluted by surface winds from cleaner
regions. According to geostrophic wind calculations, even air parcels arriving
at the site from the south on the 10th had probably been over Indiana or Ohio
a day or so previously. Significant haze and limited visibility situations
were noted on the evening weather charts for the 10th and llth. Similarly,
on the 12th, the day of interest here, winds from the southwest brought in
air which had apparently been over the more populated states east of Glasgow
a day or so before. The increased speed and the southwesterly direction of
the winds on the 12th was due to the approach of a new cold front over Iowa,
200 miles to the northwest.
29
-------
We may examine the August 12 situation from a viewpoint previously de
scribed for Ohio in the summer of 1974. In the context of the slowly migra-
tory high-pressure system model of Westberg and Rasmussen (1975), the Glasgow
sampling site was now on the northwestern side of the high-pressure system.
The center of the front was over Alabama and retreating southeastward. It
was to pass out to sea in two days, by the 14th. Figure 7 places Glasgow
in terms of this model. According to Westberg's model, this position of the
site relative to the center of the high-pressure system favors long-distance
transport of oxidant plumes and the general admixture of dispersed urban
sources jsuch as to account for the area-wide accumulation of elevated air
pollution episodes.
The plumes detected by the F-ll analyses of the 12th were, however, rela-
tively minor. Slow, variable winds carried to the site two distinct episodes
of fluorocarbon-enriched air, at the beginning and end of the day (see Figure
8). These air parcels probably had a recent urban origin, because for those
times the wind blew to the south from the St. Louis area. Between the epi-
sodes of elevated fluorocarbon, the wind was from the west-southwest for much
of the day. The significantly higher baseline F-ll concentrations (133 ppt)
observed between the episodes compared to the baseline levels (115 ppt) ob-
served in early August suggest that the source of the increased pollution
residuum is a regional airmass-air chemistry phenomenon.
HYDROCARBON COMPOSITION
Throughout this interval, from 0200 CDT to 1800 CDT on the 12th, total
hydrocarbon content (TNMHC) levels remained relatively high at 74 to 92
_3
yg m . Acetylene was only slightly elevated above the characteristically
-3 — "3
clean rural levels, averaging about 0.3 to 0.5 yg m rather than 0.2 yg m .
Olefins like ethylene and propene were at rural levels (0.6 and 0.3 yg m~^
respectively), but many light alkanes, especially ethane, were high. Many of
the higher-molecular-weight hydrocarbons were also at higher levels, including
— o
isoprene, which contributed from 4 to as much as 18 yg m (5 to 20%) to the
total hydrocarbon loading during the day of the 12th.
OXIDANT CHEMISTRY
Ozone remained above the National Ambient Air Quality Standard, 80 ppb
30
-------
|GLASGOW-I2AUG.|
SOUTH WINDS
GLASGOW 8-10 AUG.
CENTER
OF
HIGH PRESSURE
NORTHEAST
WINDS
I GLASGOW-6 AUG.
Figure 7. Model of different transport regimes prevailing in different
sectors of a slowly migratory anticyclone. Position of Glasgow, IL relative
to the moving center of high pressure is shown for various situations
described in the paper.
31
-------
250
225L
GLASGOW, ILL.
200
FREONS
H.C.
OZONE
RADIATION
Figure 8. High oxidant observations during a period of apparent
regional buildup of fluorocarbons and oxidant precursors.
32
-------
for five hours during the middle of the day, when there was no direct evidence
of the St. Louis plume in the area (see Figure 8). The midday maximum was
90 ppb. Later in the day, a south wind apparently brought in the plume,
judging from the F-ll concentrations. Under this condition, the ozone in-
creased to more than 100 ppb at 2200 CDT.
The midday oxidant maximum was accompanied by a minor decrease in the
hydrocarbon levels, and coincided with the maximum solar radiation.
The clearest consistent picture to emerge from the air chemistry of
this day is that ozone was produced in a rural area that had natural and
diluted urban hydrocarbons that were spatially well mixed. The urban hydro-
carbons with greatest reactivity, such as ethylene, propene and other olefins,
had already been consumed by photochemical oxidation as they travelled their
first day or so from the source area. Nevertheless, considerable photo-
chemical oxidant is produced from these emissions, either during their first
day of irradiation or subsequent days of irradiation through continued reac-
tions of the more slowly reacting urban hydrocarbons or from naturally emitted
hydrocarbons such as isoprene, which were abundant in the rural air.
33
-------
SECTION 8
CONCLUSIONS
For some time, there have been arguments over the source of oxidant
levels measured in rural areas, particularly those approaching or exceeding
the federally-mandated ambient air quality standard of 80 ppb. The more
pertinent questions concerning its origin are:
1) Is the oxidant produced in cities and transported into the rural
areas?
2) Is it manufactured en route to a rural site from urban precursors?
3) Is there region-wide production of elevated ozone over rural and
urban areas alike?
The evidence suggests that, in the region around St. Louis, each mode of
chemistry has its validity under different meteorological circumstances. We
have seen sharply defined urban plumes, containing high oxidant levels of
recent urban origin, as well as other plumes in which the oxidant level has
decreased (along with diurnal variation of that oxidant) in traveling dis-
tances of several hundred kilometers. Also, situations of moderately elevated
oxidant were observed at times when fluorocarbon and hydrocarbon tracers
identified air of recent urban origin, but no urban plumes. All of these
situations can be expected given the complexity of the meteorological
mixing processes.
Other conclusions also stand out. Hydrocarbons, individually and col-
lectively, are relatively variable in concentration within the period of one
day. Natural sources appear to be as important as anthropogenic sources in
rural areas. There is evidence for different degrees of reactivity of the
various hydrocarbons that compose urban plumes, resulting in variable levels
of associated ozone.
-------
BIBLIOGRAPHY
Rasmussen, R.A., R.B. Chatfield, M. Holdren, and E. Robinson. 1976. Hydro-
carbon Levels Observed in a Midwest Rural Open-Forested Area. Technical
Report being submitted to the Coordinating Research Council. Contract
Number CAPRAC-11, September, 1976.
Westberg, H.A. and R.A. Rasmussen. 1975. Measurement of Light Hydrocarbons
in the Field and Studies of Transport of Ozone beyond an Urban Area.
Monthly Technical Report on Contract Number 68-02-1232. U.S. Environ-
mental Protection Agency. To be published as an EPA Report.
35
-------
Appendix A
Hydrocarbon Data Tables for Sampling at Glasgow, Illinois
The following tables summarize the gas chromatographic measurements made
at Glasgow, Illinois. Seventeen individual compounds, those generally present
in the highest concentrations, are listed next to the time the sample was
analyzed. The integrated concentration of the remaining peaks is reported
as #19, "others." In addition, three other sums are reported: #8, the Light
Hydrocarbons, a sub-total of the C? - C, hydrocarbons; #20, the Heavy Hydro-
carbons, a sub-total of the CL - C,,, hydrocarbons; and the grand total, labeled
#21, Non-Methane Total Hydrocarbons. Blanks or "N/A" in the columns indicate
that no data is available; dashes (—) indicate that quantities were below the
0.2 micrograms per cubic meter detection limit. See Section 2 of the body of
the report for more information on the two gas chromatographs used and their
standardization and properties.
36
-------
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©OTHER PROBABLE HYDROCARBONS (g) 2COL9THRU COL.I9 ©ICOL8 AND COL.20
63
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GLASGOW, ILL
JULY 1975
AUGUST 1975
C2 THRU C4
C5 THRU C|0
in
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03
-------
Appendix B
Halocarbon, Ozone, and Wind Data and Graphs for Sampling
at Glasgow, Illinois
The following tables summarize the halocarbon, ozone, wind and radiation
measurements made continuously at Glasgow, Illinois. Units for each variable
are indicated at the column heading. See the body of this report for
description of measurement technique.
We find the graphs presented a clear way of summarizing the data. Cloudy
and stormy days are indicated by irregular radiation profiles and clear days
are indicated by sinusoidal radiation profile. Urban air intrusions are
clearly marked by sudden increases in the fluorocarbon-11 concentration above
a minimum baseline value.
65
-------
25
22
20
175
Q.
Q.
= 150
ul 125
100
75
ci I
<
OL
a:
GLASGOW, ILL.
T7/I7
200
• FREONS
a H.C.
• OZONE
* RADIATION
i i i i i i i i .1 i i i i I I 1 l 1
12
16 20
8 12 16 20
HOURS
0
12
16
20
-------
250
GLASGOW, ILL.
2OO
225
7/20
• FREONS
o HC.
• OZONE
A RADIATION
150
8 12 16 20
HOURS
4 8 12 16 20 O
-------
250
GLASGOW, ILL.
200
FREONS
KC.
OZONE
RADIATION
0
-------
25Q
GLASGOW, ILL.
f
200
7/25
7/26
FREONS
H.C.
OZONE
RADIATION
12
16 20
8 12 16
HOURS
20
12
16
20
-------
250
225
GLASGOW, ILL
200
HOURS
-------
250
225
GLASGOW, ILL
200
FREONS
HC.
OZONE
RADIATION
048
12
16
HOURS
-------
25
22
GLASGOW, ILL
200
• FREONS
o HC.
• OZONE
A RADIATION
8 12 16
HOURS
-------
250
225.
GLASGOW, ILL.
200
• FREONS
" KC.
• OZONE
RADIATION
16 20
8 12 16 20
HOURS
12
16
O
20 0
-------
25
GLASGOW, ILL.
200
FREONS
HC.
. OZONE
A. RADIATION
HOURS
-------
250
225.
GLASGOW, ILL
200
0 4
12
16 20
HOURS
-------
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-------
Appendix C
Urban-tracer Compounds — Time-series Plots for
Glasgow, Illinois Sampling
The following graphs compare the time histories of fluorocarbon-11,
carbon tetrachloride, and acetylene at Glasgow, Illinois. The halocarbon
measurements were made hourly; acetylene measurements were made less frequently,
namely in conjunction with the other hydrocarbon measurements. Despite the
lesser sensitivity and reproducibility of the flame-ionization detector tech-
nique used for acetylene, and its low rural values, we find that fluorocarbon-11
and acetylene agree very well as tracers of urban activity. Carbon tetra-
chloride (CC1.) has sources that are less easy to describe, and this may
account for the different nature of the CC1, trace.
105
-------
250
GLASGOW, ILL.
C\-
_!_
'"'I
1 !
t
.iV
*
i * i t i T i
0
8
12
16 20
8 12 16
HOURS
20 0
8
12 16 20 0
-------
250,
GLASGOW, ILL.
ro
-
_ ,
0. ' Tii t i i i7*i !
0
8 12 16
HOURS
20 0
8
12 16 20 0
-------
250
225.
GLASGOW, ILL
i°i ? i 7 i Ti i i i I i i it
I I ! 1 I I I I I I I I I I I .1 I I I I I I I I I I I I I I I I I I
0
8 12 16
HOURS
-------
250
225^
GLASGOW, ILL.
I 00
0
i i i i i i i i i i i i i i i I i i i i i
i i i i i i i i r i i i i i i .1 i I i i I i i i i i i i i i i i i i i i i i i i i
0
8
12
16
20
8 12 16
HOURS
20
O
12 ' 16
20
0
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
W0-R6T0N0°/7-77-056
3. RECIPIENT'S ACCESSIOI*NO.
4. TITLE AWDSUSTITLE
HYDROCARBON AND OXIDANT CHEMISTRY OBSERVED AT A
SITE NEAR ST. LOUIS
5. REPORT DATE
June 1977
6. PERFORMING ORGANIZATION CODE
7, AUTHOR(S)
R.A. Rasmussen, R. Chatfield and M. Holdren
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Washington State University
Pullman, Washington 99163
10. PROGRAM ELEMENT NO.
EHE625 EA-18 (FY-76)
11. CONTRACT/GRANT NO.
68-02-2254
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTF, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final 6/75-3/76
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
The data analysis of this project was funded through Purchase Order No.
DA-6-99-1993J.
16. ABSTRACT
Integrated quantitative gas chrotnatographic measurements of the nearly one
hundred individual hydrocarbons present in ambient air were made to determine the
total non-me'chane organic burden at a midwest rural site in coordination with
^ocarbon, oxidant and local meteorological variables in July and August 1975.
Although the sample location was clearly rural, it was only 100 km north of
St. Louis, Missouri, Consequently, four situations could be distinguished at this
site: clean rural air, transport from near urban areas, transport from distant
urban areas, and air-mass stagnation. In the latter situation, the rural air was
well mixed on a regional scale with natural and anthropogenic ozone precursors.
Fluorocarbon-11 and meteorological data were used to identify and describe the
four situations and to interpret the observed concentrations of hydrocarbons and
oxidant resulting from local photochemistry and transport.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
COSATl Field/Group
*Air pollution
-•Ozone
''Hydrocarbons
Gas chromatography
^Photochemical reactions
Meteorological data
St. Louis, MO
13B
07B
07C
07D
07E
04B
3. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
115
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
110
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