Ecological Research Series
ISOTOPIC COMPOSITION OF
CARBON MONOXIDE IN
ST. LOUIS, MISSOURI AREA
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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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 five series. These five broad
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The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/3-76-010
April 1976
ISOTOPIC COMPOSITION OF CARBON MONOXIDE
IN ST. LOUIS, MISSOURI AREA
by
L. E. Ross, A. Engelkemeir, and E. E. Voiland
Chemical Engineering Division
Argonne National Laboratory
Argonne, Illinois 60439
Contract No. EPA-IAG-069
Project Officer
Joseph J. Bufalini
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication. 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.
ii
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ABSTRACT
The concentration and isotopic composition of carbon monoxide
were determined for air samples taken in the vicinity of St. Louis,
Missouri, to provide information as to the movement of the pollutant
plume from the city. Urban air was detected as far as 48 miles downwind
of St. Louis; however, movement of the pollutant plume was not detected.
The effect of engine carbon monoxide produced along a highway in a rural
area was found to be minimal three miles downwind of the highway.
Diurnal studies demonstrated an inverse relationship between carbon
monoxide concentration and oxygen and carbon isotopic ratios during
the night. A parallel relation prevailed during the day.
iii
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CONTENTS
ABSTRACT iii
LIST OF FIGURES vi
LIST OF TABLES vii
ACKNOWLEDGMENTS viii
I INTRODUTION 1
II CONCLUSIONS 3
III RECOMMENDATIONS 4
IV EXPERIMENTAL PROCEDURES 5
V EXPERIMENTAL CONDITIONS 6
VI RESULTS AND DISCUSSION 8
VII REFERENCES 36
VIII APPENDICES 37
v
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LIST OF FIGURES
No. Page
1 PPM CO «(18o/160)SMOW and 5(13c/12c>pDB VS' TIME IN ST' LOUIS> 9
MISSOURI, AND VICINITY.
2 DIURNAL STUDIES, PPM CO, 6(180/160)_._fT and 8(l3C/l2C)-n., VS. 16
oMOW rUJi
TIME IN ST. LOUIS, MISSOURI, AND VICINITY.
3 OXYGEN VS. CARBON ISOTOPIC RATIOS FOR DIURNAL STUDY. 19
4 PPM METHANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 27
5 PPB ETHYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 28
6 PPB i-PENTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 29
7A PPB n- & CYCLO-PENTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND 30
VICINITY.
7B PPB PROPYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 30
8 PPB ETHANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 31
9 PPB PROPANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 32
10 PPB ACETYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 33
11 PPB n-BUTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 34
12 PPB 1-BUTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY. 35
vi
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LIST OF TABLES
No. Page
1 Atmospheric Carbon Monoxide Concentrations and Isotopic 10
Compositions for Samples Collected in St. Louis, Missouri
2 Wind Direction, Wind Speed and CO Concentration for Three 12
St. Louis County Air Monitoring Stations
3 Atmospheric Carbon Monoxide Concentrations and Isotopic 14
Compositions for Dispersion Study Along 1-55
4 Atmospheric Carbon Monoxide Concentration and Isotopic 17
Composition for Diurnal Studies, Plainfield, Illinois
5 Wind Direction and Wind Speed June 10, 11 and July 17, 18, 18
1974, Argonne, Illinois
6 Hydrocarbon Analyses of Atmospheric Samples Collected in 22
St. Louis, Missouri, June 27 and July 17, 1973
7 Hydrocarbon Analyses of Atmospheric Samples Collected in 23
St. Louis, Missouri, November 13, 14, 1973
8 Ratios of Hydrocarbon to Carbon Monoxide Concentration for 24
Samples Collected June 27 and July 17, 1973
9 Ratios of Hydrocarbon to Carbon Monoxide Concentration for 25
Samples Collected November 13 and 14, 1973
vii
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ACKNOWLEDGMENTS
We are indebted to Dr. C. M. Stevens for his advice and consulta-
tion in this work. The interest of Dr. J. Bufalini in this work is
acknowledged. Our thanks to Robert Seila and Stan Kopczynski of the
Chemistry and Physics Laboratory of the Environmental Protection Agency
for their assistance and good will. Grateful acknowledgment to meteo-
rologists, Lewis Hull, of St. Louis University; Harry Moses and Frank
Kulhanek of ANL for accurate predictions of the winds. Our thanks to
James Clark, Chief of Monitoring Services, Air Pollution Control Program,
St. Louis County, for the many data points and general information.
Our thanks to Mr. Glenn Pearson of Plainfield, Illinois, for allowing
us to take samples in his corn field.
viii
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SECTION I
INTRODUCTION
Studies by Stevens et al1 have indicated significant variations in
the abundances of oxygen isotopes found in carbon monoxide (CO) from
different sources. A conclusion of this past work is that the 9(180/160)
ratio of oxygen in CO found in rural areas is as much as 15 parts per
thousand (%o) less than that found in urban areas, where combustion
processes are the principal source of CO. Thus, it was hoped that the
variation in oxygen isotopic composition, as a function of location in
an urban area, might provide insight to the movement of air in such an
area and serve as a natural tracer. Carbon isotope ratios do not appear
to be as potentially useful, but they might in some cases be used to
identify sources of CO because of the variation in isotopic composition
of carbon in fuels.
Three experiments were conducted in the St. Louis, Missouri, area
to sample the pollutant plume as it moved from the city. Samples were
taken approximately 30 miles upwind of the city, in the city at 12th
and Clark at the Continuous Air Monitoring Project (CAMP) Station and
from 18 to 48 miles downwind of the city. In two of the cases, June 27
and November 13-14, 1973, all the downwind samples showed measurable
contributions of engine CO. In the other case, July 17, 1973, the down-
wind samples showed negligible contributions of engine CO.
Due to difficulties in exactly locating the plume, which can have a
sinuous pattern2, a location closer to the city center was chosen and
samples were taken at this point over a period of time. The 8(180/160)
ratio indicates the contribution of combustion produced CO was ^70%,
without any pronounced indication of a peak corresponding to the morning
traffic rush.
Additional samples were collected in the St. Louis area in plastic
bags for the Chemistry and Physics Laboratory (CPL) of the Environmental
Protection Agency. These samples were analyzed by them for acetylene
and other hydrocarbons.
Two experiments were conducted to evaluate the changes in concentra-
tion and isotopic composition of CO generated by automobile traffic on a
major highway in a rural area. Both CO concentration and the 3(180/160)
-------
ratio fall off very rapidly, and within three miles the contribution of
combustion CO is minimal.
Three experiments were conducted to determine the diurnal changes
in concentration and isotopic ratios of CO in a predominantly agricul-
tural area. In these experiments there appears to be a natural sink for
the CO with some fractionation also taking place.
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SECTION II
CONCLUSIONS
The oxygen isotopic ratio (180/150) of carbon monoxide is a sensi-
tive indicator for fossil fuel combustion products in the atmosphere.
Evidence of urban air was seen as far as 48 miles downwind of the city
of St. Louis, Missouri. However, movement of the pollutant plume was
not detected. Diurnal studies indicate that there is some carbon mon-
oxide removal process operating during the night, and that production
of carbon monoxide from all sources during the day appears to exceed
removal processes during the day. The relationship between methane or
ethylene and carbon monoxide is proportional for all locations and times
and either of these two hydrocarbons could be used as a tracer for carbon
monoxide. Carbon monoxide is dissipated rapidly from known sources,
e.g., highways, in open areas. The contribution of combustion carbon
monoxide to the total carbon monoxide is minimal (<5%) three miles
downward.
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SECTION III
RECOMMENDATIONS
The usefulness of this method for determining the sources and
movement of carbon monoxide could be increased by taking samples
simultaneously some distance apart. Air samples should be taken
over a period of time at one location to determine movement of the
pollutant plume from major metropolitan areas. An open area free of
major sources of carbon monoxide as close to the city as possible
would be desirable. A knowledge of the oxygen and carbon isotopic
composition of carbon monoxide from other combustible materials would
be useful in determining sources of carbon monoxide. An expansion of
the diurnal studies would be useful in determining the balance of
carbon monoxide in the atmosphere.
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SECTION IV
EXPERIMENTAL PROCEDURES
The atmospheric samples were collected in ^90 liter aluminum cylin-
ders which had been evacuated by a mechanical pump connected through a
liquid nitrogen trap. The cylinders were opened and allowed to come to
atmospheric pressure and then pumped to 30 to 40# gauge with two rubber
diaphragm compressors powered by a 12V battery. The intake port was
^30 inches above the ground, and the sampling period was VL5 minutes.
The air samples were processed according to the procedure of Stevens
and Krout3. Briefly, the procedure is as follows: The sample is passed
through a liquid N_ trap and molecular sieves to remove moisture, CO.,
NO, NO, and NO,,; through Schutze reagent (I«0 ) to oxidize the CO to C0~;
and through a liquid nitrogen trap to condense the CO formed from the
CO. The amount of C0_ formed is measured manometrically and the isotopic
ratios 13C/12C and 180/160 are determined on a modified Consolidated-Nier
Mass Spectrometer. The mass spectrometric procedure and calculations
have been discussed by Stevens et al1.
Additional air samples were taken in St. Louis in Tedlar plastic
bags for GPL. For the first two St. Louis experiments, these samples
were pumped just prior to the ANL samples. In the third experiment,
the tanks were pumped and the plastic bags filled from the tanks so
that identical samples would be analyzed by CPL and ANL.
The percent CO produced by combustion in any sample was calculated
in the following manner:
-/ ™m* «n rn 6(180/160) sample - 5(180/160) bkgd.
/. combustion CO - 6(l«0/lb0) alj _ «(lB0/lb0) bkgd?
The oxygen isotopic ratio for air, 23.5, relative to SMOW, reported by
Kroopnick and Craig4 was used in the above calculation.
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SECTION V
EXPERIMENTAL CONDITIONS
On June 27, 1973, the wind was southwest at 0630. The upwind sam-
ple was taken southwest of Otto, "Missouri, 29 miles southwest of St.
Louis. By 0830 the wind was from the west. A sample of the urban air
was taken at 12th and Clark at CAMP Station #1. Downwind samples, east
of St. Louis, were taken near New Memphis, New Minden, and Carlyle,
Illinois, respectively 31, 47 and 47 miles from the CAMP station. Con-
secutive samples were taken near New Minden, Illinois. Data are given
in Table 1-A and conditions in Appendix A-l.
On July 17, 1973, the wind was southeast at 0600. The upwind
sample was taken 18 miles southeast of St. Louis in an open field.
At sampling time, the wind was light and from the east. The urban
sample was taken at CAMP Station #1. Downwind samples were taken
25, 26, and 33 miles west of St. Louis. Data are given in Table 1-B
and conditions in Appendix A-2.
Sample collection on October 25, 1973, was terminated after a 90°
shift in the wind direction.
On November 13, 1973, with the wind out of the south, samples were
taken periodically from 0630 to 1022 at a single location, 7.8 miles
north of CAMP Station #1, in Beliefontaine. An upwind sample was taken
late in the day southwest of Otto, Missouri. Data are given in Table
1-C and conditions in Appendix A-3.
On November 14, 1973, the wind was south-southeast, and a similar
experiment was carried out. A sample further downwind was taken at
1030, 15.3 miles north of CAMP Station #1. Data are given in Table 1-D
and plotted in Fig. 1. The conditions are given in Appendix A-3. Wind
direction and speed for two nearby CAMP stations as well as the downtown
station are given in Table 2.
Two experiments were carried out near Argonne, Illinois, along
highway 1-55 on July 31 and August 9, 1973. The wind was from the
north at 8-10 mph on July 31 and from the west on August 9 at 10-12 mph.
Traffic averaged 25 cars and 2 trucks per minute. Data are given in
Table 3 and conditions in Appendix B.
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A series of samples was taken over a 24-hour period on September
5 and 6, 1973, in a field of mature corn. The local roads were 0.5
mile to the south and 2 miles to the west with a minor highway 0.5 mile
to the north. No cars passed on the road to the south during the night.
The road to the west could not be seen. The wind was from the west at
5-8 mph and decreased during the night to 2-5 mph. The field was located
3.4 miles west of Plainfield, Illinois, ^25 miles southwest of Argonne
National Laboratory. The data are given in Table 4-A, the conditions
in Appendix C-l and plotted in Fig. 2.
Two replicate experiments were carried out at the same location in
the early summer, shortly after the field was planted. On June 11, 1974,
the wind was west at 8 mph early in the evening, but by midnight was
light and variable and remained so until 0430 when the wind became 1-2
mph from the west-northwest. On July 18, 1974, the wind was out of the
southwest at 5-8 mph. Sampling was discontinued when the wind shifted
to north in the middle of the day. The data are given in Tables 4-B and
4-C; the conditions are given in Appendix C-2 and C-3. Wind direction
and speeds as reported at ANL are given in Table 5.
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SECTION VI
RESULTS AND DISCUSSION
In the attempts to sample the pollutant plume from St. Louis,
Missouri, variable results were found. The June 27 effort covered an
arc of 22° downwind, with the CO concentration and the <5(180/160)
ratio decreasing along the arc. The CO concentration decreased like-
wise as the distance from the city increased. The decrease along the
arc would appear to indicate that the plume maximum had passed the
*
sampling point, assuming that the air mass moving from the city was
being sampled. However, at the distance from the city and the reported
wind speed of 5 mph, the plume would not have reached the sample point
at sampling time.
The July 17 collection was made closer to the city with the plan
that the plume would be more easily seen. The downwind sampling arc
was only 12° with the contribution of urban CO in these samples less
than 10%. At the reported wind speed the plume should have reached
the sampling sites by the time the samples were taken. However, there
had been an inversion earlier that morning which most probably delayed
movement of the air mass over and from the city.
From the first two experiments it seemed that movement of the
plume from the city might be detected if sequential air samples were
taken downwind at a single location closer to the city center.
On November 13 and 14, 1973, at a location within the metropoli-
tan St. Louis area, ^8 miles north of CAMP Station #1, air samples were
taken during the morning from 0630. With the prevailing winds, the lo-
cation was sufficiently far from freeways and arterial roads that CO
produced thereon would have had, at the most, only a minimal effect
(see below).
Although the wind was out of the south at the time sampling was
begun and would have carried the plume over the sampling location, there
was considerable variation in both the direction and speed of the sur-
face winds during the sampling period on both days. During this time,
the wind 300 feet above ground, as measured at CAMP Station #1, was
steady with a much higher velocity, as is shown in Table 2. The inver-
sion dissipated by 1000 each morning.
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0-28
M
•^
o
fO
— -29
22
1 21
«o
O
(O
O 20
19
1.6
O.
Q.
0.8
0.4
0600
O NOV. 13,1973
V NOV. 14,1973
0800
1000
TIME
1200
FIG. 1 PPM CO, «(180/160)SMOW, and s(13C/12)
VS. TIME IN ST. LOUIS, MISSOURI.
9
'PDB
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TABLE 1. Atmospheric Carbon Monoxide Concentrations and Isotopic
Compositions for Samples Collected in St. Louis, Missouri
Sample Point
Sample No.
1 (D*
2 (2)
3 (3)
4 (4)
4a
5 (5)
1 (6)
2 (2)
3 (7)
4 (8)
5 (9)
5a(9)
1 (10)
2 (10)
3 (10)
4 (10)
5 (D
6 (10)
7 (10)
8 (10)
9 (10)
10 (10)
1
a Distance Mi Bearing
Time from St. Louis Degrees
0740
0920
1310
1415
1430
1510
0745
0850
1340
1433
1535
1550
0630
0730
0845
1022
1830
0630
0730
0920
1030
1120
1630
Auto Exhaust
29
0
31
48
48
46
18
0
25
26
33
33
7.8
7.8
7.8
7.8
29
7.8
7.8
7.8
15.3
7.8
-
1973
A.
220
113
108
108
86
B.
171
-
270
282
277
277
C.
348
348
348
348
220
D.
348
348
348
357
348
E. Sampled
_
—
Speed
(mph)
Wind
Directions Concentration CO
Degreees (ppm)
5(13C/12C)b
(ppt)
6(180/160)C
(ppt)
. Sampled June 27, 1973
5
5
5
5
5
5
225
270
270
270
270
270
0.20
2.37
0.41
0.37
0.27
0.21
-25.3
-28.9
-28.7
-26.3
-26.4
15-°d
23.3d
16. 7d
17. ld
13.7
Sampled July 17, 1973
2
2.5
2.5
5
5
5
Sampled
10-12
12
8-10
8-10
5-8
Sampled
5
5-8
11
12
16
July 25
5-8
—
90
105
90
90
90
90
November 13, 1973
180
160
160
200
247
November 14, 1973
160
160
180
180
180
, 1973 (Plainfield,
247
-
0.25
6.4
0.28
0.28
0.21
0.22
0.68
0.66
0.75
0.67
0.22
0.86
1.52
0.90
0.58
0.48
111.)
0.19
-26.5
-28.5
-27.5
-28.6
-27.2
-27.3
-28.1
-27.7
-28.2
-27.9
-27.2
-28.6
-28.7
-28.6
-27.9
-27.8
-28.5
-28.8
14.4
22.3
14.8
14.9
13.8
14.2
21.5
20.9
20.8
21.6
15.7
19.2
22.1
19.9
20.6
20.0
13.7
23.1
Locations on Map D-l.
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TABLE 1. (Con't.)
Denotes starting time - sampling period - 15 minutes.
6 13C/12C) is the relative difference in parts per thousand (ppt) between the 13C/12C ratio calculated from mass spectro-
metric data and the accepted value of the same ratio for the carbon isotopic standard, Peedee belemnite. The normal
external error is ±0.3 ppt for 6(13C/12C).
C6(180/160) SHOW - is the relative difference in parts per thousand (ppt) between the 180/160 ratio calculated from mass
spectrometric data and the accepted value of the same ratio for the oxygen isotopic standard, mean ocean water. The
normal external error is +0.5 ppt for 6(180/160).
These values may be high by as much as one part per thousand.
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TABLE 2 , Wind Direction, Wind Speed and CO Concentration
for Three St. Louis County Air Monitoring Stations^
Time
Nov. 13, 1973
0400-0500
0500-0600
0600-0700
0700-0800
0800-0900
0900-1000
1000-1100
Nov. 14, 1973
0400-0500
0500-0600
0600-0700
0700-0800
0800-0900
0900-1000
1000-1100
1100-1200
WD
191
189
192
179
180
199
202
203
190
192
185
174
198
208
200
*
1
ws
mph
23
22
22
18
21
21
18
15
15
13
14
15
18
26
27
CO
ppm
1.2
1.4
1.9
2.4
2.9
2.0
-
2.7
3.4
4.9
5.9
4.2
5.2
4.8
4.9
**
5
WD WS CO
mph ppm
0.6
0.5
0.7
1.2
1.0
0.9
0.8
0.7
0.6
0.6
1.1
1.2
0.8
1.4
0.8
WD
170
140
165
149
146
198
204
183
151
150
151
144
166
198
190
***
8
WS
mph
1.6
3.5
3.0
4.8
8.0
4.8
5.7
1.5
1.9
3.8
2.5
6.5
4.7
5.1
5.4
CO
ppm
1.2
3.1
3.4
3.8
3.9
3.9
3.6
4.6
4.6
5.0
5.9
5.7
5.2
5.1
5.0
**
***
Station 1 - Civil Courts Bldg. and instruments on 10' tower on roof >300'
above street. CO instrument at 12th and Clark.
Station 5 - On flood plain, near waterworks.
Station 8 - Routes 67 and 270, Beliefontaine State Farm. Wind instruments
on tower 20' above ground.
(1) Data courtesy of J. Clark, St. Louis County, Air Monitoring Program.
12
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Thus, it is not likely that the plume would have been detected either
morning for the movement of air was variable and not across the city,
as expected. The samples show a decided increase in the CO level which
is three to four times that found in rural locations. From the oxygen
isotopic ratios it is estimated that 70-80% of the CO is from combustion
sources. The maximum found in the 0730 sample for November 14 for both
the CO concentration and the oxygen isotopic ratios corresponds to max-
ima found in the CO concentration for CAMP Stations 1 and 8. This
increase appears to be the morning maximum that was expected to move
out from the city and could be detected as it moved away from the city.
On this day it appeared to form and accumulate in the city until the
inversion cleared, for the sample, taken at 1030, November 14, ^15
miles downwind in a rural area showed a significant proportion of urban
air. The CO concentration was ^2.5 times that normally found in rural
areas, and the contribution of CO from combustion sources was estimated
to be ^70%. In view of these results, it would have been desirable to
have taken the day's samples at this location for it appeared that
urban air was reaching this area and the plume would have been detected
as it moved out from the city.
Two experiments were carried out on July 31 and August 9, 1973, to
evaluate the dispersion of CO from a major highway to determine the
extent to which a localized source of CO would influence the composition
and concentration of CO associated with a large air mass such as that
of the St. Louis area. Since a highway is a linear source and does not
have a plume in the sense that a point source does, the CO concentration
gradient at ground level due to dispersion should only be transverse to
the highway.
The first experiment was carried out along an east-west stretch
of Interstate 55, thought to be sufficiently west of Chicago to be free
of urban air, with a north wind blowing. The second experiment utilized
a north-south stretch of 1-55 with a west wind.
Although the air mass for the first experiment appears to have been
heavily contaminated with urban air, the effect of the combustion source
of the CO is evident only in the near vicinity of the highway. The
13
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TABLE 3. Atmospheric Carbon Monoxide Concentrations and Isotopic
Compositions for Dispersion Study Along 1-55
Sample
No.
Time
Distance
Miles
Wind Concentration CO
Speed Direction
6(13C/12C)
(ppm)
A. Samples Collected July 31,
1
2
3
4
5
1
2
2a
3
4
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
0940
1000
1020
1040
1117
1700
1733
1733
1800
1823
0.8
0
0.5
1.5
3.5
3.3
0
N
S
S
s
w
Duplicate
0.5
2.0
E
E
8-10 30°
it ii
it ii
it ii
ii ii
B. Samples Collected August
10-12 240-270°
ti it
pumped at the same time
ii ti
ii ii
0
1
0
0
0
9,
0
0
0
0
0
1973
.55
.31
.60
.55
.50
1974
.15
.72
.70
.19
.16
-28
-28
-28
-27
-27
-27
-28
-28
-28
-28
.1
.0
.0
.7
.8
.9
.0
.0
.1
.6
6(180/160)
(SMOW)
21.
23.
19.
20.
19.
11.
21.
21.
15.
12.
1
0
9
6
1
5
6
6
2
6
Locations on Map D-2.
-------
effect is the same in the second experiment, only more pronounced because
of the uncontaminated nature of the air mass. The air sampled at 0.5
and 2 miles downwind is estimated to contain 31% and 9%, respectively,
of combustion CO. It appears from these data that air samples taken
at least three miles from major roads would contain a negligible amount
of engine CO.
The diurnal studies of September 5-6, 1973, were conducted in a
field of mature corn to determine the nature of any changes in the CO
concentration and isotopic ratios in a rural atmosphere. The area was
free of localized sources of CO and the wind conditions (W, SW) were
chosen so that contamination by auto CO was minimal.
During the night, the CO concentration varied inversely with the
S(180/160) and 6(130/120) ratios. This effect suggests that the
lighter CO is being preferentially scavenged by a process such as the
soil microorganism consumption studied by Inman et al5. Although Inman
reports a substantial temperature effect in the rate of absorption, this
would affect the overall process very little. During the night, the
rate of natural CO production as well as combustion CO should be greatly
decreased allowing this absorption-fractionation process to be seen.
If fractionation is occurring, the change in the oxygen isotopic
ratio would be expected to be twice that of the carbon isotopic ratio
and a plot of these ratios would have a slope of two. In this plot, the
data for the night samples of September 5-6, 1973, show a close approxi-
mation to a slope of two, and one is tempted to conclude that fractiona-
tion is occurring. However, there is not sufficient data to conclusively
demonstrate this.
The conditions for the other two diurnal studies on June 11 and
July 18, 1974, were not ideal. There was an inversion the night of
June 10 and the winds were light and variable. On July 18, the winds
were strong and had been out of the southwest for a relatively short
time. There was also a smell of wood smoke in the air although no
fire or smoke could be seen. On both nights, the CO concentration was
nearly twice that of the normal rural value, indicating contaminated air.
15
-------
a ox
0.-24
£-26
— -30
O
O
0
22
20
(8
16
14
12
0.44
Q0.36
O
0.28
0^0
0.12
1600
O SEPT. 5,6,1973
V JUNE 11,1974
0 JULY 18,1974
2400 0800
TIME
1600
FIG. 2 DIURNAL STUDIES, PPM CO, <5(180/160)<-Mnu, AND
SMOW
fi(13C/12C)pDB VS. TIME.
16
-------
TABLE 4. Atmospheric Carbon Monoxide Concentrations and Isotopic
Composition for Diurnal Studies, Plainfield, Illinois
Sample No. Time
1 * 1655
2 2030
3 0030 (9/6)
4 0230
5 0500
6 0600
7 0730
8 1001
9 1655
1 0130
2 0315
3 0445
4 0635
5 1345
1 0055
2 0230
3 0355
4 0540
5 0950
1 1300
2 1410
3 1220 (7/9)
1 1630
2 1645
Speed
(mph)
5-8
2-5
ir
if
it
ti
It
4-8
3-5
Wind
Direction CO Concentration
Degrees (ppm)
A. Sampled September
290
280
300
280
290
290
300
315
290
B. Sampled June
light and variable
1-2
1-2
15-20
5-7
8-10
5-8
8-10
5-7
4-10
4-10
5-10
5-8
8-10
calm
315
225
270
C. Sampled July
225
ii
ii
ii
ti
D. Sampled June 13 and
250
240-290
270
E. Sampled July 25 ,
250
250
5 and 6, 1973
0.20
0.14
0.16
0.15
0.14
0.13
0.19
0.22
0.20
11, 1974
0.36
0.39
0.51
0.26
0.18
18, 1974
0.35
0.42
0.38
0.36
0.40
July 9, 1974
0.19
0.18
0.20
1973
0.19
2.46
6(13C/12C)
-26.5
-24.5
-26.1
-25.1
-25.9
-24.8
-26.2
-27.3
-27.2
-26.3
-26.3
-27.0
-27.5
-27.0
-28.0
-28.3
-28.2
-28.3
-29.0
-26.0
-26.0
-30.6
-28.5
-24.1
6(180/160)
12.4
17.9
14.4
17.5
15.9
16.0
14.8
15.1
13.0
20.5
19.0
15.3
15.1
-
14.0
12.4
12.4
12.0
13.5
10.7
11.6
10.3
13.7
36.8
*A11 samples - Location 10, Map D-2.
-------
TABLE 5. Wind Direction and Wind Speed
June 10, 11 and July 17, 18, 1974
Argonne Illinois
Time WD WS
June 10, 1974
0800 230 16
1000 240 17
1400 290 18
1800 300 13
2100 310 3
2400 light and variable
June 11, 1974
0100 230 1
0300 130 0.5
0500 170 1
0700 120 2
0900 260 8
July 17, 1974
0300 180 4
0600 220 3
0900 230 5
2400 270 8
July 18, 1974
0100 230 8
0300 240 10
0600 230 11
0900 240 4
1200 320 4
1300 180 3
18
-------
20
19
18
o
J
17
O
to
16
15
14
13
12
II
I I I 1
I I
THEORETICAL
SLOPE OF 2
8 ^"™
I I
I I I I
-30 -29 -28 -27 -26 -25 -24
FIG. 3 OXYGEN VS. CARBON ISOTOPIC RATIOS FOR DIURNAL
STUDY, SEPTEMBER 5,6, 1973.
19
-------
It can be seen in the data for June 11, when the winds changed to the
southwest and the inversion cleared, the CO value dropped to that ex-
pected for rural air.
The oxygen isotopic ratios for the samples taken June 11 indicate
that approximately 70% of the CO is of combustion origin. This seems
likely in view of the inversion and the light winds which would tend
to hold the products of combustion in the area. Although the CO con-
centrations for the samples of July 18 are about the same as those for
the previous experiment, the oxygen isotopic ratios are lower and indi-
cate that 10 to 20% of the CO is due to fossil fuel combustion. The
reason for the lower oxygen isotopic ratios with that level of CO in the
latter case is not obvious. This effect may be due to other non-fossil
fuel combustion sources of CO.
All the diurnal experiments show a difference in the behavior of
CO between night and day. During the night, the oxygen isotopic ratios
change inversely to the change in the CO concentration. During the day,
these values change in a parallel manner. This is also true for the
carbon isotopic ratios, but to a lesser extent.
It would appear that the oxygen isotopic ratio is a sensitive indi-
cator of fossil fuel combustion for, as can be seen from the diurnal
experiments, with the coming of day, as the amount of CO increases so
does the oxygen isotopic ratio. This may indicate that the residence
time of CO in the atmosphere is less than has been previously estimated1'6'7.
To observe the fractionation effects is not easy. There is the
steady movement of air as well as the daily and seasonal variation in
production of CO. Stevens et al1 saw little, if any, evidence of
fractionation for a large number of samples taken over a 15-month period.
These samples were taken primarily at the same time of day (3 to 5 p.m.)
when it would appear from the data presented here that combustion CO
predominates and would obscure any fractionation effects.
It was hoped that some easily or conveniently analyzed pollutant
would serve as a tracer for the plume, e.g., S02> N02> No instruments
were immediately available for this. However, the possibility of trac-
ing with hydrocarbons was considered, and the data of CPL are included
20
-------
here in Tables 6 and 7. In Tables 8 and 9, the ratio of the CPL hydro-
carbon (HC) values to the CPL CO concentrations are given. For the
samples pumped separately from the ANL samples, the ratios are not as
consistent for each component, as the ratios are for the samples taken
from the ANL tanks. There is, however, a noteworthy consistency for
the HC/CO ratios of the latter samples. This may have been due to the
higher HC levels in the latter samples. It would appear from the
available data that these ratios might be used to spot a malfunction
of equipment or a poor sample.
To determine if there might be a useful relationship between the
hydrocarbons and CO, the CPL data for the HC has been plotted vs. the
CO concentration in Figs. 4-12. For some of the HC, i.e., methane,
ethylene, n-, i- and cyclopentane, their concentration is proportional
to the CO concentration for all samples, both rural and urban, summer
and fall. For ethane and propane there appears to be a difference
between the summer and fall samples. For acetylene, propylene, n- and
i-butane there appears to be a difference between urban and rural
samples.
It would be expected that the concentration of these hydrocarbons
would be proportional to the CO concentration since a number of them,
i.e., ethylene, methane, propylene, and acetylene, have been reported
by Hurn8 as the prinicpal constituents of engine exhaust and this is
confirmed for ethylene and methane and for the urban samples of
acetylene and propylene.
The most interesting of these hydrocarbons is methane in that
most of the points, summer and fall, rural and urban, fell along the
curve. In these samples, the methane concentration varies only by a
factor of 2 while the CO concentration varies by a factor of ^20. The
curve extrapolates to a background value of VL.4 ppm which agrees quite
well with the reported values for atmospheric methane of 1.2 + 0.2 ppm9.
This is further indication that there are natural sources of methane
greater than engine exhaust. The oil fields, which are one possible
source, may account for the two high values of rural samples, since
these samples were taken in an area which has producing oil wells.
The reason for low values of the two summer urban samples, June 27
21
-------
TABLE 6
Hydrocarbon Analyses of Atmospheric Samples
Collected in St. Louis, Missouri, June 27 and July 17, 1973
CONCENTRATION IN ppb (Vol./Vol.)'
June 27
July 17
5.3 11.6 7.8 6.7
7.6 27.4 7.6 11.8
4.0 10.3 8.4 6.0
1.0 18.3 4.1 3.5
1.1 14.2 4.1 2.7
3.5 65.0 13.0 10.3
2.3 8.9 1.5 1.2
4.3 9.3 25.8
4.7 7.3 85.4
1.9 14.6 25.1
1.9 11.9 80.3
2.1 15.2 41.2
2.3 10.7 100.9
1.0 0.3 29.9
5.2
4.3
5.0
2.5
1.5
6.0
1.7
4.9
3.5
4.6
2.7
1.9
5.7
1.9
4.5
7.6
4.2
1.1
0.9
3.0
0.6
Compound
Ethane
Ethylene
Propane
Acetylene
Isobutane
n-Butane
Propylene
Propadiene
Neopentane
Isopentane
n-Pentane +
Cyclopentane
1-Butene
2-Methyl-Propene
Trans-2-Butene
Non Methane HC (FIA)
Methane 1200. 1320. 1600. 2430. 2180. 1700. 2650. 1660. 1690. 1620,
Carbon Monoxide 230. 1200. 500. 620. 430. 320. 5700. 370. 380. 260.
Not Measurable
Analyses by Chemistry and Physics Laboratory, EPA.
22
5.7 86.8 12.3 9.8 TNM 11.6 146.2 6.8 5.8 3.4
4.4 57.0 8.0 7.9 fNM 6.6 66.3 3.2 3.1 2.3
-------
TABLE 7
Hydrocarbon Analyses of Atmospheric Samples
Collected in St. Louis, Missouri, November 13 and 14, 1973
CONCENTRATION IN ppb (Vol./Vol.)*
November
Compound
Ethane
Ethylene
Propane
Acetylene
Isobutane
n-Butane
Propylene
Propadiene
Neopentane
Isopentane
1
19.
11.
17.
9.
8.
24.
3.
5.
0
0
1
8
5
7
3
7
2_
16.5
9.0
22.6
9.1
7.6
23.7
3.6
16.1
.3
18.8
11.6
23.4
9.1
12.4
47.9
4.0
26.3
13
21
11
19
9
8
24
3
18
November 14
4_
.5
.1
.7
.1
.6
.4
.5
.0
£
34.4
13.7
54.5
9.6
21.5
35.2
28.0
22.5
]_
42.5
24.5
107.8
17.6
19.8
64.8
9.6
40.1
25
13
33
11
13
40
3
25
8 9_
.3 20.1
.0 9.1
.0 16.6
.0 7.9
.4 9.1
.4 26.0
.8 2.5
.7 16.5
113
19.2
7.3
13.1
4.8
5.6
20.2
21.0
11.8
0 9.3 12.5 10.4
13.1 20.9 13.6 8.8 6.4
n-Pentane +
Cyclopentane
1-Butene
2-Methyl-Propene
Trans-2-Butene
Non Methane HC (FIA)
Methane 1845. 1737. 1737. 1880. 2166. 2321. 1830. 1736. 1786.
Carbon Monoxide 551. 566. 646. 630. 743. 1211. 760. 517. 428,
Analyses by Chemistry and Physics Laboratory, EPA.
23
-------
TABLE 8
Ratios of Hydrocarbon to Carbon Monoxide Concentrations
for Samples Collected June 27 and July 17, 1973
1. Samples Collected June 27 and July 17, 1973:
ppb HC/ppm CO
Ethane
Ethylene
Propane
Acetylene
i-butane
n-butane
Propylene
i-Pentane
n-Pentane +
Cyclopentane
6/27
—
23
33
17
4
5
15
10
25
19
2_
10
23
9
15
12
54
7
72
48
-2-
16
15
17
8
8
26
3
25
16
—
11
19
10
6
4
17
2
16
13
A
10
11
4
4
5
5
2
-
_
i
29
23
46
37
48
33
1
36
21
7/17
-L
4
15
4
15
7
18
5
26
12
JL
14
12
14
7
4
16
5
18
9
-*.
13
9
12
7
5
15
5
15
8
—
17
14
16
4
4
12
2
13
9
Methane 5.22 1.10 3.20 3.92 5.07 5.31 0.465 4.49 4.45 6.23
(ppm/ppm CO)
CO ppb
230
1200 500
620
430 320 5700 370
380 260
24
-------
TABLE 9
Ratios of Hydrocarbon to Carbon Monoxide Concentrations
for Samples Collected November 13 and 14, 1973
ppb HC/ppm CO
November
Compound
Ethane
Ethylene
Propane
Acetylene
i-Butane
n-Butane
Propylene
i-Pentane
n-Pentane
+ cyclo-
pentane
Methane
(ppm/ppm CO)
CO ppb (ACL)
CO ppb (ANL)
Ratio ACL/
ANL
1
35
20
31
18
15
45
6
10
3.35
551
680
0.81
2
29
16
40
16
13
42
6
28
16
3.07
566
656
0.86
13
3
29
18
36
14
19
74
6
41
19
2.67
646
747
0.86
4
34
18
31
14
14
39
6
28
16
2.98
630
674
0.93
6
46
18
73
13
29
47
4
30
18
2.92
743
858
0.87
November
7
35
20
89
14
16
54
8
34
17
1.92
1211
1524
0.79
8
33
17
43
14
18
53
5
34
18
2.41
760
901
0.84
14
9
39
18
32
15
18
50
5
32
17
3.36
517
576
0.90
10
45
17
31
11
13
47
5
28
15
4.17
468
485
0.88
25
-------
and July 17, is not obvious. However, all the HC values of sample #2,
July 17, except that of acetylene, fall below the respective curves.
It would seem then that either methane or ethylene could be used
as a tracer for CO, given a portable instrument.
There are some apparent anomalies in the EC/CO ratios, i.e.,
samples 6 and 7 for propane, sample 6 for i-butane and sample 3 for
n-butane on November 13-14, 1973; and sample 2 on June 27, 1973, for
n-butane, i-pentane and n-pentane plus cyclopentane. These ratios
are high and the original values should probably be rejected.
Also included is a ratio of the CPL/ANL values for the CO con-
centration. There appears to be a consistent bias. At this point,
it is not known whether it is due to bag permeability to CO, instru-
mental problems, calibration, or some other factor.
With the natural sources of CO still uncertain, an isolated and
unrepeated occurrence is noted as possibly having some bearing on the
natural production of CO.
Unusual values for the oxygen and carbon isotopic ratios were
found one afternoon when consecutive samples were taken near Plainfield,
Illinois. The first sample was taken with the temperature at 90°F and
the sky overcast. During the pumping of the second sample, the cloud
cover and wind speed increased,j,with a thunderstorm 3-10 miles upwind,
and the temperature dropped abruptly to 82°F. Both the oxygen and
carbon isotopic ratios increased markedly. O'Neil and Epstein1^ noted
a marked changed in the oxygen isotope ratios of water vapor and rain
with the approach and passage of a cold front. The oxygen isotopic
ratio decreased in that case, however. The experiment was not repeated
because the conditions did not occur again during the course of this
study. The results are given in Table 3.
26
-------
3.0
2.5
bJ
12.0
NJ
CL
Q.
1.5
1.0
0.5
O RURAL
V URBAN
© URBAN - SUMMER
0
O
I
I
I
I
I
I
I
I
I
0.2 0.4 0.6 0.8 1.0
PPM CO
FIG. 4 PPM METHANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
1.2
-------
30
UJ
Z
LU
to
CO
OQ
D.
Q_
10
O RURAL
7 URBAN
® URBAN - SUMMER
i r
O O
I
I
0.2 0.4 0.6 0.8 1.0
PPM CO
FIG. 5 PPB ETHYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
1.2
-------
NJ
VO
40
30
LJ
1
QJ
520
CO
Q_
Q.
10
O RURAL
7 URBAN
@ URBAN - SUMMER
1
1
J L
1
I i I L
0.2 0.4 0.6 0.8 1.0
PPM CO
FIG. 6 PPB i-PENTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
1.2
-------
OJ
o
LU
o
o
c
0.
UJ
LU
2
Q.
CD
Q_
Q.
O RURAL
V URBAN
© URBAN - SUMMER
G
O
1
1
I
D 0.2 0.4 0.6 OJB 1.0 1.2
PPM CO
FIG. 7A, 7B PPB n- AND CYCLO-PENTANE AND PROPYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
-------
40
30
LJ
ti20
CO
Q.
Q.
10
O RURAL
V URBAN
® URBAN - SUMMER
I
I
I
I
I
I
I
1
1
0,2 0.4 0.6 0.8 1.0
PPM CO
FIG. 8 PPB ETHANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
1.2
-------
U)
NJ
O RURAL
V URBAN
O URBAN - SUMMER
0
0.4 0.6 0.8 1.0 1.2
PPM CO
FIG. 9 PPB PROPANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
-------
20
15
Ld
Z
CJ
810
<
CD
Q.
QL
O RURAL
7 URBAN
O URBAN - SUMMER
O
0.2 0.4 0.6 0.8 1.0
PPM CO
FIG. 10 PPB ACETYLENE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
-------
80-
CO
-p-
O RURAL
V URBAN
O URBAN-SUMMER
0.6
PPM CO
FIG. 11 PPB n-BUTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
-------
40
u>
Ul
30
UJ
L
CD
Gu
Q.
10
i i i i i i i i i i i r
O RURAL
V URBAN
© URBAN - SUMMER
O
0.2 0.4 0.6 0.8 1.0
PPM CO
FIG. 12 PPB i-BUTANE VS. PPM CO IN ST. LOUIS, MISSOURI, AND VICINITY.
-------
SECTION VII
REFERENCES
1. Stevens, C.M., Krout, L., Walling, D., Venters, A., Engelkemeir, A.
and Ross, L. E., The Isotopic Composition of Atmospheric Carbon
Monoxide. Earth and Planetary Science Letters, 16, 147-165 (1972).
2. Braham, R., University of Chicago, private communication.
3. Stevens, C.M. and Krout, L., Method for Determination of the Con-
centration and the Carbon and Oxygen Isotopic Composition of
Atmospheric Carbon Monoxide. Int. J. Mass. Spect. and Ion Physics,
J3, 265-275 (1972).
4. Kroopnick, P. and Craig, H., Atmospheric 09: Isotopic Composition
and Solubility Fractionation. Science, 175, 54 (1972).
5. Inman, R. E., Ingersoll, R. B. and Levy, E. V., Soil: A Natural Sink
for Carbon Monoxide. Science, 172, 1229 (1971).
6. Weinstock, B., The Residence Time of Carbon Monoxide in the Atmosphere.
Science. 166, 224 (1969).
7. Weinstock, B. and Niki, H., Carbon Monoxide Balance in Nature.
Science. 176, 290 (1972).
8. Hum, R. W., Air Pollution, Vol. Ill, p. 68 (1968), second edition,
edited by A. C. Stern, Academic Press, New York.
9. Air Pollution, Vol. Ill, p. 662 (1968), A. C. Stern, Editor,
Academic Press, New York.
10. O'Neil, J. R. and Epstein, S., A Method for Oxygen Isotope Analysis
of Milligram Quantities of Water and Some of Its Applications.
J. Geophys. Res.. TL, 4955 (1966).
36
-------
SECTION VIII
APPENDICES
Page
A. Conditions for Samples Collected in 38
St. Louis, Missouri
B. Conditions for Samples Collected Along 40
1-55 Argonne, Illinois
C. Conditions for Samples Collected in 41
Diurnal Studies, Plainfield, Illinois
D. Maps of Sampling Locations 42
37
-------
APPENDIX A. Conditions for Samples Collected in St. Louis, Missouri
Wind
Co
oo
Sample No. Time
1 (1) 0740
2 (2) 0920
3 (3) 1310
4 (4)
4a
5 (5)
1415
1430
1510
4 (8) 1433
Temperature
Speed Direction
(mph) Degrees
Location
1. Conditions for Samples Collected June 27, 1973
70
80
85
85
85
15
225 partly
cloudy
270 clear
270 clear
270 clear
270 clear
270 clear
At base of lookout tower, 5 miles, SSW of Otto, Mo.,
29 miles, 220° from St. Louis. Hilltop location,
valley to SW wooded area.
CAMP Station, 12th & Clark, St. Louis, traffic light.
New Memphis, 111., 1 mile W of the New Memphis L&N
station, 0.5 mile S of the tracks, along side a soy-
bean field, level open country. Few patches of woods
to W, farm buildings 1-2 miles to W, 31 miles, 113°
from St. Louis.
New Minden, 111., 47 miles, 108° from St. Louis, 1.5
miles N of New Minden on 111. Rte. 127 in open field,
soybean field to right, grass to left, woods to west,
0.5 mile N, 18 miles east of sample point 3.
As above.
Carlyle, 111., 47 miles, 86° from St. Louis, 6 miles
N of Carlyle on Rte. 127, 0.5 mile W of Rte. 127 in
open corn field. Corn 18" high, woods to W,East-
West road 260 yds. N of sample point. 16 miles N of
sample point 4.
2. Conditions for Samples Collected July 17, 1973
1
2
3
(6)
(2)
(7)
0745
0850
1340
70
72
88
2
2
2
.5
.5
90
slightly
overcast
112 slight
overcast
90 slight
overcast
85
90 clear
18 miles, 171" from St. Louis 1 mile east of 111.
Rte. 3 on New Hanover Rd. at base of microwave tower,
soybean field to east.
CAMP Station 12th & Clark.
25 miles, 270° from St. Louis on hill, 3-4 miles
south of Missouri River where U.S. 40 crosses. The
river plain to north rolling hills, woods and farms
to east.
26 miles, 282° from St. Louis., 3 miles east of Weldon
Springs on country road. Soybean field to east and
southeast, rolling, partially wooded country side.
Location on Map D-l.
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APPENDIX A. (Con't.)
u>
VO
Sample No.
5 (9)*
5a(9)
1 (10)
2 (10)
3 (10)
4 (10)
5 (1)
6 (10)
7 (10)
8 (10)
9 (11)
10 (10)
Time
1535
1550
0630
0730
0845
1022
1830
0630
0730
0920
1030
1120
Temperature Speed
<8F) (nph)
2. Conditions
85 5
85 5
3. Conditions for
10-12
12
8-10
8-10
5-8
5
5-8
11
12
16
Wind
Direction
Degrees
Location
for Samples Collected July 17, 1973
90 clear
90 clear
33 miles, 277° from St. Louis,
section of county roads D & DD
1 mile east of inter-
at former site of
lookout tower. Open field to east & southeast bounded
by woods.
Samples Collected, November 13 and 14, 1973
180 clear
160 clear
160p. cloudy
210 cloudy
250 cloudy
160 cloudy
160 cloudy
180 partly
cloudy
180 clear
130 clear
7.8 miles, 348° from St. Louis
Bethlehem, cemetery, on road to
Ravine and unused warehouse to
29 miles, 220" from St. Louis.
5 miles SW Otto, Mo. at base of
as in one above
as in one above
as in one above
. i. 300 yards east of
electric sub-station.
south.
lookout tower.
15.3 miles, 357° from St. Louis. 1.5 miles east of
Rte. 67, ^ 0.5 mile N Missouri River.
as in one above
* Location on Map D-l.
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APPENDIX B. Conditions for Samples Collected along 1-55 Argonne, 111.
Sample No.
Time
Temperature
(°F)
Speed
(mph)
Wind
Direction
Degrees
1 . Samples
l (D*
2 (2)
3 (3)
4 (4)
0940
1000
1020
1040
72
72
72
74
8-10
8-10
8-10
8-10
30°
30°
30°
30°
Location
Collected July 31, 1973
cloudy
cloudy
cloudy
cloudy
0.8 miles N 1-55, 200 yds. W
bean field to North.
30 ft. S of 1-55, 0.1 mile E
Frontange Rd., traffic light
0.5 mile S of 1-55 on E side
bean field to N, swamp grass
of
of
to
of
to
1.5 miles S of 1-55 on E side of
Williams Rd.
Williams Rd.
moderate.
Williams Rd.
E. and N.
Weber Rd.
Soy-
along
Soy-
(a con-
5 (5)
1 (6)
2 (7)
2a
3 (8)
4(9)
1117
1700
1733
74
88
85
8-10 30° cloudy
tinuation of Williams Rd.) ~ 0.5 miles S of 135th
street., cornfield to E and N, i> 6' high, intermit-
tent traffic on road, shut down during and after
traffic.
3.5 miles S of 1-55 on Weber Rd., 0.3 miles S of
Plainfield-Lockport Rd., soybean field to E and N.
2. Samples Collected August 9, 1973
10-12 240-270°
clear
10-12 240-270"
clear
Duplicate of 202, pumped at same time
1800 85 10-12 240-270°
clear
1823
85
10-12 240-270°
clear
3.3 miles W 1-55, 0.8 miles S 111. 126, 40 yds, W
County Line Rd., corn field to N, cut oat field to S.
30 ft. E of 1-55 0.2 miles S of Plainfield Rd., along
Frontage Rd., Avg. 24 cars & 3 trucks/min.
0.5 miles E of 1-55 100 yds. S of intersection of
roads 0.5 mile E of 1-55, 1 mile N of Plainfield Rd.,
level, open soybean field to 1-55.
2 miles E of 1-55, 30 yds. N of road, 1 mile N of
Plainfield Rd., in cut oat field, soybean field to W.
* Locations on Map D-2.
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APPENDIX C
Conditions for Samples Collected in Diurnal Studies
Plainfield, Illinois
1 . Samples
Sample No.
1
2
3
4
5
6
7
8
9
2 . Samples
1
2
3
4
5
3 . Samples
1
2
3
4
5
Collected
Time
1655
2030
0030
0230
0500
0600
0730
1007
1655
Collected
0130
0315
0445
0635
1345
Collected
0055
0230
0355
0540
0950
September
Temp.
79 OF
70°F
568F
50°F
46 "F
46°F
568F
72°F
75°F
June 11,
53°F
48°F
54°F
56°F
68°F
July 18,
73°F
73°F
72°F
73°F
80°F
5, and 6, 1973:
Wind
Speed
5-8
2-5
2-5
2-5
2-5
2-5
2-5
4-8
3-5
1974:
light &
variable
calm
1-2
1-2
15-20
1974:
5-7
8-10
5-8
8-10
5-7
Direction
290°
280°
300°
280°
290°
290°
300°
315°
290"
ptly cloudy
clear
315° cloudy
225° ptly cloudy
270° cloudy
225° ptly cloudy
225° cloudy
225° cloudy
225° cloudy
225° cloudy
Location
Cornfield, 3 miles
West of Plainfield,
111. 0.5 miles
South of 111. 126,
150 yards West -
Ridge Road. Samples
taken 3 feet above
ground, 6 rows from
South edge of corn-
field. Corn was
mature, but still
green, 7 to 8 feet
tall.
Weather: Clear
Location as above
but 15 yards West
of Ridge Road, at
edge of plowed
field.
Location as above,
but 0.1 mile North
at end of lane grass
and alfalfa to South
and West- ground
sloped away to South
and West.
* All samples location 10 Map D-2.
41
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APPENDIX D. Maps of Sampling Locations
1. St. Louis, Missouri
2. Plainfield, Illinois
June 27, 1973
July 17, 1973
November 13, 14, 1973
July 31, 1973
August 9, 1973
September 5, 6, 1973
June 11, 1974
July 18, 1974
Points 1-5
Points 2, 6-9
Points 1, 10, 11
Points 1-5
Points 6-9
Point 10
Point 10
Point 10
42
-------
JU 53
RISSANT-^j^f^ i 67 -•;, j%£ /I
bt Jos«pns Hill <. • t
"InlnmaiYT- 3
>'R«djr jliliDir' N . - 6,-
i j*z™ ••. ,. H^WTtCY - •• A ?M,I^ K. - ^ • - /; i r
APPENDIX D-l
Sampling Locations in St. Louis, Missouri
43
-------
rr*«>—
if
UEVILLE;;
=>*-.(
,Vs
a
-,—-i-
1
sV •,
5a
Fi«ll»
/-.
i Dli)pian»»irV ••:''*-''^.s*i-
*\-~<'(/• ''•• f •:V/;-^< ',
%^M§r -;:
SpTtew Mep-o i*';' "
ipw^x;<
Si."' «
•.-<6o^7':-» ^•;.^,T-t-i
^ddiSH
L«>
^
^
•L^?d
N,»M,n.
n—
APPENDIX D-l (Cont'd.)
-------
., .rfj ,„.„..,
-\ lit •/-
.,,..,\::l;i Zi
APPENDIX D-2
Sampling Locations in Plainfield, Illinois, and along 1-55
45
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/3-76-010
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
ISOTOPIC COMPOSITION OF CARBON MONOXIDE IN
ST. LOUIS, MISSOURI AREA
5. REPORT DATE
April 1976 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
L.E. Ross, A. Engelkemeir and E.E. Voiland
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG'\NIZATION NAME AND ADDRESS
Chemical Engineering Division
Argonne National Laboratory
Argonne, Illinois 60439
10. PROGRAM ELEMENT NO.
- fU
11. CONTRACT/GRANT NO.
EPA-IAG-069
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
14.
CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The concentration and isotopic composition of carbon monoxide were determined
in air samples taken in the St.Louis, Missouri area. This information is used to
follow the plume for a major city like St. Louis. Urban air could be detected
as far as 47 miles downwind of the city. The effect of local emissions in
rural areas was found to be minimal. Diurnal studies demonstrated an inverse
relationship between carbon monoxide concentration and oxygen and carbon isotopic
ratios during the night. A parallel relation was found during the daylight hours.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Chemical Analysis
Oxygen Isotopes
Carbon Isotopes
Carbon Monoxide
Field Tests
Diurnal variations
St. Louis, Missouri
18B
07B
07D
14B
14G
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
54
20. SECURITY CLASS (This page)
UNCLAS SIFTED
22. PRICE
EPA Form 2220-1 (9-73)
46
*USGPO: 1976 — 657-695/5397 Region 5-11
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