United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-79-227
December 1979
Research and Development
&EPA
Atmospheric
Chemistry of
Selected Sulfur-
Containing
Compounds
Outdoor Smog
Chamber Study—
Phase 1
Interagency
Energy/Environment
R&D Program
Report
-------
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
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-79-227
December 1979
ATMOSPHERIC CHEMISTRY OF SELECTED
SULFUR-CONTAINING COMPOUNDS
OUTDOOR SMOG CHAMBER STUDY-PHASE 1
by
J. E. Sickles, II
R. S. Wright
Research Triangle Institute
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2437
Project Officer
Bruce W. Gay, Jr.
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
U.S. Environmental Protection Agency
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
-------
DISCLAIMER
This 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.
-------
ABSTRACT
Selected aspects of the chemical behavior of 14 sulfur-containing
compounds were investigated under atmospheric conditions simulated in outdoor
smog chambers. In addition to propene, which was used as a control, the
following compounds were examined: hydrogen sulfide, carbonyl sulfide,
carbon disulfide, methanethiol, methyl sulfide, methyl disulfide, methyl
ethyl sulfide, ethanethiol, ethyl sulfide, ethyl disulfide, thiophene,
2-raethylthiophene, 3-methylthiophene, and 2,5-dimethylthiophene. Target
initial concentrations of 2.0 ppmC of the test compound and 0.1, 0.2, 0.5,
and 1.0 ppm NO (20 percent N02) were employed in the four outdoor smog
A
chambers. Thus, on a single day one test compound was examined at target
initial compound/NO ratios of 20, 10, 4, and 2. This approach permits
A
examination of the results of experiments conducted under identical environ-
mental conditions but at different initial NO concentrations and hence at
x
different initial compound/NO ratios. A total of twenty 2-day four-chamber
X
runs, or eighty 2-day experiments involving irradiated sulfur species-NO or
propene-NO systems was conducted.
The results of experiments conducted with each compound were analyzed
by examination of the influence of initial conditions on selected reaction
parameters. These parameters include: the time to N0-N02 crossover; maxi-
mum concentrations of 03, N02, PAN, SC>2, particulate sulfur, and CN; nitro-
gen mass balance; time to one-half consumption of the test species; and
second-day net ozone concentration. Subsequently, selected reaction para-
meters were compared across test compounds.
This report was submitted in fulfillment of Contract No. 68-02-2437 by
the Research Triangle Institute under the sponsorship of the U.S. Environ-
mental Protection Agency. This report covers the period September 1, 1976,
to February 28, 1978.
111
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CONTENTS
Abstract iii
Figures vii
Tables x
Acknowledgments xiii
1. INTRODUCTION 1
Objective 1
Background 2
2. CONCLUSIONS 6
3. RECOMMENDATIONS 13
4. EXPERIMENTAL 14
Overview 14
RTI Smog Chamber Facility 16
Air purification unit 16
Reactant injection system 20
Sampling system 22
Smog chamber operating characteristics 22
Reagents . 42
Measurement Methods 42
Ozone 45
Nitrogen oxides (NO, N02, and NO ) 45
Peroxyacetyl nitrate 49
Propene 50
Sulfur dioxide and total sulfur 51
Total particulate sulfur 52
Condensation nuclei 52
Freon-12 . . • 53
Solar radiation and ambient temperature .... 54
Environmental variables 54
Data Collection and Handling 54
Procedure 61
5. RESULTS AND DISCUSSION 63
Overview 63
Examination of the Chemical Behavior of Each
Test Compound 64
Propene 64
Hydrogen sulfide 74
Carbonyl sulfide 79
Carbon disulfide 84
-------
CONTENTS
Methanethiol 91
Methyl sulfide 99
Methyl disulfide 105
Methyl ethyl sulfide 112
Ethanethiol 121
Ethyl sulfide 130
Ethyl disulfide 137
Thiophene 144
2-Methylthiophene 151
3-Methylthiophene 158
2,5-Dimethylthiophene 165
Comparison of Chemical Behavior Among Test
Species 173
Time to N0-N02 crossover 173
Maximum first-day ozone concentration 175
Fate of nitrogen oxides 181
Disappearance rate of the test species 187
Gaseous reaction products: SOj and COS 189
Particulate sulfur and its distribution as a
reaction product 191
Nighttime ozone decay 196
Net ozone generation on the second day 199
References 202
Appendix
Detailed Data Sheets for Smog Chamber Experiments 206
vi
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FIGURES
Number Page
1 Largest [03] observed for each tested compound .... 9
ffldx
2 General design of RTI outdoor smog chambers 17
3 Overall system design of RTI Smog Chamber Facility .... 18
4 Air purification unit for RTI Smog Chamber Facility. ... 19
5 Reactant injection system for RTI Smog Chamber
Facility 21
6 Heated stainless steel manifold for volatilizing
liquid test compounds prior to injection into a smog
chamber 23
7 Sampling system for RTI Smog Chamber Facility 24
8 Ozone concentration-time profiles for matched propene-
NO experiments conducted in the four RTI smog chambers
onX8 August 1977 41
9 Flowchart of overall data handling system 55
10 Flowchart of program one 58
11 Flowchart of program two 60
12 Concentration-time profiles of various reactants and
products for the 12 and 13 September 1977 propene-NO
experiment conducted in RTI Chamber No. 3 65
13 Concentration-time profiles of various reactants and
products for the 23 and 24 September 1977 H2S-NOx
experiment conducted in RTI Chamber No. 3 75
14 Concentration-time profiles of various reactants and
products for the 18 and 19 September 1977 COS-NO exper-
iment conducted in RTI Chamber No. 1 81
15 Concentration-time profiles of various reactants and
products for the 21 and 22 September 1977 CS2-NO experi-
ment conducted in RTI Chamber No. 2 88
16 Concentration-time profiles of various reactants and
products for the 2 and 3 September 1977 CH3SH-NO experi-
ment conducted in RTI Chamber No. 4 x. . . . . 96
17 Concentration-time profiles of various reactants and
products for the 28 and 29 September 1977 CH3SCH3-NO
experiment conducted in RTI Chamber No. 3 101
vn
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FIGURES
Number
18 Concentration-time profiles of various reactants and
products for the 5 and 6 October 1977 (CH3S)2-NO
experiment conducted in RTI Chamber No. 3. . . .X 107
19 Concentration-time profiles of various reactants and
products for the 10 and 11 October 1977 CH3SC2H5-NO
experiment conducted in RTI Chamber No. 3 113
20 Concentration-time profiles of various reactants and
products for the 3 and 4 October 1977 C2H5SH-NO
experiment conducted in RTI Chamber No. 4 123
21 Concentration-time profiles of various reactants and
products for the 15 and 16 October 1977 C2H5SC2H5-NO
experiment conducted in RTI Chamber No. 2 134
22 Concentration-time profiles of various reactants and
products for the 7 and 8 October 1977 (C2H5S)2-NO
experiment conducted in RTI Chamber No. 3. . . . * . . . . 140
23 Concentration-time profiles of various reactants and
products for the 17 and 18 October 1977 thiophene-NO
experiment conducted in RTI Chamber No. 1 x. . . 145
24 Concentration-time profiles of various reactants and
products for the 30 and 31 October 1977 2-methylthio-
phene-NO experiment conducted in RTI Chamber No. 2. . . . 154
25 Concentration-time profiles of various reactants and
products for the 22 and 23 October 1977 3-methylthio-
phene-NO experiment conducted in RTI Chamber No. 3. . . • 159
26 Concentration-time profiles of various reactants and
products for the 20 and 21 October 1977 2,5-dimethyl-
thiophene-NO experiment conducted in RTI Chamber
No. 4. . . .x 169
27 Range of the duration of irradiation (hours past sunrise)
required on the first day to achieve NO-N02 crossover. . . 174
28 Range of maximum ozone concentrations produced by each
tested compound 176
29 Maximum ozone concentrations produced at various target
initial HC/NO ratios 177
30 Maximum ozone concentrations produced at various target
initial HC/NO ratios 178
31 Maximum ozone concentrations produced at various target
initial HC/NO ratios 179
32 Concentration-time profiles of selected reactants and
products for the 11 November 1977 C3H6-NO experiment
conducted in RTI Chamber No. 1 ? 183
Vlll
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FIGURES
Page
Concentration-time profiles of selected reactants and
products for the 7 October 1977 (C2H5S)2~NO experiment
conducted in RTI Chamber No. 2 ? 184
34 Range of fractions of initially present NO that could
be accounted for at the 1700 EST hour of tSe first
day 186
35 Range of the hours of irradiation past sunrise required
on the first day to consume one-half of the initially
present test compound 188
36 Range of maximum sulfur dioxide concentrations normalized
to the equivalent of an initial concentration of 1 ppmS
for each test compound 190
37 Range of maximum total particulate sulfur concentrations
normalized to the equivalent of an initial concentration
of 1 ppmS for each test compound 192
38 Range of R values (ratio of product sulfur as particulate
to the total accountable reacted sulfur) for each test
species 195
39 Ozone half-life for the experiment that produced the
largest first-day maximum ozone concentration with each
tested compound 198
40 Range of second-day net ozone concentrations produced by
each tested compound 201
IX
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TABLES
Number Page
1 Analyses of Raw Gas from Noncommercial Gasification
Facilities .......................... 3
2 Compounds Identified from Tenax Cartridge #4 from Coal
Run 80131 1L 6B2C (after 75 minutes) ............. 5
3 Summary of the Experimental Program
4 Leak Rate Coefficients in RTI Smog Chambers Based on
Freon-12 Measurements ..................... 27
5 Maximum Ozone Concentration Achieved in RTI Smog
Chambers During Purified Air Irradiation Experiments ..... 30
6 Ozone Half-Lives in RTI Smog Chambers ............. 32
7 Summary of Ozone Half-Lives for Various Smog Chambers ..... 34
8 NO Oxidation in RTI Smog Chambers ............... 35
9 Leak Rate Coefficients in RTI Smog Chambers Based on
NO Measurements ....................... 36
x
10 Sulfur Dioxide Decay in RTI Chambers ............. 39
11 Reagents ........................... 43
12 Measurement Methods ........... . .......... 44
13 NO and N02 Interference Equivalents for 2 ppmC of Each
Test Species ......................... ^8
14 Summary of Selected Results from Smog Chamber Experiments
Conducted with Propene and NO 66
15 Summary of Selected Results from Smog Chamber Experiments
Conducted with Propene and NO 68
16 Summary of Selected Results from Smog Chamber Experiments
Conducted with Propene and NO
X
70
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TABLES
Numbe
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
r
Summary of Selected Results from Smog Chamber Experiments
Conducted with H->S and NO . . '. . .
* X
Summary of Selected Results from Smog Chamber Experiments
Conducted with COS and NO
X
Summary of Selected Results from Smog Chamber Experiments
Conducted with CSo and NO
* X
Summary of Selected Results from Smog Chamber Experiments
Conducted with CH-»SH and NO
d X
Summary of Selected Results from Smog Chamber Experiments
Conducted with CH3SH and NO
Summary of Selected Results from Smog Chamber Experiments
Conducted with CHsSCHs and NO
A
Summary of Selected Results from Smog Chamber Experiments
Conducted with (CHS)2 and NO
Summary of Selected Results from Smog Chamber Experiments
Conducted with CH3SC2H5 and NO
Summary of Selected Results from Smog Chamber Experiments
Conducted with CH3SC2Hs and NO
A
Summary of Selected Results from Smog Chamber Experiments
Conducted with C2H5SH and NO
Summary of Selected Results from Smog Chamber Experiments
Conducted with C2H5SH and NO
A
Summary of Selected Results from Smbg Chamber Experiments
Conducted with C2H5SC2Hs and NO ...
Summary of Selected Results from Smog Chamber Experiments
Conducted with (C2H5S)2 and NO
A
Summary of Selected Results from Smog Chamber Experiments
Conducted with Thiophene and NO
r x
Summary of Selected Results from Smog Chamber Experiments
Conducted with 2-Methvlthioohene and NO
Pace
76
82
86
92
94
102
108
114
. . 116
124
126
138
146
152
XI
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TABLES
Number Page
32 Summary of Selected Results from Smog Chamber Experiments
Conducted with 3-Methylthiophene and NO 160
A
33 Summary of Selected Results from Smog Chamber Experiments
Conducted with 2,5-Dimethylthiophene and NO 166
XII
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ACKNOWLEDGMENTS
This project was conducted by the Research Triangle Institute under
Contract Number 68-02-2437 for the U. S. Environmental Protection Agency.
The support of this agency is gratefully acknowledged as is the advice and
guidance of Dr. J. J. Bufalini and Mr. B. W. Gay, Jr. who served as Project
Officers. In addition, Dr. T. G. Dzubay of EPA provided XRF sulfur analyses
of particulate samples collected during this project, and Mr. J. H. Rudisill
provided solar radiation and ambient temperature data.
Several persons in the Environmental Measurements Department of the
Research Triangle Institute contributed substantially to this project.
Mr. C. E. Decker was Laboratory Supervisor for the project. Mr. D. P.
Dayton, Mr. J. C. Mulroy, and Mr. D. L. Ewald conducted day-to-day chamber
operations, data reduction, and data verification. Mr. R. 0. Lyday devel-
oped the computer software for the data handling system and Mr. D. L. Ewald
used the system to generate data listings and plots.
We gratefully acknowledge these individuals for their efforts in bring-
ing this project to a successful conclusion.
Xlll
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SECTION 1
INTRODUCTION
During the next several decades, the use of coal, shale oil, and other
fossil fuels is expected to increase in the United States to satisfy growing
domestic energy needs. Many fossil fuels are dirty, bulky, and difficult to
transport, and have low heat content in their raw, natural states. To make
these raw fuels more acceptable, fuel conversion processes are being planned
and will soon be producing clean, high-energy gas, solid, and liquid syn-
thetic fuels. Operations such as coal gasification and liquefaction, shale
oil production, and petroleum refining will assume an increased role in
future energy production.
Fuel conversion facilities are potential sources of atmospheric emis-
sions. Contaminants such as mineral matter and sulfur-, nitrogen-, and
oxygen-containing compounds are removed and transformed during the proc-
essing of raw fuels. Emissions of compounds derived from fuel contaminants
are anticipated. In addition, emissions of species from the processing
operations themselves are expected to be produced. These atmospheric emis-
sions may include not only the commonly considered pollutants such as SO ,
X
NO , CO, and hydrocarbons, but also other compounds not previously considered
from either the toxic or ozone-generative viewpoints. Definition of the
identities and emission rates of emitted species as well as an understanding
of their atmospheric chemistry will permit the assessment of the impact of
synthetic fuels processing on air quality.
OBJECTIVE
The objective of the present study is to conduct smog chamber experi-
ments that are designed to elucidate selected aspects of the atmospheric
chemistry of chemical species expected to be present in emissions from fuel
conversion facilities. A major goal is to investigate the ozone-producing
potential of each test species in combination with various amounts of nitro-
gen oxides. It is anticipated that the information gained in this study
-------
will aid the EPA Office of Air Quality Planning and Standards in formulating
air pollution control strategies.
BACKGROUND
Fuel conversion technology is in the early stages of its development.
The identity and emissions rates of species emitted by fuel conversion
processes, therefore, are poorly defined. A review of emissions from emerg-
ing energy industries was conducted on an earlier RTI contract, EPA 68-02-
2258.* In this review, a broad spectrum of sulfur-containing compounds,
nitrogen-containing compounds, and hydrocarbons was identified from reported
analyses of intermediate process streams and final products. The extent to
which these species will be released to the atmosphere depends to a large
degree on currently undefined processing details. Current estimates are
based on engineering process flow diagrams, design material balances, and
pilot plant results. Emissions measurements are needed to supplement and
verify these estimates.
Coal gasification is a typical fuels conversion process. As with other
synthetic fuels processes, only bench- and pilot-scale facilities are cur-
rently in operation in the United States. Although several modern commer-
cial facilities are operational outside of the United States, detailed
resolution of atmospheric emissions from these facilities is not currently
available.
While it is recognized that processes downstream of the gasifier will
undoubtedly ameliorate emissions, analyses of the raw effluent from bench-
and pilot-scale gasification facilities should provide rough estimates of
the compounds that could potentially be emitted. Typical analyses of raw
gas from noncommercial gasifiers have been compiled and are presented in
Table 1.
Raw gas analyses from the Synthane and Bureau of Mines Fixed Bed proc-
esses are presented. In addition, the Research Triangle Institute, through
EPA Grant No. 1394 (Pollutants from Synthetic Fuels Production), is conduct-
ing a laboratory study to identify emissions from a small batch-fed gasifier.
Analyses from two experiments conducted in the RTI gasifier are also pre-
sented in Table 1.
Commercial gasification facilities are designed to be continuous opera-
tions and to have steady-state operating conditions. Thus, with the excep-
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TABLE 1. ANALYSES OF RAW GAS FROM NONCOMMERCIAL GASIFICATION
FACILITIES
Process Synthane Bureau of Mines RTI—
Coal Illinois No. 6 Western Ky. Illinois No.
Major (Volume
Species Percent) b/ c/
N2 + 47.6 22.6 26.9
CO 12.3 20.6 8.6 16.4
C02 35.3 ' 5.9 5.0 17.0
H2 35.4 13.8 32.6 36.0
CH4 • 13.9 2.8 22.7 2.4
H20 -H- 8.4
RTI-''
6 Illinois No. 6
d/ e/
58.8 21.8
2.8 7.0
3.3 17.9
8.6 46.8
15.4 7.6
Minor Species (ppm)
C2H6 15,600 NR 8,736 28
C2H4 NR NR 4,836 5
C3H8 NR NR 780 0.
C3H6 NR NR 1,036 0.
iC4Hio NR NR 50 0.
nC^o NR NR 82 0.
S02 10 NR 0.0 0.
H2S 16,200 6,000 18,986 3,979
COS 300 1,000 45 30
CS2 NR NR 39 0.
CH3SH 30 NR 90.
C2H5SH NR NR 0.0 0.
Thiophene 40 NR 576 0.
Methyl
Thiophene 10 NR NR NR
Dimethyl
Thiophene 10 NR NR NR
NO NR NR NR NR
NH3 NR , 2,500 NR NR
HCN < 10 NR NR NR
Benzene 220 NR NR NR
Toluene 50 NR NR NR
Xylenes 20 NR NR NR
+ Nitrogen- free analysis
++ Water- free analysis
a/ Because of the batch-type operation, data from the RTI
necessarily representative of commerical facilities.
W Test No. 80131I16B2C after 20 minutes; temperature 518
cj Test No. 80131I16B2C after 90 minutes; temperature 926
ji/ Test No. 6A after 18 minutes; temperature 601°C
e/ Test No. 6A after 112 minutes; temperature 778°C
25,100 270
5,000. 96
0 7,900 120-
0 5,600 52
0 600 7
0 1,200 < 1
0 65
29,400 5,900
100 44
0 27 < 1
0 45 10
0 69 < 3
0 151 < 5
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
NR NR
gasifier are not
°C
°C
-------
tion of upset conditions, the composition of the effluent from commercial
facilities should be relatively constant. In contrast, the RTI gasifier is
operated as a batch reactor. It is first heated and then charged with coal.
As the coal temperature rises, the composition of the raw evolving product
gas changes with time--rapidly at first and then more slowly. In the later
stages of a run, once a stable reactor temperature has been attained, the
effluent achieves a fairly constant composition. Raw gas analyses from both
the early and late stages of two experiments are presented in Table 1.
Thus, while the mode of operation of the RTI gasifier prevents these results
from being entirely representative of commercial facilities, they should
provide suitable estimates of compounds that could be emitted from commer-
cial units.
The raw gas composition, as indicated in Table 1 from RTI gasifier
experiments, was determined from gas samples that had been collected in
glass bulbs. Raw gas samples were also collected on Tenax and XAD sorbents
for subsequent GC/MS analyses. Compounds identified in samples collected on
sorbents during Run No. 80131116B2C are presented in Table 2. Although more
comprehensive quantitative analyses of the raw gas are not available at this
time, these- analyses are sufficient to emphasize the dominant aromatic
character of the high molecular weight species that comprise the raw gas.
For example, large amounts of toluene, benzene, and naphthalene were identi-
fied.
The following compounds were selected for smog chamber investigation in
the current study.
H2S CH3SH CH3SC2H5 (C2H5S)2 3-Methylthiophene
COS CH3SCH3 C2H5SH Thiophene 2,5-Dimethylthiophene
CS2 (CH3S)2 C2H5SC2H5 2-Methylthiophene
The RTI gasifier experiments that are summarized in Tables 1 and 2 had not
been conducted when these compounds were selected. Based on the more recent
information provided in Table 1, these still appear to have been reasonable
choices.
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TABLE 2. COMPOUNDS IDENTIFIED FROM TENAX CARTRIDGE
FROM COAL RUN 80131 IL 6B2C (AFTER 75 MINUTES).
Chromatographic Chromatographic
Peak No. Compound M9/I Peak No. Compound M9/I
1
la
2
2a
2b
4
4i
4b
4c
5
5a
5b
5c
5d
6
7
7a
8
9
9a
10
11
12
12a
12b
13
14
15
15a
16
16a
16c
17
18
18a
19
19a
19b
20
20a
20b
20c
21
21a
CO,
carbonyl sulphide
sulfur dioxide
butene isomer
(FreonlD (BKG)
acetone
furan (tent)
C4H,0 isomer (tent)
C4H100 isomer
dichtoromethane (BKG)
carbon disulfide
C,H. (tent)
CTH10 isomer
C,HI( isomer
methyl ethyl ketone
hexafluorobenzena T
C»H14 isomer
perfluorotoluene T
benzene 60
, thiophene 2.2
acetic add 9
n-heptane
toluene 872
methylthiophene isomer 4
C(HU isomer
n-octane
silane compound
ethylbenzene 1
ethylthiophene 3
xylene isomer 3
dimethylthiophena 2.6
dimethylthiophene isomer 0.7
C, H, isomer
xylene isomer 12
dimethylthiophene isomer 0.7
n-nonane
C, -benzene isomer
hydrocarbon
benzaldehyde 1.3
C, -benzene isomer (tent)
Cj-thiophena isomer
C, -benzene isomer
C, -benzene isomer 14
phenol
21b
21c
22
22a
23
23a
24
24a
24b
24c
25
25a
26
27
28
28a
28b
28c
28d
29
2Sa
29b
29c
30
31
3la
32
32a
33
33a
34
34a
35
35a
C, -benzene isomer
Cj-thiophene isomer
C, -benzene isomer
Cj-thiophene isomer
benzofuran +
C, -benzene
sulfur compound or unknown
n-decane
C, -benzene + C,H, -benzene
isomen
saturated hydrocarbon
indane
cresol isomer
indene
acetophenone
cresol isomer
C4 -benzene isomer
C4 -benzene isomer
C4H, -benzene isomer
methylbenzofuran isomer
methytbenzofuran isomer
C4 -benzene isomer
C, -phenol isomer
C4H7 -benzene
methylindene isomer
methytindene +
silane compound
saturated hydrocarbon
naphthalene
benzothiophene
0-methy (naphthalene
methyl benzothiophene
o-methylnaphthalene
C,,H10 isomer (tent)
C14HJO isomer
C,,H14 isomer
-------
SECTION 2
CONCLUSIONS
The purpose of the present study is to investigate selected aspects of
the chemical behavior of 14 sulfur-containing compounds under atmospheric
conditions simulated in outdoor smog chambers. A major goal is to examine
the ozone production of each test compound under various initial conditions.
In addition to propene, which was employed as a control, the following
compounds were examined: hydrogen sulfide, carbonyl sulfide, carbon disul-
fide, methanethiol, methyl sulfide, methyl disulfide, methyl ethyl sulfide,
ethanethiol, ethyl sulfide, ethyl disulfide, thiophene, 2-methylthiophene,
3-methylthiophene, and 2,5-dimethylthiophene. Target initial concentrations
of 2.0 ppmC* of the test compound and 0.1, 0.2, 0.5, and 1.0 ppm NO (20 per-
cent N02) were employed in the four RTI smog chambers. Thus, on a single day
one test compound was examined at target initial compound/NO ratiosf of 20,
10, 4, and 2. Twenty 2-day, four-chamber runs, or eighty 2-day experiments
involving irradiated sulfur species-NO or propene-NO systems were conducted.
A A
In addition, 8 two-day, four-chamber runs were conducted to characterize the
smog chambers. Approximately 220 chamber days of data were collected during
the current contract.
In most cases, the photochemical behavior of irradiated mixtures of
NO and individual test species was similar in various respects to that of
irradiated mixtures of NO and hydrocarbons such as propene. Except for
experiments conducted with H2S and COS, the presence of the test species
*Since H2S does not contain carbon, a target initial concentration of 2 ppmV
of this compound was used.
tFor typical photochemical smog systems the HC/NO ratio is a parameter that
is normally considered to be an indicator of the system's reactivity.
Although it is recognized that the tested sulfur-containing compounds
strictly are not hydrocarbons, the term, "HC/NO ratio," is nevertheless
used in this report instead of "compound/NO ra£io." Furthermore, this
ratio has the units ppmC/ppm for each tested compound, except I^S where
the units are ppmV/ppm.
-------
resulted in more rapid conversion of NO to N02 than would have occurred in
its absence. For the thiols, organic sulfides, and organic disulfides, con-
version from NO to N02 was extremely rapid and rather insensitive to initial
conditions. The organic disulfides displayed the most rapid conversion of
NO to N02 of all the species tested in the current study. For carbon disul-
fide and thiophene, the times to crossover were highly sensitive to initial
conditions and, in one case for thiophene, crossover occurred on the second
day. A seasonal influence on the times to crossover was exhibited in the
propene-NO experiments.
One measure of reactivity of an organic is its ozone-forming potential
when irradiated in the presence of nitrogen oxides. Since EPA is concerned
with the control of organic emissions to control ambient ozone concentration,
it is appropriate to compare ozone-production potential of the tested com-
pounds. For each tested compound, the largest maximum concentration of
ozone observed in the current study is illustrated in Figure 1. The compounds
are listed in the order of descending reactivity as measured by maximum
ozone production.
Except for the experiments conducted with H2S and COS, substantial
amounts of ozone accumulated during at least one of the experiments conducted
with each test compound. The maximum ozone concentrations were rather
sensitive to initial conditions, and the largest [03] generated by tested
QlciX
sulfur species was generated by the CH3SCH3-NO system. Among the test
species the thiols, organic sulfides, and organic disulfides had the largest
ozone-production potential, and produced their largest maximum ozone concen-
trations at low initial HC/NO ratios. The largest [03] for the thiols
x max
occurred at the target HC/NO ratio of 4. Same-day experiments suggest that
methanethiol has a larger first-day ozone-generative potential than ethaneth-
iol. For organic sulfides and disulfides the [03] decreased sharply as
max
the target HC/NO ratio was increased from 2 to 20.
«
In general, the thiophenes produced less ozone than the previously
mentioned thiols, organic sulfides, and organic disulfides.
Thiophene and 2-methylthiophene produced the largest [03] at the
DUclX
target HC/NO ratio of 10, while 3-methylthiophene and 2,5-dimethylthiophene
A
produced the largest [03] values at the target HC/NO ratio of 4. Among
IDaX X
the thiophenes, 3-methylthiophene produced the most ozone. The addition of
-------
a raethyl group onto the heterocyclic thiophene molecule modifies its reac-
tivity as indicated by maximum ozone production. In addition, these results
suggest that reactivity is significantly enhanced by the addition of a
methyl group at the 3-position in comparison to adding either one or two
methyl groups at the 2-position.
The photochemical behavior of irradiated mixtures of NO and H2S was
markedly different from that of irradiated mixtures of NO and a hydrocarbon
such as propene. Hydrogen sulfide did not act to promote the oxidation of
NO to N02- Instead, the reverse occurred; N02 was reduced rapidly to NO,
and essentially no ozone accumulated. The results indicate that the apparent
reduction of N02 to NO in the presence of H2S involves a photochemical
process.
On the first day of the experiments conducted with carbonyl sulfide,
very little NO was oxidized to N02, and essentially no ozone was produced.
In most respects the results from irradiating COS and NO were no different
A
than those expected from irradiating NO in pure air.
A
Substantial quantities of ozone accumulated in the experiments conducted
with carbon disulfide, but only at the highest HC/NO ratio. Carbonyl
sulfide was found to be a major product in each of the experiments conducted
with CS2. In addition, COS was observed as a minor product in experiments
conducted with nine of the remaining tested sulfur-containing compounds.
Strong seasonal influences on the maximum ozone concentrations were
exhibited in the propene-NO experiments. Much larger ozone maxima were
produced in September, and they were more sensitive to initial conditions
than was found in replicate experiments conducted in November. The effect
was most pronounced at the target HC/NO ratio of 2.
Many of the tested sulfur-containing compounds were found to interfere
with the chemiluminescent determination of nitrogen oxides. This is believed
to result from the chemiluminescence of species formed within the NO analyzer
by reaction of ozone with the sulfur-containing test compound.
On the average, at the maximum N02 concentration, N02 accounted for 47
percent of the initial NO in the experiments conducted with the thiophenes.
A
In the experiments conducted with the thiols, organic sulfides, and organic
disulfides, this value was 60 percent. The corresponding value in the pro-
pene-NO experiments was 73 percent.
-------
VO
C3H6 (Control)
CH3SCH3.
CH3SH
CI13SC2II5
CH3SSCH3
3-Methylthiophene
C2H5SH
CS2
2,5-Dimethyithiophene
2-Methylthiophene
Thiophene
COS
H2S
— *
*
*
II I I I
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
PP™
Figure 1, Largest [C>3]max pbseryed for each tested compound,
-------
Methyl nitrate (MN) was tentatively identified as a reaction product in
experiments conducted with propene, the tested thiols, organic sulfides,
organic disulfides, and 2,5-dimethylthiophene. Ethyl nitrate (EN) was
tentatively identified as a reaction product only in experiments that involved
C3H6, CH3SC2H5, C2H5SH, C2H5SC2H5, and (C2H5S)2. Appreciable amounts of EN
were not found in the experiments conducted with the thiophenes. In every
case where EN was found, peroxyacetyl nitrate (PAN) was also found. In .
addition, PAN was detected in appreciable amounts as a reaction product for
the three substituted thiophenes. Based on the chemical structure of H2S,
COS, CS2, CH3SH, CH3SCH3, and (CH3S)2, PAN is not expected as a reaction
product of these compounds. The formation of PAN, MN, and EN as reaction
products of the thiols, organic sulfides, and organic disulfides can be
rationalized if the photooxidation of these species involves cleavage of S-C
bond, which in the presence of air and NO leads to their formation.
A
Evidence was found for the existence of a hypothetical nitrogen-
containing species. In several cases at the highest initial HC/NO ratios
the NO concentration exhibited a loss of a few ppb with a subsequent recov-
A
ery. This behavior occurred after N0-N02 crossover and coincided with ,the
initial accumulation of PAN. The identity of this hypothetical species is
unknown.
Nitrogen balances were estimated for each test compound for the 1700
EST hour of the first day. The poorest nitrogen balances occurred for the
experiments conducted with methanethiol, methyl sulfide, and methyl disul-
fide. Generally less than 15 percent of the initially present NO could be
Jv
accounted for in these cases. For the experiments conducted with methyl
ethyl sulfide, ethanethiol, ethyl sulfide, and ethyl disulfide, the nitrogen
balances again were relatively insensitive to initial conditions and were
similar, with approximately 20 to 45 percent of the initially present NO
A
accountable at the 1700 EST hour of the first day. For the thiophenes, the
nitrogen balances differed widely, depending on the molecular structure.
The range of nitrogen balances for carbon disulfide was similar to those for
propene. In these cases, the nitrogen balances were sensitive to initial
conditions and ranged from 25 to 75 percent. Nitrogen balances approached
unity in the experiments conducted with COS and with H2S. The unaccountable
product nitrogen may have been nitric acid or some other undetermined nitro-
gen-containing species.
10
-------
The available data did not permit precise estimates of disappearance
rates for H2S, COS, and CS2; however, they do suggest that more than one day
of irradiation was required to achieve one-half consumption of each of these
compounds. In addition, it is likely that COS was the least reactive and
most stable test species under the experimental conditions employed in the
current study. The thiols and organic sulfides had similar ranges of disap-
pearance rates. Among all the tested compounds, the organic disulfides
displayed the fastest disappearance rates. Among the thiophenes, 3-methyl-
thiophene displayed the fastest disappearance rate.
Sulfur dioxide was found as a reaction product in at least one of the
experiments conducted with mixtures of NO and each tested sulfur-containing
compound except COS, where S02 data were not available.
The largest maximum S02 concentrations were produced by the CHaSH-NO
X
system. Methanethiol, methyl disulfide, ethyl disulfide, 3-methylthiophene,
and 2,5-diraethylthiophene exhibited large S02 production potentials. Methyl
sulfide, methyl ethyl sulfide, and ethyl sulfide produced low but similar
maximum concentrations of S02. Among the thiophenes, 2,5-dimethylthiophene
and 3-methylthiophene produced significantly more S02 than thiophene or
2-methylthiophene.
Condensation nuclei were produced in the experiments conducted with
each of the tested compounds. Propene and COS exhibited the smallest CN
production potential with maximum concentrations ranging between 102 and 103
_3
cm . The largest maximum CN concentrations occurred in experiments conducted
_q
with H2S and with CS2, where concentrations exceeded 10s cm . The remaining
tested sulfur containing compounds exhibited moderate CN production potential
5 -3
with maximum concentrations generally ranging between 104 and 10 cm
Particulate sulfur was found as a reaction product in at least one of
the experiments conducted with mixtures of NO and each of the tested sulfur-
containing compounds. The largest particulate sulfur (TPS) concentrations
were produced by the CHsSH-NO system. Both methanethiol and methyl disul-
fide exhibited relatively large particulate sulfur production potentials.
Methyl sulfide, methyl ethyl sulfide, ethanethiol, ethyl sulfide, ethyl
disulfide, and 3-methylthiophene exhibited moderate particulate sulfur pro-
duction potentials. The three remaining thiophenes generated small maximum
particulate sulfur concentrations. Only trace amounts of particulate sulfur
were produced by hydrogen sulfide, carbonyl sulfide, and carbon disulfide.
11
-------
The times of occurrence of maximum sulfur dioxide and particulate
sulfur concentrations were examined. Maximum TPS concentrations preceded
maximum S02 concentrations in many cases. In the experiments conducted with
H2S, COS, and CS2, either missing or low concentration data prevented mean-
ingful comparisons. In at least one of the experiments conducted with each
of the remaining test species, however, maximum TPS concentrations either
preceded.or were coincident with maximum 803 concentrations.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [S02D was determined for many of the tested
compounds. Generally, these data indicate that the majority of the account-
able product sulfur for the tested species existed as S02 and that less than
20 percent of accountable product sulfur existed in the particulate phase.
Ratios in excess of 0.2 occurred for methanethiol, methyl sulfide, methyl
disulfide, and methyl ethyl sulfide.
Dark-phase ozone half-lives were examined for many of the tested com-
pounds. These results suggest the possible presence of undefined ozone-
reactive reaction products in the experiments conducted with carbon disulfide,
the thiols, the organic sulfides, the organic disulfides, and the thiophenes.
The largest second-day net ozone concentration was produced in an
experiment conducted with methanethiol. Net ozone concentrations exceeding
0.2 ppm accumulated in at least one experiment conducted with propene, with
carbon disulfide, with methanethiol, with ethanethiol, and with 2,5-dimethyl-
thiophene. Based on the relatively large ranges of net ozone concentrations
for these species, second-day ozone production by these compounds was highly
sensitive to the (first-day) initial conditions. In contrast, essentially
no ozone accumulated on the second day of experiments conducted with H2S and
with COS.
12
-------
SECTION 3
RECOMMENDATIONS
Based on currently available information, H2S, COS, CS2, CH3SH, C2H5SH,
thiophenes, and aromatic hydrocarbons may be released within an organic
matrix from fuel conversion facilities. The emissions of sulfur species and
the composition of the organic matrix accompanying the sulfur species remain
to be defined. The raw gas analyses in Table 1 indicate that ethane, ethene,
and C6 to Cg aromatics may comprise a considerable portion of the organic
matrix. Unfortunately, the relative amounts of these constituents are
currently unknown. Source tests are required to verify the presence of
these species and more importantly to define the concentrations and relative
amounts of various species within the effluent from "typical" facilities.
With the ever-increasing demand for energy, it is likely that future
fuel conversion facilities will be located in areas not totally remote from
urban centers. Emissions are therefore expected to become mixed with urban
plumes after one or more days of transport. Thus, it is anticipated that
emissions unique to fuel conversion facilities will encounter photochemically
reactive HC-NO systems either within the effluents from the fuel conversion
A
facilities themselves, or through mixing with urban plumes, or both.
Regardless of the source, it is likely that the composition of the
organic matrix will control the reactivity of the gaseous effluent. It is
therefore reasonable to explore the impact of the presence of hydrocarbons
on the atmospheric chemistry of various sulfur species. The addition of
hydrocarbons to an irradiated mixture of nitrogen oxides and a selected
sulfur species may enhance S02 production, increase aerosol generation, and
accelerate particulate sulfur formation. The ozone-generative potential of
organosulfur-NO systems could also be modified by the addition of hydrocar-
bons. These interactions should be explored.
13
-------
SECTION 4
EXPERIMENTAL
OVERVIEW
This subsection describes the experimental design and provides a general
overview of the experiments that were conducted in this study. Detailed
descriptions of the smog chamber facility, reagents, measurement methods,
data reduction and handling, and experimental procedures are provided in
subsequent subsections.
The following compounds were selected for smog chamber investigation in
the current study.
H2S CH3SH CH3SC2H5 (C2H5S)2 3-Methylthiophene
COS CH3SCH3 C2HSSH Thiophene 2,5-'Dimethylthiophene
CS2 (CH3S)2 C2H5SC2H5 2-Methylthiophene
The investigative approach was to use target concentrations of 2.0 ppmC
of the test compound in each of the four chambers. The target NO concentra-
tions (20% N02) were 0.1, 0.2, 0.5, and 1.0 ppm. These experimental condi-
tions correspond to HC/NO ratios of 20, 10, 4, and 2. In the present
X
investigation of organosulfur species, dilution experiments were not con-
ducted--the study involved static experiments only.
A total of 20 two-day, four-chamber runs, or 80 two-day experiments
involving irradiated organosulfur-NO or HC-NO systems, were conducted.
A A
Eight four-chamber smog chamber characterization experiments were also
conducted. Approximately 220 chamber days of data were collected during the
current contract. A summary of the experimental program is presented in
Table 3. To provide rough indications of the environmental conditions that
prevailed during each run day the maximum temperature and the percentage of
the total possible minutes of direct sunshine are also tabulated for each
day.
14
-------
TABLE 3. SUMMARY OF THE EXPERIMENTAL PROGRAM-
a/
Run No.
1
3
4
5
6
18
23
24
25
27
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
46
47
Date (1977)
June 29-July 01
July 06-07
July 10-11
July 15-16
July 17-18
August 08
August 26-27
August 31-Sept. 01
September 02-03
September 12-13
September 18-19
September 21-22
September 23-24
September 28-29
October 03-04
October 05-06
October 07-08
October 10-11
October 15-16
October 17-19
October 20-21
October 22-23
October 30-31
November 09-10
November 11-12
November 13-14
November 18-19
December 03-04
*
Day 1
91
81
78
77
79
81
55
90
92
95
77
64
51
64
73
99
34
76
100
98
100
100
90
71
100
100
100
49
S& W
Day 2
93
85
43
76
77
-
49
96
80
82
74
68
36
13
76
29
29
55
17
92
85
80
49
23 .
83
89
99
0
Day 1
33.9
37.2
35.0
35.0
35.0
33.9
28.9
32.8
32.2
25.6
30.6
26.7
26.7
26.1
18.3
23.9
22.2
18.3
20.0
13.9
18.9
23.9
17.8
24.4
13.3
7.8
15.6
16.1
Day 2
33.9
37.8
33.9
35.6
36.1
-
30.0
32.2
33.9
27.8
30.6
26.1
27.8
23.9
19.4
24.4
18.9
19.4
12.8
20.0
19.4
21.7
16.1
23.9
6.9
10.6
16.1
13.9
Description
Freon-12 Leak Test-
Ozone Generation with Purified Air-
Ozone Decay-
NO Decay-''
NO Decay-'
X j *
Matched Propene-NO ^-'
CH3SH-NO , C2HsSH-NOx£j-£/
S02 Decay-'
CH3SH-NO
X i
Propene-N0xs/
COS-NO
X
CS2-NOx
H2S-NO
CH3SCH3-NOX
C2H5SH-NOx
(CH3S)2-NOX
(C2H5S)2-NOx
CH3SC2Hs-NOx
C2HsSC2Hs-NOx
Thiophene-N0x
2,5-Dimethylthiophene-NOx
3-Methylthiophene-NOx
2-Methylthiophene-NO
CH3SC2Hs-NOx
Propene-N0x
Propene-NO
K /
Thiophenes-NO -
rf /
Ozone Generation with Purified Air-
- Unless noted otherwise, data from these experiments are tabulated in .the appendix.
— Duration of solar radiation reported as percent of possible minutes of direct sunshine
(see text).
- Daily maximum temperature in °C.
- Chamber characterization experiment; data are summarized and discussed in text but are
not tabulated in the Appendix.
-' Experiment employed ambient air with no prior purification in Chamber Nos. 3 and 4.
Instead of the 2 ppmC target initial concentration of the test species that was used
in the other experiments, 5 ppmC was used in this case; replicate CH3SH-NOx experiments
were conducted in Chamber Nos. 1 and 3 and replicate C2HSSH-NO experiments were con-
ducted in Chamber Nos. 2 and 4. x
e/
f/
K/
h/
Experiment employed ambient air with no prior purification in all four chambers.
A different thiophene was used in each of the four chambers.
15
-------
Sixty-eight of the 80 experiments involved the irradiation of sulfur-
containing species in the presence of NO . The remaining 12 experiments
were conducted using the propene-NO system as a control (or typical hydro-
carbon-NO ) system. In addition, 32 chamber characterization experiments
X ®
were conducted. These were a Freon -12 leak test, NO oxidation, NO decay,
S02 decay, 03 decay, 03 generation with purified air, and matched propene-
NO experiment. Except for the chamber characterization experiments, which
X
are described in the text, the data collected during the experimental pro-
gram are tabulated in the appendix.
RTI SMOG CHAMBER FACILITY
The Research Triangle Institute Smog Chamber Facility consists of four
cylindrically shaped smog chambers. Each chamber has a surface area of 51
m2, a volume of 27 m3, and a surface-to-volume ratio of 1.9 m . Figure 2
illustrates the general design. The chambers are located outdoors, and
irradiation is provided by natural sunlight. The walls are fabricated from
®
0.13-mm (5 mil) thick fluorinated ethene propene (FEP) Type A Teflon film.
The Teflon walls are supported by an interior aluminum framework. The
floors are 0.13-ram thick FEP Teflon film laid over a reflective layer of
aluminum foil, which serves to raise the light intensity within the chambers
and thus compensate for transmission losses through the walls. Mixing in
each chamber is provided by a 0.45-m diameter aluminum fan blade on a shaft
that is driven at 345 RPM by a 185-W (1/4 hp) motor using a belt-pulley
system.
In addition to the chambers proper, provisions have been made for air
purification, reactant injection, and sample collection with subsequent in-
strumental and manual analyses. The overall system is illustrated in Figure 3.
Air Purification Unit
Details of the air purification unit are shown in Figure 4. This unit
has three modes of operation: purge, cleanup, and dilution.
During the purge mode, air is supplied by a blower from a 10-m tower.
By opening a manway in the floor and allowing the tower blower to force air
through each chamber, purge flow rates of up to 2.3 m3 min are attained.
After purging with ambient air, the chambers are sealed and air is
16
-------
3.0
METERS
ALUMINUM
FRAME
Figure 2. General design of RTI outdoor smog chambers.
17
-------
AMBIENT AIR PURGE
Ot>
AIR
PURIFICATION
UNIT
V///////////////,
MANUAL
O SAMP-
LING
PORT
AIR
PURIFICATION
UNIT
REACTANT
INJECTION
SYSTEM
MANUAL
OS AMP
LING
PORT
MANUAL
-/"^SAMP-
M^-' LING
PORT
MANUAL
SAMP
LING
PORT
/////////////////////////A V//////////////////////////////777/
INSTRUMENTATION
LABORATORY
Figure 1. Overall system design of RTI Smog Chamber Facility.
-------
-DILUTION FLOWRATE
CONTROL VALVE
AIR COOLING UNIT
HUMIDIFIER
COOLING WATER
figure 4. Air puril ication unit for R'l'I Sniog Chamber Facility.
-------
recirculated through the purification unit in the cleanup mode. The purifi-
cation unit contains the following equipment:
1. Desiccant column (6.5 kg of 4A molecular sieves);
2. Two HEPA particle filters;
3. Heated catalyst column (5 kg of 0.5 percent Pd on alumina catalyst;
operating temperature: 200°-475° C);
4. Air cooler;
®
5. Purafil column (6.5 kg of Purafil for NO and 03 removal); and
A
6. Humidifier.
Solenoid-driven valving permits the inclusion or exclusion of this equipment
as may be appropriate in achieving desired experimental conditions. In this
study, items 2, 3, 4, and 5 were included for cleanup operation. The purif-
ication or "cleanup" operation requires 8 hours at a flow rate of approx-
imately 0.28 m3 min . Pollutant removal efficiency of the purification
unit is discussed in a subsequent subsection.
To effect dilution, the chamber contents are recirculated through the
purification unit at flow rates corresponding to the desired dilution rate.
In this study, the air purification unit was not operated in the dilution
mode, since only static-mode experiments were called for in the experimental
design.
Reactant Injection System
A schematic of the reactant injection system is presented in Figure 5.
There are three injection manifolds from cylinders of compressed gases. The
flow rates are controlled by calibrated fine metering valves, and the quan-
tity of each injection is controlled by timed, manual operation of the
appropriate solenoid valves. Although a hydrocarbon mix was not employed in
the current study, the provisions for hydrocarbon injections from a copper
manifold are shown in Figure 5. Nitric oxide and N02 are injected sequen-
tially from a Teflon manifold. Ozone may be added by injecting 02 from a
copper manifold through an 03 generator, located at each chamber; this
feature is employed in 03 decay experiments. After the reactants have been
injected, each of the manifolds is flushed with nitrogen.
The test compounds are directly injected into each chamber through the
manual sampling port. Pure gases such as Freon-12, S02, H2S, CH3SH, COS,
20
-------
K>
LAMP TRANSFORMER
U.V. OZONE GENERATOR
VENT
/TO ALL
> SOLENOID
(VALVES
110 VAC
VENT
Figure 5. Reactant injection system for RTI Smog Chamber Facility.
-------
and C^HQ are introduced into the chambers via syringe injection through a
nitrogen-purged 0.5-m length of 4.8-mm ID FEP Teflon tubing. Pure liquids
such as C2H5SH, 082, and the thiophenes are injected as liquids from a
syringe into a heated, nitrogen-purged, glass and stainless steel injection
manifold where volatilization occurs. The manifold is heated to a few
degrees above the boiling point of the organosulfur compound that is being
injected. A schematic of the heated injection manifold is presented in
Figure 6.
Sampling System
The sampling system is illustrated in Figure 7. An automatic timer
activates the appropriate sampling solenoid valves and provides for a 10-
minute sample from each chamber once per hour. During the remaining 20
minutes of each hour, the instruments can automatically sample ambient air
from the 10-m tower, or the operator is free to calibrate the instruments or
analyze bag samples.
The sampled air must pass from a chamber to the laboratory through
lengths of 4.8-mm ID TFE Teflon tubing that range from 26 to 48 m, depending
on the chamber. The sample is drawn at a flow rate of 0.005 m3 rain (5 1/min)
by a Metal-Bellows MB-41 pump located in the laboratory. The sample is
delivered to a glass manifold from which the instruments draw their samples.
The residence time in the sampling line is less than 10 seconds. The instru-
ments include an 03 analyzer, a NO-N02NO analyzer, and gas chromatographs
X
designed to determine Cl to Cs hydrocarbons, PAN, and sulfur species. The
total volumetric flow requirement is 0.003 m3 rain (3 1/min).
In addition to the automated sampling system described above, a port is
located in the vertical wall of each chamber for periodic manual grab sam-
pling (see Figure 3). Condensation nuclei and filter samples for subsequent
determination of particulate sulfur are collected at this point. Typically,
grab samples are collected several times a day from each chamber (see the
appendix for exact times).
Smog Chamber Operating Characteristics
Operating characteristics of the chambers comprising the RTI Smog
Chamber Facility are documented in the following paragraphs. This informa-
22
-------
ts>
TEFLON FILM CHAMBER WALL
MANUAL SAMPLING PORT
\
VOLATIZED COMPOUND
+N2 PURGE GAS INTO
CHAMBER
STAINLESS STEEL
HEATING TAPE
STAINLESS STEEL ENCASED
CHROMEL ALUMEL
THERMOCOUPLE
CONNECTION TO
THERMOCOUPLE
READOUT
HEATING TAPE POWER LINE
(TO VARIABLE VOLTAGE
POWER SUPPLY)
GLASS LINER
?
SEPTUM
N2PURGE
GAS IN
GAS TIGHT SYRINGE
CONTAINING LIQUID
TEST COMPOUND
5 cm
]—I
Figure 6. Heated stainless steeJ manifold for volatilizing liquid test compounds prior to injection
into a sino^ chamber.
-------
AMBIENT
AIR
SAMPLE
to
TFE TEFLON
TUBING
4.8 mm 10.
6.4 mm OO
LO.
NO/NOX
ANALYZER
OZONE
ANALYZER
X"—X
n
GLASS MANIFOLD
CHROMATO-
GRAPH
PAN
CHROMATO-
GRAPH
VENT
METAL BELLOWS PUMP
5 LITERS/MINUTE
SULFUR
CHROMATO-
GRAPH
r/l
TIMER
J_
-o 115 VOLTS AC
12 VOLTS
DC POWER
SUPPLY
OUTDOORS (/, INSTRUMENTATION LABORATORY
Figure 7. Sampling system for KTI Smog Chamber Facility.
-------
tion is reported to provide a basis for assessing the performance of the RTI
chambers and to permit comparison with other chambers.
Mixing—
As noted earlier, mixing in each chamber is provided by a fan designed
for that purpose. Unless specified otherwise, the fan operated continually
during each experiment.
Air velocity measurements have been conducted within each chamber. The
minimum air velocity was measured to be greater than 0.05 m sec within
0.02 m of the floor. Air velocities increased with distance from the walls
to a maximum that was greater than 4.0 m sec near the moving fan blade.
If a smog chamber can be considered to be an agitator-stirred tank,
then a published relationship can be used to estimate the time required for
complete mixing.2 This procedure indicates that the mixing of an injected
gas should be 90 percent complete within 24 seconds and 99 percent complete
within 43 seconds after injection.
Performance of Air Purification System—
The air purification system routinely reduces the NO content of the
A
purified air to a measured zero (minimum detectable concentration (MDC):
0.005 ppm). As reported in a previous study,3 the catalytic hydrocarbon
oxidation system typically reduces €2 to C10 hydrocarbons measured by gas
chromatography to less than 20 ppbC (MDC: 0.1 ppb [v/v]). Samples collected
from three of the chambers during the current study on 10 and 11 November
1977 revealed precleanup C% to C5 hydrocarbon concentrations of 27.5, 14.2,
and 18.4 ppbC and postcleanup levels of 0.0, 2.4, and 2.2 ppbC. These
results illustrate the effectiveness of the air purification system.
Chamber Tightness—
Exchange of chamber contents with the ambient atmosphere is expected.
Chamber leaks may be attributed to replacement of the volume required by
sampling and to chamber "breathing" caused by diurnal temperature variations
and buffeting by winds. During the first two years of operation of the RTI
smog chambers, 1975 and 1976, the average daily leak rate coefficients were
observed to increase from 0.005 hr to values greater than 0.015 hr .3
Just prior to the commencement of the current study in May of 1977 the
Teflon walls were replaced, and leak rate coefficients were redetermined.
25
-------
To quantify chamber leakage, first order leak rate coefficients were
estimated by least squares regressions of In [tracer] versus time data.
Freon-12 was used as the inert tracer. Results of these experiments are
summarized in Table 4.
The nighttime leak rate coefficients ranged from 0.002 to 0.005 hr"
with a mean of 0.0035 ±0.0010 hr . The daytime values ranged from 0.003 to
0.012 hr*1 with a mean of 0.0063 ±0.0026 hr'1. Overall leak rate coeffi-
cients for the four smog chambers determined for the three-day experimental
period were in excellent agreement. The mean overall value for the four
chambers, was 0.004 ±0.0007 hr~ , which corresponds to dilution of 10 percent
in 24 hours. The leak rate coefficients observed in the RTI chambers com-
pare favorably with the value of 0.01 hr reported for the newly constructed
UNC outdoor smog chambers.4
The sampling flow rate of 0.005 m3 min for 10 minutes per hour cor-
responds to a loss coefficient of 0.002 hr or dilution of 5 percent in 24
hours. If 0.005 hr is taken to be typical for the current program, then
environmental factors account for over half of the leakage. The results in
Table 4 indicate that the daytime leak rate coefficients are approximately
twice as large as the nighttime values. This difference may be due to in-
creased wind speeds normally observed during the day and suggests that buf-
feting by winds may be responsible for leakage in excess of that required
for sample replacement.
Unless noted to the contrary, the concentration data reported in the
present study were not adjusted to correct for dilution.
Sample Line Losses—
The most distant chamber is 48 m from the instruments in'the laboratory.
When NO, N02, and 03 are present in a chamber during periods of irradiation,
a small reduction of NO and 03 and a slight increase in N02 may occur in the
dark sample line due to the dark-phase reaction of NO and 03i5 In view of
the short residence time (10 seconds), this contribution should be small in
most cases, and the data were not corrected for these effects.
The sampled air volume must pass through a considerable length of sam-
pling line (26 to 48 m) and a pump before it is delivered to the instruments
for analysis. Sample modification is expected. In a recent investigation
26
-------
TABLE 4. LEAK RATE COEFFICIENTS IN RTI SMOG CHAMBERS
BASED ON FREON-12 MEASUREMENTS
Date
Chamber 1
Leak Rate Coefficient-
-
Chamber 2
Chamber 3
Chamber 4
Comment
10
-vl
6/29, 30/77
6/30, 7/1/77
7/1, 2/77
6/29/77
6/30/77
7/1/77
6/29-7/2/77
0.0051
0.0032
0.0032
0.0086 (1.7)-
0.0042 (1.3)
0.0056 (1.8)
0.0044
0.0048
0.0033
0.0028
0.0116 (2.4)
0.0057 (1.7)
0.0076 (2.7)
0.0053
0.0048
0.0027
0.0024
0.0071 (1.5)
0.0028 (1.0)
0.0039 (1.6)
0.0037
0.0043
0.0025
0.0026
0.0090 (2.1)
0.0040 (1.6)
0.0054 (2.1)
0.0041
Nighttime, 2000 to 0400 EST
Nighttime, 2000 to 0400 EST
Nighttime, 2000 to 0400 EST
Daytime, 1000 to 1900 EST
Daytime, 0500 to 1900 EST
Daytime, 0500 to 1900 EST
Overall
a/
- First order loss coefficient as determined from the slope of least squares regressions of In [tracer]
versus time data; the tracer is Freon-12; units: hr
- The ratio of daytime to nighttime leak rate coefficients is enclosed by parentheses.
-------
of sampling line loss rates,3 single-component mixtures of air and 03, NO,
and N02 were prepared in Teflon bags at 3 to 5 concentrations ranging between
0.08 and 1.0 ppm. Concentrations were determined initially by sampling each
bag directly at the instrument in the laboratory and subsequently by con-
necting the bag to the sampling line located within each chamber and by
sampling in the usual manner. Sampling line losses for 03, NO, and N02,
were found to be less than 1 percent and to be independent of concentration.
Similar investigations were conducted in the present study for S02 and
PAN. Sampling line losses for S02 and PAN were found to be less than 8
percent and to be independent of concentration. The 03, NO, N02, S02, and
PAN data reported in the appendix were therefore NOT corrected for sample
line losses.
Characterization Experiments--
The role of surface-mediated reactions in smog chamber investigations
is unclear. Contamination or "dirty chamber" effects have been observed in
glass, aluminum, and Teflon chambers.6 7 8 The levels of background FID-
responsive contaminants that are released by Teflon film vary from batch to
batch.9 10 lx Teflon film is the currently accepted material of choice for
the fabrication of smog chamber walls. However, the experimental conditions
for which the influence of chamber-associated contaminants may be safely
neglected are yet to be defined.
In addition to the Freon-12 leak test discussed previously, five types
of chamber characterization experiments were conducted to document the
behavior of the RTI smog chambers with respect to contaminant-associated
effects: purified air irradiations, 03 decays, NO oxidations, NO decays,
A
and S02 decays. In addition to considering data from the chamber charac-
terization experiments identified in Table 3, results from selected charac-
terization experiments conducted under a subsequent study were considered.
The results of these experiments are presented in Tables 5, 6, 7, 8, 9, and
10.
The purpose of the purified air irradiations was to document the maximum
concentration of ozone, [03] , that accumulated in the RTI smog chambers
max
when purified air was irradiated. Ozone is generated by photochemical proc-
esses involving trace levels of nitrogen oxides and organics. These contami-
28
-------
nants either remain in the air after purification or desorb from the chamber
walls. Results from these experiments are summarized in Table 5. Ozone
levels generated in the RTI chambers on the first day of purified air irradi-
ations ranged from 0.02 to 0.11 ppm. A seasonal effect is apparent: the
largest [03] occurred in July of 1977; whereas, the smallest [03]
max max
occurred in December of 1977. The results of multiple-day experiments
indicate that, on the first day, ozone levels near 0.08 ppm could be achieved.
Also, second-day maximum ozone concentrations could exceed the first-day
levels. The [03] values presented in Table 5 compare favorably with the
ulcl X
range of values of 0.03 to 0.17 ppm reported for 1975 and 1976 in the RTI
smog chambers,3 with the value of 0.14 ppm reported for the outdoor UNC
facility,4 and with the values of 0.04,8 0.05,18 0.10,12 and 0.228 ppm
reported for indoor chambers.
It is unclear how the results from purified air irradiations may be
related to results from HC-NO experiments. While purified air irradiations
may indicate the level of chamber-associated contaminants relative to other
purified air irradiations, they may not be accurate indicators of the effects
of these contaminants in HC-NO experiments. These effects may be over-
A
shadowed completely in photochemically reactive HC-NO systems. It is ex-
A
pected that as the absolute reactant concentrations and their ratio change,
the impact of chamber effects on the overall behavior of the system will
also change. Chamber influences are anticipated to be nonlinear with chang-
ing reactant concentration, and the experimental conditions at which chamber-
related influences begin to dominate the behavior of chemical systems remain
to be defined.
It should be noted that the [03] that accumulates during a single
IDdX
irradiation period is the net result of both ozone-formation and destruction
reactions that occur within a smog chamber. It is possible for a given
chamber to have a low light-phase ozone-destructive component, low absolute
concentrations of background contaminants (ozone precursors) and yet achieve
a higher [03] than another more contaminated chamber with a higher light-
013 X
phase ozone-destructive component. Thus, in the comparison of [03]
luciX
values achieved in clean air irradiation experiments conducted in various
chambers, the ozone-destructive component under irradiation should be con-
sidered.
29
-------
CO
o
TABLE 5. MAXIMUM OZONE CONCENTRATION ACHIEVED IN RTI SMOG CHAMBERS
DURING PURIFIED AIR IRRADIATION EXPERIMENTS
Date
7/6/77
7/7/77
12/3/77
12/4/77
4/21/78^
4/22/78-'
%ss^
81
85
49
0
48
100
max
37.2
37.8
16.1
13.9
13.9
19.4
Chamber 1
0.111
0.177
0.021
0.014
0.015
0.052
[Oal
Chamber 2
0
0
0
0
0
0
.072
.119
.027
.017
.023
.065
max' •
ppm
Chamber 3
0
0
0
0
0
0
.101
.193
.032
.021
.027
.077
Chamber 4
0
0
0
0
0
0
. 200-/
.028
.019
. 082-/
Comment
Two -day
Two -day
Two-day
experiment
experiment
experiment
a/
- Duration of solar radiation reported as percent of possible minutes of direct sunshine (see text).
-Daily maximum temperature in °C.
c/
-A malfunction in the cleanup system reduced the effectiveness of the purification system; the listed
results are for a mixture of ambient and purified air.
-Characterization experiment conducted in a project subsequent to the present study.
-------
Ozone can disappear inside a chamber by interacting heterogeneously
with the walls or by reacting homogeneously with contaminants present inside
the chamber. Ozone decay rates reported as half-lives under both dark
conditions and irradiation have been used as measures of smog chamber reactiv-
ity. For fixed-volume smog chambers, the apparent 03 half-life is influenced
by chamber leakage. Since leak rates were not determined for the 03 decay
experiments, the 03 half-lives listed in Table 6 were not corrected for
leakage. Leak rate coefficients in the RTI chambers as shown previously in
Table 4, range from 0.002 to 0.012 hr . The half-lives for an inert tracer
that correspond to these leak coefficients are approximately 300 and 60
hours. Although in most cases the correction for leakage is small, the
apparent wintertime dark phase half-lives listed in Table 6 may be almost
entirely due to leakage rather than chemical reaction.
The ozone half-lives listed in Table 6 reflect consistent behavior from
chamber to chamber. Dark-phase half-lives range from 24 to 122 hours and
display a seasonal influence. It has been shown that in Teflon bags the
dark phase ozone half-lives increase with reduced water vapor concentra-
tion.6 The summer-to-winter increase in the dark-phase ozone half-lives may
result from the lower absolute humidity that prevails during the cooler
winter months. Although the lower wintertime temperatures may also be a
factor, the data do not permit an assessment of the relative importance of
humidity and temperature effects.
Ozone half-lives under exposure to natural irradiation range from 9.5
to 39 hours. Based on these results, a reasonable estimate of the ozone
half-life in the RTI chambers on a sunny summer day may be 10 to 12 hours.
Daytime half-lives are reduced in comparison to the corresponding dark-phase
results. During the same season for multi-day experiments, ozone half-lives
also generally decrease with increasing % SS. Since the enhanced decay of
ozone for irradiated conditions is attributed mainly to secondary reactions
following ozone photolysis,6 the observed dependence of ozone half-lives on
insolation is expected.
In addition to the effects of insolation during the same season, a sea-
sonal influence is observed as well—daytime half-lives increase from summer
to winter. Light-phase ozone half-lives have been shown to increase with
decreasing water vapor concentration.6 Thus, it is likely that the summer-
31
-------
TABLE 6. OZONE HALF-LIVES IN RTI SMOG CHAMBERS-
a/
Chamber 1
(fete
7/10, 11/77-'
2/1/78&J?/
2/1, 2/78^
2/2,3/78^''
7/21,22/78^/
7/10/77^
7/11/77-'
2/1/78^-'
2/2/78-^'
2/3/78*-^-'
7/21/78^^
1 ss&
dark
dark
dark
dark
dark
78
43
92
69
94
100
T £/
max
---
35.0
33.9
3.9
3.9
2.2
33.9
lOali-'
0.886
0.841
0.573
0.386
0.442
0.910
0.703
0.751
0.502
0.317
0.868
HS/
24.3
48.1
68.6
43.6
30.7
11. 1
13.0
26.3
27.7
21.9
13.0
Chamber 2
(Oali
0.915
0.830
0.608
0.446
0.479
0.913
0.753
0.753
0.552
0.380
0.881
t%
29.1
52.1
93.7
51.7
38.3
9.5
12.8
33.5
34.8
30.4
14.4
Chamber 3
(OaJi
0.891
0.841
0.634
0.482
0.418
0.908
0.782
0.773
0.589
0.424
0.863
t«i
43.3
60.3
121.9
66.0
30.5
13.4
17.2
35.9
38.5
34.7
12.8
Chamber 4
(Oali
0.878
0.812
0.569
0.389
0.415
0.888
0.724
0.732
0.499
0.326
0.861
t^
29.2
50.2
66.6
4U.2
30.9
11.2
14.6
27.4
28.9
27.1
13.1
a/Experiments conducted on 7/10, 11/77 employed ozonized, purified air; those conducted on 2/1,2,3/78
employed ozonized ambient air with no prior purification.
- Duration of solar radiation reported as percent of possible minutes of direct sunshine (see text).
- Daily maximum temperature in. °C.
- Initial ozone concentration in ppm.
- Half-life in hours; calculated from the slope of least squares regressions of InfO^j versus lime data.
- Experiment conducted from 2100 EST until 0500 EST.
B'Experiment conducted from 0000 tST until 0700 EST.
- Characterization experiment conducted in a project subsequent to the present study.
'^Experiment conducted from 1900 EST until 0700 EST.
^Experiment conducted from 0600 EST until 2000 EST.
-^Experiment conducted from 0500 EST until 1200 EST.
-^Experiment conducted from 0800 EST until 1800 EST.
- Experiment conducted trom 0800 EST until 1700 EST.
-------
to-winter increase of light-phase ozone half-lives is due to the reduced
duration and intensity of solar radiation in combination with drier air that
prevails during the cooler winter season. As with the dark-phase ozone be-
havior, although ambient temperature may be a factor, the data do not permit
assessment of the importance of temperature effects on the light-phase ozone
behavior.
Ozone half-lives reported for various smog chambers are summarized in
Table 7. Results from the current study are in excellent agreement with
1975 and 1976 findings for the RTI smog chambers.3 Comparison of the ozone
half-lives for the RTI chambers with those reported for other chambers
indicates that the RTI chamber surfaces are relatively unreactive with 03.
In addition, the dark-phase 0$ half-lives listed in Table 6 are in accord
with a recently reported value of 116 hours9 that was estimated for an
elevated air parcel that was traveling downwind of the St. Louis area at
night.
The oxidation of NO should proceed in the dark by the third-order
thermal reaction, NO + NO + 02 -»• 2 N02. In the dark, in the absence of
reactive organic species, the above thermal reaction should be the major
pathway for NO disappearance. For the NO oxidation experiments conducted on
15 and 16 July, apparent second order rate constants for NO disappearance
were determined from the slope of least squares regressions of [NO] versus
time data. For fixed-volume smog chambers, the apparent second order rate
constant must be corrected for chamber leakage. Leak rate coefficients
based on the simultaneous dark-phase loss of NO were estimated for each
experiment from the slope of least squares regressions of In [NO ] versus
X
time data (see Table 9). The apparent second order rate constants for NO
oxidation were then corrected for chamber leakage as reflected by NO loss.18
Ratios of both the apparent and leak-corrected rate constants to the estab-
—2 — 1 —1
lished value of 1.77 x 10 ppm hr 24 are presented in Table 8. The
uncorrected ratios of rate constants range from 1.4 to 2.0 and the corrected
ratios range from 1.1 to 1.4. These ratios are in good agreement with
values reported previously for the RTI chambers and suggest good agreement
between the established value of the dark-phase NO oxidation rate constant
and the value as determined in the RTI chambers.
33
-------
TABLE 7. SUMMARY OF OZONE HALF-LIVES FOR VARIOUS SMOG CHAMBERS
Chamber
Identity
Bureau of Mines
Bureau of Mines
Battelle
Shell
Exxon
SRI
CSARB
SAPRC
—
Lockheed
General Motors
—
UNC
UNC
RTI
RTI
Construction
Material
Al, Teflon film
Al, glass
Al, Teflon film
Stainless steel
Al, Teflon film
Teflon-coated Al
Glass
Teflon-coated Al
Teflon bag
Glass
Stainless steel
Tedlar Bag
Al, Teflon film
Al, Teflon film
Teflon bags
Al, Teflon film
Al, Teflon film
Volume, 1
1.8 x 103
2.8 x 103
1.7 x 104
4.0 x 102
4.3 x 103
7.7 x 103
3.1 x 104
5.8 x 103
1 x 102
1.9 x 103
8.4 x 103
4.4 x 102
1.6 x 10s
2.0 x 10s
1.0 x 102
2.7 x 104
2.7 x 104
Half-liv
Dark
12
14
8
1.7-6 (24° C)
13.9
20
_ —
6.8
9.5
7.2 (35° C)
10.0
11.9 ,
49-75£/
.21.2
45-150-' (25° C)
17-40^.
24-122£/
es, hr-
Light
1 (54° C)
3.6 (34° C)
6
1.5 (27° C)
1.3-2.5 (30° C)
2.7
7.8
5.8
4.2 (29° C)
3.0 (35° C)
2.0
16-23-
9 4—
9-1$
10-26-'
9.5-39£/
Illumir .
nation- Reference
A
A
A
A
A
A
A
A
A
A
A
A
N
N
N
N
N
15
15
16
17
18
19
20
21
22
23
24
25
7
26
9
6
Current study
a/
— Measured at approximately 1.0 ppm ozone.
-Artificial: A; natural sunlight: N, taken under sunny conditions unless stated otherwise.
-Range presented for simultaneous experiments conducted in two chambers in November and December of 1973.
- Experiments conducted in June of 1974.
e/
-Half-lives varied over this range with water vapor concentration; experiments conducted in June of 1975.
-Range of half-lives from experiments conducted in 1975 and 1976.
* Range of half-lives from experiments conducted after May 1977 when original Teflon film was replaced;
range reflects seasonal differences (see text and Table 6).
-------
TABLE 8. NO OXIDATION IN RTI SMOG CHAMBERS
Chamber
Date
7/15/77
7/15,16/77
7/15/77
7/16/77
%SS^
Dark
Dark
77
76
T by
max
0
0
35.0 0
35.6 0
{NO]
.79
.62
.68
.51
i^
1.
1.
0.
1.
1
t&
6(1.2)
9(1.4)
3
3
Chamber 2
{NO]
0.80
0.63
0.69
0.52
i R
1.6(1.2)
1.9(1.3)
0.4
0.8
Chamber 3
fNO]i R
0.80
0.61
0.70
0.52
1.5(1.3)
2.0(1.4)
0.6
1.6
Chamber 4
[NOli R
0.81
0.65
0.71
0.53
1.4(1.1)
1.9(1.3)
0.3
0.9
- Duration of solar radiation reported as percent of possible minutes of direct sunshine (see text).
- Daily maximum temperature in °C.
c/
-Initial (NO], in ppm.
- Ratio of experimentally determined second order rate constant for oxidation of NO to the established
(literature) value k /k,. ; ratios in parentheses have been corrected for chamber leakage; ratios
not in parentheses have not been corrected for chamber leakage.
-------
TABLE 9. LEAK RATE COEFFICIENTS IN RTI SMOG CHAMBERS BASED ON NO MEASUREMENTS
a/
Leak Rate Coefficient-'
Date
7/15/77
7/15,16/77
7/17/77
7/17,18/77
7/15/77
7/16/77
7/17/77
7/18/77
*SS-X Tmax£/ Chafflber l
Dark
Dark
Dark
Dark
77
76
79
77
0
0
0
0
35.0 0
35.6 0
35.0 0
36.1 0
.0049
.0065
.0053
.0109
.0132(2. 7)-^
.0164(2.5)
.0093(1.8)
.0149(1.4)
Chamber 2
0
0
0
0
0
0
0
0
.0043
.0061
.0061
.0087
.0129(3.0)
.0147(2.4)
.0076(1.2)
.0109(1.3)
Chamber 3
0.0037
0.0056
0.0050
0.0048
0.0115(3
0.0161(2
0.0071(1
0.0138(2
.1)
• 9)
.4)
.9)
Chamber 4
0
0
0
0
0
0
0
0
.0042
.0061
.0057
.0046
.0112(2
.0147(2
.0060(1
.0111(2
.7)
.4)
.1)
.4)
Comment
Nighttime, NO expt.
Nighttime, NO expt.
Nighttime, N02 expt
Nighttime, N02 expt
Daytime, NO expt.
Daytime, NO expt.
Daytime, N0? expt.
Daytime, N0~ expt.
a/
-First order loss coefficient as determined from the slope of least squares regressions of In [tracer]
versus time data; the tracer is NO : units: hr
b/
—Duration of solar radiation reported as percent of possible minutes of direct sunshine (see text).
c/
—Daily maximum temperature in °C.
-The ratio of daytime to nighttime leak rate coefficients is enclosed by parentheses.
-------
Loss rates of NO under irradiation in excess of the thermal rate may be
attributed to participation of organic contaminants in the normal photochem-
ical NO-oxidation reactions. Dimitriades has suggested that the rate of NO
loss under irradiated conditions provides a measure of chamber contamination
levels.12 Apparent second order rate constants for NO disappearance were
determined by the technique noted above using data collected under irradia-
tion. For these conditions, NO loss was much greater than under dark
conditions. The data, however, do not permit correction of the apparent
light-phase rate constants for leakage since the relative contributions of
mechanical and chemical interactions to NO loss are currently undefined.
X
The uncorrected ratios of rate constants determined for irradiated
conditions range from 0.3 to 1.6. These ratios compare favorably with those
determined under dark conditions and with those reported previously for the
RTI chambers.3 These results for the RTI chambers also compare reasonably
well with the value of 4.0 for the Bureau of Mines chamber12 and to values
of 4.8 and 3.0 for the outdoor UNC facility.4
The behavior of NO in the RTI smog chambers was examined under two
different sets of experimental conditions--the NO oxidation experiments dis-
cussed previously and experiments involving the irradiation of N02• If it
is assumed that NO , comprised of both NO and N02, is relatively inert in a
smog chamber in the absence of reactive organics, then leak rate coefficients
may be determined using the same technique as that was described previously
for the Freon-12 experiments. Leak rate coefficients calculated using NO
A
as a tracer are presented in Table 9.
Nighttime leak rate coefficients ranged from 0,004 to 0.011 hr with a
mean value of 0.0058 ±0.0018 hr" . The daytime values ranged from 0.006 to
0.016 hr with a mean value of 0.012 ±0.003 hr~ . As shown previously for
Freon-12, the daytime leak rate coefficients for NO are approximately twice
a
as large as the nighttime values. In addition, since the NO leak rate co-
X
efficients are approximately equal for both the NO and the N02 experiments,
NO loss does not appear to be sensitive to the relative amounts of NO or
A
N02 that are present initially. The leak rate coefficients determined by
NO loss, however, are generally higher than those determined by Freon-12
X
loss, and suggest that a mechanism in addition to leakage contributes to the
loss of N0x- Although increased daytime wind speeds may enhance the daytime
37
-------
leak rate, gas-phase or surface-mediated reactions may lead to the formation
of N205 and HN03. The subsequent removal of these compounds on the chamber
walls may also contribute to the apparent loss of NO . If a chemical mech-
A
anism were responsible for the apparent loss of NO , then such a mechanism
would likely be manifest differently at the two N0/N02 ratios employed in
these experiments. This, however, was not the case. Thus, the relative
contributions of leakage and photo-initiated reaction sequences to the
observed NO loss rates remain to be defined.
A •
Sulfur dioxide is both a product and a reactant in the current study.
Like ozone, S02 can disappear inside a chamber by interacting heterogeneously
with the walls or by reacting homogeneously with contaminants present inside
the chamber. Experiments were conducted to examine the stability of S02 in
the RTI chambers under irradiation and in the dark. The results of these
experiments are listed in Table 10.
On 31 August 1977 at 0100 EST, S02 was injected into the RTI chambers to
an approximate initial concentration of 1.5 ppm. The water vapor concen-
tration is estimated to have been 25000 ppm. By 0700 EST most of the S02
had disappeared. During the morning by approximately 1000 EST the [S02]
0)3 X
had increased slightly (10 to 15 ppb) in Chamber Nos. 1 and 3. At 1245 EST
S02 was again injected; however, the newly injected S02 concentrations
remained relatively stable until sunset. Filter samples collected during
the afternoon could account for a maximum amount of particulate sulfur
equivalent to only 20 ppb of S02. After sunset, S02 decayed rapidly as it
had done on the previous night. Filters collected during or shortly after
both nighttime experiments could account for particulate sulfur equivalent
to less than 10 ppb of S02.
For the experimental conditions employed, S02 disappeared more rapidly
at night than during the day--this behavior is the opposite of that displayed
by ozone. Although nighttime S02 loss appears to be more complex than that
of a first order process, such a process was nevertheless assumed, and
half-lives were calculated. Estimates of dark phase half-lives ranged from
0.7 to 6.1 hours based on the August 1977 data and from 3.6 to 9.2 hours
based on the March 1978 data. Daytime S02 loss rate followed a first order
decay with half-lives of 17 to 26 hours in the August experiments and 9 to
12 hours in those conducted in March.
38
-------
TABLE 10. SULFUR DIOXIDE DECAY IN RTI CHAMBERS
Date
8/31/778/
B/3J. 9/1/77-'
3/2,3/78^'
3/3, 4/78^'
B/31/77-'
3/3/78-^
X SS2'
Dark
Dark
Dark
Dark
yo
31
Chamber 1
T^' |Mjl|i£' t^/
1.30
1.17
. 0.71
0 . 63
32 . 8 1.50
1.7 0.27
1.8
4.4
5.6
3.6
16.6
9.0
Chamber 2
JS02|i tlj
1.22
1.26
0.82
0.74
1.50
0.46
1.1
1.4
9.2
6.6
19.0
11.6
Chamber 3
|SU|i t!»
1.50^
1.27
0.77
0.65
1.50
0.36
2.2
6.1
7.4
5.1
25.6
10.0
Chamber 4
|SO|i llj
1.06 0.7-'
1.16 1.4-'
- -
-
1.50 17. 3-'
-
CO a/
VO - Duration of solar radiation reported as percent ot possible minutes of direct sunshine (see text).
!>/
- Daily maximum temperature in °C.
- Initial concentration of SO2 in ppm.
- Half-life in hours: calculated from the slope of least squares regressions of ln|SO2| versus time data.
- Concentration is greater than 1.5 ppw, exceeding the instrument's linear range and has been set to a
default value of 1.50 ppu.
- Experiment was conducted in Chamber 4 with SO2 added to ambient air that had not undergone prior purification.
^'Experiment conducted from 0100 EST until 0700 KST.
- Experiment conducted from 1900 ESI until 0200 EST.
- Characterization experiment conducted in a project subsequent to the present study.
^Experiment conducted trow 2100 EST until 0500 EST.
-^Experiment conducted trow 1300 EST until 1900 KST.
-^Experiment conducted from 0600 EST until 1700 EST.
-------
Environmental factors such as relative humidity, temperature, and solar
radiation may influence S02 behavior in smog chambers. A peripheral experi-
ment in the current study examined the stability of S02 in a mixture with
clean dry air contained in a 200 1 Teflon bag under room lighting and tempera-
ture. The resulting 45 hour half-life is in good agreement with the dry
dark phase half-life of 76 hours reported for a Tedlar bag.22 Other
studies25 26«have shown the deposition velocity of S02 on gloss paint and
on aluminum to increase by a factor of 30 as the relative humidity was
increased from 20 to 80 percent. Although the literature is lacking on the
effects of temperature and solar radiation on the interaction of S02 with
various surfaces, two observations from the present study provide additional
evidence linking environmental factors with the apparent S02 loss. First,
the daytime loss rate was much smaller than the nighttime value. Secondly,
following a nighttime loss of almost 1.5 ppm, the [S02] increased slightly
DQ3X
during midmorning. This, coupled with low particulate sulfur measurements,
suggests that some of the S02 was deposited on the walls and that this
deposition was not totally reversible. Although the mechanism by which S02
was lost remains to be defined, it is likely that the observed loss of S02
in the RTI chambers resulted from interactions with the chamber walls which
may have been influenced by relative humidity, temperature, and solar radia-
tion. Since these variables exhibit diurnal cycles, it is difficult to
separate the effects of each variable on the apparent S02 behavior.
In addition to the above characterization experiments, matched experi-
ments conducted during the experimental program show consistent behavior
from chamber to chamber. For example, matched propene NO experiments were
conducted on 8 August 1977. Mean initial conditions across the four chambers
were: 1.43 ±0.03 ppmC C3H6 and 0.59 ± 0.01 ppm NO (20 percent N02). The
A
N0-N02 crossovers for the four chambers occurred within 19 minutes of each
other at approximately 0643 EST, and the maximum N02 concentrations ranged
from 0.46 to 0.49 ppm. Ozone concentration profiles from each of the four
RTI chambers on 8 August 1977 are illustrated in Figure 8. The 03 maxima on
the first day of the experiment occurred between 1408 and 1518 EST and were
in good agreement: 0.96, 0.96, 0.99, and 0.93 ppm. This agreement is
consistent with that of previously reported matched experiments conducted in
the RTI chambers3 and with simultaneous matched experiments conducted in
40
-------
1.50
1.00
Q_
Q_
O
rvi
O
0.50
0.00
OZONE, 8 flUGUST 1977 "
1.50
1.00
O
M
CD
Z
m
0.50
0000
OfOO
0800 1200
TIME (EST)
1600
2000
0.00
0000
Figure 8. Ozone concentration-time profiles for matched propene-NOx experiments conducted in
the four RTI smog chambers on 8 August 1977. Initial conditions: 1.43 ppmC
0.59 ppm NOX (20 percent
-------
the RTI and UNC outdoor smog chambers.27 The agreement demonstrated in
these and other matched experiments increases confidence in the reliability
of data obtained in the RTI smog chambers.
REAGENTS
Air used in the smog chamber experiments was supplied from the air
purification systems that are located under each chamber. The other reagents
used in this study are listed in Table 11. Additional information including
molecular weight, boiling point, injection mode, purity, and supplier is
also provided.
The 02 that was used for 03 injections was zero (Z-2) grade. The N2
that was used to purge the injection lines was Matheson "Oxygen Free" grade.
Nitrogen oxides were introduced from separate tanks that contained NO in N2
and N02 in N2. The NO injection gas was prepared at RTI, and the N02 gas
mixture was supplied by Scott. Single component gas and liquid reagents
employed in this study were acquired from commercial suppliers with stated
purities generally better than 95 percent. These single-component reagents
were used as received from the suppliers without further purification.
MEASUREMENT METHODS
The measurement methods that were employed in the present study are
described below. A summary of these methods is presented in Table 12.
Both automated and manual analytical techniques were employed. Ozone,
nitrogen oxides, peroxyacetyl nitrate, hydrocarbons, Freon-12, sulfur dioxide,
and total sulfur were monitored by automated instruments. Concentration
data from each chamber were recorded hourly during the corresponding 10-
minute sampling period. The reported ©3, NO, and N02 concentrations were
reduced from strip chart records at the eighth minute of each 10-minute
sampling period. The PAN, HC, and sulfur analyzers are gas chromatographs.
They were operated such that samples were injected at the eighth minute of
each 10-minute sampling period. Manual operations were performed at various
times during each experiment. These activities included the collection of
filter samples for particulate sulfur determination and the determination of
the number concentration of condensation nuclei. Total solar radiation and
ambient temperature data were collected at one-minute intervals but were
42
-------
TABLE 11. REAGENTS
Reagent
Oxygen, 02 (Z-2)
Nitrogen, N2 (Oxygen Free)
Nitric oxide, NO
Nitrogen dioxide, N02
Propene, C3H6
Dif luorodichloromethane, C12CF2
(Freon-12)
Sulfur dioxide, S02
Hydrogen sulfide, H2S
Carbonyl sulfide, COS
Carbon disulfide, CS2
Methanethiol, CH3SH
Ethanethiol, C2H5SH
Methyl sulfide, CH3SCH3
Methyl ethyl sulfide, CH3SC2H5
Ethyl sulfide, C2H5SC2H5
Methyl disulfide, (CH3S)2
Ethyl disulfide, (C2H5S)2
Thiophene, C4H4S
2-Methylthiophene , C5H6S
3-Methylthiophene, C5H6S
2, 5-Dimethylthiophene, C6H8S
c/
. Injection-
MVR BP-7 Mode
32
28
30
46
42
121
64
34
60
76
48
62
62
76
90
94
122
84
98
98
112
-183
-195.8
-151.7
21.1
-47.7
-155
-10
-60.7
-50.2
46.3
6.2
35
37.3
66.6
92.1
109.7
154
84.2
112.6
115.4
136.7
IS
IS
IS
IS
G
G
G
G
G
V
G
V
V
V
V
V
V
V
V
V
V
Purity-7
99. 95%-'
99 . 998%-7
659 ppm in N2
110 ppm in N2
99%
NS
99.98%
C.P.
97.5%
99+%
99.5%
97%
98%
NS
98%
NS
NS
99+%
95%
98%
98.5%
Supplier
Scientific Gas Products
Matheson
RTI Blend
Scott
Phillips
Virginia Chemical Co.
Matheson
Linde
Matheson
MD&B
Matheson
Aldrich
Aldrich
K&K labs
Aldrich
K&K labs
Aldrich
Aldrich
Aldrich
Aldrich
Aldrich
—Molecular weight.
-Boiling point, °C; taken from Handbook of Chemistry and Physics.28
c/
-Injection mode: IS--injection of gas via smog chamber injection system; G--direct injection of gas
via N2-purged line into chamber; V-Volatilization of liquid via heated injection manifold.
-As designated by supplier; NS--not specified by supplier.
e/
-Contains less than 0.5 ppmC of total hydrocarbons.
-------
TABLE 12. MEASUREMENT METHODS
Measured Quantity
03 Chemiluminescent
NO, H02, N0x
Peroxyacetyl Nitrate (PAN)
Method
Bendix Model 8002
Chemi lumines cent
Model 14B
Gas Chromatography/
Manufacturer
0-1 ppm
Thermo-Electron
. Varian Model 1440
Range
0.001 ppm
0-1 ppm
>1 ppb
MDC-/
0.001 ppm
1 ppb
Electron Capture
Hydrocarbons (Propene)
Flame lonization
S02 and Total Sulfur
Flame Photometry
Total Particulate Sulfur
(TPS)
Condensation Nuclei (CN)
Nucleus Counter
Gas Chromatography/ Modified Bendix
Model 8201
Gas Chromatography/ Tracor Model 270HA
0-10 ppm (v/v) 0.005 ppm (v/v)
Freon-12
Spectroscopy
Solar Radiation-
d/
Ambient Temperature
% Possible Minutes
Sunshine-
d,e/
Filter Collection/
X-Ray Fluorescence
Photoelectric
Type CN
Long Path Infrared
Miran I
Pyranometer
Thermistor
0-1.5 ppm
0-4000
0.03 ppm
-' 5 Mg/m3^
Gardner Associates, 0-107 CN/cm3 100 CN/cm3
Wilks Scientific
(0-1 AU)
Eppley Model 2
(cal/cm2)
0-700 ppm
0-4 Langleys
0.08 ppm
Photoelectric Cells Foster Sunshine
Switch
a/
- Minimum detectable concentration as reported by the manufacturer.
— This value depends on sampling rate and duration.
c/
—This value depends on the species and on sampling rate and duration.
-Data collected by the U.S. EPA, Division of Meteorology, Research Triangle Park, North Carolina.
collected by NWS Forecast Office at RDU.29
-------
reported as hourly averages. The data from the measurements described above
are reported in the appendix.
Ozone
Ozone was monitored with a Bendix Model 8002 Ozone Analyzer. The prin-
ciple of operation employs the chemiluminescent gas-phase reaction between
ozone and ethene. The instrument operates in the continuous mode with a
range of 0 to 1 ppm and an MDC of 0.001 ppra. Calibration was performed
prior to each experiment using a stable ultraviolet light ozone generator.
The output of the 03 generator was determined by gas-phase titration of 03
with known NO concentrations that were blended from air and certified stand-
ard mixtures of NO in nitrogen.30
Nitrogen Oxides (NO, N02. and NO ]_
Nitrogen oxides were monitored with a Thermo-Electron (TECO) Model 14B
NO-NO Analyzer. The principle of operation employs the chemiluminescent
A
gas-phase reaction between NO and 03. Two modes of operation are required
to determine NO, N02, and NO . Nitric oxide is measured first using the
reaction of NO and 03. The determination of N02 and NO , however, requires
A
catalytic reduction of N02 to NO prior to the reaction of NO with ozone.
The NO analyzer used in this study employed a molybdenum catalyst operated
at 450° C to reduce N02 to NO. After reduction of N02 to NO, the signal
from the total NO in the sample is taken to be the NO concentration.
Electronic subtraction of the original NO signal from the NO signal yields
the N02 concentration. The instrument,operates with a 90-second cycle time:
NO concentration is updated at the end of the first portion of the cycle,
and N02 and NO concentrations are updated at the end of the cycle.
A
The instrument was calibrated prior to each experiment. Calibration of
NO and NO channels was performed by dilution of a known concentration of NO
from a certified cylinder of NO in nitrogen. Calibration of N02 was per-
formed by using the N02 produced from the gas-phase titration of known NO
concentrations with 03 from the calibrated ozone generator.
The NO analyzer was usually operated on the 0 to 1 ppm full scale (FS)
range, although both the 0 to 0.2 and the 0 to 0.5 ppm FS ranges were used
occasionally. In contrast to the MDC of 0.001 ppm as specified by the manu-
facturer, the effective MDC in the current study was approximately 0.005 ppm
45
-------
on the 0 to 1 ppra FS range. This is determined by instrument noise and the
width of the strip chart trace. In addition, the zero baseline for the NO
and the NO channels displayed a strong temperature dependence. Diurnal
A
variations of the room temperature could produce as much as 10 percent FS
shift in the zero baseline over the course of an experiment. Frequent zero
checks reduced the impact of this behavior. The N02 channel did not exhibit
this behavior because N02 is the difference between the NO and NO channels,
which were both shifting by equal amounts.
It has been demonstrated that nitric acid, PAN, and ethyl nitrate
interfere with N02 and NO determinations in instruments of the type employed
X
in this study.31 32 It is anticipated that the interference is quantitative
for most nitroxy compounds and that, to a first approximation, the chemiluraine-
scent NO concentration is indicative of the concentration total gaseous
A
nitroxy species that are delivered to the instrument. Although PAN, MN, and
EN were determined in this study, the N02 and NO data were not corrected
A
for these interferences.
During the course of the present study, many of the test species were
found to interfere with the NO and N02 measurements. Immediately following
the injection of an organo-sulfur compound into the chambers, positive step
shifts in the NO readings and negative step shifts in the N02 readings were
observed. Such shifts occurred even when NO had not yet been injected into
the chambers. This and the rapidity of the shifts suggest that gas-phase
chemical reactions within the chambers were not responsible for the observed
behavior. Rather, it is hypothesized that the organo-sulfur species were
acting as positive interferents for the NO measurements. It is further
hypothesized that these test species were partially or totally destroyed as
they passed through the instrument's catalytic converter (molybdenum at
450° C). This would have resulted in a reduced interference with the NO
measurement in comparison to the interference with the NO measurement.
Since the N02 reading is obtained by subtraction of the NO measurement from
the NO measurement, the organo-sulfur species would appear as negative
interferents for the N02 measurements.
The chemiluminescent reactions of ozone with organic sulfides have been
investigated.33 34 35 The chemiluminescence emission spectra of H2S, CH3SH,
and CH3SCH3 were found to display a broad structureless band that is centered
46
-------
at approximately 340 nanometers. This band is associated with the decay of
electronically excited S02 which is produced by the reaction of 03 with an
intermediate SO radical. However, it is doubtful that chemiluminescence in
this band could be responsible for the interferences in the NO and N02
measurements. The NO analyzer has an optical filter positioned between the
X
reaction chamber and the photomultiplier tube, which prevents the transmis-
sion of light at wavelengths below 600 nanometers. As a result, the instru-
ment should not detect chemiluminescence emission spectra at 340 nanometers.
Weaker emission bands have been reported for H2S, CH3SH, and CH3SCH3.35
These emission bands for H2S occurred between 520 and 810 nanometers. The
emitting species was suggested to have been the excited HSO radical, which
is produced by the reaction of 03 with an intermediate SH radical. These
emission bands may have been responsible for the interference due to H2S.
However, this does not account for the interference due to CH3SH and CH3SCH3,
since the reaction of 03 with these compounds does not produce SH radicals.35
These reactions produce free hydrogen atoms, which react with 03 to form
vibrationally excited OH radicals. The Meinel band emission of these radi-
cals extends from 550 nanometers to wavelengths longer than the 900-nanometer
cutoff of the photomultiplier tube. Consequently, the Meinel band emission
may have been responsible for the CH3SH and CH3SCH3 interferences with the
NO and N02 measurements.
The reaction of 03 with thiophene has been found to produce a chemilum-
inescent emission spectrum similar to that of H2S.36 The interference due
to thiophene may have been caused by the excited HSO radical.
To assess the magnitude of the interference, pure gas mixtures of the
test species in zero air were analyzed using the NO instrument. First,
70-liter Teflon bags were filled with zero air. A sufficient quantity of
one of the test species was injected into a bag to produce a 2 ppmC concen-
tration. This bag was then connected to the sampling inlet of the instru-
ment. The measurement of each test species was immediately preceded by a
measurement of zero air to obtain an accurate value for the instrument's NO
and N02 zero baseline. The results of this study are given in Table 13.
In most cases, the interference of the test species with the NO and N02
measurements was not serious. The interference equivalent exceeded 10 ppb
47
-------
TABLE 13. NO AND N02 INTERFERENCE EQUIVALENTS FOR
2 ppmC OF EACH TEST SPECIES
NO N02
Interference Interference
Test Species Equivalent Equivalent
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Disulfide
Methanethiol
Ethane thiol
Methyl Sulfide
Ethyl Sulfide
Methyl Ethyl Sulfide
Methyl Disulfide
Ethyl Disulfide
Thiophene
2-Methylthiophene
3-Methylthiophene
2,5-Dimethylthiophene
+ .004 ppm
+ .008 ppm
.000 ppm
+ .017 ppm
+ .014 ppm
+ .007 ppm
+ .014 ppm
+ .006 ppm
+ .007 ppm
+ .010 ppm
+ .002 ppm
+ .003 ppm
+ .037 ppm
+ .005 ppm
- . 004 ppm
+ .001 ppm
+ .001 ppm
- .017 ppm
- .011 ppm
- .003 ppm
- .008 ppm
- .003 ppm
- .005 ppm
- .007 ppm
- .001 ppm
.000 ppm
- .030 ppm
- .004 ppm
48
-------
for four species: methanethiol, ethanethiol, ethyl sulfide, and 3-methylthio-
phene. In the current study the interference was significant in those cases
where the interference equivalent was large and the initial NO concen-
tration was small (e.g., with 3-methylthiophene and an initial [NO ] of
A
0.1 ppm). In such cases, it is likely that the measured NO and N02 reaction
profiles were significantly distorted from the actual profiles by the inter-
ference .
Interference-corrected estimates of the initial NO, N02, and NO concen-
X
trations were made and are noted in the appendix. In the later stages of an
experiment, interference corrections are difficult to establish due to the
decreasing concentration of the interferent. Thus, the bulk of the NO, N02,
and NO data in the appendix have NOT been corrected for interference due to
x
the test species.
Peroxyacetyl Nitrate
Peroxyacetyl nitrate (PAN) was monitored with a Varian Model 1440 Aero-
graph Gas Chromatograph equipped with a Sc3H electron capture detector. A
1.8-m long by 2-mm ID glass column packed with 60 to 80 mesh Chromosorb W-HP
coated with 10 percent Carbowax 400 was operated at room temperature. The
carrier gas was 5 percent methane in argon. A Hewlett-Packard Model HP-3352
Laboratory Data System acquired the output signal, integrated peak areas,
and converted the areas into concentration values that were printed by a
teletype. Strip chart records of output signals were maintained to supple-
ment data system records. The minimum detectable concentration is 1 ppb.
Sampling was controlled by a Carle Valve Minder II. Injections took
place at 10-minute intervals and were synchronized with the overall chamber
sampling cycle.
Elution times were adjusted in an attempt to prevent the water peak
from one sample from interfering with the PAN measurement in the successive
sample. This permitted the successful recovery of the majority of the PAN
data.
The PAN calibration factor for those experiments conducted prior to
18 October (2.7 x 10 ppm/area count) was established by a multipoint
calibration performed on this date. Calibration was performed by using gas
mixtures of known PAN concentrations. Calibration mixtures were prepared by
49
-------
EPA using a technique that involves the irradiation of a mixture of chlorine,
acetaldehyde, and N02.37 Following the calibration, the instrument was
modified, and its sensitivity was increased. Replicate experiments with
methyl ethyl sulfide were conducted both before and after 18 October (on
10 October and 9 November). Since a PAN calibration factor was not performed
after 18 October, the calibration (0.68 x 10 ppm/area count) was estimated
based on the assumption of equivalent PAN production for the two sets of
experiments conducted with methyl ethyl sulfide. The PAN data in the current
study show consistent trends both within individual experiments and across
different experiments conducted on the same day. Although the precision in
the PAN data is good, the accuracy is uncertain. The estimated uncertainty
in PAN concentrations is ±50 percent for those experiments conducted before
18 October and may be as high ±100 percent for those conducted after 18 Octo-
ber.
In several cases, two peaks were found in addition to PAN. They have
been tentatively identified as methyl nitrate (MN) and ethyl nitrate (EN).
These species were quantified based on PAN calibration factors. Since the
MN and EN concentration data were erratic, daily median values were reported.
The estimated uncertainty in MN and EN concentrations is ±200 percent.
Propene
Propene was monitored with a modified Bendix Model 8201 Reactive Hydro-
carbon Analyzer equipped with a flame ionization detector (FID). In its
modified configuration, the instrument separates and quantifies individual
hydrocarbon species in the C^ to Cs range. A 2.4-m long by 3.2-mm OD stain-
less steel column packed with 100 to 120 mesh Durapak Phenyl Isocyanate/
Porasil C was operated at 30° C. The carrier gas was zero grade helium.
Concentrations were calculated from area counts under individual peaks that
were identified and measured by a Hewlett-Packard Model 3352 Laboratory Data
System. Strip chart records of output signals were maintained to supplement
data system records. The minimum detectable concentration is 5 ppb (v/v).
Sampling was controlled by a Carle Valve Minder II. Injections took
place at 10-minute intervals and were synchronized with the overall chamber
sampling cycle.
50
-------
The instrument was calibrated prior to each propene run with a certi-
fied calibration mixture of propene in air that had been cross-compared with
RTI calibration standards.
Sulfur Dioxide and Total Sulfur
Sulfur dioxide and other sulfur compounds were monitored with a Tracor
Model 270 HA Atmospheric Sulfur Analyzer equipped with a flame photometric
detector (FPD). Other sulfur-containing compounds were measured as total
sulfur by direct injection of'the sample to the FPD. Sulfur dioxide was
detected following chromatographic separation. A 1.8-m long by 3.2-mm OD
FEP Teflon column packed with a proprietary silica gel packing was operated
at 60° C. The carrier gas was zero grade air. The electrometer output was
linearized by an internal logarithmic amplifier. The instrument's response
is linear over a range from 0 to approximately 1.5 ppm. Strip chart records
of the chromatograms were maintained, and concentrations were determined
from peak heights using an S02-air mixture as a reference. The minimum
detectable S02 concentration is 0.03 ppm.
The sampling cycle was controlled by a Carle Valve Minder II. Injec-
tions took place at 10-minute intervals and were synchronized with the
overall chamber sampling cycle.
The instrument was calibrated prior to each experiment. Calibration of
the S02 peak heights was performed by dilution of a known concentration of
S02 from a certified cylinder of S02 in air. Originally, the sulfur analyzer
was employed to determine the concentration of only S02. During the analysis
of the results, the peak heights of total sulfur and of individual sulfur
species were used to permit estimates of reactant and product concentrations.
In many cases reactant concentrations were estimated by the difference
between the total sulfur and S02 peak heights. It should be noted that the
response of the sulfur analyzer to sulfur-containing compounds other than
S02 may not be equivalent to that for S02. Thus, the reported total sulfur,
CH3SH, COS, H2S, and CS2 concentration data should be considered only as
qualitative indicators of the behavior of the gaseous sulfur species during
any experiment.
Concentration data for S02, total sulfur, and other sulfur-species
reported in the appendix contain default parameters that require identifica-
51
-------
tion. For those cases in which no peaks were found, the corresponding
concentrations are listed as 0.0. In several cases, peaks were identified
but were too small to be quantified—these are set at 0.010. Since the
response of the sulfur analyzer is not linear above 1.5 ppm, concentrations
in excess of 1.5 ppra are listed as 1.500 ppm.
Total Particulate Sulfur
Total particulate sulfur (TPS) concentrations were determined by the
collection of particulate samples on Teflon membrane filters with subsequent
sulfur analysis by X-ray fluorescence. Sampling frequency varied from
experiment to experiment. During a normal two-day experiment, 3 to 8 samples
per day were collected at the manual sampling ports of each chamber.
The 37-mm diameter filters have a l-|Jm pore diameter and are mounted on
51-mm by 51-rara polyester filter frames. The filter holder is designed for
in-line sampling through 4.6-mm OD Teflon tubing. Typically, air is pulled
through the filter for a period of 15 minutes at a flowrate of 3 1/min.
Sampling lines are short (0.5 m) to reduce particle deposition on the in-
terior walls of the tubing.
The filters were analyzed by an energy-dispersive X-ray fluorescence
spectrometer operated by EPA.38 The detection limit for sulfur is reported
as 29 ng/cm2 of filter surface. This corresponds to a minimum detectable
sulfur concentration of 5 (Jg/m3 at the flow rate employed in the present
study.
Condensation Nuclei
The number of condensation nuclei (CN) per cubic centimeter of sampled
air was determined with a Gardner Associates Type CN Small Particle Detector.
The principle of operation is the photoelectric measurement of water droplets
that are formed by the condensation of supersaturated water vapor on small
particles. The sampling frequency varied from experiment to experiment.
Normally, CN determinations were performed from 3 to 8 times per day. The
samples were taken directly at the manual sampling ports of each chamber
through a 0.5-m length of 4.8-mm ID Teflon tubing. A short sampling line
was used to reduce particle deposition on the interior walls of the tubing.
Measurements conducted at two piston positions permit qualitative size
52
-------
discrimination. Piston "position 1" permits the determination of CN having
diameters greater than 0.26 fjm while "position 5" corresponds to CN having
diameters greater than 0.002 |Jm. CN determinations were normally performed
at piston "position 5". In most of the cases where measurements were conduct-
ed at two piston positions, there were no significant differences in the
measured concentrations. Thus, only the CN concentration on data determined
at piston "position 5" are reported in the appendix.
Instrument meter deflections were recorded in laboratory notebooks.
Subsequently, the calibration curve provided by the manufacturer was used to
convert the meter deflections into number concentration of CN. The CN data
reported in the appendix should be considered to be qualitative indicators
of the number of small particles within the chambers at a given time.
Replicate determinations usually showed a precision of ±20 percent, but
comparison with other instruments of similar design showed agreement to
within ±50 percent.
Freon-12
Freon-12 (difluorodichloromethane) was used as a tracer in several
experiments that were designed to quantify chamber leakage. It was moni-
tored by a Wilks Miran I Variable Filter Ipfrared Analyzer. This instrument
uses a single-beam spectrophotometer in conjunction with a 20-m variable
pathlength White cell. When Freon-12 is present in the cell, the spectrum
of infrared light will show a strong absorption band (44 atm cm for 1
cm resolution) at a spectral frequency of 930 cm" . Typical instrumental
resolution in this spectral region is 20 cm" . The instrument is equipped
with a linear absorbance accessory that produces an output signal propor-
tional to the Freon-12 concentration. This signal was recorded on a strip
chart recorder.
The Metal Bellows pump of the sampling system was used to flush air
continuously though the White cell. This was accomplished by connecting the
cell's intake port to the vent of the glass sampling manifold (see Figure 7).
Initial Freon-12 concentrations in the chambers were approximately 100
ppm. Bags also containing mixtures of approximately 100 ppm Freon-12 in air
were prepared by injecting pure Freon-12 via a syringe into 100-liter bags
that contained breathing air. Periodic span checks were made using these
53
-------
mixtures. The instrument's zero was established during the ambient air
portion of the sampling cycle.
Solar Radiation and Ambient Temperature
Total solar radiation and ambient air temperature data were collected
by the U.S. Environmental Protection Agency, Division of Meteorology, at a
point approximately 0.5 km from the RTI Smog Chamber Facility. The solar
radiometer, an Eppley Precision Spectral Pyranometer, employs a thermopile
sensing element and determines light intensity at wavelengths longer than
295 nm. Ambient air temperature was determined by a thermistor located in a
gill aspirated temperature-radiation shield and is accurate to within ±0.05° C.
Solar radiation and temperature were recorded at one-minute intervals
by EPA's Data Acquisition System and were provided to RTI on magnetic tape.
These data were read and converted to the hourly average values that appear
in the appendix.
Environmental Variables
Other environmental variables reported in this study are the daily
maximum temperature (T ) and the percent of possible minutes of direct
Q93.X
sunshine (% SS). The % SS is determined by a Foster Sunshine Switch, which
consists of two photoelectric cells and a recorder. One cell is shaded from
direct sunlight; the other is not. These cells are connected such that the
recorder is actuated when the intensity of direct sunshine is sufficient to
produce a shadow. The temperature and the sunshine data are collected by
the National Weather Service (NWS) Forecast Office at the Raleigh-Durham
Airport (RDU).29 RDU is located approximately 10 km from the RTI Campus,
DATA COLLECTION AND HANDLING
The data handling system employed in the present study is composed of a
sequence of manual and machine processing steps that are depicted in Figure
9. As a result of the number of parameters (e.g., 03, NO, N02, etc.) being
measured, their temporal density, and the diversity of their output formats,
the data were introduced into the system at a time following the experiments
rather than on a real-time basis. Raw data were manually transferred from
some form of hard copy output onto computer cards. Calibration information
54
-------
OUTPUT
VOLTAGES
CALIBRATION
INFORMATION
SEARCH CONTROL
RAW DATA
AND CALIBRATION
INFORMATION FOR
ALL EXPERIMENTS
SELECTED RAH DATA AND
CALIBRATION INFORMATION
FOR A SINGLE EXPERIMENT
CALCULATED
DATA
SUMMARY OF ALL
DATA CONTAINED IN
THE CHEMICAL DATA SET
RAM SOLAR RADIATION
AND TEMPERATURE DATA
FOR ALL EXPERIMENTS
DATA RETRIEVAL CONTROL INPUT
DIAGNOSTIC OUTPUT CONTROL INPUT
ALTERNATE RAW DATA AND
CALIBRATION INFORMATION INPUT
*- OPTIONAL DIAGNOSTIC OUTPUT
ENVIRONMENTAL
DATA SET
ON TAPE
D/
„ FETCH
DATA ,
\Tft PI nT** "
PROGRAM
TWO
>
~* PLOT CONTROL INPU"
r*f »r«iA*»Tt/- /Mi-rniiT
DATA LISTINGS
Figure 9. Flowchart of overall data handling system.
55
-------
was also handled in this manner. Both are retained in the permanent records
of the project.
The format in which the data were originally collected was dependent on
the measurement method. The output of the ozone and nitrogen oxides instru-
ments, and the automatic sulfur gas chromatograph, were recorded on strip
chart recorders. A Hewlett-Packard Model 3352 Laboratory Data System with
teletype output was used to collect data from the gas chromatographs that
monitored PAN and propene. The results of EPA's analyses of the filter
samples were reported on computer print-out. Condensation nuclei measure-
ments were recorded in notebooks from instrument meter deflections. Total
solar radiation and ambient air temperature data were obtained from EPA on
magnetic tape.
In addition to their physical form, the raw data were also varied in
their temporal structure. The automatic stepping of the sampling system
from one chamber to the next resulted in the multiplexing of the measure-
ments from the ozone and nitrogen oxides instruments, and the automatic gas
chromatographs. Ozone and nitrogen oxides raw data were taken from the
eighth minute of each 10-minute sampling period. One measurement per samp-
ling period was made by the automatic gas chromatographs. Solar radiation
and temperature measurements were recorded at one-minute intervals. Samples
were collected at irregular intervals with the TPS filter sampler and the CN
counter.
At the end of an experiment, all data pertaining to that experiment
were organized and stored in a folder. Subsequently, the raw data were
transferred to computer coding forms along with identifying information,
such as the time and chamber number, which is associated with each measure-
ment. The raw data were recorded in the units in which they were originally
outputted (e.g., percent of recorder full scale). They remained in the
multiplexed format in which they were originally measured. Calibration
information which was used to convert the data from raw data units to concen-
tration units was also entered on the coding forms. In general, several
sets of coding forms were needed to record all the parameters which were
measured in an experiment. This meant that parameters were handled by the
computer as groups of parameters rather than as individual parameters or as
an entire ensemble of measurements. During processing each parameter within
56
-------
a group was identified by its SAROAD number (e.g., ozone = 44201). The
information contained on the coding form was then keypunched onto cards.
Either the cards or a magnetic tape, which was created from the cards, could
be used as input for the data handling programs.
The data handling programs which were used in the current study were
designed to maximize the use of calibration information while minimizing
manual calculation and data manipulation. This approach helps insure the
validity of the reported data. The calculation of parameter concentrations
from the raw data is made possible by calibration subroutines in the pro-
grams. In addition to the advantages of storing the data in the rawest
possible state, this also permits the calibration information to be modified
without alteration of the data itself. The programs also have the capability
of separating the multiplexed data by the chamber in which each measurement
was made and of merging different groups of parameters into a single ensemble
of measurements.
As is indicated in Figure 10, the raw data are converted into calculated
data in concentration units by Program One. The first step in this process
is the calculation of calibration values for each measurement. Since several
parameters can experience calibration shifts over the course of a single
experiment, error would result if a fixed calibration value were used. This
problem is avoided by the calculation of linearly interpolated calibration
values between measured calibration points. These interpolated calibration
values are then used to convert the measurements to concentration units. In
addition to employing routine zero-and-span type calibrations, Program One
has the capability of handling more complex nonlinear calibration calcula-
tions and data validity assessments via special algorithms, which are tailored
to individual parameters.
At this stage, the data are still multiplexed and are still separated
into parameter groups. The final step of Program One is to demultiplex the
data within each parameter group. The data are separated by chamber number
and are put into chronological order. The data are then passed to Program
Two and may also be placed in a data set for output by a digital plotter.
The purpose of Program Two is to reorganize further the data such that
all the measurements for a particular chamber and time are merged into a
single- ensemble and then to output this reorganized data. This process is
57
-------
RAW DATA AW) CALIBRATION INFORMATION FOR AN
ENTIRE EXPERIMENT
IDENTIFICATION AND
SEPARATION OF DATA
BY PARAMETER GROUPS
I
RAM DATA AND
CALIBRATION
INFORMATION STRATIFIED
BY PARAMETER GROUP
SEPARATION OF
RAW DATA FROM
CALIBRATION INFORMATION
DIAGNOSTIC OUTPUT
in
00
SPAN CALIBRATION
RAM
DATA
ZERO CALIBRATION INFORMATION
CALCULATION OF
ZERO-CORRECTED
DATA
INFORMATION
ZERO CORRECTED
DATA
CALCULATION OF
SLIDING SPAN
VALUES
SLIDING SPAN
VALUES
SLIDING ZERO
VALUES
CALCULATION OF
SLIDING ZERO
VALUES
-*- OPTIONAL DIAGNOSTIC OUTPUT
CALCULATION OF ZERO-
AND SPAN CORRECTED
DATA
CALCULATED DATA
STRATIFIED BY
PARAMETER GROUP,
DATA
SPECIAL
ALGORITHMS
•*- OPTIONAL DIAGNOSTIC OUTPUT
DEMULTIPLEXING OF DATA
BY CHAMBER NUMBER
OUTPUT TO
DIGITAL PLOTTER
DATASET
DATA
TEMPORARY
DATASET
DIAGNOSTIC OUTPUT
CALCULATED DATA TO PROGRAM
TWO STRATIFIED BY CHAMBER
NUMBER AND PARAMETER GROUP
Figure 10. Flowchart of program one.
-------
illustrated in Figure 11. Since different groups of measurements were made
at different times, a common time base for all the parameter groups must be
established. This is the first step in Program Two.
In the present study, the times of all the measurements have been
adjusted to the time of the ozone measurement in the same whole hour. In
general, the listed times correspond to the eighth minute of a sampling
period. It should be noted that these data were converted by the Program
One to fractional hours (EST). Since TPS and CN determinations involved
manual operations, the times assigned to these measurements correspond to
the automated instrument sampling period for the hour during which the
manual measurement was performed.
The next step taken in Program Two is to merge all the data associated
with a given time and chamber from the various parameter groups into a
single ensemble of data. At this stage, the data is used to calculate
derived parameter concentrations from the measured data. Examples of this
feature are the calculation of NO concentrations from NO and N02 measure-
X
ments, of time in fractional hours from time in hours and minutes, and of
integrated light intensities (CU-SR) from instantaneous solar radiation
measurements. The following formulae were used in these computations:
NO = NO + N02
Time = h + m/60
h-1
CU-SR = I SR(i) + fn SR (h)
i=0 60
Where th
SR(i) is the average solar radiation for the i complete hour;
h is the number of the indicated hour; and
m is the number of minutes from the top of the indicated hour until the
indicated time.
It should be noted that the SR data are listed in the appendix as hourly
_o -l
averages in units of Langleys per minute (cal cm min ). The CU-SR is a
measure of the cumulative solar radiation that had occurred up to the indi-
_o
cated time and is expressed in Langleys (cal cm ).
The final step in Program Two is the listing and plotting of the data
on a line printer. In addition to listing the data in their final form, the
two programs output various diagnostics data listings to facilitate verifies-
59
-------
CALCULATED DATA FROM PROGRAM ONE
STRATIFIED BY CHAMBER NUMBER AND
PARAMETER GROUP
CREATION OF A COMMON TIME
BASE FOR ALL PARAMETER
GROUPS
SOLAR RADIATION AND
TEMPERATURE DATA
•*- DIAGNOSTIC OUTPUT
MERGER OF ALL DATA FOR A
GIVEN TIME AND CHAMBER
NUMBER
TEMPORARY
DATA SET
CALCULATED DATA STRATIFIED BY
TIME AND CHAMBER NUMBER
CALCULATION OF
COMPUTED DATA
LISTING
ROUTINE
PLOTTING
ROUTINE
DATA LISTING
PRINTER PLOTS
Figure 11. Flowchart of program two.
60
-------
tion and correction of the data. In the present study, the data handling
programs were normally used at least twice. Initially, listings and plots
were generated to facilitate verification and correction of the data. Next,
the final listings of the verified data were produced and are displayed in
the appendix.
The data tabulated in the appendix contain default entries that require
identification. Blank spaces indicate that data are not available. Measured
zero values and negative outputs resulting from instrumental zero drift are
designated as 0.0. Values measured to be greater than zero but less than
0.001 measurement units (usually ppm) are indicated by 0.000. In addition,
special designations are used for the total sulfur and SOg data: concentra-
tions too small to be quantified are listed as 0.010; and those concentra-
tions that exceed the linear range of the instrument are set equal to 1.500.
PROCEDURE
The experiments conducted in the present study involved the irradiation
of each of 14 organosulfur species in the presence of nitrogen oxides. The
research plan was designed to investigate selected aspects of the chemical
behavior of the sulfur-containing compounds under simulated atmospheric
conditions. Two-day experiments were performed in the outdoor RTI Smog
Chamber Facility described earlier. The chambers were operated in the
static mode (no dilution) to simulate stagnation, conditions. The procedure
employed in these experiments is described in this subsection.
A normal two-day run involved only 36 hours of data collection—one
dark and two daylight periods. Chamber preparation and air purification
operations consumed the remaining time. A run was normally begun at 1700
EST when the previous run was terminated. The chambers were then purged at
a flow rate of up to 2.3 m3 rain for 1 to 2 hours. During this period the
air purification unit was activated and achieved .its normal operating temper-
atures and flow rates.
At approximately 1900 EST the purging operation was terminated, each
chamber was sealed, and the cleanup operation was begun. Hydrocarbon and
NO contaminants in the chamber air were removed by recirculation of the
chamber contents through the air purification unit for approximately 8 hours
at a flow rate of 0.28 m3 rain . In the present study the humidity of the .
61
-------
chamber contents was not altered during cleanup operations. This was accom-
plished by "bypassing" both the desiccant column and the humidifier during
the cleanup.
At approximately 0300 EST, 2 to 3 hours before sunrise, the cleanup was
terminated, and reactants were injected. Appropriate amounts of NO and N02
were introduced sequentially into each chamber from separate gas cylinders
using the reactant injection system (see Figure 5). After the NO injec-
X
tion, the test species (the sulfur-containing compound or propene) was
introduced into each chamber by syringe injection of the pure compound (for
more details see the appropriate subsection). Injection operations were
completed by approximately 1 hour before sunrise. This permitted time for
mixing and initial reactant sampling prior to sunrise.
The contents of each chamber were sampled and monitored for the next 36
hours. Ozone, NO, N02, PAN, propene (when appropriate), total sulfur, and
SOg were monitored once per hour for each chamber. Manual operations for
TPS and CN determinations were performed periodically—normally 6 to 8 times
during the first daylight period and 3 to 6 times during the second daylight
period. Generally, each two-day run was terminated at 1700 EST on the
afternoon of the second day.
62
-------
SECTION 5
RESULTS AND DISCUSSION
OVERVIEW
The objective of the present study is to investigate selected aspects
of the chemical behavior of 14 sulfur-containing compounds under atmospheric
conditions simulated in smog chambers. A major goal is to examine the ozone
production of each test compound under various initial conditions.
The experiments conducted in the present study are identified in Table
3 along with rough indicators of the environmental conditions that prevailed
on each run day. Data collected during these experiments are presented in
tabular form in the appendix.
In addition to propene, which was used as a control, the following
compounds were examined:
H2S CH3SH CH3SC2H5 (C2H5S)2 3-Methylthiophene
COS CH3SCH3 C2H5SH Thiophene 2,5-Dimethylthiophene
CS2 (CH3S)2 C2H5SC2H5 2-Methylthiophene
Four experiments with each compound were conducted simultaneously in
the four-chamber RTI facility described earlier. Target initial conditions
were 2.0 ppmC of the test species and 0.1, 0.2, 0.5, and 1.0 ppm of NO (20
percent N02). Thus, each species was examined at target initial HC/NO
A
ratios of 20, 10, 4, and 2 on the same days. For each compound this approach
permits examination of the results of experiments conducted under identical
environmental conditions but at different initial NO concentrations and
A
hence at different initial HC/NO ratios.
The data are analyzed in two stages. First, the results of the same-day
experiments conducted with each test compound are examined. These results
are discussed for each compound separately. Next, selected reaction parame-
ters for the 14 test species are intercompared. This permits a relative
assessment among the test compounds of such reaction parameters as maximum
ozone, sulfur dioxide, and particulate sulfur production.
63
-------
EXAMINATION OF THE CHEMICAL BEHAVIOR OF EACH TEST COMPOUND
In this analysis results of the four experiments conducted with each
test compound are examined. A tabular summary of selected reaction parame-
ters is given for these experiments. A graphical display of concentration-
time profiles of selected reactants and products for a representative exper-
iment is also presented. Among the four experiments, the one that achieved
the highest maximum ozone concentration is normally the one that was chosen
for graphical presentation. These tabular and graphical results are used to
identify and describe the effects that occurred when each test species was
irradiated in the presence of different initial concentrations for NO .
X
In the examination of the behavior of each test species, observed
trends are discussed. Since the target initial concentration of each test
species was fixed and the initial NO concentrations were varied, trends can
a
be interpreted to occur with either changing initial NO concentration or
A
with changing initial HC/NO ratio. For example, if across four experiments
the maximum ozone concentrations decrease with decreasing initial NO concen-
A
trations, then for a fixed initial test species concentration, they decrease
with increasing initial HC/NO ratios. For conventional hydrocarbon species
A
the photochemical reactivity as indicated by ozone production is sensitive
to the initial HC/NO ratio. Although the choice was somewhat arbitrary,
A
trends are identified and discussed in the current analysis with respect to
target initial HC/NO ratios rather than initial NO concentrations.
x x
Propene
Since propene has been investigated extensively in smog chambers over
the past 10 to 15 years, it was employed as a control test species in.the
current study. Experiments were conducted near the beginning and again near
the end of the current study period. Mixtures of propene and NO were
irradiated on 12 and 13 September, on 11 and 12 November, and on 13 and 14
November 1977. Selected results from these experiments are summarized in
Tables 14, 15, and 16. Concentration-time profiles for various reactants
and products are presented in Figure 12 for the 12 September experiment
conducted in Chamber No. 3.
In each of these experiments NO was oxidized rapidly to N02. The
duration of irradiation required to achieve NO-N02 crossover decreased with
64
-------
1.00
0.80
OJ
o
; 0.60 -
z O.fO -
o
M
0 0.20
0.00
0000
000*00
0800
1.00
1600 0000 0800
TIME (EST)
1600
0.80
O.GO
m
:z:
rn
- 0.40 -8
0.20
0000
0.00
Figure 12. Concentration-time profiles of various reactants and products for the 12 and 13
September 1977 propene-NOx experiment conducted in RTI Chamber No. 3. Target
initial conditions: 2.0 ppmC C3Hfc and 1.0 ppm NOX. Symbol key: (o) 03; (Q) NO;
(A) N02; and (x) C3H6.
-------
TABLE 14. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH PROPENE AND NO
TEST COMPOUND^7 DATE-7
Propene, 9-12-77
C3H6 9-13-77
SMOG CHAMBER NUMBER
max
25.6
27.8
3
%SS^7
95
32
4
CU-SR-7
527
509
1
SUNRISE-7
5.90
2
FIRST DAY PARAMETERS
Target Initial HC/NO^ (ppmC/ppra)
Time of N0-N02 Crossover,
(hrs EST)
(NOj)^, ppm
Time of [N02] (hrs EST)
max,
[03J , ppm
Time of [03]max. (&« EST^
Tiae of [pAN)max,.(hrs EST)
[MM] ppm*7
[EN] ppm
[NO J. . . ,h/
x'initial-
{NOxJ @ 1700 EST
fNO^ @ 1700 EST-7
fC3Ha (hrs EST)
Night-time 03 Half -Life (hrs)5/
2
9.12
0.648
11.47
0.978
16.47
ND
NA
ND
ND
0.954
0.218
0.229
ND
10.11
NA
NA
NA
NA
NA
950
15.47
33
4
8.32
0.358
9.63
0.963
15.63
ND
NA
ND
ND
0.487
0.167
0.343
ND
10.76
NA
NA
NA
NA
NA
NA
620
15.63
34
10
7.46
0.145
8.13
0.604
16.13
ND
NA
ND
ND
0.192
0.101
0.526
ND
9.39
NA
NA
NA
NA
NA
NA
430
6.13
24
20
NA*7
0.058&'
8.30*7
0.344
16.30
ND
NA
ND
ND
0.074P-7
0.060
ND .
10. IS*7
NA
NA
NA
NA
NA
NA
S.SOO*7
3.30*7
20
(continued)
NOTES: Abbreviation*: ND * no data are available; MA = aot applicable;
0 3 aot detected; tr = detected, but aot quantified; X a concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
66
-------
TABLE 14. (continued)
SMOG CHAMBER NUMBER
SECOND DAT
[03] ,
A03, ppnr
[S02] :
DoX
4S02, ppi
[TPS]max
tC»lm.x-
PARAMETERS
ppo
)/
, ppm
n/
, Mg/mJ
(ppmS)
cm'3
3
0.920
0.283
NA
XA
NA
NA
ND
4
0.303
0.170
NA
NA
NA
MA
ND
I
0.580
0.215
MA
NA
NA
NA
ND
2
0.4S8
0.312
NA
MA
MA
MA
MD
-Target initial concentration 2.0 ppmC or 0.67 ppm (V/V).
-Dates of first and second days of the experiment.
-Daily maximum temperature in °C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
- Cumulative daily solar radiation expressed in Langleys (cal cm "); aoce that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
& Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
- The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise? the table entry has SOT been corrected for possible interferences.
-Fraction of initial NO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent MO analyzer.
^'Fraction of accountable test compound at the 1700 EST hour.
k/
- Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02] : ([TPS]/([TPS]+[S02])).
, max
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, S 5.545/ln ([03]2000/[03]0400).
-This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Met concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: dO-, = [03] -[031 and
----- max aim
£'Due to an operational problem during reactant injection, the initial concentrations
in Chamber No. 2 are not clearly defined; these tabulated results should be con-
sidered with caution.
67
-------
TABLE 15. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH PROPENE AND NO
TEST COMPOUND2'
Propene ,
C3H«
SMOG CHAMBER NUMBER
DATE^
11-11-77
11-12-77
T £/
max
13.3
8.9
4
%ssi/
100
83
3
CTJ-SRS'
331
316
2
SUNRISE-'
6.88
1
FIRST DAf PARAMETERS
Target Initial HC/NOx
(ppmC/ppm)
Tine of N0-N02 Crossover,
(hrs EST)
[N02] , ppm
Time of [N02lmax (hrs
Time of I03lmax> (ars
(PAN] , ppm
Time of [PANI,,^! (hrs
(MS] ppm*'
EN] ppm
NO 1 . . . , h/
xjinitial-
[NO ] @ 1700 EST
fNO @ 1700 ESTi/f
X
EST)
EST)
EST)
fCjH, @ 1700 ESTi' . .
Time of [C3H8], (hrs EST)-'
[S02] , ppm
Tine of [S02]max> (hrs
(ppmS)
Time of (TPS]max, (hrs
Ri'
EST)
EST)
.-a
f C V t j~mt
I \*fl j f CO
Time of [CNlmax, (hrs EST)
Night-time 03 Half-Life (hrs)a/
2
10.92
0.639
14.63
0.043
14.63
0.024
16.63
0.003
0
0.956
0.632
0.661
0.28
13.11
NA
NA
NA
NA
NA
NA
950
14.63
NA
4
9.78
0.371
11.47
0.446
14.47
0.078
16.47
0.001
0
0.482
0.157
0.326
0.04
11.96
NA
NA
NA
NA
NA
NA
320
14.47
41
10
9.01
0.145
10.30
0.393
12.30
0.042
17.30
tr
0
0.186
0.087
0.468
0.06
11.08
NA
NA
NA
NA
NA
NA
950
• 14.30
22
20
8.74
0.065
10.13
0.266
11.13
0.021
16.13
tr
tr
0.090
0.046
0.511
0.17
11,12
NA
NA
NA
NA
NA
2,600
13.13
9»/
NOTES: Abbreviations: ND = no data are available; NA = not applicable;
0 a act detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
irized in this table.
(continued)
68
-------
TABLE 15. (continued)
SMOG CHAMBER NUMBER
4
3
2
1
SECOND DAY PARAMETERS
(03jmax'oppm
S!mppm*/P1B
ITPS] , ug/mj
max
CppmS)
''"'max' «'3 Z/
0.169
0.169
NA
NA
NA
NA
620
X
NA
NA
NA
NA
NA
460
X
NA
NA
NA
NA
NA
750
0.051
0.018
NA
NA
NA
NA
2500
-Target initial concentration 2.0 ppmC or 0.67 ppm (V/V).
-Dates of first and second days of the experiment.
- Daily maximum temperature ia °C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.*9
-Cumulative daily solar radiation expressed in LangLeys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated--usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
* Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise'; the table entry has NOT been corrected for possible interferences.
- Fraction of initial NO^ remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. • *
•'•Fraction of accountable test compound at the 1700 EST hour.
k/
- Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of (SOj]^: ([TPS]/([TPS] + (S02])).
- Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/(03]0400).
-This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
- Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration:
-------
TABLE 16. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH PROPENE AND NO
TEST COMPOUND-'' DATE-''
Propene, 11-13-77
C3H« 11-14-77
SMOG CHAMBER NUMBER
max
7.8
10.6
4
VS&
100
89
3
CU-SR-/
340
293
2
SUNRISE-''
6.92
1
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppm)
Time of NO-NOj Crossover,
(brs EST)
[NOj] , ppm
Time of IN02]MX (hrs EST)
^°3'«ax' pp"*
Time of [03] , (hrs EST)
UMi A
[PAN] ppm
01**
Time of [PAN] . '(hrs EST)
(BaX
. (UN) ppm*7
EN) ppm
[NOx] initial^
[N0x] @ 1700 EST
fNO @ 1700 ESTi/
x
fC3K, 9 1700 ESTJ-'' k/
Time of [CaHa]^ (hrs EST)-'
(S02JMX, pp.
Time of [S02]max, (hrs EST)
(ppmS)
Time of [TPS]aax( (hrs EST)
Ri'
[CN]Mx, cm'3
Time of [CN](MxF (hrs EST)
Night-time 03 Half -Life (hrs)2/
2
11.36
0.607
14.63
0.018
14.63
0.018
16.63
0.002
0
0.970
0.726
0.748
XD
14.29
NA
NA
NA
NA
NA
280
11.63
NA
4
10.12
0.361
12.47
0.318
15.47
0.061
16.47
0.002
0
0.491
0.124
0.253
NO
12.92
NA
NA
NA
NA
MA
NA
320
11.47
27
10
9.28
0.151
10.30
0.360
12.30
0.043
15.30
tr
tr
0.200
0.084
0 . 420
ND
11.67
NA
NA
NA
NA
NA
NA
460
11.30
25
20
8.83
0.076
10.13
0.247
12.13
0.023
17.13
0
0
0.102
0.045
0.441
MD
11.53
MA
MA
MA
MA
MA
MA
1,400
11.13
11^
NOTES: Abbreviations: NT) = no data are available; NA 3 not applicable;
0 * not detected; tr = detected, but not quantified; X * concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
(continued)
70
-------
TABLE 16. (continued)
SMOG CHAMBER NUMBER
4
3
2
1
SECOND DAY PARAMETERS
[Oj] , ppm
ao,,"^
[S02] , ppm
* aax i
AS02, ppm2
[IPS] , Hg/«,• CT"3
0.138
0.138
NA
NA
NA
NA
650
X
NA
NA
NA
NA
NA
0
X
NA
NA
NA
NA
NA
200
X
NA
NA
NA
NA
NA
200
-Target initial concentration 2.0 ppraC or 0.67 ppm (V/V).
- Dates of first and second days of the experiment.
- Daily maximum temperature in "C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
— Cumulative daily solar radiation expressed in Langleys (cal cm ); note chat the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
8'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial (NO^) is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
-'Fraction of initial NO^ remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. x
i/ *
•i'Fraction of accountable test compound at the 1700 EST hour.
- Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02]oax: ([TPSj/([TPS]+[S02])).
-'Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, = 5.545/ln ([03]2000/(03]0400).
»
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: &Q3 = [0,1 -[03J and
-
71
-------
increasing initial HC/NO ratios (i.e., the rate of conversion increased
with decreasing initial NO concentrations). The photooxidation of NO to
N02 proceeded more rapidly in the September experiments than in those con-
ducted in November. For the slowest case, a target initial HC/NO ratio of
X
2, crossover occurred after approximately 3.2 hours of irradiation at 0907
EST on 12 September; however, at the same initial conditions, crossover
occurred approximately 4.2 hours after sunrise at 1055 and 1121 EST on 11
and 13 November.
Ozone accumulated during each experiment, maximum concentrations were
dependent on the initial HC/NO ratio. The maximum ozone concentration,
0.98 ppm, was produced on 12 September at a target HC/NO ratio of 2.
Maximum concentrations of 0.45 and 0.36 ppm occurred on 11 and 13 November
at target HC/NO ratios of 4 and 10 respectively. Although the [03]
X UlaX
generally occurred during the 1600 hour in the September experiments irre-
spective of initial conditions, in November the (®3] occurred during the
1400 hour at low HC/NO ratios and two to three hours earlier at the higher
ratios .
Both the decrease. in the absolute values of the maximum ozone concen-
trations and the shift from occurring at a low HC/NO ratio to higher ratios
were probably caused by environmental differences. The temperature, the
sunlight intensity, and the duration of sunshine were greater for the Sep-
tember than for the November experiments. On 12 September the cumulative
-2
daily solar radiation was 527 cal cm with 95 percent of the possible
minutes of direct sunshine, and a maximum temperature of 25.6° C. Both 11
and 13 November were 100 percent sunshine days and had comparable cumulative
_2
daily solar radiation data--331 and 340 cal cm . The maximum temperature
of 13.3° C on 11 November was 5.5° warmer than that on 13 November and may
have been responsible for the slight enhancement of such reactivity parame-
ters as time to NO-N02 crossover and [03] on 11 versus 13 November. This,
niaX
however, is somewhat speculative, since the absolute propene concentrations
were on the average 13 percent higher on 11 November than on 13 November.
The PAN data for the November experiments suggest that the conditions
which result in the production of high maximum concentrations of ozone also
lead to the production of high concentrations of PAN. High yields of PAN
were produced at high HC/NO ratios. In addition, peaks tentatively identi-
72
-------
fied as methyl nitrate (MN) were found. Although never more than a few ppb,
the highest concentrations of MN occurred at low initial HC/NO ratios (high
X
initial NO concentrations). Ethyl nitrate (EN) concentrations were detected
X
in only two of the eight experiments and these concentrations were low.
Inspection of the first-day NO data in the appendix revealed unusual
behavior for the three sets of propene-NO experiments. Generally, at the
A
two highest initial HC/NO ratios, between 0900 and 1400 EST, the NO concen-
A A
tration exhibited a loss of a few ppb and a subsequent recovery. The timing
of this phenomenon coincided with the initial buildup of PAN. This behavior
was not observed in the remaining two experiments, although it may have been
obscured by the higher NO concentrations employed in these experiments. It
A
is likely that a transient nitrogen-containing species was responsible for
this behavior. This species was either not delivered to the NO monitor as
A
a result of interactions with chamber walls or the sampling system, or it
could not be detected by the chemiluminescent NO monitor that was employed.
X
At any rate, the identity of this hypothetical species is unknown.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
X
the 1700 EST hour of the first day. In general, the nitrogen balance was
the poorest for those conditions under which high ozone concentrations were
generated. Typically, only 0.25 to 0.40 of the intial NO could be accounted
X
for at optimum ozone-generative conditions, while up to 0.75 could be account-
ed for at other conditions. The unaccountable product nitrogen is presuma-
bly comprised of nitric acid or other undetermined nitrogen-containing
species that may be in the gas phase or on the walls of the chamber. The
fate of NO in photochemically reacting systems is largely unknown and
should be investigated.
Propene was consumed rapidly during these experiments. Estimates were
made of the fraction of CsHg that remained unreacted at the 1700 EST hour.
These results as well as the times to one-half consumption of C^HQ suggest
that the C3He disappearance rate was dependent on the initial HC/NO ratio.
X
For the four experiments conducted on 11 November, the fraction of initial
that remained ranged from 0.04 to 0.28. The experiment in which reac-
tion of propene was most nearly complete also produced the highest maximum
ozone concentrations. The ordering of the accountable fraction of C3H6 was
73
-------
similar to that observed earlier for the other reactant--NO . These results
A
suggest that for the propene-NO systems employed in the current study, the
A
conditions under which the maximum fraction of each reactant is consumed
coincides with maximum reactivity as measured by ozone production.
The photooxidation of propene did not produce large numbers of conden-
sation nuclei. Maximum CN levels were generally less than 3000 cm and
displayed no apparent trends with HC/NO ratio.
A
High ozone concentrations approaching the first-day maximum concentra-
tions were achieved on the second day during the September experiments in
three of four cases. At the target HC/NO ratio of 20, the second-day
maximum ozone concentration exceeded the first-day value. The net ozone
concentrations generated were less than the first-day maxima and ranged from
0.17 to 0.31 ppm. During the November experiments at HC/NO ratios of 4,
A
10, and 20, second-day ozone concentrations generally decayed from the
first-day maxima. At the HC/NO ratio of 2, however, excessive initial NO
X
under light-limited conditions yielded little ozone on the first day. By
the second day most of the initial NO had been converted to N02, the system
was no longer light-limited, and significant amounts of ozone were produced.
Second-day maximum and net ozone concentrations .were identical. These
values were 0.17 on 12 November and 0.14 ppm on 14 November. In addition,
the target HC/NO ratio of 2 was the only condition where second-day net
A
ozone concentrations exceeded the first-day maximum concentrations for
CsHg-NO systems, and this only occurred in the November experiments.
Hydrogen Sulfide
Mixtures of hydrogen sulfide and NO were irradiated on 23 and 24
September 1977. On 23 September the cumulative daily solar radiation was
421 cal cm with 51 percent of the possible minutes of direct sunshine and
a maximum temperature of 26.7° C. Selected results from the ^S-NO experi-
A
meats are summarized in Table 17. Concentration-time profiles of various
reactants and products for the experiment conducted in Chamber No. 3 are
presented in Figure 13.
The photochemical behavior of irradiated mixtures of NO and H2S was
A
markedly different from that of irradiated mixtures of NO and a hydrocarbon
A
74
-------
1.50
X|XXKXjKX )(|>OO(XpO(
z:
o_
Q_
OJ
CD
1.00
Ln
0.50
O
M
O
0.00
r | r | i
23-2'f SEPTEMBER 1977 11
R
Beef
0000
Figure 13.
0800
b^#
QboQQDOOobQOODOOOboOQ'O
1600 0000
TIME (EST)
0800
OQ'OOO
1600
1.50
I. 00
0.50
CO
o
JZ
ro
CO
~0
0000
0.00
Concentration-time profiles of various reactants and products for the 23 and 24
September 1977 H2S-NOX experiment conducted in RTI Chamber No. 3. Target initial
conditions: 2.0 ppm
H2S; and (+) S02.
and 1.0 ppm NOX. Symbol key: (o) 03; (D) NO; (A) N02;
-------
TABLE 17. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH H2S AND NO
£. v
TEST COMPOUND-'' DATE-'
Hydrogen Sulfide, 9-23-77
H2S 9-24-77
SMOG CHAMBER NUMBER
T ^
max
26.7
27.8
3
*SS^
51
36
4
CU-SR-/
421
385
1
SUNRISE-''
6.00
2
FIRST DAY PARAMETERS
Target Initial HC/NO (ppraV/ppn)
Time of N0-N0.> Crossover,
(.hcs EST)
'N0*]max' PpB1
Time of [N02j (hrs EST)
max,
[031 . ppo
' •'•'max' "
Time af [03] , (hrs EST)
in ax
[PA»]MX, ppm
Time of IPAN)^, (hrs EST)
(MM) ppm*'
EN] ppm
«°J initial
[NOJ @ 1700 EST
fNOx @ 1700 EST^
[H2S] @ 1700 EST^
Time of [HjSl^iy-*'
[S02jmaj{, ppm
Time of [S02]fflax, (hrs EST)
[TPSImax' M8/mJ
(ppmS)
Time of [TPS]^, (hrs EST)
Ri7
(CMl»ax' Cm*3
Time of [CN)nax, (hrs EST)
Night-time 03 Half-Life (hrs)27
2
NA
0.213
6.47
0.002
14.47
ND
MA
ND
ND
0.954
0.918
0.962
>1.5
>T day
0.376
16.47
5.1
0.004
15.47
0.01
110,000
17.47
MA
4
MA
0.104
6.63
0.002
14.63
XD
JJA
ND
ND
0.489
0.493
1.008
>1.5
>T day
0.262
15.63
2.9
0.002
4.63
0
105,000
14.63
NA
10
MA
0.041
5.13
0.001
15.13
ND
HA
ND
ND
0.202
0.229
1. 134
>1.5
>T day
0. 169
15.13
3.8
0.003
4.13
0
125,000
17.13
MA
20
NA
0.022
5.30
0.001
14.30
ND
NA
ND
ND
0.103
0.138
1.340
>1.5
>T day
0.191
16.30
4.6 "
0.004
4.30
0
130,000
14.30
MA
— - "•' "
( continued )
MOTES: Abbreviations: ND * ao data are available; NA = not applicable;
0 = not detected; tr = detected, but not quantified; X = concen-
tration decreased, ao maxiaum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
76
-------
TABLE 17. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
[°3]max' Ppm
A03, ppn£
^'max' W",
aSOj/Ppo^
[TPS1max' M'"*
(ppnS)
t^max' cn~3
0
NA
0.257
MA
14.8
0.011
21,000
0
NA
0.200
NA
10.5
0.008
32,000
0
NA
0.198
NA
5.9
0.005
37,000
0.002
0.002
0.194
NA
11.7
0.009
47,000
- Target initial concentration 2.0 ppra (V/V), or 2.0 ppmS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
- Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
^ Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial (NOX] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
— Fraction of initial NO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer.
J-'Concentration of accountable test compound at the 1700 EST hour.
I,/
-Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
tiae of [S02]a)ax: ([TPS]/([TPS] + [S02D).
- Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, = 5.545/ln ([03]2000/(03]0400).
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: A03 = (03) -[03] . and
AS02 » lS02]Mx - [SO,]Bia. MX min
° The available data suggest that the time to one-half consumption of H2S in these
experiments exceeded 1 day.
^'Too few S02 data are available to permit the determination of iS02 for these
experiments.
77
-------
such as propene. Hydrogen sulfide did not act to promote the oxidation of
NO to N02. In these experiments the reverse occurred—N02 was reduced to NO
at such a rate that the conversion was essentially complete by 1000 EST.
Thus, the maximum N02 concentrations listed in Table 17 are the initial
values.
It is likely that the reduction of N02 to NO in the presence of H2S in-
volves a photochemical process, since the concentration of N02 decayed
sharply during the first day but increased after sunset. The dark-phase
increase in the N02 concentration presumably resulted from the thermal
oxidation of NO. On the second day shortly after sunrise the N02 concentra-
tion decreased but then increased as if the remaining H2S was no longer at a
sufficient concentration to influence its behavior. This behavior was not
as pronounced in chamber No. 3 as it was in the other chambers where the
experiments were conducted at lower initial NO concentrations.
A
Since NO was not oxidized to N02, essentially no ozone accumulated on
either day of the two-day experiments. In contrast, sulfur dioxide was
generated during each experiment on both days. With the exception of Cham-
ber No. 1 on the first day, the maximum concentrations of S02 increased with
increasing initial NO (and N02) on both days. On the first day, maximum
A
S02 concentrations occurred during the 1500 and 1600 EST hours. They also
occurred late in the day on the second day.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. The fraction of initial NO that could
be accounted for increased as the initial NO concentration was reduced.
For the four experiments the fraction of the original NO that could be
A
accounted for on the first day ranged from 0.96 at the highest initial NO
x
concentration to 1.34 at the lowest. As noted in an earlier section, many
of the tested sulfur compounds interfered with the chemiluminescent determin-
ation of nitrogen oxides. Since the target initial (H2S] was identical for
each chamber and the percentage of accountable NO increased with decreasing
initial [NO ], the apparent increase in [NO ] may have resulted from inter-
A A
ference by H2S or by an unknown reaction product. This point deserves
additional investigation.
78
-------
For the most part, the initial concentrations of H2S exceeded the
linear range of the instrument. However, by the end of the first day suffi-
cient H2S had been consumed such that the concentration had dropped from the
target initial value of 2.0 ppm to within the measurable range, less than
1.5 pptn. During the night the concentration of H2S decreased in all four
chambers and continued to drop after a small discontinuity that occurred
shortly after sunrise on the second day. Although S02 data were not availa-
ble, the IPS concentration data did not reflect a corresponding increase.
Subsequent experiments conducted in Teflon bags also suggest that H2S in the
presence of N02 and sunlight decays with a concurrent conversion of N02 to
NO. Additional dark-phase experiments, however, indicate that in the absence
of irradiation mixtures of H2S and N02, and H2S and NO are relatively stable.
The nighttime decrease of [H2S] may be the result of interaction with pro-
ducts of the photochemical reactions that occurred during the previous day
or with interactions with the chamber walls.
Copious quantities of condensation nuclei were generated in these
experiments on the first day. They were not appreciably different for the
_3
four experiments, ranging from 105,000 to 130,000 cm . Although the largest
[CN] occurred at the target HC/NO ratio of 20, first-day [CN] displayed
1 'max x * max r
no apparent trends with initial HC/NO ratio. Moderate quantities of CN
were produced on the second day. Maximum concentrations ranged from 21,000
3
to 47,000 cm . The largest second-day maximum CN concentration also occurred
at the larget HC/NO ratio of 20 and maximum CN concentrations increased
A
with increasing HC/NO ratios.
X
In spite of the formation of both S02 and CN, the concentrations of
total particulate sulfur were low. Maximum concentrations ranged from 2.9
to 5.1 (Jg/m3 which correspond to the equivalent of 2 to 4 ppb of sulfur.
Since the TPS concentrations were low for each experiment, the ratios of
product sulfur as particulate to the total accountable reacted sulfur ([TPS]
plus [S02]) were also low. In three cases the ratio was zero; in the fourth
it was 0.01. Second-day TPS maxima were also low, although they exceeded
first-day concentrations by a factor of approximately 2.
Carbonyl Sulfide
Mixtures of carbonyl sulfide and NO were irradiated on 18 and 19
September 1977. On 18 September the cumulative daily solar radiation was
79
-------
_
463 cal cm with 77 percent of the possible minutes of direct sunshine and
a maximum temperature of 30.6° C. Selected results from the COS-NO experi-
2C
ments are summarized in Table 18. Concentration-time profiles of various
reactants and products for the experiment conducted in Chamber No. 3 are
presented in Figure 14.
The photochemical behavior of irradiated mixtures of NO and COS was
different from that of irradiated mixtures of NO and hydrocarbons. In most
A
respects, the results from irradiating COS and NO were no different than
those expected from irradiating NO in pure air. Carbonyl sulfide did not
X
act to promote the oxidation of NO to N02, and NO-N02 crossover occurred in
only one chamber, No. 2. In that case crossover occurred late in the day,
at approximately 1640 EST, in the experiment with the lowest initial NO
A
concentration.
Organic chamber contaminants can act to mediate the photooxidation of
NO to N02- When the ratio of organics to nitrogen oxides is low and the NO
exists primarily as NO, the apparent conversion of NO to N02 is slow and the
'system is said to be "NO inhibited." As the initial concentration of NO is
A
reduced, the ratio of organics to NO is increased, the apparent conversion
of NO to N02 becomes more rapid, and the system becomes less "NO inhibited."
It is likely that the conversion of NO to N02 that occurred in Chamber No. 2
was mediated by chamber contaminants and not by the presence of COS.
On the first day ozone accumulated in only two of the four experiments,
and the maximum concentrations were low in these two cases. Maximum
concentrations were dependent on the initial HC/NO ratio (i.e., the initial
NO concentration). Ozone maxima ranged from 0.000 to 0.011 ppm, and the
nonzero maxima occurred during the 1300 EST hour. Maximum concentrations
increased with increasing HC/NO ratio (i.e., decreasing NO concentration).
X X
For the four experiments the largest first-day maximum ozone concentration
was 0.011 ppm and was achieved at the target initial HC/NO ratio of 20.
PAN, MN, and EN concentration data were not available for these experi-
ments. Their formation, however, is unlikely in view of the chemical struc-
ture of COS.
A nitrogen balance was estimated for each experiment based on chemilumi-
nescent NO^ concentrations determined initially and again during the 1700
EST hour of the first day. The nitrogen balance was good for all the COS
80
-------
0.30
I|i|r-
18-19 SEPTEMBER 1977
t»
(—"
a.
o_
oj
o
o
o
o
0.20
0.10
0.00
0000
0800
0.30
0.20
o
CD
O
o
0.10
1600 0000
TIME (EST)
0800
1600
0.00
0000
Figure 14. Concentration-time profiles of various reactants and products for the 18 and 19
September 1977 COS-NOX experiment conducted in RTI Chamber No. 1. Target initial
conditions: 2.0 ppmC COS and 0.2 ppm NOXO Symbol key: (o) 03; (O) NO; and (A) N02.
-------
TABLE 18. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH COS AND NO
TEST COMPOUND*'' DATE-/
Carboayl Sulfide 9-18-77
COS 9-19-77
SMOG CHAMBER NUMBER
T S/
max
30.6
30.6
3
ttS^
77
74
4
CU-SR-/
463
408
1
SUNRISE-7
5.95
2
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppaC/ppm)
Tin* of N0-N02 Crossover,
(hrs EST)
Wtl^,. PP«
Time of (M^]^ (hrs EST)
(°3i «/BJ
(ppmS)
Time of (TPS] , (hrs EST)
ID*X
Ri/
I«l... «'3
Time of [CM] , , (hrs EST)
O41X
Jfight-time Oa Half-Life (hrs)2/f
2
MA
0.439
5.47
0
NA
ND
NA
HD
ND
1.176
1.071
0.911
>1.5
>2 days
ND
XA
3.4
0.003
S.47
ND
8,100
9.47
NA
4
NA •
0.124
7.63
0
XA
ND
NA
KD
ND
0.491
0.431
0.878
>1.5
>2 day*
ND
NA
0
0
NA
ND
220
10.63
NA
10
NA
0.048
7.13
0.002
13.13
ND
NA
ND
ND
0.204
0.184
0.902
>1.5
>2 days
ND
NA
0
0
NA
ND
8,100
9.13
NA
20
16.68
0.049
20.30
0.011
13.30
ND
NA
ND
ND
0.100
0.089
0.890
>1.5
>2 days
ND
NA
6.3
0.005
6.30
ND
5,600
9.30
NA
(continued)
NOTES: Abbreviations: ND * no data are available; NA » not applicable;
0 = not detected; tr = detected, but not. quantified; X = concen-
tration decreased, ao maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
82
-------
TABLE 18. (continued)
SMOG CHAMBER NUMBER
3 4
1
2
SECOHD DAY PARAMETERS
l°3lmax' Ppln
A03, ppm—
[SO,] , ppm
ZJmax'o^y
[TPS] , Mg/">J
(ppraS)
I"'-.. ^
0 0.001
NA 0.001
ND ND
NA NA
0 0
0 0
0 0
0.007
0.007
ND
NA
0
0
840
0.028
0.028
ND
MA
0
0
0
-Target initial concentration 2.0 ppraC, 2.0 ppm (V/V) , or 2.0 ppmS.
- Dates of first and second days of the experiment.
-Daily maximum temperature in SC.29
-Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
- Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until Che experiment was
terainated--usually 1700 EST.
- Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
* Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
- The initial (NO ] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
^'Fraction of initial N0x remaining at the 1700 EST hour calculated from MO concentra-
tions as determined by the chemiluminescent NO analyzer. x
\l x
•'•'Concentration of accountable test compound at the 1700 EST hour.
k/
- Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of (S02]max: ([TPS]/([TPS]+[SOZ])) .
- Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ( [03]2000/ [03]0400) .
-/ \
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: i03 = [031 -[03] . and
was stable in these experiments; the available data suggest that the :ime Co
one-half consumption of COS in these experiments exceeded 2 days.
83
-------
experiments. For the four experiments the fraction of initial NO that
X
could be accounted for ranged from 0.88 to 0.91. This fraction showed no
apparent trends with initial HC/NO ratio. The unaccountable product nitro-
A
gen may be nitric acid or other undetermined nitrogen-containing species.
The fate of NO in photochemically reacting systems is largely unknown.
X
Irradiation of COS in the presence of NO resulted in the production of
small quantities of condensation nuclei. Maximum concentrations ranged from
•3
220 to 8100 cm and occurred early on the first day, displaying no apparent
trends with initial HC/NO ratio.
X
.Maximum total particulate sulfur concentrations were low and displayed
no apparent trends with initial HC/NO ratio. Particulate sulfur was detected
X
in only two of the four experiments . Maximum TPS concentrations ranged from
0 to 6.3 |Jg/m3, which correspond to the equivalent of 0 to 5 ppb of sulfur.
In each chamber the most frequent TPS concentration was 0 jjg/m3.
Neither COS nor SQ2 concentration data were available for these experi-
ments. This deficiency prevents an assessment of the extent of reaction for
COS or whether S02 was a reaction product. The slow oxidation of NO, the
formation of negligible quantities of 03, the low maximum CN concentrations,
and the very low maximum TPS concentrations , however, suggest that COS is
relatively unreactive in the presence of NO and sunlight.
X
Second day results also suggest that COS is unreactive. Aside from the
experiment where N0-N02 crossover was achieved on the first day, N0-N02
crossover was not achieved in the three remaining experiments on either day.
Ozone maxima on the second day increased with increasing initial HC/NO
A
ratio as had occurred on the first day. Although second-day [0^] general-
ly exceeded the first day levels, ozone accumulated in only three experiments
and ranged from 0.000 to 0.028 ppm. The largest second-day [03] was
max
0.028 ppm and was achieved in the experiment conducted at a target HC/NO
X
ratio of 20. Condensation nuclei were detected in only one chamber, and
particulate sulfur was not detected in any chamber on the second day.
Carbon Bisulfide
Mixtures of carbon disulfide and NO were irradiated on 21 and 22
X
September 1977. On 21 September the cumulative daily solar radiation was
-------
_2
451 cal cm with 64 percent of the possible minutes of direct sunshine and
a maximum temperature of 26.7° C. Selected results from the CS2_NO experi-
A
meats are summarized in Table 19. Concentration-time profiles of various
reactants and products for the experiment conducted in Chamber No. 2 are
presented in Figure 15.
Nitric oxide was oxidized to N02 in the presence of CS2 and sunlight at
a rate that was dependent on the initial HC/NO ratio. The duration of
A
irradiation required to achieve NO-N02 crossover decreased with increasing
HC/NO ratios (i.e., decreasing initial concentrations of NO ). The most
X A
rapid conversion occurred at the target HC/NO ratio of 20 where crossover
was achieved at 0703 EST, approximately one hour after sunrise. In contrast,
at the target HC/NO ratio of 2, crossover was not achieved during the
A
complete 2-day experimental period.
Ozone accumulated on the first day during three of the four experiments.
Maximum concentrations were dependent on the initial HC/NO ratio (i.e., the
A
initial NO concentration). Ozone was not observed in the one experiment
where N0-N02 crossover had not been achieved. For the remaining three
experiments ozone maxima ranged from 0.005 to 0.33 ppm and occurred during
the 1500 and 1600 EST hours. Maximum ozone concentrations increased with
increasing HC/NO ratios (i.e., decreasing NO concentrations). The largest
A A
[03] , 0.33 ppm was achieved at the target HC/NO ratio of 20, the condi-
tion that had resulted in the most rapid oxidation of NO.
PAN, MN, and EN concentration data were not available for these experi-
ments. Their formation, however, is unlikely in view of the chemical struc-
ture of CS2-
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. For the four experiments the fraction
of initial NO that could be accounted for ranged from 0.32 to 0.81. This
A-
fraction decreased with increasing HC/NO ratios (i.e., decreasing NO
A A
concentrations). Moreover, reduction of the accountable NO was associated
A
with increased maximum ozone concentrations. The unaccountable product
nitrogen may be nitric acid or other undetermined nitrogen-containing species.
85
-------
TABLE 19. SUMMARY OF SELECTED
CONDUCTED
RESULTS FROM SMOG CHAMBER EXPERIMENTS
WITH CS2 AND NO
TEST COMPOUND^ DATE-/
Carbon Disulfide 9-21-77
CS2 9-22-77
SMOG CHAMBER NUMBER
T ^
max
26.7
26.1
3
%SS^
64
63
4
CU-SR£/
451
413
1
SUNRISE-'
5.98
2
FIKST DA* PARAMETERS
Target Initial HC/NOx (ppmC/ppm)
Time of N0-N02 Crossover,
(hrs EST)
(N02]MX, ppm
Tine of [N02] „ (hrs EST)
luaX t
^raax' ppm
Time of [03]fflax, (n« EST)
[PAN]fflax, pp.
Time of [PAN]^, (hrs EST)
[MN] pprn^
EN] ppm
[NO ] . . . ,h/
1 x initial-
[N0x] @ 1700 EST
fNO^ 1? 1700 EST-''
fCS2 EST-J-7 ,
Tia« of [CSj]^**-^
[cos]max, ppm^
Time of [COS] , (hrs EST)
max
(TPS]Mx, Mg/"«J
(ppmS)
Time of [TPSlfflax, (hrs EST)
Ri/
[CN1max' Cffl"3
Time of [CN]^^, (hrs EST)
Night-time 03 Half-Life (hrs)s/
2
NA
NA
.VA
0
NA
ND
NA
ND
ND
0.977
0.789
0.308
0.86
>1 day
0.271
22.47
0
0
NA
ND
91,000
8.47
NA
4
12.41
0.206
16.63
0.005
15.63
ND
NA
ND
ND
0.486
0.349
0.718
0.78
>1 day
0.439
18.63
4.3
0.003
15.63
ND
150,000
7.63
NA
10
3.69
0.118
11.13
0.052
15.13
ND
NA
ND
ND
0.204
0.131
0.642
0.72
>1 day
0.551
18.13
0.
0
NA
JTO
180,000
8.13
NA
20
7.05
0.074
8.30
0.333
16.30
ND
NA
ND
ND
0.102
0.033
0.324
0.62
>1 day
0.763
17.30
11.4
0.009
15.30
ND
120,000
7.30
16
(continued)
NOTES: Abbreviations: ND - no data are available; NA = not applicable;
0 s not detected; tr = detected, but not quantified; X a concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
86
-------
TABLE 19. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
[03]n|ax, ppra
AQ-f ppro—
[S02]|Bax, ppm
. „. o/
ASOj , ppm-
[COS]max' ppm
ACOS. ppm
[TPS] , Mg/m"4
max
(pp»S)
tCN]MX, cm'3
0
NA
0.132
0.132
0.526
0.294
3.3
0.003
83,000
0.048
0.048
0.168
0.168
0.320
0.413
3.9
0.003
100,000
0.295
0.295
0.163
0.163
1.145
0.631
5.4
0.004
61,000
0.333
0.191
0.139
0. 139
1.071
0.389
7.5
0.006
27,000
-Target initial concentration 2.0 ppmC, 2.0 ppm (V/V), or 4.0 ppraS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
- Duration 'of direct solar radiation reported as percent of possible minutes of sunshine.29
- Cumulative daily solar radiation expressed in Langleys (cal cm" ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
- Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
* Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
h/
- The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise'; the table entry has MOT been corrected tor possible interferences.
- Fraction of initial K0x remaining at the 1700 EST hour calculated from MO concentra-
tions as determined by' the cherailuminescent NO analyzer. x
•1 Estimated fraction of accountable test compound at the 1700 EST hour.
k/
-Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of (SOal^: ([TPS]/([TPS]
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t. 3 5.545/ln ([0312000/(03]0400) .
-This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
- Met concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: AQj = [0~] -[03] . and
AC/I - Inn 1 fen 1
aso2 - [so2]max - (so2]mia.
The available data suggest th
experiments exceeded one day.
£ The available data suggest that the time to one-half consumption of CS2 in these
^ Note that S02 data were not available on the first day.
87
-------
oo
00
a
o
o
OJ
o
en
o
«—I
X
X
O
1.50
1.00 -
0.50 -
0.00
i 1 1 1 1
21-22 SEPTEMBER 1977
0.50
0000
Figure 15.
0800
1600 0000
TIME (EST)
0800
1600
O.HO
- 0.30
- 0.20
0.10
0000
0.00
Concentration-time profiles of various reactants and products for the 21 and 22
September 1977 CS2-NOX experiment conducted in RTI Chamber No. 2. Target initial
conditions: 2.0 ppmC CS2 and 0.10 ppm NOX.
(+) S02; and (*) COS.
Symbol key: (o) 03; (Q) NO; (A) N02;
g
z
m
-------
It is difficult, however, to devise mechanisms that could account for the
formation of organic nitrates or even nitric acid from the photooxidation of
CS2 in the presence of NO . The fate of NO in photochemically reacting
X A
systems is largely unknown.
During these experiments the concentrations of CS2 exceeded the linear
range of the instrument and were not determined. Product species, however,
were quantified. Carbonyl sulfide,.in addition to S02, was found in each of
the four experiments as a product of the photooxidation of CS2 in the pres-
ence of NO . Too few data were available to permit assessment of first-day
A
maximum S02 concentrations. Maximum COS concentrations were dependent on
the initial HC/NO ratio. Maximum first-day COS concentrations ranged from
X
0.27 to 0.76 ppm and generally occurred late in the day during the 1700 and
1800 EST hours. The apparent relationship between [COS] and initial
HC/NO ratio was similar to that observed earlier for another reaction
X
product, ozone. Maximum COS concentrations increased with increasing HC/NO
A
ratio (i.e., decreasing initial NO concentration). For the four experiments
X
the largest [COS] was 0.76 ppm and was achieved at the target initial
IDdX
HC/NO ratio of 20. Since the COS formation is an unexpected finding,
additional work is needed to explore possible formation mechanisms.
Based on an assumed COS yield of unity for the photooxidation of CS2
and on having achieved the target initial CS2 concentration of 2 ppm (V/V) ,
estimates were made of the fraction of initial CS2 that remained unreacted
at the times of the maximum COS concentrations. These results suggest that
the disappearance rate of CS2 was dependent on the initial HC/NO ratio. At
the target HC/NO ratio of 20 the smallest fraction of the initially present
X
CS2 could be accounted for. The fraction of initial CS2 that remained
ranged from 0.62 to 0.86. The ordering of the accountable fraction of CS2
is similar to that of NO , the other reactant. In both cases the accountable
X
fractions decreased with increasing initial HC/NO ratio (i.e. with decreas-
ing initial NO concentration) .
A
Based on the previous assumption of unity COS yield, a similar yield
for S02 might also be anticipated for the second sulfur atom in the CS2
molecule. Sulfur dioxide concentration data were too few to provide conclu-
89
-------
sive evidence. The available data, however, indicate that the concentration
of S02 in each experiment was substantially smaller than that of COS. This
suggests that either the S02 yield was not unity or that after its for-
mation, the S02 was being rapidly removed by an undefined mechanism. The
removal processes could include gas-phase reactions as well as deposition on
the chamber walls.
Irradiation of CS2 in the presence of NO yielded copious quantities of
X
condensation nuclei. Maximum concentrations ranged from 91,000 to 180,000
_O
cm and generally occurred early (before 0900 EST) on the first day. Al-
though the [CN] displayed no apparent trends with initial HC/NO ratio,
X
in the three experiments where N0-N02 crossover occurred, the maximum CN
-3
values exceeded 100,000 cm .
In spite of the formation of both CN and S02 , only a small portion of
the reacted CS2 was detected as particulate sulfur. Maximum particulate
sulfur concentrations ranged from 0 to 11.4 pg/m3 and correspond to the
equivalent of 0 to 9 ppb of sulfur. In the two experiments where particulate
sulfur was detected, the maximum TPS concentrations occurred during the 1500
EST hour. The TPS data displayed no apparent trends with HC/NO ratio,
although the largest [TPS] was achieved in the same experiment where the
largest [03] and [COS] values occurred.
* l JJmax l Jmax
Second-day [TPS] , were also small, ranging from 3.3 to 7.5 M8/m3 (3
ID3X
to 6 ppbS) . In contrast, significant quantities of CN, S02, COS, and 03
were generated on the second day. Maximum [CN] on the second day were
Dla AIM
generally high, ranging from 27,000 to 100,000 cm , but did not exceed the
first day values. Second-day [S02] ranged from 0.13 to 0.17 ppm. The
ID3 X
highest second-day [CN] and [S02] were achieved at the target HC/NO
ulflX 2£
ratio of 4, and both decreased as the initial target ratio was moved away
from 4. In every case the second-day maximum COS concentration exceeded the
corresponding first-day maximum, and in two cases the second-day net COS
concentration exceeded the first-day maximum. Net COS concentrations ranged
from 0.29 to 0.63 ppm. At target initial HC/NO ratios of 4, 10, and 20,
A
second-day [03] and net 03 equaled or exceeded the first-day maxima. Net
03 concentrations ranged from 0 to 0.30 ppm. The ordering of the net COS
90
-------
and net 03 concentrations were similar with respect to HC/NO ratio. The
highest net ozone and net carbonyl sulfide concentrations were produced at
the target HC/NO ratio of 10, and both decreased as the initial target
X
ratio was moved away from 10.
Methanethiol
Mixtures of methanethiol and NO were irradiated in Chamber Nos. 1 and
3 on 26 and 27 August and in all four chambers on 2 and 3 September 1977.
_2
On 26 August the cumulative daily solar radiation was 417 cal cm with 55
percent of the possible minutes of direct sunshine and a maximum temperature
of 289° C. On 2 September the cumulative daily solar radiation was 468 cal
_9
cm with 92 percent of the possible minutes of direct sunshine and a maximum
temperature of 32.2° C. Selected results from the CH3SH-NO experiments are
summarized in Tables 20 and 21. In general, only the September experiments
are considered in the current discussion. Concentration-time profiles of
various reactants and products for the 2 September experiment conducted in
Chamber No. 4 are presented in Figure 16.
The photochemical behavior of irradiated mixtures of NO and CH3SH was
A
similar in many respects to that of irradiated mixtures of NO and a hydro-
carbon such as propene. In each of these experiments conversion of NO to
N02 was rapid. Approximately 2 hours of irradiation were required to achieve
NO-NOg crossover with the maximum N02 concentrations occurring during the
0800 EST hour. Among the four experiments conversion was the slowest at the
target HC/NO ratio of 4, and conversion became more rapid as the target
HC/NO ratio was moved away from 4. In contrast to the propene NO system,
x x
however, the time to crossover was not strongly dependent on HC/NO ratio.
Ozone accumulated during each experiment. Maximum concentrations and
the times required to achieve them were dependent on the initial HC/NO
A
ratio (i.e., initial NO concentration). Ozone maxima ranged from 0.30 to
X
0.59 ppm and generally occurred between the 1000 and 1300 EST hours. For
the four experiments an [03] occurred first in Chamber No. 4 at the
tudX
target HC/NO ratio of 4. The largest [03] , 0.59 ppm, also occurred
X ID3X
at the target HC/NO ratio of 4. As the target HC/NO ratio was moved away
X X
from 4, maximum ozone concentrations decreased. These reductions in maximum
ozone concentrations are also associated with small decreases in the times
to N0-N02 crossover.
91
-------
TABLE 20. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH CH3SH AND NO
o v
TEST COMPOUND^/ DATE-/
Methanethiol, 8-26-77
CHSSH 8-27-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppin)
Time of N0-N02 Crossover,
(hrs EST)
Time of [N02laax (hrs EST)
[Oil , ppm
1 3Jm«x' ef
Time of (03]max, (hrs EST)
[PANl,nax' PPB1
Time of [PANlnax> (hrs EST)
[MN] ppm4/
Of] ppn.
(NO ]. ... ,h/
1 xjinitial-
[NO ] @ 1700 EST
fNO @ 1700 EST^
[CH3SH] (Jg/o3
(ppmS)
Time of fTPS]MX, (hrs EST)
Ri/
[CM]MX, cm'3
Time of [CN)max, (hrs EST)
Night-time 03 Half-Life (hrs)5/
T -/ 11SS-/
28.9 55
30 . 0 49
1
10
8.25
0.464
9.13
0.641
11.13
0
0.033
0.655
0.036
0.055
ND
ND
ND
NA
372.4
0.285
11.13
ND
14,000
12.13
8
CU-SR-/ SUNRISE^7
417 5.65
404
3
10
7.79
0.442
8.47
0.702
10.47
0
NA
0.028
ND
0.660
0.035
0.053
ND
ND
ND
NA
232.8
0.178
11.47
ND
20,000
20.47
12
NOTES: Abbreviations: ND = no data are available; NA = not applicable;
0 3 act detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
(continued)
92
-------
TABLE 20. (continued)
SMOG CHAMBER NUMBER
SECOND DAY
t°«W
AS02, ppi
max
-------
TABLE 21. SUMMARY OF SELECTED RESULTS FROM SMOG
CONDUCTED WITH CH3SH AND NO
CHAMBER EXPERIMENTS
TEST COMPOUND^ ' DATE-7
Methanethiol 9-2-77
CH3SH 9-3-77
SMOG CHAMBER NUMBER
T C->
max
32.2
33.9
3
%ss4'
92
80
4
CU-SR^
468
529
1
SUNRISE-7
5.77
2
FIRST DAY PARAMETERS
Target Initial HC/NO (ppraC/ppm)
Time of N0-N02 Crossover,
(hrs EST)
tff°2W Pp°
Time of [N02]MX) (hrs EST)
fOt , ppm
13 max' vv
Time of [03]max, Urs EST)
[pANl0ax> ?P1S
Time of [PAN]max, (hrs EST)
[MM] ppni*'
EN1 ppm
[^initial*'
[NO ] § 1700 EST
fNO @ 1700 ESTi'
(CH3SH]
-------
TABLE 21. (continued)
SMOG CHAMBER NUMBER
SECOND
*£!'
[soa;
[Oil,
DAY PARAMETERS
***'<>?"
'-•.r
, ppm-
(ppmS)
.ax' Cm"3
3
0.358
0.187
ND
NA
3.6
0.003
92,000
4
• 0.355
0.189
ND
NA
2.8
0.002
140,000
1
0.291
0.247
ND
NA
5.4
0.004
80,000
2
0.388
0.375
0.398
NA
16.7
0.013
52,000
-Target initial concentration 2.0 ppmC, 2.0 ppra (V/V), or 2.0 ppraS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-'Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
- Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day oaly.
*'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
- The initial [NO^] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has HOT been corrected for possible interferences.
-Fraction of initial N0x remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. x
i/ X
•»•'Concentration of accountable test compound at the 1700 EST hour.
k/
-Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as participate to the total accountable reacted sulfur at the
time of [SO,]MX: ([TPS]/((TPS] + [S02])).
- Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ({03J2000/(03J0400).
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppra were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: A03 = [03] -[03] . and
95
-------
0.75
VO
a*
Q_
Q_
co
OJ
O
o
UJ
o
CD
|XXX
0.50 -
0.25 -
0.00
I ' I
2-3 SEPTEMBER 1977
1.50
05
i.oo S
O
IE
CO
CO
IE
0.50 3
0000
Figure 16.
0800
1600 0000
TIME CEST)
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 2 and 3
September 1977 CH3SH-NOX experiment conducted in RTI Chamber No. 4. Target initial
conditions: 2.0 ppmC CHjSH and 0.5 ppm NOX. Symbol key: (o) 03; (D) NO; (A) N02,
(x) CH3SH; (+) S02; and (#) TPS.
-------
Peaks tentatively identified as MN were found in the experiments conduc-
ted with CH3SH on both 26 August and 2 September. PAN was not detected in
these experiments. The retention time of EN was too long in these experi-
ments to permit its resolution. The formation of either PAN or EN is unlikely
in view of the chemical structure of CH3SH. The tentative identification of
MN suggests that the photooxidation of methanethiol involves cleavage of the
methyl-sulfur bond which, in the presence of air and NO leads to the forma-
A
tioa of MN.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO. concentrations determined initially and again during
the 1700 EST hour of the first day. The nitrogen balances were extremely
poor for the CH3SH-NO experiments—much worse than for the propene-NO
A. A
experiments. For the four CH3SH-NO experiments the fraction of initial NO
A H
that could be accounted for ranged from 0.03 to 0.15. This fraction general-
ly increased with increasing HC/NO ratios (i.e., decreasing NO concentra-
X X
tions). A reduction in the accountable NO was associated with an increase
A
in maximum ozone concentrations in three of four cases. The unaccountable
product nitrogen may be nitric acid or other undetermined nitrogen-containing
species. The fate of the NO in photochemically reacting systems is largely
X
unknown.
Initially, the concentrations of both total sulfur and CHsSH exceeded
the linear range of the sulfur analyzer. The test species, CH3SH, was
consumed very rapidly during these experiments, and concentrations fell to
within the measureable range after only an hour of irradiation. The concen-
trations of CH3SH that remained unreacted at the 1700 EST hour of the first
day approached zero in three cases and was only 0.17 ppm in the fourth case.
At target HC/NOx ratios of 2, 4, and 10 the CH3SH had been essentially
consumed by 1100 EST; whereas, at a target ratio of 20 it persisted through-
out the day. Inspection of the times to one-half consumption of CH3SH also
indicates that the disappearance rate of CH3SH was dependent on the initial
HC/NO ratio—increasing with decreasing ratios.
In each of the four experiments sulfur dioxide was found as a product
of the photooxidation of CH3SH in the presence of NO . Sulfur dioxide
maxima exceeded 1.0 ppm and occurred between the 0900 and 1100 EST hours. A
maximum S02 concentration first occurred at the target HC/NO ratio of 4.
A
97
-------
In contrast to the behavior of f°3]max> there was no apparent relationship
between [S02] and initial HC/NO ratios. For the four experiments the
X
largest [S02J exceeded 1.5 ppm and was achieved at the target initial
max
HC/NO ratio of 10.
Moderate quantities of condensation nuclei were produced on the first
_3
day. Maximum CN concentrations ranged from 23,000 to 34,000 cm and oc-
curred during the 0800 EST hour. In addition, the CN maxima displayed no
apparent trends with HC/NO ratio.
The conversion of methanethiol to particulate sulfur was rapid, and a
considerable portion of the reacted CH3SH was converted to particulate sul-
fur. Maximum concentrations occurred before 1100 EST and displayed a
similar dependence on HC/NO ratio as that of maximum ozone concentrations.
A
The maximum TPS concentrations ranged from 180 to 760 |Jg/m3 or the equivalent
of 0.14 to 0.58 ppm of sulfur. The ratio of product sulfur as particulate
to the total accountable reacted sulfur [(TPS) plus (S02)] was determined
for each experiment. This ratio was based on data collected during or
interpolated for the hour of occurrence of the maximum S02 concentration and
permits an assessment of the distribution of accountable product sulfur
between the gas and particulate phases. This> fraction ranged from 0.06 to
0.34 and displayed similar trends with HC/NO ratios as were observed for
[03] . The largest [TPS] , 0.58 ppmS, was achieved at the target HC/NO
max max x
ratio of 4. Under these conditions both the fs°2]max and the [TPS]
occurred at 0938 EST. Thus, after less than four hours of irradiation, most
of the target initial 2 ppmS of CHaSH had disappeared and 87 percent was
measured as products. Of the 1.73 ppmS that could be accounted for, 34
percent was as particulate sulfur and the remainder was as S02 . At the
other HC/NO ratios, particulate sulfur comprised smaller percentages of the
accountable product sulfur.
Data presented in the appendix indicate that both S02 and TPS concen-
trations decayed rapidly from their maximum levels during the afternoon and
evening hours of the first day. These observations were made not only for
CHaSH but for many of the other sulfur-containing test species. They are
discussed in more detail in other sections of this report. The mixing fans
operated continuously during these experiments. It is likely that deposition
98
-------
on the chamber walls was a major factor that influenced the measured concen-
trations of both S02 and TPS. This deposition was undoubtedly enhanced by
the turbulence induced by the mixing fans. Poor definition of these proces-
ses hindered estimates of sulfur mass balances in all experiments of the
current project. Future experiments should be performed such that mechanical
mixing is conducted briefly to mix the reactants and is then terminated.
The second day, 3 September, was sunny with 80 percent sunshine and a
-3
cumulative daily solar radiation of 529 cal cm . Second-day maximum TPS
concentrations were low, accounting for 2.8 to 16.7 pg/m3 or 0.002 to 0.013
ppmS. In three cases [TPS] were 5 pg/m3 or less. The case with 16.7 pg/m3
occurred at the target HC/NO ratio of 20, where first-day conversion of
both CH3SH and NO were observed to have been incomplete. Thus, the slight
enhancement of TPS in this case may have resulted from second-day reaction
of residual CHsSH, NO , and reaction products from the first day.
X
Although second-day S02 concentration data were insufficient to define
net concentrations, significant quantities of S02 as well as CN and 03 were
measured. At the target HC/NO ratio of 20, where the first-day conversion
of reactants had been incomplete, a second-day S02 maximum of 0.398 ppm was
achieved. Second-day CN maxima generally exceeded first-day levels by a
factor of 2 or more, ranging from 52,000 to 140,000 cm . The largest
second-day [CN] occurred at the target HC/NO ratio of 4 and decreased as
max x
this ratio was moved away from 4. Net ozone concentrations ranged from 0.19
to 0.38 ppm and increased with increasing HC/NO ratios. The largest net
ozone concentration was achieved at the target HC/NO ratio of 20, where
X < ,
first-day conversion of both CH3SH and NO had been the least complete. In
X
addition, both the net and maximum ozone concentrations at this condition
exceeded the first-day maximum ozone concentration; whereas, at target
HC/NO ratios of 2, 4, and 10 the net ozone concentrations were substantially
less than first-day maxima.
Methyl Sulfide
Mixtures of methyl sulfide and NO were irradiated on 28 and 29 Septem-
ber 1977. On 28 September the cumulative daily solar radiation was 414 cal
cm with 64 percent of the possible minutes of direct sunshine and a maximum
temperature of 26.1° C. Selected results from the CH3SCH3-NO experiments
99
-------
are summarized in Table 22. Concentration-time profiles of various reactants
and products for the experiment conducted in Chamber No. 3 are presented in
Figure 17.
The photochemical behavior of irradiated mixtures of NO and CH3SCH3
A
was similar in many respects to that of irradiated mixtures of NO and
A
hydrocarbons such as propene. In each of these experiments conversion of NO
to N(>2 was rapid. Approximately 1.5 hours of irradiation were required to
achieve NO-N02 crossover, and the maximum N02 concentrations occurred during
the 0800 EST hour. The duration of irradiation required to achieve crossover
decreased with increasing initial HC/NO ratios. Crossover occurred first
X
at the target HC/NO ratio of 20. In contrast to the propene-NO system,
X X
however, the time to crossover was not strongly dependent on HC/NO ratio.
A
Ozone accumulated during each experiment. Maximum concentrations were
dependent on the intial HC/NO ratio (i.e., initial NO concentration).
X A
Ozone maxima ranged from 0.32 to 0.86 ppm and generally occurred between the
0900 and 1100 hours. A maximum ozone concentration was first achieved in
Chamber No. 4 at the target HC/NO ratio of 4. For the four experiments the
A
largest maximum ozone concentration was 0.86 ppm and occurred at the
target initial HC/NO ratio of 2. Maximum ozone concentrations decreased
X
with increasing initial HC/NO ratio (i.e., decreasing NO concentration).
' X A
These reductions in maximum ozone concentrations are also associated with
the small reductions in the times to NO-N02 crossover noted earlier.
Neither PAN nor EN concentration data were available for these experi-
ments. Their formation is unlikely in view of the chemical structure of
CHsSCHj. Methyl nitrate was detected in two of the four experiments, and
data were not available for the other two. The larger MN concentration
occurred at the target HC/NO ratio of 2. The tentative identification of
X
MN suggests that the photooxidation of methyl sulfide is similar to that of
methanethiol. Cleavage of the methyl-sulfur bond may occur and, in the
presence of air and NO , may lead to the formation of MN.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
A\
the 1700 EST hour of the first day. The nitrogen balances were worse than
for the propene-NO experiments and similar to those of the CH3SH-NO exper-
* x
iments. For the four CH3SCH3-NO experiments the fraction of initial NO
100
-------
1.50
1.00
s:
Q_
Q_
CVJ
O
O
Z
uJ 0.50
-ZL
O
M
O
0.00
T|i|r—
28-29 SEPTEMBER 1977
bc»
0000
Figure 17.
0800
1600 0000
TIME (EST)
gnJnWrfrfriAWift^
1.50
i
C/3
1.00
ro
—I
CO
X
0.50
~D
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 28 and 29
September 1977 CH3SCH3-NOX experiment conducted in RT1 Chamber No. 3. Target
initial conditions: 2.0 ppmC Cl^SCH-j and 1.0 ppm NOX. Symbol key: (o) 03; (Q)
NO; (A) N02; (x) Total Sulfur; (+) S02; and (#0 TPS.
-------
TABLE 22. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH CH3SCH3 AND NO
TEST COMPOUND^7 DATE-/
Methyl Sulfide, 9-28-77
CH,SCH3 9-29-77
SMOG CHAMBER NUMBER
T C->
max
26.1
23.9
3
XSS^
64
13
4
CU-SR-/
414
366
1
SUNRISE-/
6.03
2
FIRST DAJT PARAMETERS
Target Initial. HC/NOx (ppmC/ppra)
Time of MO-MO, Crossover,
(hrs EST)
[M°2lBwx' ppn
Tim* of [N02] (hrs EST)
fo*W PPB
Time of (03]max, (hrs EST)
[PANloux' ppin
Time of [PAN) , (hrs EST)
max
[MM] ppm*/
EN] ppm
K]initial&/
(S0xl 9 1700 EST
fNOx
-------
TABLE 22. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
eel.'**?'*'
[SO«]m.x'oPpin
(ppmS)
[«'«• C""3
0.308
0.112
ND
NA
0
0
5,300
0.265
0.188
ND
NA
0
0
1,700
0.139
0.181
ND
NA
0
0
2,700
0.212
0.199
ND
NA
0
0
2,600
-'Target initial concentration 2.0 ppmC, 1.0 ppm (V/V), or 1.0 ppmS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
-Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-'Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
&'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [NOX] is taken to be the concentration that existed at approximately the
tine of sunrise; the table entry has NOT been corrected for possible interferences.
-'Fraction of initial NO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent MO analyzer.
" /
I'Concentration of accountable test compound at the 1700 EST hour.
- Estimate of the time at which approximately one-half of the test compound was consumed.
-'Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [SOa]Mx: ([TPS]/((TPS]+[S02])).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/(03]0400).
-'This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: i03 = [03] -[03] . and
[so,i - [so,]., .
103
-------
that could be accounted for ranged from 0.03 to 0.15. This fraction gener-
ally increased with increasing initial EC/NO ratios (i.e., decreasing
initial NO concentrations) and was also associated with decreasing maximum
A
ozone concentrations. The unaccountable product nitrogen may be nitric acid
or other undetermined nitrogen-containing species. The fate of NO in
photochemically reacting systems is largely unknown.
Initially, the total sulfur concentration exceeded the linear range of
the sulfur analyzer. The test species was consumed rapidly during these
experiments, and within a few hours after sunrise its concentration could be
approximated by the difference between the total sulfur and S02 concentra-
tions. Estimates were made of concentrations of CH3SCH3 that remained
unreacted at the 1700 EST hour of the first day. The ordering of the concen-
trations of remaining CH3SCH3 was similar to that observed earlier for the
fraction of remaining NO . In both cases, the fractions of unreacted react-
ants increased with increasing initial HC/NO ratios. For the four experi-
ments the concentration of initial CH3SCH3 that remained ranged from 0.05 to
0.74 ppm. At the target HC/NO ratio of 2, the smallest amount of the
A
initially present CH3SCH3 could be accounted for at the 1700 EST hour, and
thus, at this condition conversion to product species was the most nearly
complete. Inspection of the times to one-half consumption of CH3SCH3 also
indicates that the CH3SCH3 disappearance rate was dependent on the initial
HC/NO ratio—increasing with decreasing ratios.
In each of the four experiments sulfur dioxide was found as a product
of the photooxidation of CH3SCH3 in the presence of NO . Concentrations
A
sufficiently high for quantification were found in only two of these experi-
ments. Maximum concentrations were dependent on the initial HC/NO ratio
X
(i.e., initial NO concentration). Sulfur dioxide maxima ranged from trace
A
quantities to 0.17 ppm and generally occurred before 1100 EST. For the four
experiments the largest maximum S02 concentration was 0.17 ppm and was
achieved at the target initial HC/NOx ratio of 2. The apparent relationship
between [S02]fflax and initial HC/NOx ratio was similar to that observed
earlier for another reaction product, ozone. In both cases maximum concen-
trations decreased with increasing HC/NO ratio (i.e., decreasing NO con-
centrations), although the absolute concentrations of the 03 maxima far
exceeded the S02 maxima.
104
-------
Moderate quantities of condensation nuclei were produced on the first
• 3
day. Maximum concentrations ranged from 9,100 to 36,000 cm and generally
occurred early, before 1000 EST. Maximum CN concentrations generally de-
creased with increasing initial HC/NO ratios. For the four experiments the
X
largest maximum CN concentration occurred at the target HC/NO ratio of 2.
A
Conversion of CH3SCH3 to particulate sulfur was fairly rapid. A small
to moderate portion of the reacted test species was detected as particulate
sulfur. Maximum IPS concentrations generally occurred during the morning of
the first day. They displayed no apparent trends with initial HC/NO ratio.
These maxima ranged from 97 to 151 |Jg/m3 and correspond to the equivalent of
0.075 to 0.116 ppm of sulfur.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur [(TPS) plus (S02)] was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum S02 concentration and permits an assessment of the
distribution of accountable product sulfur between the gas and particulate
phases. Data were available to permit an assessment of this ratio in only
two of the four cases. These results, 0.36 and 0.38, suggest that for
CHaSCHs almost 40 percent of the accountable product sulfur existed as
particulate. In addition, results in the appendix suggest that a substan-
tial portion of the product sulfur cannot be accounted for.
The second day was mostly cloudy with only 13 percent sunshine. As a
result, moderate quantities of 03 were generated, but only small amounts of
CN, S02 and TPS were observed on the second day. Both second-day maximum
and net ozone concentrations were substantially less than the first-day
maxima, and net ozone levels ranged from 0.11 to 0.20 ppm. Second-day
[CN] were much less than their respective first-day values and in no case
exceeded 6000 cm . The few S02 concentration data that were available on
the second day indicated small but detectable levels of S02. Particulate
sulfur was not detected in any chamber on the second day.
Methyl Disulflde
Mixtures of methyl disulfide and NO were irradiated on 5 and 6 October
X -2
1977. On 5 October the cumulative daily solar radiation was 440 cal cm
105
-------
with 99 percent of the possible minutes of direct sunshine and a maximum
temperature of 23.9° C. Selected results from the (CH3S)2-NOx experiments
are summarized in Table 23. Concentration-time profiles of various reactants
and products for the experiment conducted in Chamber No. 3 are presented in
Figure 18.
The photochemical behavior of irradiated mixtures of NO and (CH3S)2
was similar in many respects to that of irradiated mixtures of NO and
X
hydrocarbons such as propene. In each of the (CH3S)2-NO experiments convers-
A
ion of NO to N02 was rapid. The disulfides, methyl and ethyl, displayed the
most rapid conversion of NO to N02 of all the species tested in the current
study. For the experiments conducted with methyl disulfide approximately
0.82 hours of irradiation were required to achieve N0-N02 crossover, and the
maximum N02 concentration occurred during the 0700 EST hour. In contrast to
the propene-NO system, the time to crossover displayed no apparent trends
A
with the initial HC/NO ratio. As with ethyl disulfide, however, crossover
occurred first at the target HC/NO ratio of 10.
A
Ozone accumulated during each experiment. Maximum concentrations and
the times required to achieve them were dependent on the initial HC/NO
x
ratio (i.e., initial NO concentration). Ozone maxima ranged from 0.11 to
0.39 ppm. As was also observed for methanethiol, an ozone maximum occurred
first at the target initial HC/NO ratio of 4. For the remaining experi-
ments, the ozone maxima occurred later in the day, during the 1400 and 1500
EST hours. For the four experiments the largest maximum ozone concentration
was 0.39 ppm and was achieved at the target initial HC/NO ratio of 2.
A
Maximum ozone concentrations decreased with increasing initial HC/NO ratio
A
(i.e., decreasing NO concentration).
Neither PAN nor EN were detected in these experiments. Their formation
is unlikely in view of the chemical structure of (CH3S)2. Methyl nitrate,
however, was detected in each experiment. Median concentrations of MN were
dependent on the initial HC/NO ratio. The largest MN concentration for the
four experiments occurred at the target HC/NO ratio of 2, and concentrations
decreased with increasing initial ratios (i.e., decreasing initial NO
X
concentrations). The tentative identification of MN suggests that the
photooxidation of methyl disulfide is similar to that of the methane thiol
and methyl sulfide. Cleavage of the methyl-sulfur bond may occur and, in the
presence of air and NO , may lead to the formation of MN.
106
-------
1.50
I ' I
5-6 OCTOBER 1977 ~3
0.50
- (MO
0.00
0000
0800
1600 0000 0800
- TIME (EST)
1600
0000
Figure 18. Concentration-time profiles of various reactants and products for the 5 and 6
October 1977 (CH3S)2-NOX experiment conducted in RTI Chamber No. 3. Target
initial conditions: 2.0 ppmC (CH3S)2 and 1.0 ppm NOX. Symbol key: (o) 03;
(D) NO; (A) N02; (x) Total Sulfur; (+) S02; and (#) TPS.
o
M
O
0.30 :
m
0.20
- 0.10
0.00
-------
'ABLE 23. SUMMARY OF SELECTED RESULTS FROM SMOG
CONDUCTED WITH (CH3S)2 AND NO
TEST COMPOUND^ DATE-'
Methyl Disulfide 10-5-77
(CH3S)2 10-6-77
SMOG CHAMBER NUMBER
T £/
max
23.9
24.4
3
VS^
99
29
4
CHAMBER
X
CU-SR^
440
315
1
EXPERIMENTS
SUNRISE-7
6.15
2
FIRST DAY PARAMETERS
Target Initial HC/NO (ppmC/ppm)
Time of NO-NOj Crossover,
(hrs EST)
(NO?) , pom
1 ZJaax' **
Time of (N02]inax (hrs EST)
[°3]max' PPIB
Time of [03Jma)t, (hrs EST)
(PAN]max, ppm
Time of [PAN]^, (hrs EST)
[MM] ppm^
ISK] PPm
[KOx] initial^
[NO ] @ 1700 EST
fNOx 9 1700 ESTi/f
[(CH3S)2] @ 1200 ESTJ-' ,
Time of [(CH3S)2], (hrs EST)-'
[S02]Mx> ppm
Time of lS02lmaX, (hrs EST)
[TPS]max, ug/raj
(ppmS)
Time of [TPSJ^, (hrs EST)
»i/
[CN]max, cm'3 24,
Time of [CN)Bax> (hrs EST)
Night-time 03 Half-Life (hrs)S/
2
6.99
0.612
7.47
0.385
14.63
0
SA
0.025
0
0.972
0.025
0.026
0.081
7.09
0.707
7.47
276.3
0.211
8.47
0.17
000 24,
13.47
12
4
7.14
0.290
7.63
0.311
12.63
0
KA
0.015
0
0.486
0.017
0.035
0.042
7.18
0.495
7.63
182.6
0.140
8.77
0.18
000
12.63
15
10
6.35
0. 102
7.13
0.129
14.30
0
NA
0.007
0
0.193
0.013
0.067
0.104
7.89
0.662
9.18
502.4
0.384
8.13
0.30
27,000
10.63
t&
20
6.90
0.050
7.30
0.112
15.30
0
NA
0.001
0
0.089
0.011
0.124
0.117
9.42
0.514
10.80
177.4 '"
0.136
10.80
0.21
22,000
12.30
&
NOTES: Abbreviations: NT) = no data are available; XA = not applicable;
0 = not detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data chat are not
summarized in this table.
(continued)
108
-------
TABLE 23. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
[0»]max'oppnl
iiO 3 i PPI^^
[SOol t ppffl
o/
ASO^, ppot-
(ppmS)
[CN] , cm"3
013 X
0.197
0.082
tr
NA
4.7
0.004
750
0.166
0.057
tr
NA
3.2
0.002
810
0.114
0.107
0.083
NA
8.9
0.007
1,000
0.125
0.110
tr
NA
4.5
0.003
690
-Target initial concentration 2.0 ppmC, 1.0 ppm (V/V), or 2.0 ppmS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
- Duration of direct solar radiation reported as percent of possible minutes or suashiae.29
- Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
- Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
* Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
- The initial [N0x] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
-Fraction of initial NO^ remaining at the 1700 EST hour calculated from MO concentra-
tions as determined by the chemiluminescent NO analyzer. x
. I X
J- Concentration of accountable test compound at the 1200 EST hour.
- Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of tS08]m8X: ([TPS]/([TPS]*[S02])).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5-545/ln ([03]2000/[03]0400).
n/
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Met concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: £03 = [0,] -[0-,] . and
\en 9 fen 1 fen 1 max J nin
-
109
-------
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
X
the 1700 EST hour of the first day. The nitrogen balances were worse than
for the propene-NO experiments and similar to those of the CHsSH-NO and
x x
CH3SCH3-NO experiments. For the four (CHsS^-NO experiments the fraction
X X
of initial NO that could be accounted for ranged from 0.03 to 0.12. This
A
fraction generally increased with increasing initial HC/NO ratios (i.e.,
X
decreasing initial NO concentrations) and was also associated with decreas-
ing maximum ozone concentrations . These results suggest that the presence
of a CHs- or CHsS- group in the test species renders as unaccountable at the
end of the first day, at least 85 percent of the initially present NO . The
X
unaccountable product nitrogen may be nitric acid or other undetermined
nitrogen-containing species. The fate of NO in photochemically reacting
systems is largely unknown.
Initially, the total sulfur concentration exceeded the linear range of
the sulfur instrument. The test species, (CH3S)2, was consumed rapidly
during these experiments, and by the 0900 EST hour its concentration could
be approximated by the difference between the total sulfur and the S02
concentrations. Since reaction was very rapid, estimates were made of the
concentrations of (^38)2 that remained unreacted at the 1200 EST hour of
the first day. With a single exception, the ordering of the concentrations
of remaining (CHsS)2 was similar to that observed earlier for the fraction
of remaining NO (at the 1700 EST hour) . In both cases the fractions of
unreacted reactants increased with increasing initial HC/NO ratios. For
X
the four experiments the concentrations of remaining (^38)2 ranged from
0.04 to 0.12 ppm. Inspection of the times to one-half consumption of (CH3S)2
also indicates that the (CHsS)2 disappearance rate was dependent on the
initial HC/NO ratio — increasing with decreasing ratios.
X
In each of the four experiments sulfur dioxide was found as a. product of
the photooxidation of (CH3S)2 in the presence of NO . Maximum concentrations
and their times of occurrence were dependent on the initial HC/NO ratio.
X
Sulfur dioxide maxima ranged from 0.50 to 0.71 ppm. Maximum concentrations
were first achieved during the 0700 EST hour at target ratios of 2 and 4.
The times required to reach [S02] increased with increasing HC/NO ratios.
x
The largest [S02] , 0.71 ppm, occurred at the target HC/NO ratio of 2.
X
no
-------
With a single exception, maximum S02 concentrations decreased with increasing
initial HC/NO ratios. Other reaction products such as ozone and MN exhibit-
ed similar behavior in which decreasing maximum concentrations were associ-
ated with increasing HC/NO ratios.
A
Moderate quantities of condensation nuclei were produced on the first
day. Maximum concentrations generally occurred between the 1000 and 1300 EST
hours. They were not appreciably different for the four experiments, ranging
_q
from 22000 to 27000 cm . The largest [CN] occurred at the target HC/NO
max x
ratio of 10.
Conversion of (CH3S)2 to particulate sulfur was rapid. Maximum TPS
concentrations were achieved before 1100 EST and, in three of four cases,
occurred during the 0800 EST hour. The maximum TPS concentrations ranged
from 177 to 502 Mg/m3 and correspond to the equivalent of 0.14 to 0.38 ppmS.
Based on the narrow spread among the S02 maxima and on the ordering of the
maximum ozone concentrations, the maximum TPS concentrations might be expec-
ted to decrease with increasing initial HC/NO ratios. This was the case,
A
with a single exception: at the target HC/NO ratio of 10, where the largest
A
[TPS] , 502 |Jg/m3, was determined. This value appears to be unusually
max
high. However, since no reason has been identified to invalidate the value,
it was retained.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [802]) was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum S02 concentration, and it permits an assessment of
the distribution of accountable product sulfur between the gas and particu-
late phases. For the (CH3S)2-NO system this ratio ranged from 0.17 to
A
0.30. The maximum ratio, 0.30, occurred at the target HC/NO ratio of 10,
as did the [TPS] , and decreased as the target HC/NO ratio was moved away
X
from 10. Thus, most of the accountable product sulfur existed as S02. In
addition, results in the appendix suggest that a substantial portion of the
product sulfur cannot be accounted for.
Although only 29 percent sunshine occurred on the second day, the
_o
cumulative daily solar radiation on this day was substantial, 315 cal cm
Second-day maximum TPS and CN concentrations were low. Maximum TPS concen-
111
-------
trations ranged from 3.2 to 8.9 |Jg/m3 or 0.003 to 0.007 ppraS on the second
-3
day, and maximum CN concentrations did not exceed 1000 cm . The largest
secondary maximum concentrations of both IPS and CN occurred at the target
HC/NO ratio of 10. Sulfur dioxide concentration data were available for
only 3 hours on the second day. Thus, it is uncertain whether the maxima
from the available data were identical to the daily maxima. Nonquantifiable
trace amounts were found in three of the four chambers. At the target
HC/NO ratio of 10, however, SOg was determined, and the largest concentra-
A
tion was found to be 0.083 ppm. Second-day ozone maxima were less than the
corresponding first-day levels in three of four cases. At the target HC/NO
x
ratio of 20 the second-day maximum ozone concentration exceeded the first-day
value. Net ozone concentrations were less than the first-day maxima and
ranged from 0.06 to 0.11 ppm. Although the net ozone concentrations displayed
no clear trends with respect to the various initial conditions, the largest
net ozone concentration was achieved at the target HC/NO ratio of 20, where
A
first-day conversion of NO had been the least complete.
A
Methyl Ethyl Sulfide
Mixtures of methyl ethyl sulfide and NO were irradiated on 10 and 11
October 1977, and the experiments were repeated on 9 and 10 November. On 10
_2
October the cumulative daily solar radiation was 377 cal cm with 76 percent
of the possible minutes of direct sunshine and a maximum temperature of
18.3° C. On 9 November, although the percent of possible minutes of direct
sunshine was similar at 71 percent, seasonal changes reduced the possible
duration of sunshine and hence the cumulative solar radiation to 280 cal
_2
cm . In addition, 9 November, with a maximum temperature of 24.4° C, was
slightly warmer than 10 October. Selected results from the CH3SC2H5-NO
A
experiments are summarized in Tables 24 and 25. As evidenced by comparison
of the parameters listed in these tables, the results of experiments conduc-
ted on 10 October and 9 November were similar. In view of this comparison,
the 10 October experiments were chosen for emphasis in the current discussion.
Concentration-time profiles of various reactants and products for the 10
October experiment conducted in Chamber No. 3 are presented in Figure 19.
The photochemical behavior of irradiated mixtures of NO and CH3SC2H5
was similar in many respects to that of irradiated mixtures of NO and
hydrocarbons such as propene. In each of the CH3SC2H5-NO experiments,
A
112
-------
i.50
z:
Q_
Q_
1.00 -
X
CO
Q_
0.50 -
0.00
10-11 OCTOBER 1977
0.75
- 0.50
o
o
m
s-~\
3?
12
- 0.25
0.00
0000
Figure 19.
0800
1600 0000
TIME (EST)
0800
1600
0000
Concentration-time profiles of various reactants and products for the 10 and 11
October 1977 CH-jSC2H5-NOx experiment conducted in RTI Chamber No. 3. Target
initial conditions: 2.0 ppmC CH3SC2H5 and 1.0 ppm NOX. Symbol key: (o) 03; (O)
NO; (A) N02; and (4f) TPS.
-------
TABLE 24. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH CH3SC2H5 AND NO
TEST COMPOUND^7 DATE-7
Methyl Ethyl Sulfide 10-10-77
CH3SC2HS 10-11-77
SMOG CHAMBER NUMBER
T ^
max
18.3
19.4
3
WS*/
76
55
4
CU-SR-7
377
276
1
SUNRISE-7
6.23
2
FIRST DAY PARAMETERS
Target Initial HC/MO (ppmC/ppra)
Time of MO-ffOj Crossover,
(hrs EST)
tNO*]max' ppo
Time of [N0a)max (n« EST)
[03] , ppm
3 max
Time of (03]max, (h« EST)
(PANlmax' ppnl
Time of [PANlmax, (&rs EST)
[MN] ppnX
EN] ppm
K] initial
[NO ] @ 1700 EST
fNO @ 1700 EST-''
[OJ3SC2HS] 9 1700 EST-J-7 ,
Time of [CHaSCjHj^ (hrs EST)-'
(SO*]max' ppm
Time of [SOa]Mx, (hrs EST)
[TPS] , jig/n-"
max
(ppmS)
Ti4a« of [TPS)max, (hrs EST)
«V
'CNlm.x' OT~3
Time of [CN] , (hrs EST)
max
Might-time 03 Half -Life (hrs)5/<
2
7.91
0.611
8.47
0.428
15.47
0.113
12.47
0.006
0.007
0.993
0.222
0.224
tr
8.95
0.0 79^
9.47
141.9
0.109
9.47
0.58
31,000
10.47
16
4
7.76
0.316
8.63
0.274
10.63
0.062
11.63
0.002
0.004
0.503
0.120
0.239
tr
9.04
0.054^
9.63
79.2
0.061
9.63
0.53
29,000
10.63
&
10
7.65
0. 117
8.13
0.185
10.13
0.021
16.13
tr
0.001
0.189
0.056
0.296
0.258
9.63
tr
.VA
73.2
0.056
9.13
.TO
31,000
10. 13
&
20
7.55
0.052
8.30
0.138
9.30
0.019
14.30
0
0.001
0.099
0.040
0.404
0.409
12 . 05
tr
NA
31.5
0.024
9.30
m
22,000
10.30
3a>
MOTES: Abbreviations: KD * no data are available; .VA = not applicable;
0 = oot detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are act
summarized in this table.
(continued)
114
-------
TABLE 24. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
[Oil , ppm
1 3JB*x' y
403. PP"-
[SOflJ , ppn
o/
(ppmS)
I«l«.' Cm~3
0.389
0.186
tr
MA
0
0
1,800
0.251
0.187
tr
NA
0
0
2,300
0. 148
0.144
tr
HA
0
0
1,600
0. 137
0.133
tr
HA
0
0
1,200
-Target initial concentration 2.0 ppmC, 0.67 ppm (V/V), or 0.67 ppmS.
-Dates of first and second days of the experiment.
- Daily Maximum temperature in °C.29
-Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
* Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
- The initial [NO^J is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
infraction of initial MO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the cheniluminescent NO analyzer. *
J- Concentration of accountable test compound at the 1700 EST hour.
-Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [SO,]MX: ([TWl/dTPSWSO,])).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([0312000/(03]0400).
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
- Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: iOi - [03] -(Oil and
2.' Since SOj concentrations were quantifiable for only one measurement in this experiment,
this value may not truly represent the maximum concentration.
115
-------
ABLE 25. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH CH3SC2H5 AND NO
TEST COMPOUND1' DATE-7
Methyl Ethyl Sulfide 11-9-77
CHSSC2H5 11-10-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppm)
Time of N0-N02 Crossover,
(hrs EST)
(NO 2 ] , ppm
Time of [N02] (hrs EST)
(03j . ppm
1 3'max' "
Time of [03]MX, (hrs EST)
[PAN] , ppm
Time of [PAN] , (hrs EST)
max
[MN) ppm*7
EN] ppra
K initial^
[NOJ IP 1700 EST
fNO & 1700 ESTi7
[CH3SC2HS] @ 1700 ES^7 . .
Time of [CH3SC2HS]^ (hrs EST)-
[SOj , ppm
Time of [S02]max, (hrs EST)
(ppmS)
Time of (TPS] , (hrs EST)
01 AX
Ri7
Tim« of (CNlmax, (hrs EST)
Night-time 03 Half-Life (hrs)5/
max
24.4
23.9
4
2
8.73
0.591
9.63
0.469
14.63
ND
NA
0.008
0.014
0.948
0.177
0.187
tr
9.52
tr
NA
26.3
0.020
10.63
ND
24,000
7.63
14
VH&
71
23
3
4
8.63
0.309
9.47
0.335
11.47
ND
NA
0.003
0.013
0.478
0.107
0.224
tr
9.87
tr
NA
20.5
0.016
10.47
ND
23,000
7.47
8 .
CU-SR-7
277
105
2
10
8.41
0.121
9.80
0.227
11.30
ND
NA
ND
0.002
0.203
0.050
0.246
0.268
10.59
cr
NA
19.3
0.015
10.30
ND
18,000
7.30
<£'
SUNRISE^''
6.83
1
20
8.38
0.053
9.13
0.135
10.13
ND
NA
tr
0.001
0.095
0.032
0.337
0.332
12.77
tr
NA
31.4 '
0.024
10.13
ND
18,500
7.13
3a7
NOTES: Abbreviations: TO = no data are available; NA - aot applicable;
0 = oot detected; tr = detected, but aot quantified; X = concea-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are aot
summarized ia this table.
(continued)
116
-------
TABLE 25. (continued)
SMOG CHAMBER NUMBER
4
3
2
1
SECOND DAY PARAMETERS
[03] , ppm
o/
ISO,]..,. PP.
iiS02, PP«-
[TPS)MX, Mg/nJ
(ppmS)
l«W ™3
0.214
0.039
0
NA
0
0
1,500
0.143
0.069
tr
NA
0
0
2,100
0.091
0.057
0
NA
0
0
2,100
0.065
0.060
tr
NA
0
0
14,300
-^Target initial concentration 2.0 pptnC, 0.67 ppn (V/V), or 0.67 ppmS.
-Dates of first and second days of the experiment.
-'Daily maximum temperature in °C.Z9
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
- 'Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the secoad-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
- Time of sunrise in hours (EST); since the tines of sunrise are approximately the same
for both days, the time is given for the first day oaly.
5'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [fO^] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has MOT been corrected for possible interferences.
-Fraction of initial NO^ remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. x
^Concentration of accountable test compound at the 1700 EST hour.
-'Estimate of the time at which approximately one-half of the test compound was consumed.
- Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of (S02]|nax: UTPSl/UTPSMSO,])).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.5457 In ([03]2000/[03]0400).
-^This half-life may be suspect, since ozone concentrations smaller than 0.1 ppra were
involved in its determination.
-'Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: A03 - (Q3| -[0<<1 . and
117
-------
conversion of NO to N02 was rapid. Approximately 1.5 hours of irradiation
were required to achieve NO-NOg crossover on 10 October, and 1.7 hours on 9
November. The maximum N02 concentrations occurred during the 0800 EST hour
on 10 October and during the 0900 EST hour on 9 November. The duration of
irradiation required to achieve NO-N02 crossover decreased with increasing
initial HC/NO ratios. Crossover occurred first at the target HC/NO
X X
ratio of 20, and conversion occurred more slowly at smaller ratios. In
contrast to the propene-NO system, however, the time to crossover was not
strongly dependent on HC/NO ratio.
A
Ozone accumulated during each experiment. Maximum concentrations and
the times required to achieve them were dependent on the initial HC/NO
ratio. Ozone maxima ranged from 0.14 to 0.43 ppm on 10 October and from 0.14
to 0.47 ppm on 9 November. In both cases a maximum ozone concentration
first occurred at the target HC/NO ratio of 20 in the morning, one hour
A
after the corresponding maximum N02 concentration. Longer times were required
at smaller initial HC/NO ratios and at the target ratio of 2, maximum ozone
concentrations occurred approximately 2 to 3 hours after noon. The largest
maximum ozone concentrations, 0.43 and 0.47 ppm, occurred at the target
HC/NO ratio of 2. Maximum ozone concentrations decreased with increasing
initial HC/NO ratios (i.e., decreasing initial NO concentrations). These
x x
reductions in maximum ozone concentrations are also associated with the
small reductions in the times to NO-N02 crossover noted earlier.
PAN, MN, and EN were found as reaction products. Maximum PAN, as well
as median MN and EN concentrations, were dependent on the initial HC/NO
A
ratio. The Largest concentrations of these species occurred at the target
HC/NO ratio of 2 and decreased with increasing ratios (i.e., decreasing
initial NO concentrations). On 10 October the ordering of PAN, MN, and EN
concentrations with respect to initial HC/NO ratio was similar to that of
A
the maximum ozone concentrations. The tentative identification of EN in
addition to the identification of PAN suggests that the photooxidation of
methyl ethyl sulfide involves the cleavage of the ethyl-sulfur bond. Al-
though MN may be a reaction product of PAN in the presence of NO and air,
its tentative identification may also be indicative of a photooxidation step
involving the cleavage of the methyl-sulfur bond.
118
-------
Inspection of the first-day NO data in the appendix revealed unusual
A
behavior. At the target HC/NOx ratio of 20, between 0900 and 1400 EST, the
NO concentration exhibited a loss of few ppb and a subsequent recovery.
The timing of this phenomenon coincided with the initial buildup of PAN.
This behavior was not observed at lower HC/NO ratios, although it may have
X
been obscured by the higher NO concentrations employed in these experiments.
X
It is likely that a transient nitrogen-containing species was responsible
for this behavior. This species was either not delivered to the NO monitor
X
as a result of interactions with chamber walls or the sampling system, or it
could not be detected by the chemiluminescent NO monitor that was employed.
In any event, the identity of this hypothetical species is unknown.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. The nitrogen balances were similar to
those for the propene-NO , C2HSSH-NO , (C2H5S)2-NO , and C2H5SC2H5-NO
« X X X
experiments. The fraction of initial NO that could be accounted for in the
10 October experiments ranged from 0.22 to 0.40 and in the 9 November experi-
ments, 0.19 to 0.34. The accountable fraction increased with increasing
initial HC/NO ratios (i.e., decreasing initial NO concentrations). The
*» X
unaccountable product nitrogen may be nitric acid or other undetermined
nitrogen-containing species. The fate of NO in photochemically reacting
X
systems is largely unknown.
The test species, CH3SC2H5, was consumed rapidly during these experi-
ments. Since in most cases only trace amounts of S02 were detected, the
CHsSCaHs concentration could be approximated by the total sulfur concentra-
tion. Estimates were made of the concentrations of CH3SC2H5 that remained
unreacted at the 1700 EST hour of the first day. The ordering of the concen-
trations of remaining CHsSC^s was similar to that observed earlier for the
fraction of N0x that remained at the 1700 EST hour. In both cases the
fractions of unreacted reactants increased with increasing initial HC/NO
ratios. On 10 October the concentrations of remaining CH3SC2H5 ranged from
a trace to 0.41 ppraS and on 9 November, from a trace to 0.33 ppmS. Inspec-
tion of the times to one-half consumption of CH3SC2H5 also indicates that
the CH3SC2H5 disappearance rate was dependent on the initial HC/NO ratio--
• X
increasing with decreasing ratios.
119
-------
Sulfur dioxide was found as a product of the photooxidation of CH3SC2He
in the presence of NO , although in 2 of the 10 October experiments and in
A
all of the 9 November experiments only trace quantities were detected. In
the 10 October results, sulfur dioxide maximum concentrations appear to
depend on the initial HC/NO ratio. On this day [S02] values ranged from
X OldX
a trace to 0.08 ppm. Maximum concentrations were quantified at target
HC/NO ratios of 2 and 4, and were achieved during the 0900 EST hour. The
largest [802] was 0.08 ppm and occurred at the target HC/NO ratio of 2.
max x
Maximum SOg concentrations on 10 October appeared to decrease with increasing
in HC/NO ratios and exhibited behavior similar to that observed earlier for
X
another reaction product, ozone.
Moderate quantities of condensation nuclei were produced on the first
day. Maximum concentrations generally occurred early in the day ranging from
-3
22,000 to 31,000 cm during the 1000 EST hour on 10 October and from 18,000
-3
to 24,000 cm during the 0700 EST hour on 9 November. Maximum concentrations
of condensation nuclei displayed no apparent trends with initial HC/NO
A
ratio.
Conversion of CHaSCgHs to particulate sulfur was rapid, and maximum TPS
concentrations were dependent on the initial HC/NO ratio. Maximum TPS
concentrations were achieved during the 0900 EST hour on 10 October and
during the 1000 EST hour on 9 November. Only a small portion of the reacted
test species was detected as particulate sulfur, although the fraction was
higher on 10 October than 9 November. On 10 October maximum TPS concentra-
tions ranged from 32 to 142 [ig/m3, the equivalent of 0.02 to 0.11 ppmS, and
decreased with increasing initial HC/NOx ratios (i.e., decreasing initial
NO concentrations). On this date the largest [TPS] , 142 H8/™3, occurred
X max
at the target HC/NO ratio of 2. On 9 November maximum TPS concentrations
were significantly smaller than the corresponding values observed on 10
October, and ranged from 20 to 31 pg/m3. Although maximum TPS concentrations
decreased with increasing HC/NO ratios with only a single exception, the
narrow spread among the maximum concentrations obscures the generality of
this finding. The reduced light intensity on 9 November may have contributed
to the reduced TPS concentrations observed on 9 November in comparison to
those on 10 October.
120
-------
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [S02]) was determined for each experiment. This
ratio was based on data collected during the hour of occurrence of the
maximum SOg concentration, and it permits an assessment of the distribution
of accountable product sulfur between the gas and particulate phases. Data
were available to permit an assessment of this ratio in none of the 9 Novem-
ber experiments and in only 2 of the 4 experiments conducted on 10 October.
These results, 0.53 and 0.58, suggest that for at least two CH3SC2H5-NO
a
experiments almost 60 percent of the accountable product sulfur existed as
particulate. In addition, results in the appendix indicate that a substan-
tial portion of the product sulfur cannot be accounted for.
Second-day solar radiation was reduced in comparison to the first-day
values on both 11 October and 10 November, although the reduction was not as
large for the October experiment as for the November experiment. Only trace
quantities of S02 were detected on the second day, and concentrations of
TPS, CN, and Og were generally less than the corresponding first-day levels.
As seen in Tables 24 and 25, TPS was not detected on 11 October or on 10
November. Second-day maximum CN concentrations were low in both cases,
_3
exceeding 3000 cm only once and displaying no apparent trends with initial
conditions. On 11 October second-day ozone maxima approached but did not
exceed the corresponding first-day maxima, although the ordering with respect
to initial conditions was the same on both days. In addition, net ozone
concentrations ranged from 0.13 to 0.19 ppm and generally decreased with
increasing initial HC/NO ratios. On 10 November second-day ozone maxima
did not exceed first-day maxima, and the ordering with respect to initial
conditons was the same on both days. The net concentrations ranged from
0.04 to 0.07 ppm and displayed no apparent trends with initial conditions.
Moreover, the small net ozone concentrations indicate that little ozone was
generated under the cloudy conditions that prevailed on 10 November.
Ethanethiol
Mixtures of ethanethiol and NO were irradiated in Chamber Nos. 2 and 4
A
on 26 and 27 August and in all four chambers on 3 and 4 October 1977. On 26
_o
August the cumulative daily solar radiation was 417 cal cm with 55 percent
121
-------
of the possible minutes of direct sunshine and a maximum temperature of
— •)
28.9° C. On 3 October the cumulative daily solar radiation was 395 cal cm
with 73 percent of the possible minutes of direct sunshine and a maximum
temperature of 18.3° C. Selected results from the C2H5SH-NO experiments
are summarized in Tables 26 and 27. In general, only the October experiments
are considered in the current discussion. Concentration-time profiles of
various reactants and products for the 3 October experiment conducted in
Chamber No. 4 are presented in Figure 20.
The photochemical behavior of irradiated mixtures of NO and C2H5SH was
similar in many respects to that of irradiated mixtures of NO and hydrocar-
X
bons such as propene. In each of the CgHsSH-NO experiments conversion of
A
NO to N02 was rapid. Approximately 1.4 hours were required to achieve
NO-N02 crossover with the maximum N02 concentration occurring during the
0700 and 0800 EST hours. Among the four experiments, N0-N02 crossover
occurred first at the target HC/NO ratio of 4, and slightly longer times
A
were required as the target HC/NO ratios were moved away from 4. In con-
trast to the propene-NO system, however, the time to crossover was not
strongly dependent on the target HC/NO^ ratio.
Ozone accumulated during each experiment. Maximum concentrations were
dependent on the initial HC/NO ratio. Ozone maxima occurred during the
A
1500 EST hour and ranged from 0.08 to 0.36 ppm. The largest [03] 0.36
luclX
ppm, occurred at the target HC/NO ratio of 4. As the target HC/NO
A 4\
ratio was moved away from 4, maximum ozone concentrations decreased. These
reductions in maximum ozone concentrations are also associated with the
small increases in the times to NO-N02 crossover noted earlier.
For these experiments, PAN as well as MN and EN concentration data were
erratic, and as a result are reported in Table 27 but not in the appendix.
Maximum PAN and median MN and EN concentrations were dependent on the initial
HC/NO ratio. The concentrations of both MN and EN increased with decreasing
HC/NO ratios (i.e. with increasing initial NO concentrations). In contrast
A A
the ordering of the maximum PAN concentrations with respect to initial
HC/NO ratio was similar to that of the maximum ozone concentrations. The
largest maximum PAN concentration for the four experiments occurred at the
target HC/NO ratio of 4. PAN maxima generally occurred between the 1400
122
-------
0.75
0.50 -
OJ
CM
O
O
O
M
O
0.25 -
0.00
3-
*
-H
CO
X
0.50
0000
Figure 20.
0800
1600 0000
TIME CEST)
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 3 and 4
October 1977 C2H5SH-NOX experiment conducted in RTI Chamber No. 4. Target
initial conditions: 2.0 ppmC C2H5SH and 0.5 ppm NOX. Symbol key: (o) 03; (O)
NO; (A) N02; (x) Total Sulfur; (+) S02; and (#) TPS.
-------
TABLE 26. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH C2H5SH AND NO
TEST COMPOUND^7 DATE-7
Ethanethiol 8-26-77
C2H5SH 8-27-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial HC/SOx (ppmC/ppra)
Time of NO-N02 Crossover,
(hri EST)
( N02 ] , ppm
Time of (N02J (hrs EST)
[°3lmax> ppm
Time of [03] , (hrs EST)
[PAN] , ppm
Time of (PAN) , (hrs EST)
max
[MS] ppm^'
EM] ppm
NV initial*7
[NO ] @ 1700 EST
fNO @ 1700 EST-7
[C2HSSH] 9 1700 ESTJ-7 .
Tim* of (C2HSSH)^ (hrs ESTp'
[SO;] , ppm
Time of [S02]max, (hrs EST)
(ppmS)
Time of (TPS]Mx, (hrs EST)
*y
(CH]Mx, cm'3
Time of [CN]naJt, (hrs EST)
Night-time 03 Half -Life (hrs )-'
T™ax£/ XSS-/
28.9 55
30.0 49
2
10
7.46
0.477
8.30
0.556
15.30
0.132
11.30
0.010
ND
0.635
0.169
0.266
MD
ND
SD
MA
76.0
0.058
11.30
ND
135,000
19.30
8
CU-5R-' SUNRISE-7
417 5.65
404
4
10
7.42
0.425
3.63
0.548
15.63
0.125
12.63
0.010
ND
0.636
0.175
0.275
ND
ND
ND
NA
103.0
0.079
10.63
ND
185,000
20.63
9
NOTES: Abbreviations: ND = ao data are available; NA = not applicable;
0 a QOt detected; tr = detected, but not quantified; X - concen-
tration decreased, ao maximum observed.
The appendix should be consulted for additional data that are not
sunnurized ia this table.
(continued)
124
-------
TABLE 26. (continued)
SMOG CHAMBER NUtlBER
SECOND DAY
[03] ,
max (
A03, ppm-
tS0^«ax
AS02, pp«
[TPS]
I^Ux-
PARAMETERS
ppm
>/
, ppm
&
, M8/»3£/
(ppmS)£/
cm'3
2
0.649
0.508
KD
HA
0
0
107,000
4
0 . 634
0.483
ND
NA
0
0
112,000
-Target initial concentration 5.0 ppmC, 2.5 ppm (V/V) , or 2.5 ppmS.
- Dates of first and second days of the experiment.
-^ Daily maximum temperature in °C.29
-Duration of direct solar radiation reported as percent of possible oinutes of sunshine.29
-'Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second*
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-/Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
*' Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-^The initial [K0xl is taken to be the concentration that existed at ipproximately the
time of sunrise; the table entry has MOT been corrected for possible interferences.
-^Fraction of initial MO^ remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent MO analyzer. x
. , x
1' Concentration of accountable test compound at the 1700 EST hour.
-/Estimate of the time at which approximately one-half of the test compound was consumed.
-/Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02]nax: ([TPS]/([TPSI+(S02D) .
-^Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/ [03]0400) .
S/This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
£/Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration:
-------
TABLE 27. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH C2H5SH AND NO
TEST COMPOUND^-/
Ethanethiol
C2HSSH
DATE^
10-3-77
10-4-77
SMOG CHAMBER NUMBER
FIRST DAY
max
13.
19.
3
3
4
73
76
4
OJ-SR-7
395
423
1
SUNRISE-/
6
2
.10
PARAMETERS
Tatget Initial HC/NO^ (ppmC/ppm)
Tiae
(hrs
[NO^
Tiae
(03]a
Tiae
[PAtfJ
Time
(MNJ
(£81
(MOx]
[sox]
fNOx
[C?HS
Tiae
[S02]
Tiae
[TPSl
Tiae
Ri'
of N0-N02 Crossover,
EST)
max
of
iax'
of
of
ppm
ppm
.. PP"»
(N02]max (hrs EST)
ppm
[°3]max'
, ppn^
tPA*i*ax
il
(hrs EST)
, (hrs EST)£/
initial^
@ 1700 EST
SH]
of
max
of
max
of
lC!"».x'
Tiae
of
@ 1700 E
9 1700
[C2H5SH]
, ppm
[S02]
* max
• Mg/m3
(ppmS)
[TPSlm,x
«-J
'"I..,'
ST-
ESTi/ k/
, (hrs EST)-7
, (hrs EST)
, (hrs EST)
(hri EST)
Nignt-time 03 Half-Life (hrs)-
2
7.
0.
a.
0.
15.
0.
14.
0.
0.
0.
0.
0.
0.
8.
0.
9.
141.
0.
8.
0.
39,000
8.
14
44
611
47
313
47
104
47
035
037
948
220
232
043
06
366
47
5
109
47
18
37
"*
7
0
8
0
15
0
15
0
0
0
0
0
0
8
0
9
125
0
3
0
42,000
9
18
.32
.322
-63
.364
.80
.124
.80
.009
.009
.491
.184
.375
.054
.19
• 374
-63
.0
.096
• 63
.17
.63
10
7
0
3
0
15
0
16
0
0
0
0
0
8
0
9
68
0
9
0
41,000
8
4-
.54
.088
.13
.142
-63
.051
.13
tr
.006
.179
.069
.385
.357
.49
.280
.13
. 4
.052
.13
.16
.13
Z/
20
7
0
7
0
15
0
14
0
0
0
0
0
0
11
0
10
48
0
9
0
39,000
9
]
.70
.040
.30
.080
.30
.024
.30
.003
.036
.035
.407
.537
.64
.160
.30
.2
.037
.30
.13
.30
ros/
MOTES: Abbreviations: KD = no data are available; NA = not applicable;
0 = not detected; tr = detected, but not quantified; X - concen-
tration decreased, no naxlmun observed.
The appendix should be consulted for additional data that are not
summarized in this table.
(continued)
126
-------
TABLE 27. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DAY PARAMETERS
[°3]max' pplD
403, PP"2'
IS021MX, ppm
AS02, ppm2
[TPS]MX, Mg/«J
(ppmS)
[CN1».x- CT"3
0.442
0.323
ND
NA
4.9
0.004
6,300
0.414
0.235
TO
NA
5.7
0.004
5,700
0.171
0.165
ND
NA
5.8
0.004
14,500
0.112
0.112
ND
KA
5.0
0.004
17,500
-Target initial concentration 2.0 ppoC, 1.0 ppm (V/V) , or 1.0 ppoS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
- Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-'Cumulative daily solar radiation expressed in Langleys (cal cm ) ; note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated — usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
^'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-'The initial [N0xl is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has' NOT been corrected for possible interferences.
^Fraction of initial N0x remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiliuninescent NO analyzer. x
" I
•!•' Concentration of accountable test compound at the 1700 EST hour.
u /
-Estimate of the time at which approximately one-half of the test compound was consumed.
i'Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02Jmaj(: ([TPSJ/UTPSJ
2/Estiaate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 2 S.545/ln ([03J2000/ [03]0400) .
2^ This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-'Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: 40 •> = (Oil -[0-,] . and
3 13J
data erratic; only maximum concentration reported; data are not listed in the
Appendix .
127
-------
and 1600 EST hours. The tentative identification of MN and EN in addition
to the identification of PAN suggests that the photooxidation of ethanethiol
involves the cleavage of the ethyl-sulfur bond, which in the presence of air
and NO leads to the formation of MN, EN, and PAN.
Inspection of the first-day NO data in the appendix revealed unusual
A
behavior. At the target HC/NO ratio of 20, between 0800 and 1100 EST, the
X
NO concentration exhibited a loss of a few ppb and a subsequent partial
recovery. This behavior was not observed in the remaining three experiments,
although it may have been obscured by the higher NO concentrations employed
A
in these experiments. It is likely that a transient nitrogen-containing
species was responsible for this behavior. This species was either not
delivered to the NO monitor as a result of interactions with chamber walls
or the sampling system, or it could not be detected by the chemiluminescent
NO monitor that was employed. At any rate, the identity of this hypotheti-
cal species is unknown.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. The nitrogen balances were similar to
those for the propene-NO experiments and much better than for the CH3SH-NO
x x
experiments. For the four C2HgSH-NO experiments the fraction of initial
NO that could be accounted for ranged from 0.23 to 0.41. This fraction
x
generally increased with increasing initial HC/NO^ ratios (i.e., decreasing
initial NO concentrations). The unaccountable product nitrogen may be
X
nitric acid or other undetermined nitrogen-containing species. The fate of
NO in photochemically reacting systems is largely unknown.
Initially the total sulfur concentration exceeded the linear range of
the sulfur instrument. The test species, C2H5SH, was consumed rapidly
during these experiments, and within a few hours after sunrise its concentra-
tion could be approximated by the difference between the total sulfur and
the SOg concentrations. Estimates were made of the concentrations of C2H5SH
that remained unreacted at the 1700 EST hour of the first day. The ordering
of the concentrations of remaining C2H5SH was similar to that observed
earlier for the fraction of remaining NO . In both cases the fractions of
X
unreacted reactants increased with increasing initial HC/NO ratios. For
128
-------
the four experiments the concentrations of remaining C2H5SH ranged from 0.04
to 0.54 ppraS. At the initial target HC/NO ratio of 2, the smallest amount
of CgHgSH could be accounted for at 1700, although it was not significantly
smaller than the corresponding value at the target ratio of 4. Inspection
of the times to one-half consumption of C2H5SH also indicates that the
C2HSH disappearance rate was dependent on the initial HC/NO ratio—
increasing with decreasing ratios.
In each of the four experiments sulfur dioxide was found as a product
of the photooxidation of C2H5SH in the presence of NO . Maximum concentra-
A
tions were dependent on the initial HC/NO ratio. Sulfur dioxide maxima
ranged from 0.16 to 0.37 ppm and with one exception occurred during the 0900
EST hour. The largest (S02lmax was 0.374 ppm and was achieved at the target
initial HC/NO ratio of 4, although it was not significantly larger than the
X
corresponding maximum value of 0.366 ppm that was achieved at the target
ratio of 2. The apparent relationship between [S02] and initial HC/NO
OlclX X
ratio was similar to that observed earlier for another reaction product,
ozone. In both cases the largest maximum concentrations occurred at the
target initial HC/NO ratio of 4 and decreased as the initial HC/NO ratios
•» X
were moved away from 4.
Moderate quantities of condensation nuclei were produced on the first
day- Maximum concentrations generally occurred early, before 1000 EST.
They were not appreciably different for the four experiments, ranging from
39,000 to 42,000 cm" . Although the largest [CN] occurred at the target
HC/NO ratio of 4, the narrow spread among the maximum concentrations pre-
A
vented a meaningful evaluation of trends with respect to the various initial
conditions. Comparison of the 26 August CN data for the C2H5SH-NO experi-
ments with those of the CH3SH-NO experiments indicated comparable concentra
tions of CN with diameters greater than 0.26 |jm. However, the C2H5SH experi
ments produced large numbers of CN with diameters between 0.002 and 0.26 |Jm
that were not found in the experiments conducted with CH3SH.
Conversion of C2H5SH to particulate sulfur was rapid, and maximum [TPS]
concentrations were dependent on the initial HC/NO ratio. Maximum [TPS]
concentrations were achieved before 1000 EST. Only a small portion of the
reacted test species was detected as particulate sulfur, with maximum con-
centrations ranging from 48 to 142 |Jg/m3 or the equivalent of 0.04 to 0.11
129
-------
ppmS. Maximum TPS concentrations decreased with increasing initial HC/NO
ratios (i.e., decreasing initial NO concentrations). The largest [IPS]
x max*
142 Mg/m3, occurred at the target HC/NOx ratio of 2.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ((TPS) plus (802)] was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum S02 concentration, and it permits an assessment of
the distribution of accountable product sulfur between the gas and particu-
late phases. For the C2H5SH-NO system, this ratio was small, ranging from
A
0.13 to 0.18, and it decreased with increasing initial HC/NO ratios (i.e.
X
decreasing initial NO concentrations). Thus, most of the accountable
product sulfur existed as S02 in the C2HsSH-NO system, and S02 comprised
X
increasing proportions with increasing initial HC/NO ratios. In addition,
results in the appendix suggest that a substantial portion of the product
sulfur cannot be accounted for.
Second-day maximum TPS concentrations were low, accounting for 4.9 to
5.8 Mg/m3 or approximately 0.004 ppmS. Although S02 data were not available
on the second day, significant quantities of both CN and ozone were measured.
Second-day CN maxima were less than the corresponding first day maxima and
-3
ranged from 5700 to 17500 cm . They also generally increased with increas-
ing initial HC/NO ratios. Second-day maximum ozone concentrations exceeded
first-day maxima. Net ozone concentrations ranged from 0.11 to 0.32 ppm and
exceeded the first-day maxima in three of four cases. Second-day maximum as
well as net ozone concentrations decreased with increasing initial HC/NO
ratios (i.e., decreasing initial NO concentrations). The largest net ozone
A
concentration, 0.32 ppm, was achieved at the target HC/NO ratio of 2, the
A
experiment that had had the largest initial NO concentration and the largest
A
absolute concentration of NO remaining at the 1700 EST hour of the first
day.
Ethyl Sulfide
Mixtures of ethyl sulfide and NO were irradiated on 15 and 16 October
1977. On 15 October the cumulative daily solar radiation was 404 cal cm
with 100 percent of the possible minutes of direct sunshine and a maximum
130
-------
temperature of 20.0° C. Selected results from the C2H5SC2H5-NO experiments
are summarized in Table 28. Concentration-time profiles of various reactants
and products for the experiment conducted in Chamber No. 2 are presented in
Figure 21.
The photochemical behavior of irradiated mixtures of NO and C2HsSC2H5
A
was similar in many respects to that of irradiated mixtures of NO and
hydrocarbons such as propene. In each of the C2H5SC2H5-NO experiments
conversion of NO to N02 was rapid. Approximately 1.7 hours of irradiation
were required to achieve NO-N02 crossover, and in three of four cases the
maximum N02 concentrations occurred before 1000 EST. Among the four exper-
iments, N0-N02 crossover was first achieved at the target HC/NO ratio of
A
10 and slightly longer times were required as the ratios were moved away
from 10. In contrast to the propene-NO system, the time to crossover was
not strongly dependent on the initial HC/NO ratio.
A
Ozone accumulated during each experiment. Maximum concentrations and
the times required to achieve them were dependent on the initial HC/NO
X
ratio. Ozone maxima ranged from 0.16 to 0.48 ppm. A maximum ozone concentra-
tion occurred first at the target HC/NO ratio of 10 during the 1000 EST
hour, and longer times were required as the target HC/NO ratios were moved
away fr°m 10- Tne largest [Os]max> °-^8 ppm, occurred at the target HC/NO
ratio of 2. Maximum ozone concentrations decreased with increasing initial
HC/NO ratios (i.e., decreasing initial NO concentrations).
PAN, MN, and EN were found as reaction products. Maximum PAN concen-
trations occurred during the 1200 EST hour at the target HC/NO ratios of 4
and 10; they occurred several hours earlier at ratios of 2 and 20. Maximum
PAN as well as median MN and EN concentrations were dependent on the initial
HC/NO ratio. The largest concentrations of these species occurred at the
target HC/NO ratio of 2 and decreased with increasing ratios (i.e., decreas-
ing initial NO concentrations). For the four experiments the ordering of
PAN MN» an<* ^ concentrations with respect to initial HC/NO ratio was
similar to that of the maximum ozone concentrations. In addition, the
ordering of MN and EN with respect to initial HC/NO ratio was similar to
that observed for the ethanethiol experiments. The tentative identification
of MN and EN in addition to the identification of PAN suggests that the
photooxidation of ethyl sulfide involves the cleavage of the ethyl-sulfur
131
-------
TABLE 28. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH C2H5SC2H5 AND NO
TEST COMPOUND^ DATE-'
Ethyl Sulfide 10-15-77
CjH,SC2H5 10-16-77
SMOG CHAMBER NUMBER
T S/
max
20.0
12.3
2
V&
100
17
1
CU-SR2''
404
149
4
SUNRISE-/
6.33
3
FIRST DAY PARAMETERS
Tar |et Initial HC/NOx (pptnC/ppm)
Tine of MO-NO] Crossover,
hrs EST)
[N02]MX, ppm
Time of [NOaJMX (hrs EST)
[03JMX, ppm
Time of (Ojl , (hrs EST)
(PAN]max> ppm
Time of (PAN]nax, (hrs EST)
[MN] ppm*7
EN] ppm
KliniUal*'
[NOJ 9 1700 EST
fNOx
NOTES: Abbreviations: XD « no data are available; NA = not applicable;
0 * not detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized ia this table.
(continued)
132
-------
TABLE 28. (continued)
SMOG CHAMBER NUMBER
SECOND DA?
SI'S
AS02, ppi
tTOlmax
[CN].ax-
PARAMETERS
ppm
»J
, Mg/md
(ppmS )
cm'3
2
0
0
0
2
0
250
.200
.002
NA
.3
.002
1
0.084
0.010
0
NA
0
0
250
4
0.
0.
064
017
0
NA
3.
0.
210
4
003
3
0
0
0
0
0
250
.037
.037
NA
"•^Target initial concentration 2.0 ppmC, 0.50 ppm (V/V), or 0.50 ppmS.
-Dates of first and second days of the experiment.
-Daily maximum temperature in °C.29
-Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-'Tine of sunrise in hours (EST); since the tines of sunrise are approximately the same
for both days, the time is given for the first day only.
V Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise? the table entry has NOT been corrected for possible interferences.
^Fraction of initial N0x remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. x
•1'Concentration of accountable test compound at the 1700 EST hour.
-Estimate of the time at which approximately one-half of the test compound was consumed.
-'Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of (S02IMJC: ([TPS]/([TPSMS02])).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/[03]0400).
-This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-'Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration:
-------
1.50
X
CO
o_
o
«—«
X
CO
f\J
o
o
1.00 -
0.50 -
0.00
I ' -
15-16 OCTOBER 1977 "I
0.75
- 0.50
o
h>4
O
Z
m
CO
- 0.25 -o
0000
Figure 21.
0800
1600 0000
TIME (EST)
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 15 and 16
October 1977 C2H5SC2H5-NOX experiment conducted in RTI Chamber No. 2. Target
initial conditions: 2.0 ppmC C2H5SC2H5 and 1.0 ppm NOX. Symbol key: (o) 03;
(O) NO; (A) N02; (x) Total Sulfur; (+) S02; and (#) TPS.
-------
bond, which in the presence of air and NO leads to the formation of UN, EN,
A
and PAN.
Inspection of the first-day NO data in the appendix revealed unusual
A
behavior. At the two highest initial HC/NO ratios between 0900 and 1200
A
EST, the NO concentration exhibited a loss of approximately 10 ppb and a
subsequent recovery. The timing of this phenomenon coincided with the
initial buildup of PAN. This behavior was not observed in the remaining two
experiments, although it may have been obscured by the higher NO concentra-
tions employed in these experiments. It is likely that a transient nitrogen-
containing species was responsible for this behavior. This species was
either not delivered to the NO monitor as a result of interactions with
chamber walls or the sampling system, or it could not be detected by the
chemilumirescent NO monitor that was employed. At any rate, the identity
A
of this hypothetical species is unknown.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. The nitrogen balances were similar to
those for the propene-NO , CH3SC2H5-NO , and C2H5SH-NO experiments. The
XX X
fraction of initial NO that could be accounted for in the four C2H5SC2H5-
jjO experiments ranged from 0.25 to 0.61 and increased with increasing
initial HC/NO ratios (i.e., decreasing initial NO concentrations). The
A> A
unaccountable product nitrogen may be nitric acid or other undetermined
nitrogen-containing species. The fate of NO in photochemically reacting
systems is largely unknown.
The test species, C2HsSC2H5, was consumed rapidly during these experi-
ments. Its concentration could be approximated by the difference between the
total sulfur and the S02 concentrations. Estimates were made of the concen-
trations of C2H5SC2H5 that remained unreacted at the 1700 EST hour of the
first day. The ordering of the concentrations of remaining C2H5SC2H5 was
similar to that observed earlier for the fraction of NO that remained at
the 17°0 EST hour. In both cases the fractions of unreacted reactants in-
creased with increasing initial HC/NO ratios. The concentrations of remain-
ing CjHsSCjtHs ranged from 0.02 to 0.31 ppmS. At the initial target HC/NO
ratio of 2 the smallest amount of C2H5SC2H5 could be accounted for. Inspec-
tion of the times to one-half consumption of C2H5SC2H5 also indicates that
135
-------
the C2H5SC2H5 disappearance rate was dependent on the initial HC/NO ratio—
X
increasing with decreasing ratios.
Sulfur dioxide was found as a product of the photooxidation of C2H5SC2HS
in the presence of NO in each of the four experiments, although only trace
X
quantities of S02 were found in three of the experiments. The largest, and
only, maximum S02 concentration was 0.12 ppm. It occurred at the target
HC/NO ratio of 2 during the 1100 EST hour. The largest maximum concentra-
A
tions of ozone, MN, EN, and PAN were also achieved in this experiment.
Moderate quantities of condensation nuclei were produced on the first
_3
day. Maximum concentrations ranged from 16000 to 58000 cm and occurred
during the 0800 EST hour in three of four cases. The largest maximum CN
concentration occurred at the HC/NO ratio of 2. Maximum concentrations de-
X
creased with increasing HC/NO ratios (i.e., decreasing initial NO concen-
A X
trations).
Conversion of C2H5SC2H5 to particulate sulfur was rapid, and maximum
TPS concentrations were dependent on the initial HC/NO ratio. Maximum IPS
concentrations were achieved during the 0900 EST hour. Only a small portion
of the reacted test species was detected as particulate sulfur. Maximum TPS
concentrations ranged from 24 to 64 pg/m3 or the equivalent of 0.02 to 0.05
ppmS. The largest [TPS] , 64 |J/m3, occurred at the target HC/NO ratio of
fllaX X
4, although it was not significantly larger than the corresponding value at
the target ratio of 2. At the higher HC/NO ratios of 10 and 20, smaller
[TPS] values were generated. Maximum TPS concentrations generally de-
ulflX
creased with increasing initial HC/NO ratios (i.e., decreasing initial NO
concentrations).
The ratio of product sulfur as particulate to. the total accountable
reacted sulfur [(TPS) plus (S02)] could be determined for only one experiment.
This ratio was based on data interpolated for the hour of occurrence of the
maximum S02 concentration, and it permits an assessment of the distribution
of accountable product sulfur between the gas and particulate phases. For
the C2H5SC2H5-NO system at the target HC/NO ratio of 2, this ratio was
X X
0.16 indicating that in this case most of the accountable product sulfur
existed as S02. In addition, results in the appendix indicate that a sub-
stantial portion of the product sulfur cannot be accounted for.
136
-------
The second day was mostly cloudy with 17 percent sunshine and a cumula-
-2
tive daily solar radiation of only 149 cal cm . As a result, the photo-
chemical behavior was somewhat subdued, and second-day concentrations of S02
XPS, CN, and 03 were less than the corresponding first-day levels. Sulfur
dioxide was not detected on the second day. Maximum IPS concentrations
ranged from 0 to 3.4 ug/m3 or 0 to 0.003 ppmS. In addition, second-day
maximum CN concentrations did not exceed 300 cm . Neither IPS nor CN maximum
concentrations displayed any apparent trends with initial conditions.
Second-day maximum ozone concentrations did not exceed the corresponding
first-day maxima, although the ordering with respect to initial conditions
was the same in both cases. Second-day ozone concentrations generally
decayed from the elevated first-day levels. Net ozone concentrations ranged
from 0.002 to 0.037 ppm. These small net ozone concentrations indicate that
little ozone was generated under the cloudy conditions that prevailed on the
second day.
Disulfide
Mixtures of ethyl disulfide and NO were irradiated on 7 and 8 October
-2
1977. On 7 October the cumulative daily solar radiation was 373 cal cm
with 34 percent of the possible minutes of direct sunshine and a maximum
temperature of 22.2° C. Selected results from the (C2H5S)2-NO experiments
are summarized in Table 29. Concentration-time profiles of various reactants
and products for the experiment conducted in Chamber No. 3 are presented in
figure 22.
The photochemical behavior of irradiated mixtures of NO and (C2H5S)2
A
was similar in many respects to that of irradiated mixtures of NO and
A
hydrocarbons such as propene. In each of the (C2H5S)2-NO experiments
conversion of NO to N02 was rapid. The disulfides, ethyl and methyl, dis-
played the most rapid conversion of NO to N02 of all the species tested in
thc current study. For the experiments conducted with ethyl disulfide approx-
imately 0.74 hours of irradiation were required to achieve N0-N02 crossover,
and the maximum N02 concentration occurred during the 0700 EST hour. In
contrast to the propene-NO system, the time to crossover displayed no
apparent trends with the initial HC/NOx ratio. As with methyl disulfide,
however, crossover was first achieved at the target HC/NO ratio of 10.
137
-------
TABLE 29. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH (C.H.S). AND NO
252 x
TEST COMPOUND*' DATE-7
Ethyl Bisulfide 10-7-77
(C2HjS)2 10-8-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial KCyNO^ (ppmC/ppm)
Tim* of N0-N03 Crossover,
(hrs EST)
[H02J|MX, pp«
Tim* of lN°j]MX (hrs EST)
'°3lnwx' ppm
Tim* of (03J|Mx. (hrs EST)
(PAM|iMX' pp"
Tim* of [PAM](Mx, (hrs EST)
[MM] ppm*7
EN] OP«
NO*J initial*/
[N0x] @ 1700 EST
fJJOx I? 1700 EST^
[(C2H,S)2J 9 1200 ESTJ-' . .
Time of ((C2HsS)2J,i (hrs EST)^'
[S02JMjt, ypm
Tim* of (S02]MX, (hrs EST)
ITPSJ««' M«/mJ
(pp«S)
Tim« of (TPS]max, (hrs EST)
ii/
1«1M, a-'3
TitM of tCMl^,,, (hrs EST)
Hijht-tiB» 03 Half-life (hrs)*'
T £/
MX
22.2
18.9
3
2
6.89
0.732
7.47
0.560
15.47
0.200
13.47
0.029
0.047
0.965
0.262
0.272
0.089
7.01
0.729
7.47
231.3
0.177
7.47
0.20
27,000
7.47
9
»8^
34
29
4
4
7.12
0.329
7.63
0.472
15.63
0.191
11.63
0.007
0.010
0.538
0.230
0.428
0.094
7.18
0.651
7.63
161.9
0.124
3.63
0.16
25,000
11.63
9
OJ-SR-7
373
38
1
10
6.68
0.122
7.13
0.189
15.13
0.051
11.13
0
0.007
0.191
0.080
0.419
0.128
7.60
0.552
11.13
104.8
0.080
8.13
0.06
56,000
10.13
3«/
SUNRISE^
6.18
2
20
6.98
0.041
7.30
0.104
15.30
0.040
13.30
0
0.004
0.093
0.041
0.441
0.164
8.44
0.614
12.30
77.3 "
0.059
8.30
0.02
41,000
10.30
&
MOTES: Abbreviations: MD » ao data are available; XA * not applicable;
0 * aot detected; tr * detected, but not quantified; X = concen-
tration decreased, no ouxiaum observed.
The appendix should be consulted for additional data that are aot
suMurized In this table.
(continued)
138
-------
TABLE 29. (continued)
SMOG CHAMBER NUMBER
3
4
1
2
SECOND DA* PARAMETERS
o/
60s. PP°-
tXSOj > ppfl*""
(TPS } t M8/fo3
(ppraS)
!«'«• -~3
0.200
0.048
ND
NA
0
0
10,700
0.172
0.038
ND
NA
3.0
0.002
4,600
0.055
0.048 "
ND
• NA
20.3
0.016
5,700
0.045
0.041
ND
HA
3. 1
0.002
3,100
-Target initial concentration 2.0 ppmC, 0.5 ppm (V/V), or 1.0 ppmS.
-'Daces of first and second days of the experiment.
-'Daily maximum temperature in °C.29
— Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
£/Cumulative daily solar radiation expressed in Langleys (cal cm); note that the second-
day value is the cumulative solar radiation on that day unfcil the experiment was
terminated—usually 1700 EST.
-Tine of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
8 Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-^The initial [NO J is taken to be the concentration that existed at approximately the
tine of sunrise; the table entry has NOT been corrected for possible interferences.
-^Fraction of initial N0x remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chemiluminescent NO analyzer. x
. , x
1'Concentration of accountable test compound at the 1200 EST hour.
-/Estimate of the time at which approximately one-half of the test compound was consumed.
-'Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
tine of [S02]MX: ([TPS]/((TPS] + [S02j)).
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/[03]0400).
- This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: AO* = (05j -[Oil and
139
-------
1.50
Q_
Q_
LP
£1.00
CM
O
0.50
-------
Ozone accumulated during each experiment. Maximum concentrations were
dependent on the initial HC/NO ratio. Ozone maxima occurred during the
1500 EST hour and ranged from 0.10 to 0.56 ppm. The largest [03] , 0.56
ppm, was achieved at the target HC/NO ratio of 2. Maximum ozone concentra-
tions decreased with increasing initial HC/NO ratio (i.e., decreasing
initial NO concentration).
X
In contrast to the experiments conducted with methyl disulfide, where
neither PAN nor EN were detected, PAN, MN, and EN were found as reaction
products in the experiments with ethyl disulfide. At the target HC/NO
ratios of 4 and 10, maximum PAN concentrations were achieved during the 1100
EST hour—approximately two hours before they were achieved at ratios of 2
and 20. Maximum PAN as well as median MN and EN concentrations were depen-
dent on the initial HC/NO ratio. The largest concentrations of these
species occurred at the target HC/NO ratio of 2 and decreased with increas-
ing HC/NO ratios (i.e., with decreasing initial NO concentrations). For
the four experiments the ordering of the PAN, MN, and EN concentrations with
respect to initial HC/NO ratio was similar to that of the maximum ozone
concentrations. In addition, the ordering of MN and EN with respect to
initial HC/NO ratio was similar to that 'observed for the ethanethiol and
tjjC ethyl sulfide experiments. The tentative identification of MN and EN in
addition to the identification of PAN suggests that the photooxidation of
ethyl disulfide involves the cleavage of the ethyl-sulfur bond, which in the
presence of air and N0x leads to the formation of MN, EN, and PAN.
Inspection of the first-day NO data in the appendix revealed unusual
A
behavior. At the two highest initial HC/NO ratios, between 0800 and 1200
EST, the NO concentration exhibited a loss of approximately 10 ppb and a
subsequent recovery. The timing of this phenomenon coincided with the
.0itial buildup of PAN. This behavior was not observed in the remaining two
experiments, although it may have been obscured by the higher NO concentra-
tions employed in these experiments. It is likely that a transient nitrogen-
ontaining species was responsible for this behavior. This species was
cither not delivered to the NO monitor as a result of interactions with
chamber walls or the sampling system, or it could not be detected by the
chemiluminescent NO monitor that was employed. At any rate, the identity
f this hypothetical species is unknown.
141
-------
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. The nitrogen balances were similar to
those for the propene-NO , CH3SC2H5-NO , CH5SH-NO , and C2H5SC2H5-NO
XXX X
experiments. For the four (C2H5S)2-NO experiments, the fraction of initial
NO that could be accounted for ranged from 0.27 to 0.44 and with a single
A
exception generally increased with increasing HC/NO ratios (i.e., decreas-
A
ing initial NO concentrations). The unaccountable product nitrogen may be
A
nitric acid or other undetermined nitrogen-containing species. The fate of
NO in photocheraically reacting systems is largely unknown.
Initially, the total sulfur concentration exceeded the linear range of
the sulfur instrument. The test species, (C2H5S)2> was consumed rapidly
during these experiments, and by the 0700 EST hour its concentration could
be approximated by the difference between the total sulfur and the S02
concentrations. Since reaction was very rapid, estimates were made of the
concentrations of (C2H5S)2 that remained unreacted at the 1200 EST hour of
the first day. The ordering of the concentrations of remaining (C2H5S)2 was
similar to that observed earlier for the fraction of remaining NO (at the
A
1700 EST hour). In both cases the fractions of unreacted reactants increased
with increasing initial HC/NO ratios. For the four experiments the concen-
A
trations of remaining (C2H5S)2 ranged from 0.09 to 0.16 ppmS. At the initial
target HC/NO ratio of 2, the smallest amount of (C2HSS)2 could be accounted
for, although it was not significantly smaller than the corresponding value
at the target ratio of four. Inspection of the times to one-half consump-
tion of (C2HsS)2 also indicates that the (C2HsS)2 disappearance rate was
dependent on the initial HC/NO ratio — increasing with decreasing ratios.
In each of the four experiments sulfur dioxide was found as a product
of the photooxidation of (C2HgS)2 in the presence of NO . Maximum concen-
trations and their times of occurrence were dependent on the initial HC/NO
x
ratio. Sulfur dioxide maxima ranged from 0.55 to 0.73 ppm. Maximum concen-
trations were first achieved during the 0700 EST hour at target ratios of
two and four. The times required to reach [S02] increased with increasing
IDflX *
HC/NO ratios. The largest [S02] was 0.73 ppm and was achieved at the
X
target HC/NO ratio of 2. With a single exception, maximum S02 concentra-
tions decreased with increasing initial HC/NO ratios. Other reaction
A
142
-------
products such as ozone, PAN, MN, and EN, exhibited similar behavior in which
Decreasing maximum concentrations were associated with increasing initial
HC/NO ratios.
A
Moderate quantities of condensation nuclei were produced on the first
_3
day- Maximum concentrations ranged from 25000 to 56000 cm and generally
occurred before 1200 EST. The largest maximum CN concentration occurred at
the HC/NO ratio of 10; however, there were no apparent trends between
A
maximum CN concentrations and initial conditions.
Conversion of (C2H5S)2 to particulate sulfur was rapid, and maximum IPS
concentrations were dependent on the initial HC/NO ratio. Maximum IPS
concentrations were achieved before 0900 EST. Only a small portion of the
reacted test species was detected as particulate sulfur. Maximum TPS con-
centrations ranged from 77 to 232 Mg/m3, the equivalent of 0.06 to 0.18
ppfflS, and decreased with increasing initial HC/NO ratios (i.e., decreasing
initial NO concentrations). The largest [TPS] , 232 Mg/m3, occurred at
^ X DttclX
the target HC/NOx ratio of 2.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [S02]m ) was determined for each experiment.
»c UlOA UJaA
This ratio was based on data collected during or interpolated for the hour
of occurrence of the maximum 803 concentration, and it permits an assessment
of the distribution of accountable product sulfur between the gas and particu-
late phases. For the (C2HsS)2-NO system this ratio was small, ranging from
0 02 to 0.20, and it decreased with increasing initial HC/NO ratios (i.e.,
decreasing initial NO concentrations). Thus, most of the accountable
oroduct sulfur existed as S02, and S02 comprised increasing proportions with
increasing initial HC/NO ratios. In addition, results in the appendix
suggest that a substantial portion of the product sulfur cannot be accounted
for.
The second-day was mostly cloudy with 29 percent sunshine and a cumula-
_2
tive daily solar radiation of only 88 cal cm . As a result, the photo-
chemical behavior was somewhat subdued and second-day concentrations of TPS,
QJ and Os were less than the corresponding first-day levels. Maximum TPS
concentrations ranged from 0 to 20.3 Hg/m3 or 0 to 0.02 ppmS. In addition,
second-day maximum CN concentrations ranged from 3100 to 10700 cm" .
TPS nor CN maximum concentrations displayed any apparent trends with
143
-------
initial conditions. Second-day S02 data were not available. The ordering
of second-day ozone maxima with respect to initial conditions was the same
as that of the first-day maxima. This behavior largely reflects the decay
of ozone concentrations from the first-day maxima. Net ozone concentrations
were almost identical for the four experiments and ranged from 0.038 to
0.048 ppm. These small net ozone concentrations indicate that little ozone
was generated under the cloudy conditions that prevailed on- the second day.
Thiophene
Mixtures of thiophene and NO were irradiated on 17, 18, and 19 October,
and an additional thiophene-NO experiment was conducted on 18 and 19 Novem-
ber 1977. In general, only the October experiments are considered in the
current discussion. On 17 October the cumulative daily solar radiation was
_o
425 cal cm with 98 percent of the possible minutes of direct sunshine and
a maximum temperature of 13.9° C. Selected results from the October C4H4S-
NO experiments are summarized in Table 30. Concentration-time profiles of
X
various reactants and products for the 17 October experiment conducted in
Chamber No. 1 are presented in Figure 23.
The photochemical behavior of irradiated mixtures of NO and C4H4S was
A
similar in various respects to that of irradiated mixtures of NO and hydro-
carbons such as propene. The time of occurrence of NO-N02 crossover was
strongly dependent on the initial HC/NO^ ratio. Crossover was first achieved
at the target HC/NO ratio of 20 at approximately 0854 EST. The duration of
X
irradiation required to achieve N0-N02 crossover increased with decreasing
initial HC/NO ratios, and at the target ratio of 2, crossover was not
achieved until 1304 EST on the second day (18 October). The timing of the
maximum N02 concentrations was also strongly dependent on the initial HC/NO
X
ratio and generally occurred within 2 hours after N0-N02 crossover.
Ozone accumulated during each experiment. Maximum concentrations and
their times of occurrence were dependent on the initial HC/NO ratio. Ozone
maxima ranged from 0.002 to 0.124 ppm. The largest maximum ozone concentra-
tion, 0.12 ppm, occurred at the target HC/NO ratio of 10. As the initial
X
HC/NO ratio was moved away from 10, maximum ozone concentrations decreased.
X
At the target HC/NO ratio of 2 the system was rich in NO and "NO inhibited "
X X *
failed to achieve crossover, and produced negligible amounts of ozone.
144
-------
0.30
I ' I
17-18 OCTOBER 1977 ~D
0.75
- 0.50
i
CO
"D
- 0.25
0.00
0000
0800
1600 0000
TIME (EST)
0800
1600
0000
0.00
Figure 23. Concentration-time profiles of various reactants and products for the 17 and 18
October 1977 thiophene-NOx experiment conducted in RTI Chamber No. 1. Target
initial conditions: 2.0 ppmC thiophene and 0.2 ppm NOX. Symbol key: (o) 0^;
(O) NO; (A) N02; and (*) Total Sulfur.
-------
TABLE 30. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH THIOPHENE AND NO
TEST COMPOUND^ DATE-7
Thiophene 10-17-77
C4H4S 10-18-77
SMOG CHAMBER DUMBER
FIRST
DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppra)
Time of S0-K02 Crossover,
(hn EST)
'N°2'max' ppn
Time of [NO,! (hrs EST)
max ,
Timt
> PP<°
"f [0,]^. (h» EST)
[PAN] , ppra
Time of [PAN] , (hrs EST)
ID3X
[EMI ppn,
NO ] . . t . . h/
x' initial-
[NO ] @ 1700 EST
fNOx 9 1700 EST^
fC4H4S @ 1200 EST^ . ,
Time of [C4H4S], (hrs EST)-
Tiae of (S02lmax, (hrs EST)a/
(ppmS)
Time of [TPS] , (hrs EST)
max
*y
[CN]Mx, cm'3
Time of [CN]fflax( (hrs EST)
[fight-time 03 Half-Life (hrs)^
max
13.9
20.0 '
3
2
13. 07^
0.291
15.47
0.002
MA
0.001
XA
0
0.001
0.974
0.737
0.757
0.834
7.93E7
0.050
15.47
11.4
0.009
14.47
0.14
21,000
8.47
MA
MS*/
98
92
4
4
11.95
0.213
13.63
0.017
14.63
0.002
SA
0
tr
0.496
0.296
0.597
0.784
22.96
0.060
15.63
10.6
0.008
14.63
0.12
16,000
8.63
NA
CU-SR-7
425
397
I
10
9.57
0.093
10.13
0.124
14.13
0.007
NA
0
0
0.194
0.017
0.088
0.701
13.80
0.078
15.13
24.1
0.018
14.13
0.18
14,000
8.13
4S/
SUNRISE-''
6.37
2
20
8.90
0.051
9.30
0.112
11.30
0.002
NA
0
0
0.101
0.013
0.129
0.712
16.30
0.096
15.30
15.2
0.012
10.30
0.09
10,300
8.30
&
MOTES: Abbreviations: MB = no data are available; NA = aot applicable:
0 a not detected; tr = detected, but aot quantified; X = concen-
tration decreased, ao maximum observed.
The appendix should be consulted for additional data that are aot
summarized in this table.
(continued)
146
-------
TABLE 30. (continued)
SMOG CHAMBER NUMBER
SECOND
£!•
i£!
[TPSl
lai.
DAY PARAMETERS
-»-or
ppm-'
"£**
max' |J8/mJ
(ppmS)
«x' -"3
3
0
0
0
0
4
0
2,000
.007
.007
.072
.072
.8
.004
4
0.
0.
0.
0.
3.
0.
2,200
083
083
067
067
1
006
1
0.055
0.051
tr
HA
0
0
6,000
2
0.
0.
0,
0.
5
0
4,350
060
057
.071
.071
.6
.004
i/Target initial concentration 2.0 ppmC, 0.5 ppm (V/V), or 0.5 pptaS.
-/Dates of first and second days of the experiment.
- Daily maximum temperature in 8C.29
—/Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
£/Cumulative daily solar radiation expressed in Langleys (cal cm" ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually ?700 EST.
—/Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
4/Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in toe appendix.
-/The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise? the table entry has NOT been corrected for possible interferences.
i/Fraction of initial NO remaining at the 1700 EST hour calculated from >iO concentra-
tions as determined by*the chemiluminescent N0x analyzer. x
i/Fraction of accountable 'test compound at the 1200 EST hour.
'/Estimate of the time at which approximately one-half of the test compound was consumed.
'/Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of ISO«JMX: ([TPS]/([TPS] + [SO»])).
S/Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 5 5.545/ln ([03]2000/[03J0400).
ft/This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
'/Met concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: i03 = [03] -[03] and
ww - - - * max nin
2/On th« second day (18 October).
fl/Since few S02 concentration data are available, these data may not truly represent
maximum values.
147
-------
Among the remaining 3 cases, as the initial HC/NO ratio was increased the
X
maximum ozone concentration was achieved more rapidly.
In contrast to the experiments conducted with the open-chain sulfur
species that produced significant amounts of PAN, UN, and EN, the concen-
trations of PAN and EN were very small in the experiments conducted with
thiophene, and MN was not detected. Although the PAN and EN concentrations
displayed trends with the various initial conditions, the low concentrations
involved do not provide strong evidence for these trends. The largest
maximum PAN concentration occurred at the target HC/NO ratio of 10 and
decreased as this ratio was moved away from 10. The ordering of the maximum
PAN concentrations with respect to initial HC/NO ratio was similar to that
A
of the maximum ozone concentrations. The absence of MN and the very low
concentrations of PAN and EN observed as products of thiophene photooxidation
suggest that few precursor radicals of these nitrates were produced. Compari-
son of the chemical structures of thiophene and the open-chain sulfur species
suggests that the formation of the free radicals necessary to produce PAN,
MN, and EN is more complex for thiophene. It is likely that the major
oxidation steps for thiophene resulted in ring cleavage and the formation of
relatively complex radicals. Subsequent degradation of these radicals in
the presence of NO probably accounted for the observed PAN and EN concentra-
tions.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. For the four C4H4S-NOx experiments the
fraction of initial NO that could be accounted for ranged from 0.09 to
x
0.76. The nitrogen balances were similar to those for the propene-NO
experiments—in general the nitrogen balance was the poorest for those
conditions under which high ozone concentrations were generated. At the
1700 EST hour only 0.09 of the original NO could be accounted for at the
target HC/NO ratio of 10. The accountable fraction increased as target
ratios were moved away from 10. The absence of MN and the low concentrations
of PAN and EN, coupled with the poor nitrogen balances raise questions
concerning the fate of NO in the thiophene-NO experiments. The unaccount-
« A
able product nitrogen may be nitric acid or other undetermined nitrogen
species. The fate of NO in pbotochemically reacting systems is largely
unknown.
148
-------
The test species, C4H4S, was consumed slowly during these experiments.
Its concentration could be approximated by the difference between the total
sulfur and the S02 concentrations. Estimates were made of the fraction of
initially present C4H4S that remained unreacted at the 1200 EST hour of the
first day. For the four experiments the fraction of initial C4H4S that
could be accounted for ranged from 0.70 to 0.83. The ordering of the account-
able fractions of C4H4S was similar to that observed earlier for the fractions
of NO remaining at the 1700 EST hour. In both cases the fractions of
unreacted reactant were the smallest at the target HC/NO ratio of 10 and
increased as the target ratios were moved away from 10. Times to one-half
consumption of C4H4S also indicates that the C4H4S disappearance rate was
dependent on the initial HC/NO ratio—it was the most rapid at the target
HC/NO ratio of 10, and it became less rapid as this ratio was moved away
A
from 10.
Sulfur dioxide was found as a product of the photooxidation of C4H4S in
the presence of NO in each of the four experiments. Since S02 concentration
data are available only through the 1500 EST hour on 17 October, it is
uncertain whether the maximum concentrations through this hour were identical
to the daily maxima. The available S02 maxima occurred during the 1500 EST
hour and ranged from 0.050 to 0.096 ppm. The largest [S02] was 0.096 ppm
and occurred at the target HC/NOx ratio 20.
Moderate quantities of condensation nuclei were produced on the first
_0
A y 17 October. Maximum concentrations ranged from 10800 to 21000 cm and
urred
-------
largest maximum [IPS] occurred at the initial HC/NO ratio of 10 and
rndx x
generally decreased as this ratio was moved away from 10.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [SOaD was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum SC>2 concentration, and it permits an assessment of
the distribution of accountable product sulfur between the gas and particu-
late phases. For the C4H4S-NO system this ratio was small, ranging from
0.09 to 0.18. The largest ratio, 0.18, occurred at the target HC/NO ratio
of 10. In addition, results in the appendix suggest that a substantial
portion of the product sulfur cannot be accounted for.
Second-day cumulative solar radiation values were high during both the
October and November thiophene-NO experiments. Maximum TPS concentrations
A
on 18 October ranged from 0 to 8.1 pg/m3 or 0 to 0.006 ppmS. The largest
second-day maximum TPS concentration was achieved at the target HC/NO ratio
X
of 4. The maximum CN concentrations were also low on 18 October, ranging
_3
from 2000 to 6000 cm . However, on 19 November the maximum CN concentration
_Q
of 29000 cm approached the first-day value. No apparent associations with
initial conditions were noted for second-day maximum TPS or CN concentrations.
Sulfur dioxide concentration data were available for only 3 to 4 hours on 18
October. Thus, it is uncertain whether the maxima from these available data
were identical to the daily maxima. Since is is likely that the S02 concen-
trations decayed to trace amounts during the evening and night of the first
day, second-day maximum and net concentrations were assumed to have been
identical. In the three cases where the first-day C4H4S consumption had
been the least complete, the available second-day S02 maxima were approxi-
mately equal (0.07 ppm). They slightly exceeded the corresponding first day
maxima at target HC/NO ratios of 2 and 4, but did not do so at 20. At the
target ratio of 10, where first-day thiophene consumption had been the most
complete, only trace amounts of S02 were found on the second day. Second-day
maximum and net ozone concentrations exceeded the first-day maxima on 18
October at the target HC/NO ratios of 2 and 4, and also on 19 November at
target HC/NO ratio of 6.7. On 18 October the net ozone concentrations
ranged from 0.007 to 0.083 ppm. Previous experiments with the thiophene-NO
x
150
-------
system conducted at RTI have also indicated that for static (nondilution)
conditions , second-day net and maximum ozone concentrations can exceed
first-day maxima.42 For the three cases in the current study where this
occurred, the target HC/NO ratios (2, 4, and 6.7) were sufficiently low
that NO was in relative excess on the first day, and thus, only small
A
Quantities of ozone accumulated under the prevailing light-limited conditions.
By the second day, much of the initial NO had been converted to N02 , the
systems were no longer as severely light-limited, and significantly higher
concentrations of ozone accumulated. Thus, the high initial NO concentra-
tions that inhibited ozone production on the first day resulted in enhanced
ozone production on the second day. As an example, the largest net ozone
concentration, 0.083 ppm, was achieved at the target HC/NO ratio of 4
Bather than 10 where the largest first-day ozone maximum had occurred.
2-Methylthiophene
Mixtures of 2-methylthiophene and NO were irradiated on 30 and 31
A
October, and an additional experiment was conducted on 18 and 19 November
1977. In general, only the October experiments are considered in the current
discussion. On 30 October the cumulative daily solar radiation was 349 cal
"2 w££h 90 percent of the possible minutes of direct sunshine and a maximum
tefflPerature °^ 17.8° C. Selected results from the October 2-methylthiophene-
tfO experiments are summarized in Table 31. Concentration-time profiles of
various reactants and products for the 30 October experiment conducted in
cbaBiber No. 2 are presented in Figure 24.
The photochemical behavior of irradiated mixtures of NO and 2-methyl-
X
thiophene was similar in many respects to that of irradiated mixtures of NO
ad hydrocarbons such as propene. In each of the 2-methyl thiophene-NO
_>eriments, conversion of NO to N02 was rapid. The time of occurrence of
«IO-N°2 crossover was dependent on the initial HC/NO ratio. The duration of
a
-------
TABLE 31. SUMMARY OF SELECTED
CONDUCTED WITH 2
RESULTS FROM SMOG CHAMBER
METHYLTHIOPHENE AND NO
EXPERIMENTS
TEST COMPOUND*'' DATE-'
2-Methylthiophene 10-30-77
C5H«S 10-31-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppm)
Time of MO-;V02 Crossover,
(hrs EST)
[N02] , ppm
Time of [N02] (hrs EST)
max •
l°3]max' ppa
Time of [03JMX, (hrs EST)
[PAN] , ppm
Time of (PAN]max, (hrs EST)
[UN] ppm*'
TEN] ppm
[N0xii •tialh/
[N0x] @ 1700 EST
fJTO^ 9 1700 EST^
fCsH6S @ 1200 EST-i' . ,
Time of [CsH-eS]^ (hrs EST)-'
[S02] , ppm
Time of (SOjl^, (hrs EST)
[TPSJMx, (jg/mj
(ppmS)
Time of [TPS] , (hrs EST)
(DAX
Ri/
(CN]MX, cm'3
Tim. of (CN]MX, (hrs EST)
Night-time 03 Half-Life (hrs)5/
T £'
max
17.8
16.1
4
12.56
0.386
13.63
0.006
12.63
0.006
13.63
NO
0
0.980
0.588
0.600
0.500
12.63
0.048
16.63
24.6
0.019
11.63
0.13
33,500
7.63
NA
MS*/
90
49
3
10.20
0.253
11.47
0.084
14.47
0.016
16.47
0.002
0
0.500
0.155
0.310
0.438
11.74
0.053
16.47
28.9
0.022
13.47
0.15
29,000
7.47
2a/
CU-SR-'
349
243
2
10
9.26
0.104
10.30
0.129
12.30
0.023
13.30
tr
0
0.206
0.044
0.214
0.488
12.15
0.089
14.30
29.3
0.022
11.30
0.13
26,000
7.30
3fi/
SUNRISE-'
6.62
1
20
3.96
0.051
9.13
0.073
10.13
0.013
13.13
tr
0
0.114
0.026
0.228
0.551
12.39
tr
MA
21.6
0.017
11.13
NA
26,000
7.13
3S/
NOTES: Abbreviation*: ND ~ oo data are available; NA = not applicable;
0 s not detected; tr = detected, but not quantified; X - concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
(continued)
152
-------
TABLE 31. (continued)
SMOG
SECON
(63
[SO
osc
ITT
[0
CHAMBER NUMBER
D DAY PARAMETERS
1 , ppm
W&
lj'max' ppm
(ppmS)
''max' C1B"3
4
0.007
0.007
tr
HA
14.4
3,600
3
0.120
0.120
tr
HA
2.8
6,000
2
0.077
0.064
tr
NA
0
0
13,500
1
0.027
0.026
tr
NA
0
0
10,700
-'Target initial concentration 2.0 ppmC, 0.4 ppm (V/V), or 0.4 ppmS.
-Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
-Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
S'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [NO^] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has HOT been corrected for possible interferences.
infraction of initial HO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined by the chetniluminescent NO analyzer. x
J-^Fraction of accountable test compound at the 1200 EST hour.
-/Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02]max: UTPS]/([TPS]i-[S02])).
2/Estiaate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, = 5.545/ln ((03]2000/(03]0400).
-This half-life may be suspect, since ozone concentrations smaller than 0.1 ppm were
involved in its determination.
2/Het concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: AQ3 = [03] -[03] . and
153
-------
0.30
/—\
tn
I ' I
30-31 OCTOBER 1977
0.00
0.50
0.40
- 0.30 r
0000
0800
1600 0000
TIME (EST)
0800
1600
0000
Figure 24. Concentration-time profiles of various reactants and products for the 30 and 31
October 1977 2-methylthiophene-NO experiment conducted in RTI Chamber No. 2.
Target initial conditions: 2.0 ppmC 2-methylthiophene and 0.2 ppm NOX.
key: (o) 03; (Q) NO; (A) N02; (*) Total Sulfur; and (+) S02.
Symbol
CO
o
IV)
0.20
- 0.10
0.00
-------
Ozone accumulated during each experiment. Maximum concentrations and
their times of occurrence were dependent on the initial HC/NO ratio. Ozone
maxima ranged from 0.006 to 0.129 ppm. A maximum ozone concentration was
first achieved at the target HC/NO ratio of 20 during the 1000 EST hour. At
A
the lower ratios ozone maxima were achieved much later — during the 1200 and
1400 EST hours. The largest [03] , 0.13 ppm, was achieved at the target
Ilia X
HC/NO ratio of 10, and as the initial ratio was moved away from 10, maximum
ozone concentrations decreased. Except for the position of the methyl
group, 2-methylthiophene and 3-methylthiophene are identical; however, the
largest [03] for the 2-methylthiophene experiments amounted to only
one-third of the corresponding value for the 3-methylthiophene experiments.
Thus, the position of the methyl group signficantly affected the reactivity
of methylthiophene as indicated by ozone generation.
In contrast to thiophene, which produced small concentrations of PAN,
2-methylthiophene as well as 3-methylthiophene and 2,5-dimethylthiophene
produced significant amounts of PAN. Although small quantities of MN were
detected during the 2-methylthiophene experiments, appreciable concentrations
of MN and EN were not found. Maximum concentrations of PAN were dependent
on the initial conditions. The largest [PAN] occurred at the target
HC/NO ratio of 10, and as the initial ratio was moved away from 10, maximum
A
PAN concentrations decreased. Thus, the ordering of the maximum PAN concen-
trations with respect to the initial HC/NO ratio was similar to that of the
A
maximum ozone concentrations. In addition, PAN maxima in 3 of 4 cases
occurred during the 1300 EST hour.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
A
the 1700 EST hour of the first day. For the 2-methylthiophene-NO experi-
A
ments the fraction of initial NO that could be accounted for ranged from
A
0.21 to 0.60. The nitrogen balances were similar to those for the propene-
UO experiments — in general the nitrogen balances were the poorest for those
J*
conditions where the highest ozone concentrations were generated. At the
1700 EST hour, 0.21 of the original NO could be accounted for at the target
A
HC/NO ratio of 10. The accountable fraction increased as the target HC/NO
x . 5c
ratios were moved away from 10. The unaccountable product nitrogen may be
acid or other undetermined nitrogen-containing species. The fate of
HO in photochemically reacting systems is largely unknown.
155
-------
The test species, 2-methylthiophene, was consumed at moderate rates
during these experiments. Its concentration could be approximated by the
difference between the total sulfur and the S02 concentrations. Estimates
were made of the fraction of initially present CsHgS that remained unreacted
at the 1200 EST hour of the first day. For the 4 experiments the fraction
of initial C5H6S that could be accounted for ranged from 0.44 to 0.55. The
fraction of unreacted reactant was the smallest at the target HC/NO ratio
of 4 and increased as this ratio was moved away from 4. Inspection of the
times to one-half consumption of 2-methylthiophene also indicates that the
C5H6S disappearance rate was dependent on the initial HC/NO ratio. General-
A
ly, the disappearance rate was faster at the target HC/NO ratios of 4 and
10 than at 2 or 20.
Sulfur dioxide was found as a product of the photooxidation of 2-methyl-
thiophene in the presence of NO in each of the 4 experiments . Maximum con-
A
centrations and their times of occurrence were dependent on the initial
HC/NO ratio. Sulfur dioxide maxima ranged from trace quantities to 0.09
ppm. A maximum concentration was first achieved at the target HC/NO ratio
of 10; whereas, at target ratios of 2 and 4 the S02 maxima occurred later —
during the 1600 EST hour. The largest [S02] was 0.09 ppm 'and also occur-
red at the target HC/NO ratio of 10. As the target ratio was moved away
from 10, maximum S02 concentrations decreased. Maximum concentrations of
other reaction products such as ozone and PAN exhibited behavior that was
similarly associated with initial HC/NO ratios.
Moderate quantities of condensation nuclei were produced on the first
-3
day. Maximum concentrations ranged from 26000 to 33500 cm and occurred
during the 0700 EST hour. Although the CN maxima were not appreciably dif-
ferent, the largest maximum CN concentration occurred at the target HC/NO
A
ratio of 2, and maximum CN concentrations generally decreased with increas-
ing HC/NO ratios.
Maximum TPS concentrations were dependent on the initial HC/NO ratio.
A
Conversion of 2-methylthiophene to particulate sulfur was rapid with maximum
TPS concentrations occurring during the 1100 EST hour in 3 of 4 cases. Only
a small portion of the reacted test species was detected as particulate
156
-------
sulfur. Maximum IPS concentrations were not appreciably different and
ranged from 22 to 29 ug/m3 or the equivalent of 0.017 to 0.022 ppmS. As
with Oa, PAN, and S02 maxima, the largest maximum IPS concentration, 29
jjg/B3, occurred at the target HC/NO ratio of 10, and the IPS maxima de-
creased as the target ratios were moved away from 4.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([IPS] plus [S02]) was determined for 3 of the 4 experiments.
This ratio was based on data collected during or interpolated for the hour
of occurrence of the maximum S02 concentration, and it permits an assessment
of the distribution of accountable product sulfur between the gas and parti-
culate phases. For the 2-methylthiophene-NO system this ratio was small,
A
ranging from 0.13 to 0.15. Differences in these ratios were not considered
to be significant among the 3 experiments under consideration. Thus, this
ratio displayed no apparent trends with initial conditions. These results
do suggest, however, that approximately 85 percent of the accountable product
sulfur existed as S02. In addition, results in the appendix suggest that a
substantial portion of the product sulfur cannot be accounted for.
The second day, 31 October, was partly cloudy with 49 percent sunshine
_2
and a cumulative daily solar radiation of 243 cal cm . Second-day maximum
TPS and CN concentrations were low. Second-day maximum TPS concentrations
ranged from 0 to 14 pg/m3 or 0 to 0.011 ppmS. The largest second-day [TPS]
occurred at the target HC/NO ratio of 2, and the. second-day maxima decreased
X
with increasing initial ratios. Second-day CN maxima ranged from 3600 to
_0
13500 cm . The largest second-day CN maximum concentration occurred at the
target HC/NO ratio of 10, and the second-day CN maxima decreased as this
ratio was moved away from 10. Although only nonquantifiable trace amounts
of S02 were found, S02 was produced on the second day. Second-day maximum
and net ozone concentrations exceeded the first-day maxima at target HC/NO
A
ratios of 2 and 4. Net ozone concentrations ranged from 0.007 to 0.120 ppm.
The largest net ozone concentration, 0.120 ppm, was achieved at the target
HC/NO ratio of 4, rather than 10, where the largest first-day maximum
ozone concentration had occurred. Thus, more initial NO was required to
A
generate the largest second-day ozone concentration than was required to
generate the largest first-day concentration. This behavior is similar to
157
-------
that for the experiments conducted with thiophene and for those with the
2,5-dimethylthiophene.
3-Methylthiophene
Mixtures of 3-methylthiophene and NO were irradiated on 22 and 23
October, and an additional experiment was conducted on 18 and 19 November
1977. In general, only the October experiments are considered in the current
discussion. On 22 October the cumulative daily solar radiation was 366 cal
_2
cm with 100 percent of the possible minutes of direct sunshine and a
maximum temperature of 23.9° C. Selected results from the October 3-methyl-
thiophene-NO experiments are summarized in Table 32. Concentration-time
profiles of various reactants and products for the 22 October experiment
conducted in Chamber No. 3 are presented in Figure 25.
The photochemical behavior of irradiated mixtures of NO and 3-methyl-
X
thiophene was similar in various respects to that of irradiated mixtures of
NO and hydrocarbons such as propene. In each of the 3-methylthiophene-NO
X X
experiments conversion of NO to N02 was rapid. The time of occurrence of
N0-N02 crossover was dependent on the initial HC/NO ratio—the duration of
A
irradiation required to achieve crossover increased with decreasing initial
HC/NO ratios. Crossover was first achieved at the target HC/NO ratio of
X X
20. For the 4 experiments crossover occurred between 0907 and 1030 EST,
requiring 2.7 to 4.0 hours of irradiation. The timing of the maximum N02
concentration was also dependent on the initial HC/NO ratio and generally
occurred within the hour following crossover. The timing of both NO-N02
crossover and maximum N02 concentration with respect to initial HC/NO
ratios for the 3-methylthiophene experiments was almost identical to that
for the 2,5-dimethylthiophene experiments.
Ozone accumulated during each experiment. Maximum concentrations and
their times of occurrence were dependent on the initial HC/NO ratio. Ozone
X
maxima ranged from 0.05 to 0.37 ppm. A maximum ozone concentration was
first achieved at the target HC/NO ratio of 20 during the 1000 EST hour.
A
At the lower ratios ozone maxima were achieved much later—during the 1400
and 1500 EST hours. The largest [03] , 0.37 ppm, was achieved at the
01£»X
target HC/NO ratio of 4, and as the initial ratio was moved away from 4,
maximum ozone concentrations decreased. In addition, 3-methylthiophene
158
-------
Q_
Q_
OJ
O
z:
O
LU
z
O
(XI
O
0.75
0.50 -
0.25 -
O.QO
I ' I ' I
22-23 OCTOBER 1977 "3
0.50
I
CO
- 0.30 .r
- 0.20
CO
o
"U
- 0.10
0000
Figure 25.
0800
1600 0000
TIME (EST)
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 22 and 23
October 1977 3-methylthiophene-NOx experiment conducted in RTI Chamber No. 3.
Target initial conditions: 2.0 ppmC 3-methylthiophene and 0.5 ppm NOX. Symbol
key: (o) 03; (O) NO; (A) N02; (*) Total Sulfur; and (+) S02
-------
TABLE 32. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENTS
CONDUCTED WITH 3-METHYLTHIOPHENE AND NO
TEST COMPOUND*7 DATE-7
3-Methylthiopheae 10-22-77
CSH«S 10-23-77
SMOG CHAMBER NUMBER
max
23.9
21.7
4
%SS^7
100
80
3
CU-SR-7
366
323
2
SUNRISE-7
6.47
1
FIRST DAY PARAMETERS
Target Initial HC/NO (ppmC/ppn)
Time of N0-N02 Crossover, ^
(hrs EST)
Time of [M021MX (hrs EST)£7
[°3jmax' pp"
Time of [03]nux, (hrs EST)
[PAN] , ppm
Time of [PAN]fflax, tars EST)
[MM] ppm*7
(EN I ppm
(NOx] initial^7 .
[MOXJ 1? 1700 EST£/
fNO § 1700 EST*^-27
fCsH,S @ 1200 ESTJ-7 . ,
Time of [CSH8S], (hrs EST)-'
[S02] , ppm
Time of [S02)max, (hrs EST)
[TPSJ , Mg/nJ
(ppmS)
Time of (TPS]inax, (hrs EST)
Ry
lonMx, cm'3
Tim. of [CN1 (hrs EST)
max
Might-time 03 Half-Life (hrs)s/
2
10.50
0.462
11.63
0.054
14.63
0.008
19.63
MD
0
0.962
0.390
0.405
0.243
10.78
0.350
15.63
29.2
0.022
14.63
0.04
24,000
7.63
MA
4
9.74
0.260
10.47
0.369
15.47
0.028
19.47
MD
0
0.504
0.073
0.145
0.216
10.46
0.389
13.47
57.0
0.044
14.47
0.08
22,000
7.47
7
10
9.46
0.086
9.30
0.197
15.30
0.017
11.30
0.001
0
0.222
0.043
0.194
0.226
10.20
0.321
13.30
28.9
0.022
10.30
0.05
16,000
7.30
5S/
20
9.13
0.027
9.13
0.077
10.13
0.010
12.13
tr
0
0.139
0.028
0.201
0.406
10.92
0.293
15.13
16.0
0.012
10.13
0.03
16,000
7.13
MA
(continued)
MOTES: Abbreviations: MD = no data are available; MA = not applicable;
0 3 not detected; tr = detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
160
-------
TABLE 32. (continued)
SMOG CHAMBER KUMBER 4
SECOND DA? PARAMETERS
l°alm«' PP™ °-094
.. fflaX o/ 0.094
UU*| » Ppl"~"
(S02J , ppa 0.136
ASOj, PPn- 0.136
(TPS „„. Mg/raJ 8.4
in AX
(ppmS) 0.006
(CN)MX, cm"3 5,000
3
0.243
0.189
0.103
0.103
6.0
0.005
3,400
2
0.181
0.158
0.071
0.071
3.5
0.003
2,400
1
0 . 106
0.106
0.136
0.136
3.9
0.003
1,800
* Target initial concentration 2.0 ppraC, 0.4 ppm (V/V), or 0.4 ppmS.
- Dates of first and second days of the experiment.
- Daily maximum temperature in °C.29
— Duration of direct solar radiation reported as percent of possible minutes of sunshine.29
-Cumulative daily solar radiation expressed in Langleys (cal cm ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminated—usually 1700 EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
^ Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial (NOX1 is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
-'Fraction of initial NO remaining at the 1700 EST hour calculated from UQ concentra-
tions as determined by' the chemiluoinescent NO analyzer.
J-'Fraction of accountable test compound at the 1200 EST hour.
it/
-Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
CiM of [S08] : ([TPS]/([TPS] + [S02])).
. • iDaJC
-Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.5457In ([03]2000/[03]0400).
- This half-life may be suspect, since-ozone concentrations smaller than 0.1 ppm were
involved in its determination.
-'Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: A03 = [03] -[03] and
£SO, » [S02] - [SO,] . . °"x min
* l ZIIMX 2 »in
£ Since 3-Methylthiophen« acted as a strong interferent with the cheniluminescent
determination of nitrogen oxides, parameters based on NO data are uncertain.
161
-------
produced the largest maximum ozone concentration among the four tested
thiophenes and thus had the largest ozone-generative potential.
In contrast to thiophene, which produced small concentrations of PAN,
3-methylthiophene, as well as 2-methylthiophene and 2,5-dimethylthiophene,
produced significant amounts of PAN. Although small quantities of MN were
detected during the 3-methylthiophene experiments, appreciable concentrations
of MN and EN were not found. Maximum concentrations of PAN were dependent
on the initial conditions. The largest [PAN] occurred at the target
UlojC
HC/NO ratio of 4, with the remaining maxima decreasing as this ratio was
A
moved away from 4. Thus, the ordering of the maximum PAN concentrations
with respect to the initial HC/NO ratio was similar to that of the maximum
a
ozone concentrations. Missing data prevent an evaluation of timing of the
maximum PAN concentrations (see appendix).
Inspection of the first-day NO data in the appendix revealed unusual
A
behavior. Inflections in the NO concentration-time profiles occurred in
the experiments conducted at the two highest initial HC/NO ratios. The
timing of these inflections coincided with the initial buildup of PAN that
occurred during the 1000 and 1100 EST hours. This behavior was not observed
at lower HC/NO ratios, although it may have been obscured by the higher NO
x x
concentrations employed in these experiments. Similar behavior has been
noted previously in the current study and has been tentatively attributed to
unknown transient nitrogen-containing species. In the previously noted
cases the unusual behavior was associated with the presence of an ethyl
group in the test species. The photooxidation of 3-methylthiophene involves
the formation of radicals that contain ethyl groups as evidenced by PAN
formation. However, an additional factor which complicates these findings
was the discovery that 3-methylthiophene interferes strongly with chemilumi-
nescent NO and N02 measurements (see Table 13). This interference introduces
uncertainty into all the tabulated parameters that involved chemiluminescent
NO measurements. At low initial NO concentrations (i.e., high HC/NO
X X x
ratios) and early in the experiment when the 3-methylthiophene concentration
was high, the relative impact of the interference was the largest. Since
the NO concentration data cannot be corrected for the observed interference
the cause of the unusual NO behavior cannot be resolved at this time.
162
-------
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. For the 3-methylthiophene-NO experiments,
the fraction of initial NO that could be accounted for ranged from 0.15 to
X
0.41. The nitrogen balances were similar to those for the propene-NO
A
experiments—in general the balances were the poorest for those conditions
where the highest ozone concentrations were generated. At the 1700 EST
hour, 0.15 of the original NO could be accounted for at the target HC/NO
x x
ratio of 4. The accountable fraction increased as the target ratios were
moved away from 4. The unaccountable product nitrogen may be nitric acid or
other undetermined nitrogen-containing species. The fate of NO in photo-
X
chemically reacting systems is largely unknown.
The test species, 3-methylthiophene, was consumed rapidly during these
experiments. Its concentration could be approximated by the difference be-
tween the total sulfur and the SC>2 concentrations. Estimates were made of
tbe fraction of initially present CsHgS that remained unreacted at the 1200
EST hour of the first day. For the four experiments the fraction of initial
C_H6S that could be accounted for ranged from 0.22 to 0.41. The ordering of
the accountable fractions of C5H6S was similar to that observed earlier for
the fractions of NO remaining at the 1700 EST hour. In both cases the
fractions of unreacted reactant were the smallest at the target HC/NO ratio
X)
of 4 and increased as the target ratios were moved away from 4. Inspection
of the times to one-half consumption of 3-methylthiophene also indicates
that the CsH6S disappearance rate was dependent on the initial HC/NO ratio.
Generally, the disappearance rate was faster at the target HC/NO ratios of
4 and 10 than at 2 or 20.
Sulfur dioxide was found as a product of the photooxidation of 3-methyl-
thiophene in the presence of NO in each of the four experiments. Maximum
A
concentrations and their times of occurrence were dependent on the initial
HC/NO ratio. Sulfur dioxide maxima ranged from 0.29 to 0.39 ppm. Maximum
concentrations were first achieved during the 1300 EST hour at target HC/NO
X
ratios of 4 and 10, and at ratios 2 and 20 [SC^] occurred during the 1500
max
EST hour. This behavior is consistent with that of the 3-methylthiophene
disappearance rates noted earlier. The largest [S02] was 0.39 ppm and
max
163
-------
occurred at the target HC/NO ratio of 4. As the target ratio was moved
X
away from 4, maximum S02 concentrations decreased. Maximum concentrations
of other reaction products such as ozone and PAN exhibited behavior that was
similarly associated with initial HC/NO ratios.
X
Moderate quantities of condensation nuclei were produced on the first
-3
day. Maximum concentrations ranged from 16000 to 24000 cm and occurred
during the 0700 EST hour. The largest maximum CN concentration occurred at
the target HC/NO ratio of 2, and maximum CN concentrations decreased with
increasing HC/NO ratios.
X
Maximum IPS concentrations and their times of occurrence were dependent
on the initial HC/NO ratio. In the experiments conducted at target ratios
of 10 and 20, [IPS] were achieved during the 1000 EST hour; however, at
flldX
target ratios of 2 and 4 [TPS] occurred during the 1400 EST hour. Only a
IDwA
small portion of the reacted test species was detected as particulate sulfur,
and maximum TPS concentrations ranged from 16 to 57 Mg/n>3 or the equivalent
of 0.012 to 0.044 ppmS. As with 03, PAN, and S02 maxima, the largest maxi-
mum TPS concentration occurred at the target HC/NO ratio of 4, and the TPS
maxima decreased as the target ratios were moved away from 4.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [S02]) was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum SO2 concentration, and it permits an assessment of
the distribution of accountable product sulfur between the gas and particu-
late phases. For the 3-methylthiophene-NO system this ratio was small,
A
ranging from 0.03 to 0.08. The largest ratio, 0.08, occurred at the target
HC/NO ratio of 4 and decreased as the target HC/NO ratio was moved away
X X
from 4. Other tabulated parameters also indicated that the reactivity of
the 3-methylthiophene-NO system was large at the target HC/NO ratio of 4.
X *»
Thus, although most of the accountable product sulfur existed as S02, partic-
ulate sulfur comprised increasing proportions of accountable product sulfur
as the reactivity of the system was increased. In addition, results in the
appendix suggest that a substantial portion of the product sulfur cannot be
accounted for.
The second day, 23 October, was sunny with 80 percent sunshine and a
-2
cumulative daily solar radiation of 323 cal cm . Second-day maximum TPS
164
-------
and CN concentrations were low. Second-day maximum IPS concentrations
ranged from 3.5 to 8.1 jJg/m3 or 0.003 to 0.006 ppmS and generally decreased
with increasing initial HC/NO ratios . Second-day CN maxima ranged from
-3
1800 to 5000 cm and also decreased with increasing initial HC/NO ratios.
A
Second-day maximum and net S02 concentrations, although substantial, did not
exceed the first-day maxima. Since the S02 concentrations decayed to non-
quantifiable trace amounts during the evening and night of the first day,
second-day maximum and net concentrations were identical. These values
ranged from 0.07 to 0.14 ppm. The highest concentrations occurred at target
HC/NO ratios of 2 and 20, the two experiments where the first-day consump-
A
tion of 3-methylthiophene had been the least complete. In addition to an
increase in S02 concentration, the total sulfur concentration also increased
on the second day. This also occurred in the experiments conducted with
2 5-dimethylthiophene. This behavior suggests that a sulfur-containing
species was sorbed by the chamber walls on the evening of the first day and
was subsequently released during the second day. The identity of the respon-
sible sulfur species is unknown. There is some evidence to suggest that S02
can be deposited on and released in small amounts from the chamber walls
(see the section on Characterization Experiments). It is possible that the
sulfur compound was S02, an intermediate product, unreacted reactant, or
some combination of these species. Second-day maximum and net ozone concen-
trations exceeded the first-day maxima at target HC/NOx ratios of 2 and 20.
The net ozone concentrations ranged from 0.09 to 0.19 ppm. As with the
first-day ozone maxima, the largest net ozone concentration occurred at the
target HC/NO ratio of 4, and the net concentrations decreased as the initial
HC/NO ratio was moved away from 4.
o 5-Dimethylthiophene
Mixtures of 2, 5-dimethylthiophene and NO were irradiated on 20 and 21
October, and an additional experiment was conducted on 18 and 19 November
1977. In general, only the October experiments are considered in the current
discussion. On 20 October the cumulative daily solar radiation was 386 cal
on"* with 100 percent of the possible minutes of direct sunshine and a
maximum temperature of 18.9° C. Selected results from the October C6H8S-NO
experiments are summarized in Table 33. Concentration-time profiles of
165
-------
TABLE 33. SUMMARY OF SELECTED RESULTS FROM SMOG CHAMBER EXPERIMENT
CONDUCTED WITH 2,5-DIMETHYLTHIOPHENE AND NO
..X
TEST COMPOUND^ DATE-'
2,5-Dimethylthiophene 10-20-77
C«H(S 10-21-77
SMOG CHAMBER NUMBER
FIRST DAY PARAMETERS
Target Initial HC/NOx (ppmC/ppm)
Time of N0-X02 Crossover,
(hrs EST)
Time of [N021 (hrs EST)
max,
[03] , ppm
"max' **
Time of [03Jnax. (hrs EST)
[PANl«n.x' ppm
Time of lPAN]aax, (hrs EST)
[MM] ppm*/
[EN] ppm
[M0x] (8 1700 EST
fHOx 9 1700 ESTi/
fCsH,S @ 1200 ESTJ-/ .
Time of [CsHgS]^ (hrs EST)-'
[S02] , ppm
Time of [S02IMX, (hrs EST)
(ppmS)
Time of [TPS] , (hrs EST)
Si/
[CHJ , on
Tim* of (CN]^, (hrs EST)
Night-time 03 Half-Life (hrs)5/
Tc/
—
max
18.9
19.4
3
2
10.23
0.535
11.47
0.144
15.47
0.042
19.47
0.007
0
1.032
0.288
0.279
0.236
10.76
0.444
14.47
34.8
0.027
12.47
0.05
31,000
12.47
2a/
*ss detected, but not quantified; X = concen-
tration decreased, no maximum observed.
The appendix should be consulted for additional data that are not
summarized in this table.
(continued)
166
-------
TABLE 33. (continued) •
SMOG CHAMBER NUMBER
SECOND
^3J«
[SOj
ITPS
[orj,
DAY PARAMETERS
•#"
1 , Ppm
, nf
'max' Mg/m'i
(ppmS)
3
0
0
0
0
3
0
2,400
.283
.283
.120
.120
.6
.003
4
0
0
0
0
4
0
2,900
.248
.211
.068
.068
.4
.003
1
0
0
0
0
0
0
5,700
.048
.048
.116
.116
2
0
0
0
0
0
0
5,000
.042
.042
.112
.112
-/Target initial concentration 2.0 ppmC, 0.33 ppm (V/V), or 0.33 ppnS.
-Dates of first and second days of the experiment.
-Daily maximum temperature in °C.29
— Duration of direct solar radiation reported as percent of possible minutes of sunshine.2
-' emulative daily solar radiation expressed in Langleys (cal cm" ); note that the second-
day value is the cumulative solar radiation on that day until the experiment was
terminajted—usually 1700 _EST.
-Time of sunrise in hours (EST); since the times of sunrise are approximately the same
for both days, the time is given for the first day only.
8'Daily median concentrations of species tentatively identified to be methyl and ethyl
nitrate; they are not listed in the appendix.
-The initial [NO ] is taken to be the concentration that existed at approximately the
time of sunrise; the table entry has NOT been corrected for possible interferences.
-Fraction of initial NO remaining at the 1700 EST hour calculated from NO concentra-
tions as determined byxthe chemiluminescent NO analyzer.
* /
•1'Fraction of accountable test compound at the 1200 EST hour.
-Estimate of the time at which approximately one-half of the test compound was consumed.
-Ratio of product sulfur as particulate to the total accountable reacted sulfur at the
time of [S02] : ([TPS]/([TPS]i-[S02])).
. max
-'Estimate of ozone half-life based on data collected during the 2000 EST hour of the
first day and the 0400 EST hour of the second day: t, 3 5.545/ln ([03]2000/[03]0400).
-'This half-life may be suspect, since ozone concentrations smaller than 0.1 ppra were
involved in its determination.
- Net concentration on the second day is the difference between the second-day maximum
concentration and the preceding minimum concentration: 103 » [03] -(Oil . and
/ISO, » [SO,]^ - [S02]ffl.n.
167
-------
various reactants and products for the 20 October experiment conducted in
Chamber No. 4 are presented in Figure 26.
The photochemical behavior of irradiated mixtures of NO and C6H8S was
X
similar in various respects to that of irradiated mixtures of NO and hydro-
X
carbons such as propene. In each of the C6H8S-NO experiments, conversion
X
of NO to N02 was rapid. The time of occurrence of N0-N02 crossover was
dependent on the initial HC/NO ratio. With a single exception, the duration
of irradiation required to achieve NO-NOg crossover increased with decreasing
HC/NO ratios. Crossover was first achieved at the target HC/NO ratio of
A. X
10, although the time of occurrence was not appreciably different from that
at the target ratio of 20. For the 4 experiments crossover occurred between
0917 and 1013 EST, requiring 2.9 to 3.8 hours of irradiation. The timing of
the maximum N02 concentration was also dependent on the initial HC/NO ratio
X
and generally occurred within the hour following NO-N02 crossover.
Ozone accumulated during each experiment. Maximum concentrations and
their times of occurrence were dependent on the initial HC/NO ratio. Ozone
X
maxima ranged from 0.08 to 0.25 ppm. Maximum ozone concentrations occurred
first at the target HC/NO ratios of 10 and 20, and these maxima were achieved
during the 1100 EST hour. As the initial HC/NO ratio was decreased, ozone
X
maxima occurred later in the day. The largest [03] , 0.25 ppm, occurred
013 X
at the target HC/NO ratio of 4, and as the target ratio was moved away from
4, maximum ozone concentrations decreased.
In contrast to thiophene, which produced small concentrations of PAN,
2,5-dimethylthiophene, as well as 2-methylthiophene and 3-methylthiophene,
produced significant amounts of PAN. Among the thiophenes, however, only
2,5-dimethylthiophene produced appreciable amounts of MN. In addition, none
of the thiophenes produced appreciable amounts of EN. For the 2,5-dimethyl-
thiophene experiments both PAN and MN concentrations displayed similar
trends with initial conditions. The largest maximum concentrations of these
species occurred at the target HC/NO ratio of 4 with the remaining maxima
decreasing as this ratio was moved away from 4. Thus, the ordering of the
maximum PAN concentrations with respect to the initial HC/NO ratio was
similar to that of the maximum ozone concentrations. In addition, the
timing of the maximum PAN concentrations also paralleled that of ozone
maxima—occurring later in the day as the initial HC/NO ratio was decreased.
168
-------
0.75
20-21 OCTOBER 1977 3
0.75
- 0.50
o
ro
0.25
0.00
0000
Figure 26.
0800
1600 0000
TIME (EST)
0800
1600
0000
0.00
Concentration-time profiles of various reactants and products for the 20 and 21
October 1977 2,5-dimethylthiophene-NOx experiment conducted in RTI Chamber No. 4.
Target initial conditions: 2.0 ppmC 2,5-dimethylthiophene and 0.5 ppm NOX.
Symbol key: (o) 03; (Q) NO; (A) N02; (x) Total Sulfur; and (+) S02.
-------
The identification of PAN and the tentative identification of MN will provide
clues that may permit elucidation of the chemistry of the 2,5-dimethylthio-
phene-NO system.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. For the four C6H8S-NO experiments the
A
fraction of initial NO that could be accounted for ranged from 0.26 to
A
0.34. At the 1700 EST hour, 0.26 of the original NO could be accounted for
A
at the target HC/NO ratio of 10. The accountable fraction increased as the
A
target ratios were moved away from 10. At target ratios of 2, 4, and 10,
however, the fractions of accountable nitrogen were not appreciably different.
The narrow spread for the nitrogen balances among the 4 experiments with
2,5-dimethylthiophene was in contrast to the large ranges estimated for the
remaining three thiophenes that were tested. The unaccountable product
nitrogen may be nitric acid, or other undetermined nitrogen-containing
species. The fate of NO in photochemically reacting systems is largely
unknown.
The test species, C6H8S, was consumed at a moderate-to-rapid rate
during these experiments. Its concentration could be approximated by the
difference between the total sulfur and the S02 concentrations. Estimates
were made of the fraction of initially present CeHgS that remained unreacted
at the 1200 EST hour of the first day. For the four experiments the fraction
of initial C6H8S that could be accounted for ranged from 0.24 to 0.70 and
was dependent on the initial HC/NO ratio. The fraction of accountable
C6H8S increase with increasing HC/NO ratios. Inspection of the times to
X
one-half consumption of 2,5-Dimethylthiophene also indicates that the C6H8S
reaction rate was dependent on the initial HC/NO ratio. The disappearance
A
rate of C6H8S was the most rapid at the target HC/NO ratio of 2, and it
became less rapid as the initial HC/NO ratio was increased.
Sulfur dioxide was found as a product of the photooxidation of C6H8S in
the presence of NO in each of the four experiments. Maximum concentrations
X
and their times of occurrence were dependent on the initial HC/NO ratio.
X
Sulfur dioxide maxima ranged from 0.19 to 0.44 ppm. Maximum concentrations
were first achieved during the 1400 EST hour at target HC/NO ratios of 2
A
170
-------
and 4, while at ratios of 10 and 20 ls°2lmax occurred during the 1500 and
1600 EST hours. This behavior is consistent with that of the C6H8S disap-
pearance rates noted earlier. The largest [S02] ax was 0.44 ppm and occurred
at the target HC/NO^ ratio of 2. As the initial HC/NOx ratio increased,
maximum S02 concentrations decreased. In addition, 2,5-dimethylthiophene
produced the largest maximum S02 concentration observed among the four
tested thiophenes.
Moderate quantities of condensation nuclei were produced on the first
_q
day, 20 October. Maximum concentrations ranged from 5700 to 31000 cm and
occurred between the 0900 and the 1300 EST hours. The largest maximum CN
concentration occurred at the target HC/NO ratio of 2. The CN maxima de-
creased with increasing initial HC/NOx ratios.
Maximum TPS concentrations were dependent on the initial HC/NO ratio.
A
These maxima were achieved during the 1200 EST hour in 3 of 4 cases. Only a
small portion of the reacted test species was detected as particulate sulfur.
Maximum TPS concentrations ranged between 3 and 35 Mg/m3 or the equivalent
of 0.003 to 0.027 ppmS. The ordering of the maximum TPS concentrations with
respect to the initial HC/NO ratio was similar to that of the maximum S02
concentrations. The largest maximum TPS concentration occurred at the
target HC/NO ratio of 2, amd maximum TPS concentrations decreased with
increasing initial HC/NO ratios (i.e., decreasing initial N0x concentrations)
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [S02]) was determined for each experiment. This
ratio was based on data collected during or interpolated for the hour of
occurrence of the maximum S02 concentration, and it permits an assessment of
the distribution of accountable product sulfur between the gas and particu-
late phases. For the C6H8S-NO system this ratio was small, ranging from 0
to 0.05. The largest ratio, 0.05, occurred at the target HC/NO ratio of 2
and decreased with increasing HC/NO ratios. Thus, although most of the
accountable product sulfur existed as S02> particulate sulfur comprised
increasing proportions of accountable product sulfur at decreasing initial
HC/NO ratios. In addition, results in the appendix suggest that a substan-
tial portion of the product sulfur cannot be accounted for.
171
-------
Second-day cumulative solar radiation values were high during both the
October and November 2,5-dimethylthiophene-NO experiments. Maximum IPS
a
concentrations on 21 October ranged from 0 to 4.4 pg/m3 or 0 to 0.003 ppmS.
The largest second-day maximum TPS concentration was achieved at the target
HC/NO ratio of 4. The results in the appendix also indicate that maximum
CN concentrations were low on both 21 October and 19 November, ranging from
2400 to 5700 cm . No apparent associations with initial conditions were
noted for second-day maximum TPS and CN concentrations. Second-day maximum
and net S02 concentrations, although substantial, did not exceed the first-
day maxima. Since the S02 concentrations decayed to nonquantifiable trace
amounts during the evening and night following the first day, second-day
maximum and net concentrations were identical. These values ranged from
0.07 to 0.12 ppm and displayed no apparent trends with initial conditions.
In addition to an increase in S02 concentration, the total sulfur concentra-
tion also increased on the second day. Similar behavior was noted in the
experiments conducted with 3-methylthiophene. This behavior suggests that a
sulfur-containing species was sorbed by the chamber walls on the evening of
the first day and was subsequently released during the second day. The
identity of the responsible sulfur species is unknown. There is some evi-
dence to suggest that SOg can be deposited on and released in small amounts
from the chamber walls (see the section on Characterization Experiments).
It is possible that the sulfur compound was S02, an intermediate product,
unreacted reactant, or some combination of these species. Second-day maximum
and net ozone concentrations exceeded the first-day maximum on 21 October at
the target HC/NO ratio of 2 and on 19 November at the target ratio of 6.7.
Second-day maxima as well as net ozone concentrations decreased with increas-
ing initial HC/NO ratios (i.e., decreasing initial NO concentrations).
X «
For the four October experiments, net ozone concentrations ranged from 0.04
to 0.28 ppm. The largest net ozone concentration, 0.28 ppm, occurred at the
target HC/NO ratio of 2, rather than 4, where the largest first-day maximum
ozone concentration had occurred. Thus, more initial NO was required to
generate the largest second-day ozone concentration than was required to
generate the largest first-day concentration. This behavior is similar to
that noted previously in the thiophene and 2-methylthiophene experiments.
172
-------
COMPARISON OF CHEMICAL BEHAVIOR AMONG TEST SPECIES
In this analysis, selected aspects of the chemical behavior of the
tested compounds are compared. Illustrations depicting the range of a
single reaction parameter for each test species were prepared for several
reaction parameters. Visual inspection of these illustrations permits a
relative assessment among all tested compounds of the reaction parameters
under consideration. It should be noted, however, that these comparisons
are drawn from data collected on different days over the 3-month period from
September through November of 1977. Thus, the reaction parameters under
consideration are not from experiments conducted under identical environmen-
tal conditions. Seasonal and daily differences in such environmental varia-
bles as light intensity, sunlight duration, and temperature will influence
tke results considered in this portion of the analysis. The relative impor-
tance of these factors cannot be resolved at this time, and no attempt was
made in this portion of the analysis to account for them. In spite of this
complication, the current analysis should provide a rough basis for comparing
the chemical behavior of the tested compounds.
Time to NO-NO? Crossover
In most cases, the photochemical behavior of irradiated mixtures of NO
and individual test species was similar in various respects to that of
irradiated mixtures of NO and hydrocarbons such as propene. Except for
experiments conducted with H2S and with COS, the presence of the test species
resulted in more rapid conversion of NO to N02 than would have occurred in
its absence. For each test compound, the range of hours of irradiation past
sunrise required to achieve N0-N02 crossover is presented in Figure -27. For
the thiols, organic sulfides, and organic disulfides, conversion from NO to
HO* was extremely rapid and rather insensitive to initial conditions, as
indicated by the narrow ranges of times. The organic disulfides displayed
the most rapid conversion of NO to N02 of all the species tested in the
current study. For carbon disulfide and thiophene, the times to crossover
were highly sensitive to initial conditions and, in one case for thiophene,
occurred on the second day. In addition, as methyl groups were added onto
the thiophene molecule, the times to crossover became less sensitive to
initial conditions. A seasonal influence on the times to crossover was
173
-------
C3H6 (9-12-77)
C3H6 (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-26-77)
CH3SSCH3 (10-5-77)
CH3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2H5SH (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2H5 (10-7-77)
Thiophene (10-17-77)
2-Methylthlophene (10-30-77)
3-Mechylthiophene (10-22-77)
2,5-DimeChylthiophene (10-20-77)
H
H
M
H
H
H
H
J I I
1 I 1
I I I I I I
I I I
J I
••xo,
6
In
10
11 Day 2
Figure 27. Range of the duration of irradiation (hours past sunrise) required on the
first day to achieve NO-N02 crossover; * indicates that crossover occurred
on the second day of irradiation.
-------
exhibited in the propene-NO experiments. Slightly longer times were re-
A
quired in November, and they were more sensitive to initial conditions than
they were in September. It is interesting to note that the 1-month separa-
tion in the two sets of CH3SC2Hs-NO experiments did not have a strong in-
fluence on times to crossover for these experiments.
Maximum First-Day Ozone Concentration
Except for the experiments conducted with H^S and with COS, substantial
amounts of ozone accumulated during at least one of the experiments con-
ducted with each test compound. The range of maximum ozone concentrations
found on the first day of the experiment is presented in Figure 28 for each
test compound. As indicated by the relatively large ranges, the maximum
ozone concentrations were rather sensitive to initial conditions. The
largest [03] generated by tested sulfur species was generated by the
system. Among the test species the thiols, organic sulfides,
and organic disulfides had the largest ozone-production potential. In gen-
eral, the thiophenes produced less ozone, although the addition of methyl
groups onto the thiophene molecule enhanced its ozone production. On the
first day of the experiments conducted with hydrogen sulfide and with car-
bonyl sulfide, very little NO was oxidized to N02, and essentially no ozone
was produced. Carbon disulfide produced a substantial amount of ozone, but
only at tne highest initial HC/NO ratio. Strong seasonal influences on the
X
maximum ozone concentrations were exhibited in the propene-NO experiments.
A
Much larger ozone maxima were produced in September, and they were more
sensitive to initial conditions than was found in November. In contrast,
the 1-month separation in the two sets of CH3SC2H5-NO experiments did not
X
have a strong influence on maximum ozone concentrations observed in these
two cases .
To explore the ozone generative potential of several of the tested com-
pounds in more detail, graphical displays were prepared of maximum ozone
concentrations produced at various target initial HC/NO ratios. These
illustrations are presented in Figures 29, 30, and 31.
The thiols, organic sulfides, and organic disulfides produced high
[03] at low initial HC/NO ratios. As indicated in Figure 29, the largest
IDdX X
[03] occurred at the target HC/NO ratio of 4 for the thiols. This
x
175
-------
C3H6 (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
CH3SSCH3 (10-5-77)
CH3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2H5SH (10-3-77)
C2H5SC2U5 (10-15-77)
C2HjSSC2Hs (10-7-77)
Thlophene (10-17-77)
2-Methylthiophene (10 30-77)
3-Methylthiophene (10-22-77)
2,5-Dimethylthiophene (10-20-77)
1 " 1
(I
1
i ,_., . 1
1 ^n
- 1
- 1
I i
1 1
I j
I 1
i |
1 1
1 • 1
1 1
i . . j
t 1
I i
1 ._, LJ^j
i .... i
1 1
i _j
1 1
1.__. . __j
1
_ i j
r i
• ,j
- r 1
i . ..... . ,_i
i 1
_ L ... , I
I I I I I I I I I I I I I I I I I I I I I
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Figure 28. Range of maximum ozone concentrations produced by each tested compound,
-------
1.0-
0.9-
0.8
0.7-
0.6
0.5
0.4
0.3
0.2
0.
0.0
X CH3SH
0 C2H5SH
A C3H6 (9-12-77)
E C3H6 (11-11-77)
10
HC/NOxrppMC/ppM
15
Figure 29. Maximum ozone concentrations produced at various
target initial HC/NOX ratios.
177
-------
l.0r-
0.9-
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
X CH3SCH3
O C2H5SCH3 (11-9-77)
& C2H5SC2H5
O (CH3S)2
O (C2H5S)2
X
10
, PPMC/PPM
15
20
Figure 3i).
Maximum ozone concentrations produced at various
target initial HC/NOX ratios.
178
-------
X Thiophene
O 2-Methylthiophene
& 3-Methylthiophene
Q 2,5-Dimethylthiophene
Figure 31. Maximum ozone concentrations produced at various
target initial HC/NOX ratios.
170
-------
contrasts with the organic sulfides and organic disulfides that exhibited
monotonic decreases in [03] as the target HC/NO ratio was increased from
max x
2 to 20. At each HC/NO ratio, methanethiol produced more ozone on 2 Septem-
A
ber than did ethanethiol on 3 October. The impact of seasonal differences
in the ambient temperature and sunlight profiles that occurred during the
1-month period that separated these experiments obscures the generality of
this finding. Same-day experiments conducted at higher but equivalent
target thiol concentrations (5 pptnC) on 26 August also suggest that methane-
thiol has a larger first-day ozone-generative potential than ethanethiol.
The shape of the ozone-surface curves for the thiols resembles those also
shown in Figure 29 for propene.
The relationship between the initial HC/NO ratio and the resulting
A
[03] is presented graphically in Figure 30 for the organic sulfides and
organic disulfides. As with the thiols, these compounds exhibit distinctive
shapes for their ozone surfaces. For the organic sulfides, the [031
max
decreases sharply with increasing initial HC/NO ratio. The curves for
A
methyl ethyl sulfide and ethyl sulfide are nearly coincident. Although the
[03] curve for methyl sulfide is nearly parallel to those for the other
sulfides, the photooxidation of methyl sulfide produces significantly more
ozone than any of the other tested organosulfur species. The increased
efficiency of ozone production for this compound in comparison to other
tested species of similar structure must await mechanistic and modeling
analyses.
As shown in Figure 31, the thiophenes exhibited maximum ozone production
at intermediate HC/NO ratios. Thiophene and 2-methylthiophene produced the
largest [03] at the target HC/NO ratio of 10, while 3-methylthiophene
HiaX X
and 2,5-dimethylthiophene produced the largest [03] values at the target
max
HC/NO ratio of 4. Among the thiophenes, 3-methylthiophene produced the
most ozone. The addition of a methyl group onto the heterocyclic thiophene
molecule modifies its reactivity as indicated by maximum ozone production.
In addition, these results suggest that reactivity is significantly enhanced
by the addition of a methyl group at the 3-position in comparison to adding
either one or two methyl groups at the 2-position.
A distinct seasonal effect is apparent from the replicate propene runs
(see Figure 29). The reduced temperature, sunlight intensity, and duration
180
-------
of sunshine between September 12 and November 11 reduced the [03] at each
(Dcix
HC/NO ratio. In addition, the effect was most pronounced at the lowest
HC/NO ratio. The duration of sunshine on each day was 718 and 624 minutes
or 95 and 100 percent of the total possible. Maximum temperatures were 25.6
and 13.3° C. Based on computer simulations of photochemical HC/NO systems
conducted by RTI, [031 has been found to be sensitive to both the tempera-
ture and sunlight profiles. The relative importance of each seasonal influ-
ence in this case has not been examined.
Ozone generation at the lowest HC/NO ratio for propene was the most
A
sensitive to seasonal influences. For these conditions, NO was in excess,
and the system was both light- and hydrocarbon-limited. For a fixed initial
hydrocarbon concentration, more time is required to oxidize the increased
amounts of NO to N02 at low initial HC/NO ratios than at higher ratios . As
a result, ozone production is delayed, and, if the duration of irradation is
limited, as it is in the diurnal cycle, then maximum ozone concentrations
are reduced as well. The intensity and duration of sunlight in November was
insufficient to generate significant ozone on the first day at the lowest
HC/NO ratio. If the day could have been lengthened, it is likely that the
[Oi] would have been considerably higher. On the second day of the
1 •* max
November experiments, the highest second-day [03] were generated at the
lowest initial HC/NO ratio. This also suggests that the low HC/NO ratio
system was light-limited.
Fate of Nitrogen Oxides
On the average, at the maximum N02 concentration, N02 accounted for 47
percent of the initial NO in the experiments conducted with the thiophenes.
In the experiments conducted with the thiols, organic sulfides, and organic
disulfides, this value was 60 percent. The corresponding value in the
propene-NO experiments was 73 percent. These results suggest that different
chemical species and reactions determine the fate of NO in these three
different chemical systems.
PAN data as determined by GC-EC were available for many of the experi-
ments conducted in the current study. In several cases, two additional
EC-responsive compounds were detected. These compounds have been tentatively
identified as methyl and ethyl nitrate (MN and EN) . The absolute concentra-
181
-------
tions of these species are questionable, and this uncertainty does not
permit a relative comparison of PAN, MN, and EN concentrations across the
tested compounds.
Methyl nitrate was detected as a reaction product for propene and for
the tested thiols, organic sulfides, and organic disulfides. Among the
experiments conducted with the thiophenes > MN was found in appreciable
amounts only for 2,5-dimethylthiophene. These findings are reasonable in
view of the chemical structure of the organics involved.
Ethyl nitrate was detected as a reaction product only in experiments
that involved C3H6, CH3SC2H5> C2H5SH, C2H5SC2H5, and (C2H5S)2. Appreciable
amounts of EN were not found in the experiments conducted with the thiophenes.
These findings are also reasonable in view of the chemical structure of the
organics involved.
In every case where EN was found, PAN was also found. In addition, PAN
was detected in appreciable amounts as a reaction product for the three
substituted thiophenes. Based on the chemical structure of H2S, COS, CS2,
CH3SH, CH3SCH3, and (CH3S)2, PAN is not expected as a reaction product of
these compounds. Available data permit the verification of this hypothesis
only for methylthiol and methyl disulfide.
The formation of PAN, MN, and EN as reaction products of the thiols,
organic sulfides, and organic disulfides can be rationalized if the photo-
oxidation of these species involves cleavage of S-C bond, which in the
presence of air and NO leads to their formation. The formation of PAN and
MN, but not EN, by the thiophenes provides clues that may elucidate the
chemistry of the thiophene-NO systems.
Inspection of the first-day NO data in the appendix revealed unusual
X
behavior in the experiments conducted with C3H6, CH3SC2H5, C2H5SH, C2H5SC2H5,
(C2H5S)2, and 3-methylthiophene. At the highest initial HC/NO ratios, the
A
NO concentrations exhibited a loss of 5 to 20 ppb and a subsequent recovery.
Examples of this behavior for experiments conducted with C3H$ and NO and
with (C2H5S)2 and NO are presented in Figures 32 and 33. Since the behavior
was observed in experiments conducted both with propene and with organo
sulfur compounds, the responsible product species does not necessarily
contain sulfur. In addition, this behavior was generally associated with
those reactants that contained an ethyl group in their structure, and the
182
-------
0.10
0.08 -
a.
0.06 -
o
. 0.04 -
OJ
o
5 0.02 -
0.00
i i i i
11 NOVEMBER 1977
0000
0.30
o 'o o
- 0.20
o
M
O
rn
- 0.10
0400
0800 1200
TIME (EST)
1600
2000
0.00
0000
Figure 32. Concentration-time profiles of selected reactants and products for the 11 November
1977 C3H6~NOX experiment conducted in RTI Chamber No. 1. Target initial conditions:
2.0 ppmC C3H6 and 0.1 ppm NOX. Symbol key: (o) 03; (Q) NO; (A) N025 (O) NOX; and
(V) PAN.
-------
oo
0.10 r-
0.08
Q_
Q_
0.06 -
X
o
. O.OH -
C\l
O
§ 0.02 -
0.00
7 OCTOBER 1977
0000
OHOO
0800 1200 1600
TIME (EST)
2000
0.30
0.20
o
ixl
O
z
m
*- 0.10
0.00
0000
Figure 33. Concentration-time profiles of selected reactants and products for the 7 October
1977 (C2H5S>2-NOX experiment conducted in RTI Chamber No. 2. Target initial con-
ditions: 2.0 ppmC (C2H5S)2 and 0.1 ppm NOX. Symbol key: (o) 03; (O) NO; (A) N02;
(O) NOX; and (V) PAN.
-------
timing of this phenomenon coincided with the initial accumulation of PAN.
This behavior was not observed at the low initial HC/NO ratios, although it
X
may have been obscured by the higher NO concentrations employed in these
A
experiments. It is likely that a transient nitrogen-containing species was
responsible for this behavior. This species was either not delivered to the
NO analyzer as a result of interactions with chamber walls or the sampling
system or it could not be detected by the chemiluminescent NO analyzer that
A
was employed. Although the identity of this hypothetical species is. unknown,
such species as pernitric acid and its organic analogues may have been
involved.
A nitrogen mass balance was estimated for each experiment based on
chemiluminescent NO concentrations determined initially and again during
the 1700 EST hour of the first day. For each tested compound, the range of
these nitrogen balances is presented in Figure 34. The best nitrogen balances
occurred in the experiments conducted with H^S. Since the fraction of
accountable NO exceeded unity in this case, interferences by I^S or reaction
A
products may have been responsible. The nitrogen balances, also approached
unity in the experiments conducted with COS. In this case the nitrogen
balances were not sensitive to initial conditions, as indicated by the small
range. The poorest nitrogen balances occurred for the experiments conducted
with methanethiol, methyl sulfide, and methyl disulfide. Generally less
than 15 percent of the initially present NO could be accounted for in these
A
cases. In addition to being nearly identical, these nitrogen balances were
insensitive to initial conditions . For the experiments conducted with
methyl ethyl sulfide, ethane thiol, ethyl sulfide, and ethyl disulfide, the
nitrogen balances again were relatively insensitive to initial conditions
and were similar, with approximately 20 to 45 percent of the initially
present NO accountable at the 1700 EST hour of the first day. For the
thiophenes, the nitrogen balances -differed widely depending on the molecular
structure. These balances became decreasingly sensitive to initial conditions
with the substitution of methyl groups on to the thiophene molecule. The
range of nitrogen balances for carbon disulfide was similar to those for
propene. In these cases, the nitrogen balances were very sensitive to
initial conditions and ranged from 25 to 75 percent. It is interesting to
note that no seasonal influences on the ranges of nitrogen balances were
exhibited in either the C3H6-NO experiments or the CH3SC2H5-NO experiments.
* X
185
-------
00
°3n6 v *-•<•*-"/
f* oH £ S 1 1 _ 1 1 7 7 \
p u * / 1 1 1 "l_77\
**3B6 ^ Ai— IJ—//^
u.c (a_2i«77\
COS (9-18-77)
/*e _ / Q 01 7 7 \
CHjSn (9-2-77)
LM^aLH^ \y—£.a—ll)
CH3SSCH3 (10-5-77)
IsH^M^Hc iAO-lU-"//)
LH2^*-2"5 viA— ^1— / /^
02115811 (10-3-77)
C2H5SC2Hj (10—15-77)
2"5 **^*2 5 \*^"'"'*/
ihiopnene (10-17-7/)
2-Methylthiophene (10-30-77)
3-Methylthiophene (10-22-77)
2,5-Dimethylthiophene (10-20-77)
r —i
I i
i ~i
L , ,.J
r — 1
L. , I
1 1
H
t __i
i i
L_ _|
1 1
I 1
1 1
1 . ., J
f 1
I I
1 1
L __l
r — 1
L i
r 1
l .,, i
r 1
i,.,,. , ..i
I I
i J
r 1
i .. ... ,. _. . i
r 1
1 1
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 | 1 l l 1 1 | 1 1 1 1 1 1 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4
fNOx & 1700
Figure 34. Range of fractions of initially present NOX that could be accounted for at the 1700 EST
hour of the first day.
-------
The unaccountable product nitrogen may be nitric acid, or other undeter-
mined nitrogen-containing species. These nitrogen species were presumably
deposited on the chamber walls. The extent to which this deposition is
reversible is currently undefined. Interaction of these species between the
chamber walls and the gas phase may contribute to unusual second-day NO
A
behavior. In the experiments conducted at the target HC/NO ratio of 20,
the lowest initial NO concentration, the second-day N02 concentration
increased by 10±5 ppb. This increase occurred between the 0500 and 1200 EST
hours (±2.5 hours). The magnitude of the second-day increases in N02 concen-
tration was examined for associations with duration of sunshine and with
daily maximum temperatures for 23 cases. No associations were found.
Although second-day increases of NO concentrations have been noted for
other chemical systems, they are unexpected and cannot be explained at this
time. The fate of NO in photochemically reacting systems is largely unknown.
A
Disappearance Rate of the Test Species
Estimates were made of the times at which approximately one-half of the
originally present test compound had been consumed. Each estimate was based
on a measured or assumed initial concentration and the time, interpolated
from the data in the appendix, where the concentration had fallen to one-half
of its original value. For each test compound the range of hours of irradia-
tion past sunrise required to consume one-half of the initially present
compound is presented in Figure 35.
If the time to one-half consumption is a rough indicator of disappear-
ance rate, then Figure 35 suggests that many of the tested compounds were
consumed rapidly during these experiments. The available data did not
permit precise estimates for H2S, COS, and CS^', however, they do suggest
that more than one day of irradiation was required to achieve one-half
consumption of each of these compounds. In addition, it is likely that COS
was the least reactive and most stable test species under the experimental
conditions employed in the current study. The thiols and organic sulfides
had similar ranges of disappearance rates. Among all the tested compounds,
the organic disulfides displayed the fastest disappearance rates. As noted
earlier, the fastest conversion of NO to N02 also occurred in the experiments
187
-------
00
30
C3H6 (9-12-77)
(11-11-77)
(11-13-77)
(9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3Sli (9-2-77)
CU3SCH3 (9-28-77)
CU3SSCH3 (10-5-77)
CH3SC2HS (10-10-77)
CH3SC2H5 (11-9-77)
C2H5SH (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2H5 (10-7-77)
Thlophene (10-17-77)
2-Methylthiophene (10-JO-77)
3-Methylthiophene (10-22-77)
2,5-Dlmethylthiophene (10-20-77)
1 I I I I I I I
I I I | I i I I
i i
456
[Test Species]
10
11
12
hr
Figure 35. Range of the hours of irradiation past sunrise required on the first day to
consume one-half of the initially present test compound; * indicates that for
the experimental conditions employed more than one day of irradiation was
required to achieve one-half consumption.
-------
conducted with these two compounds. Among the thiophenes, 3-methylthiophene
displayed the fastest disappearance rates. For 3-methylthiophene and 2-methyl-
thiophene, the disappearance rates were insensitive to initial conditions.
This contrasts with the behavior of thiophene and 2,5-dimethylthiophene,
which displayed large ranges of disappearance rates. Thiophene itself
displayed the slowest disappearance rates among the tested thiophenes. A
seasonal influence was exhibited in the C3H6-NO experiments: the propene
disappearance rates were slightly slower and more sensitive to initial
conditions in November than in September. However, no significant seasonal
influence on methyl ethyl sulfide disappearance rates was apparent for the
replicate CH3SC2H5-NO experiments conducted 1 month apart.
Gaseous Reaction Products: S02 and COS
Sulfur dioxide was found as a reaction product in at least one of the
experiments conducted with mixtures of NO and each tested sulfur-containing
compound except COS, where S02 data were not available. Since the target
initial concentrations of the sulfur compounds were equivalent on a carbon
basis but not on a sulfur basis, the measured maximum S02 concentrations
were normalized to the equivalent of an initial concentration of 1 ppraS.
The initial concentrations used were identical to the measured and assumed
concentrations used earlier in the determination of the times to one-half
consumption of the test compound. For each test compound, the range of
normalized maximum S02 concentrations found on the first day of the experi-
ment is presented in Figure 36.
The largest normalized maximum S02 concentrations were produced by the
CHsSH-NO system. Methanethiol, methyl disufide, ethyl disulfide, 3-methyl-
thiophene, and 2,5-dimethylthiophene exhibited large S02 production potentials.
Maximum normalized S02 concentrations in excess of 0.25 ppm were produced in
the experiments conducted with these compounds. Methyl disulfide and ethyl
disulfide produced similar ranges of [802] . la addition, they were
UlaX
previously indicated to have been highly reactive by their short times both
to one-half consumption and to NO-N02 crossover. Methyl sulfide, methyl
ethyl sulfide, and ethyl sulfide produced low but similar normalized concen-
trations of S02. Based on these apparent associations between molecular
structure and S02 production, the large difference in S02 production by
189
-------
10
o
(9-12-77)
(11-11-77)
(11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
01388013 (10-5-77)
CH3SC2HS (10-10-77)
(11-9-77)
(10-3-77)
(10-15-77)
(10-7-77)
Thiophene (10-17-77)
2-Hethylthiophene (10-30-77)
3-Methylthlophene (10-22-77)
2,5-Dlmethylthiophene (10-20-77)
- I
I I I I i I i I I ' I i I I I—I 1 1—I 1—I
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
[S02]max, ppmS
Figure 36. Range of maximum sulfur dioxide concentrations normalized to the
equivalent of an initial concentration of 1 ppmS for each test com-
pound; * indicates missing data.
-------
methanethiol and ethanethiol was unexpected. Among the thiophenes, 2,5-di-
methylthiophene and 3-methylthiophene produced significantly more S02 than
tbiophene or 2-raethylthiophene. In addition, based on the ranges of [802]
values, S02 production by 2,5-dimethylthiophene was highly sensitive to
initial conditions. The normalized S02 maxima generated by the CH3SC2H5-NO
A
system on 10 October exceeded the trace quantities detected on 9 November.
These differences suggest but are not sufficiently large to be conclusively
indicative of seasonal effects.
In addition to sulfur dioxide, carbonyl sulfide was observed in many
cases as a reaction product. It was observed as the major product in the
experiments conducted with the CS2-NO system, where first-day maximum
concentrations ranged from 0.24 to 0.76 ppmS. Small peaks were detected by
the sulfur analyzer in the experiments conducted with methyl sulfide, methyl
ethyl sulfide, methyl disulfide, ethanethiol, ethyl disulfide, and each of
the thiophenes. These peaks had retention times similar to that for COS and
thus have been tentatively identified as COS. Although the peak heights
were observed to increase during the day, they were not sufficiently large
to permit quantification. These findings indicate that COS was a minor
reaction product for at least nine of the tested sulfur-containing compounds.
Particulate Sulfur and Its Distribution as a Reaction Product
Particulate sulfur was found as a reaction product in at least one of
the experiments conducted with mixtures of NO and each of the tested sulfur-
containing compounds. Since the target initial concentrations of the sulfur
compounds were equivalent on a carbon basis but not on a sulfur basis, the
measured maximum TPS concentrations were normalized to the equivalent of an
initial concentration of 1 ppmS. The initial concentrations used were
identical to the measured and assumed concentrations used earlier in the
normalization of maximum S02 concentrations. For each test compound, the
range of normalized maximum TPS concentrations found on the first day of the
experiment is presented in Figure 37.
The largest normalized particulate sulfur concentrations were produced
by the CH3SH-NO system. Both methanethiol and methyl disulfide exhibited
relatively large particulate sulfur production potentials. Maximum normal-
ized TPS concentrations exceeded 0.15 ppmS in at least one of the experiments
191
-------
<£>
C3H6 (9-12-77)
C3H6 (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
CH3SSCH3 (10-5-77)
CH3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2U5SH (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2U5 (10-7-77)
Thiophene (10-17-77)
2-Methylthiophene (10-30-77)
3-Methylthiophene (10-22-77)
2,5 Dimethylthiophene (10-20-77)
- I
- H
- H
H
J I I I I I I I I I l_J I I I I I I I I I
tr
0.1
0.2 0.3
, PP»»S
0.4
0.5
Figure 37. Range of maximum total particulate sulfur concentrations normalized
to the equivalent of an initial concentration of 1 ppmS for each
test compound.
-------
conducted with these compounds. In addition, based on the ranges of maximum
[TPS] values, particulate sulfur production by methanethiol and methyl disulfide
was highly sensitive to initial conditions. Methyl sulfide, methyl ethyl
sulfide, ethanethiol, ethyl sulfide, ethyl disulfide, and 3-methylthiophene
exhibited moderate particulate sulfur production potentials. Maximum [TPS]
fell between 0.05 and 0.10 ppraS for at least one of the experiments conducted
with each of these compounds. The three remaining thiophenes generated
small [TPS] maxima, which ranged between trace amounts and 0.05 ppmS. The
smallest amounts of particulate sulfur were produced by hydrogen sulfide,
carbonyl sulfide, and carbon disulfide. Only trace amounts of particulate
sulfur were detected in the experiments conducted with these compounds.
Seasonal influences were manifest in the [TPS] maxima of the two sets of
CjI3SC2Hs-NO experiments conducted approximately 1 month apart. Significantly
higher maximum [TPS] values were found on 10 October than on 9 November. This
is somewhat unexpected, since significant seasonal differences were not
apparent in times to N0-N02 crossover, nitrogen balances at 1700 EST, disap-
pearance rates of the test species, and maximum ozone concentrations. This
suggests that the photochemical generation of particulate sulfur by compounds
such as those tested in the current study is more sensitive to seasonal
environmental factors such as solar radiation than are the gas-phase processes
that lead to ozone production.
The times of occurrence of maximum sulfur dioxide and particulate
sulfur concentrations were examined. Since S02 concentrations were monitored
once an hour, whereas, TPS data were collected once every 2 or 3 hours, the
time scales were not entirely compatible for such comparisons. Despite this
shortcoming, maximum TPS concentrations preceded maximum S02 concentrations
in many cases. In the experiments conducted with H2S, COS, and CS2, either
missing or low concentration data prevented meaningful comparisons. In at
least one of the experiments conducted with each of the remaining test
species, however, maximum TPS concentrations either preceded or were coinci-
dent with maximum S02 concentrations. This finding suggests.points for
additional investigation.
The particulate sulfur may be hypothesized to exist as sulfate.
Alternatively, since its identity is unknown, it is conceivable
that the particulate sulfur could exist as an organic-sulfur
complex. Efforts should be directed at speciation of particulate
sulfur.
193
-------
The oxidation of most of the tested sulfur species may be hypothe-
sized to first yield S02 with subsequent generation of particulate
sulfur, presumably as sulfate. The near coincident timing of
[TPS] and [SC^] maxima does not support this hypothesis.
Alternate pathways or particulate sulfur formation that do not
require S02 as an intermediate should be examined.
Irradiated mixtures of S02, hydrocarbons, and nitrogen oxides are
known to yield particulate sulfur as an oxidation product. The
chemical behavior of such systems should be compared to that of
systems which include one or more of the test species from the
current study, in addition to hydrocarbons and nitrogen oxides.
Findings from such an investigation may elucidate further the
particulate sulfur formation mechanism.
The ratio of product sulfur as particulate to the total accountable
reacted sulfur ([TPS] plus [SC^]) was determined for many of the tested
compounds. This ratio, R, was calculated based on data collected during or
interpolated for the hour of occurrence of the maximum S02 concentration.
It permits an assessment of the distribution of accountable product sulfur
between the gas and particulate phases. For each compound, where available
data permit, the range of first-day R values is presented in Figure 38.
Generally, these data indicate that the majority of the accountable
product sulfur for the tested species existed as S02 and that less than 20
percent of accountable product sulfur existed in the particulate phase.
Ratios in excess of 0.2 occurred for methanethiol, methyl sulfide, methyl
disulfide, and methyl ethyl sulfide. The relatively high R values for
methanethiol and methyl disulfide are associated with the large particulate
sulfur production potential exhibited by these compounds and noted previously
(see Figure 37). Based on the large range of R values of the experiments
conducted with methanethiol, the distribution of product sulfur between the
gas and particulate phases was highly sensitive to initial conditions for
this species. Data were available to permit the determination of R values
in only two of the four experiments conducted with methyl sulfide and in two
of the eight experiments conducted with methyl ethyl sulfide. These cases,
however, represent the highest R values found among all the compounds tested.
Although the high R values appear to be associated with the presence of the
methyl-sulfur grouping in the test species, the factors responsible for this
behavior remain to be defined.
194
-------
VO
en
C3H6 (9-12-77)
C3H6 (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
CH3SSCH3 (10-5-77)
CH3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2h5SU (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2H5 (10-7-77)
Thlophene (10-17-77)
2-Methylthiophene (10-30-77) ,
3-Mechylthiophene (10-22-77)
2,5-Dimethylthiophene (10-20-77)
- H
H
H
h M
j i
i i i
o
0.1 0.2 O.J 0.4
0.5
R
0.6 0.7 0.8 0.9
1.0
Figure 38. Range of R values (ratio of product sulfur as particulate to the total accountable
reacted sulfur) for each test species; * indicates that missing data prevented the
determination of R in one or more cases.
-------
Losses of particulate sulfur to the chamber walls affect the particulate
sulfur concentration and parameters that are based on the particulate sulfur
concentrations. The measured [IPS] values are the net result of production
IDdX
and removal processes. Presumably, the production processes are photochemi-
cal, whereas the major removal process is deposition on the chamber walls.
Wall losses of particulate sulfur are significant in the current study.
Particulate sulfur decay constants were determined for those cases where two
or more [TPS] data were available on the first day during the period between
max
the time of occurence of the maximum [TPS] and of sunset. TPS half-lives
Ola A
ranged from 1.7 to 7.3 hours with a mean of 3;4 hours. Such variables as
temperature, sunlight, humidity, and particle size distribution are expected
to influence the TPS half-lives. The role of these factors and their impact
on particulate losses remain to be defined. Thus, the seasonal differences
noted above in the experiments conducted with methyl ethyl sulfide as well
as the relative ranking of the ranges of [TPS] shown in Figure 37 were
nicix
influenced to an unknown extent by particulate sulfur losses to the chamber
walls. These results should be interpreted with some caution.
Nighttime Ozone Decay
The behavior of mixtures of ozone and purified air in the RTI smog
chambers has been examined under irradiation and in the dark using initial
ozone concentrations ranging between 0.4 and 1.0 ppm. The results indicate
that dark phase ozone decay in the RTI chambers is approximately first
order. First order behavior has not been established at initial concentra-
tions below 0.4 ppm, although it seems reasonable to expect this behavior at
lower concentrations. Ozone decay was discussed in an earlier s.ection on
chamber characterization, and test results summarized in Table 6 indicate
that dark phase ozone half-lives in the RTI chambers ranged from 24 to 122
hours.
Previous experiments conducted in our laboratory have indicated that
ozone is relatively stable in the presence of methanethiol, methyl sulfide,
or methyl disulfide.42 Dark-phase ozone half-lives exceeded 50 hours in
the presence of approximately 5 ppmV of each of these compounds. It may be
reasonable to expect similar behavior for methyl ethyl sulfide, ethanethiol,
ethyl sulfide, and ethyl disulfide. Although ozone has been shown to be
196
-------
more reactive with thiophene than methanethiol, methyl sulfide, or methyl
disulfide, the shortest dark-phase ozone half-life in the presence of thio-
phene (at 4.3 ppmV) was found to be 15 hours. Thus, mixtures of ozone and
any of the tested thiophenes might be expected to exhibit shorter ozone
half-lives than mixtures of ozone and the tested alkyl-sulfur species. In
addition, carbon disulfide is known to react with ozone; however, it is
difficult to extrapolate these findings to the experimental conditions employed
in the current study.43 44
In many of the two-day experiments performed in the current study,
ozone was a reaction product. To infer the presence of ozone-reactive
product species, dark-phase ozone half-lives were determined for the night-
time period between 2000 EST on the first day and 0400 EST on the second
day. The ozone half-life for the experiment that produced the largest
first-day [03] is represented in Figure 39 for each of the tested compounds.
IDdX
The half-lives in Figure 39 fall into three general categories. The
experiments conducted with propene exhibited the longest half-lives, ranging
from 25 to 40 hours. These values are not significantly different from
those measured in the presence of purified air. Half-lives ranging from 9
to 18 hours were observed in experiments conducted with carbon disulfide,
methanethiol, methyl sulfide, methyl disulfide, methyl ethyl sulfide, ethane-
thiol, ethyl sulfide, and ethyl disulfide. Relatively short half-lives
occurred in the experiments conducted with the thiophenes. These values
ranged from 3.6 to 6.6 hours.
In many cases, by the 2000 EST hour on the first day of the experiment,
the initial reactant had been essentially consumed. This was the case for
the experiments conducted with propene, methanethiol, methyl sulfide, methyl
disulfide, methyl ethyl sulfide, ethanethiol, ethyl sulfide, and ethyl
disulfide. Thus, even if these species were reactive with ozone (as is
propene, for example), they did not exist at sufficient concentration levels
to act as ozone-destructive agents. Thus, these results suggest the possible
presence of undefined ozone-reactive reaction products in the experiments
conducted with methanethiol, methyl sulfide, methyl disulfide, methyl ethyl
sulfide, ethanethiol, ethyl sulfide, and ethyl disulfide.
Although CS2 concentration data were not available, if the target
initial concentration was achieved and if its reaction produced COS with a
197
-------
C3H6 (9-12-77)
C3Hfc (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
CH3SSCH3 (10-5-77)
CH3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2H5SH (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2H5 (10-7-77)
Thiophene (10-17-77)
2-Methylthiophene (10-30-77)
3-Methylthiophene (10-22-77)
2,5-Dimethylthiophene (10-20-77)
I I I I I 1
I I 1 I 1
12
16
20
"3 t
24
2, hr
28
32
36
44
Figure 39. Ozone half-life for the experiment that produced the largest first-day
maximum ozone concentration with each tested compound.
-------
yield of unity, then at 2000 EST approximately 1.6 ppraV of CS2 remained
uareacted. Since ozone is known to react with CS2, the moderate ozone
half-life in the experiment conducted with CS2 (17 hours) may have resulted
from the reaction of ozone with previously unreacted CS2- The lack of
information on the rate of the 03-CS2 reaction for the experimental condi-
tions employed prevents confirmation of this hypothesis; however, it does
not prevent speculation on the presence of ozone-reactive products.
For the conditions under consideration in this analysis, significant
amounts of the thiophenes remained unreacted at the 2000 EST hour. If the
ozone-thiophene reaction rate discussed previously is representative of
ozone destruction by reaction with each of the tested thiophenes, then the
concentrations of these species were too low to account for the short ozone
half-lives that were observed. The largest ozone maxima for three of the
tested thiophenes were low. Among all the tested compounds only those
experiments conducted with thiophene, 2-methylthiophene, and 2,5-dimethyl-
thiophene failed to generate at least one [03] .value in excess of 0.3
max
ppra. As the ozone concentration is reduced, it becomes a sensitive indicator
of destructive agents. Since first-order ozone decay has not been verified
to occur at concentrations below 0.4 ppm in the RTI chambers, wall effects
or other factors may have influenced ozone behavior at low concentrations.
The available data do not permit resolution of the importance of ozone
destruction by residual reactants or of wall-related factors at low ozone
concentrations on the short ozone half-lives observed during the thiophene
experiments. The results do suggest the formation of undefined ozone-reactive
reaction products in the experiments conducted with the thiophenes.
Net Ozone Generation on the Second Day
The accumulation of ozone in smog chambers is the net result of synthe-
sis and destructive processes. Ozone is synthesized by photochemical proces-
ses. At night .in the absence of sunlight, ozone-destructive processes
prevail. During the night following the first day of an experiment, the
ozone concentration declines as the ozone that was generated during the
previous daylight period is destroyed by homogenous reactions with various
reactants and products and by heterogeneous interactions with the chamber
walls. On the morning of the second day, ozone synthesis begins with the
199
-------
reintroduction of sunlight to the system. When the ozone synthesis rate
begins to exceed the destruction rate, the concentration profile passes
through a minimum and the ozone concentration increases. In the current
investigation, the difference between this minimum and the maximum concentra-
tion that accumulates on the second day is known as the net ozone concentra-
tion. The second-day net ozone concentration presumably reflects the ozone
production potential of a chemical system after one diurnal cycle. For many
of the tested compounds, the ranges of second-day net ozone concentrations
are presented in Figure 40. Data were not presented in cases where the
-2
second-day CU-SR was less than 200 cal cm . In addition, those compounds
were identified wherein the second-day net ozone concentration exceeded the
first-day maximum ozone concentration in at least one of the four experiments,
The largest second-day net ozone concentration was produced in an
experiment conducted with methanethiol. Net ozone concentrations exceeding
0.2 ppm accumulated in at least one experiment conducted with propene, with
carbon disulfide, with methanethiol, with ethanethiol, and with 2,5-dimethyl-
thiophene. Based on the relatively large ranges of net ozone concentrations
for these species, second-day ozone production by these compounds was highly
sensitive to the (first-day) initial conditions. In contrast, essentially
no ozone accumulated on the second day of experiments conducted with H2S and
with COS.
A seasonal effect on net ozone production was apparent in the results
of the propene-NO experiments. Net ozone production was significantly
A
higher in the September experiments than in the November experiments. In
addition, the second-day net ozone concentration exceeded the first-day
maximum in at least one experiment conducted with propene, with carbonylsul-
fide, with carbon disulfide, with each thiol, and with each thiophene.
These findings are discussed in more detail in the earlier sections that
address the chemical behavior of each tested compound.
200
-------
C3H6 (9-12-77)
C3H6 (11-11-77)
C3H6 (11-13-77)
H2S (9-23-77)
COS (9-18-77)
CS2 (9-21-77)
CH3SH (9-2-77)
CH3SCH3 (9-28-77)
CH3SSCH3 (10-5-77)
CU3SC2H5 (10-10-77)
CH3SC2H5 (11-9-77)
C2H5SH (10-3-77)
C2H5SC2H5 (10-15-77)
C2H5SSC2H5 (10-7-77)
- H
Thlophene (10-17-77)
2-Methylthiophene (10-30-77)
3-Methylthiophene (10-22-77)
2,5-Dimethylthlophene (10-20-77) + -
I i
I i
i i i i i i i i
0.1
0.2 0.3
0.4 0.5 0.6
A03, ppm
0.7 0.8 0.9 1.0
Figure 40.
Range of second-day net ozone concentrations produced by each tested
compound. (* indicates that the second-day CU-SR was less than 200
cal cm"2; and + indicates that in at least one case the second-day
net ozone concentration exceeded the first-day maximum ozone concen-
tration) .
-------
REFERENCES
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1977. Literature Survey of Emissions Associated With Emerging Energy
Technologies. Environmental Protection Agency Publication No. EPA 600/
7-77-104.
2. Khang, S. J., and Levenspiel, 0., 1976. The Mixing Rate Number for
Agitator-Stirred Tanks. Chemical Engineering, October 11, p. 141.
3. Sickles, J. E., II, Ripperton, L. A., Eaton, W. C. , and Wright, R. S.,
1979. Oxidant-Precursor Relationships Under Pollutant Transport Condi-
tions: Outdoor Smog Chamber Study Volume 1. Environmental Protection
Agency Publication No.sEPA-600/3-79-078a.
4. Jeffries, H., Fox, D., and Kamens, R., 1975. Outdoor Smog Chamber
Studies: Effect of Hydrocarbon Reduction on Nitrogen Dioxide. Envir-
onmental Protection Agency Publication No. EPA-650/3-75-011.
5. Butcher, S. S., and Ruff, R. E., 1971. Effect of Inlet Residence Time
on Analysis of Atmospheric Nitrogen Oxides and Ozone. Analytical
Chemistry, 43: No. 13, p. 1890.
6. Sickles, J. E., II, 1976. Ozone-Precursor Relationships of Nitrogen
Dioxide, Isopentane and Sunlight Under Selected Conditions. Doctoral
Dissertation. Department of Environmental Sciences and Engineering,
University of North Carolina, Chapel Hill, North Carolina.
7. Bufalini, J. J., Kopczynski, S. L., and Dodge, M. C., 1972. Contaminat-
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8. Bufalini, J. J., Walter, T. A., and Bufalini, M., 1977. Contamination
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9. Decker, C. E., Sickles, J. E., II, Bach, W. D., Vukovich, F. M., and
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10. Jones, A. C., and Mindrup, R. F., Jr., 1976. Regional Air Pollution
Study: Gas Chromatograph Laboratory Operations. Environmental Protec-
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11. Seila, R. L., Lonneman, W. A., and Meeks, S. A., 1976. Evaluation of
Polyvinyl Fluoride as a Container Material for Air Pollution Samples.
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202
-------
12. Dimitriades, B., 1967. Methodology in Air Pollution Studies Using
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13. Scofield, F., Levy, A., and Miller, S. E., 1969. I. Design and Valida-
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14. Grasley, M. H., Appel, B. R., Burstain, I. G., Laity, J. L. , and Richards,
H. F., 1969. The Relationship of Smog Chamber Methodology to Hydrocar-
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Organic Coating and Plastics Chemistry, 29, p. 422.
15. Powers, T. R., 1977. Effect of Hydrocarbon Composition on Oxidant-
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No. EPA-600/3-77-109a.
16. Doyle, G. J., 1970. Design of a Facility (Smog Chamber) for Studying
Photochemical Reactions Under Simulated Tropospheric Conditions.
Environmental Science and Technology, 4: No. 11, p. 907.
17. O'Brien, R. J., 1974. Photostationary State in Photochemical Smog
Studies. Environmental Science and Technology, 8: No. 6, p. 579.
18. Pitts, J. N., Jr., Darnall, K. R., Winer, A. M., and McAfee, J. M.,
1977. Mechanisms of Photochemical Reactions in Urban Air: Volume II.
Chamber Studies. Environmental Protection Agency Publication No.
EPA-600/3-77-Ol4b.
19. Bufalini, J. J., and Altshuller, A. P., 1965. Kinetics of Vapor Phase
Hydrocarbon-Ozone Reactions. Canadian Journal of Chemistry, 43, p.
2243.
20. Jaffe, R. J., Smith, F. C., Jr., and Last, K. W. , 1974. Study of
Factors Affecting Reactions in Environmental Chambers: Final Report on
Phase II. Environmental Protection Agency Publication No. EPA-650/3-74-
004a.
21. Heuss, J. M., February 10-12, 1975. Smog Chamber Simulation of the Los
Angeles Atmosphere. A paper presented at the Environmental Protection
Agency Scientific Seminar on Automotive Pollutants, Washington, D.C.
22. McNeils, D. N., 1974. Aerosol Formation from Gas-Phase Reactions of
Ozone and Olefin in the Presence of Sulfur Dioxide. Environmental
Protection Agency Publication No. EPA-650/4-74-034.
23. Kuhlman, M. R., 1974. The Ambient Aerosol Research Facility: Design
Criteria and Validation. Master's Thesis. Department of Environmental
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203
-------
24. Hampson, R. F., Jr., and Garvin, D., Eds., 1975. Chemical Kinetics and
Photochemical Data for Modeling Atmospheric Chemistry. NBS Technical
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25. Cox, R. A., and Penkett, S. A., 1972. Effect of Relative Humidity on
the Disappearance of Ozone and Sulphur Dioxide in Contained Systems.
Atmospheric Environment, 6, p. 365.
26. Spedding, D. J., 1969. Uptake of Sulphur Dioxide by Barley Leaves at
Low Sulfur Dioxide Concentrations. Nature, 224, p. 1229.
27. Wright, R. S., Sickles, J. E., II, Kamens, R. M., Jeffries, H. E., and
Eaton, W. C., 1978. Comparison Between Two Outdoor Smog Chambers:
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28: No. 3, p. 248.
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Rubber Publishing Company, Cleveland, Ohio.
29. Local Climatological Data: National Weather Service Forecast Office,
Raleigh-Durham Airport. U.S. Department of Commerce, National Climatic
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30. Federal Register, 1976. Measurement of Photochemical Oxidants in the
Atmosphere. 4].: No. 195, p. 44049.
31. Winer, A. M., Peters, J. W., Smith, J. P., and Pitts, J. N., Jr., 1974.
Response of Commercial Chemiluminescent No-N02 Analyzers to Other
Nitrogen-Containing Compounds. Environmental Science and Technology
8: No. 13, p. 1118.
32. Joseph, D. W., and Spicer, G. W., 1978. Chemiluminescence Method for
Atmospheric Monitoring of Nitric Acid and Nitrogen Oxides. Analytical
Chemistry, 50: No. 9, p. 1400.
33. Kummer, W. A., Pitts, J. N., Jr., and Steer, R. P., 1971. Chemilumines-
cent Reactions of Ozone with Olefins and Sulfides. Environmental Science
and Technology. 5: No. 10, p. 1045.
34. Akimoto, H., Finlayson, B. J., and Pitts, J. N., Jr., 1971. Chemilumi-
nescent Reactions of Ozone with Hydrogen Sulfide, Methyl Mercaptan,
Dimethyl Sulfide, and Sulfur Monoxide. Chemical Physics Letters. 12:
No. 1, p. 199.
35. Becker, K. H., Inocencio, M. A., and Schurath, U., 1975. The Reaction
of Ozone with Hydrogen Sulfide and Its Organic Derivatives. Interna-
tional Journal of Chemical Kinetics, Symposium Series, 1^, p. 205.
36. Toby, S., Toby, F. S., and Kaduk, B., 1978. Chemiluminescence in
Reactions of Ozone in 12th Informal Conference on Photochemistry.
National Bureau of Standards Publication No. 526, pp. 21-23.
204
-------
37. Gay, B. W., Jr., Noonan, R. C., Bufalini, J. J., and Hanst, P. L.,
1976. Photochemical Synthesis of Peroxyacyl Nitrates in Gas Phase via
Chlorine-Aldehyde Reaction. Environmental Science and Technology, 10:
No. 1, p. 82.
38. Jaklevic, J. M., Gatti, R. C., Goulding, F. S., Loo, B. W., and Thompson,
A. , 1978. Automated Elemental Analysis Using Energy Dispersive X-ray
Fluorescence Analysis in Proceedings of Fourth Joint Conference on
Sensing of Environmental Pollutants. American Chemical Society, pp.
697-702.
39. Sickles, J. E., II, Ripperton, L. A., Eaton, W. C., and Wright, R. S.,
1978. Atmospheric Chemistry of Potential Emissions from Fuel Conversion
Facilities: A Smog Chamber Study. Environmental Protection Agency
Publication No. EPA-600/7-78-029.
40. Wood, W. P., and Heicklen, J., 1971. The Photooxidation of Carbon
Disulfide. Journal of Physical Chemistry, 75: -No. 7, p. 854.
41. Zhuravlev, I. E., Zhitnev, Yu. N., Popovich, M. P., Kashnikov, G. N.,
and Filippov, Y. V., 1975. Inhibition of the Reaction of Carbon Disul-
fide with Ozone in the Gaseous Phase. Moscow University Vestnik Seriia
Khimiia, 16: No. 6, p. 19.
205
-------
APPENDIX
DETAILED DATA SHEETS FOR SMOG CHAMBER EXPERIMENTS
206
-------
NOTES
1.
2.
3.
4.
5.
6.
Data sheets are listed in chronological order; see Table 3 in the text
for a summary of the experimental program.
Except where noted otherwise, the target initial concentration of the
tested compound was 2.0 ppraC.
Blank spaces indicate that data are not available.
Measured zero values and negative outputs (resulting from instrumental
zero drift) are designated as 0.0.
Values measured to be greater than zero, but less than 0.001 measurement
units are indicated by 0.000.
For the total sulfur and SQz data: concentrations too small to be quan-
tified are listed as 0.010; and those concentrations that exceed the
linear range of the instrument are designated as 1.500.
7. Key:
SAROAD No.
44201
42601
42602
42603
44301
43205
42269
42402
42404
42403
43901
42401
12169
31114
62100
63301
63300
Name
Units
Ozone
NO
N©2
NO
PAN
Prop
T-Sul
H2S
COS
CS2
CH3SH
S02
T-P-S
CN-5
Temp
SR
CU-SR
ppm
ppm
ppm
ppm
ppm
ppraV
ppmS
ppraS
ppraS
ppmS
ppmS
ppmS
pg/m3
K-CN/CM3*
°Celsius
L/Mint
Langt
Description
Ozone
Nitric oxide
Nitrogen dioxide
Total nitrogen oxides
Peroxyacetyl nitrate
Propene
Total sulfur
Hydrogen sulfide
Carbonyl sulfide
Carbon disulfide
Me thane thiol
Sulfur dioxide
Total particulate sulfur
Condensation nuclei (PDP=5)
Hourly average ambient temperature
Total solar radiation
Cumulative total solar radiation
*To be read "Thousand condensation nuclei per cubic centimeter."
tL = Lang = Langley = CAL/CM2
207
-------
CHAMBEH NO. 1
OA» 1, 6-26-77
RUN 23 I c
55 i SUNSHlNt.
KII SMOG CHAMbCH SIUUY
UStPA CONTRACT NO. 60-02.-24i7
ro
o
oo
TIMt
(CST)
0.13
2.' 80
5.80
0.13
7.80
8.13
8.80
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
OZONt
(PPM)
0.008
0.0
0.0
0.0
• 0.0
0.0
0.0
0.003
0.025
0.5/2
0.641
0.586
0.526
0.4/3
0.431
0.394
0.361
0.335
0.312
0.291
0.273
0.258
0.241
a/ Tdtuel initial
IIMt
(ESF)
0.13
1.13
2.13
3.13
4.13
5.13
6.13
7.13
8.13
9.13
10.13
11.13
12.13
13.13
H.I3
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
02 UUt
(PPM)
0.224
0.207
0.169
0.167
0.146
0.124
0.103
0.085
0.096
0.121
0.187
0.239
0.279
0.293
0.29}
0.295
0.266
0.277
0.264
0.246
0.233
0.219
0.205
NO
(PPM)
0.001
0.592
0.579
0.554
0.575
0.408
0.342
0.189
0.075
0.005
0.0
0.0
0.0
0.002
0.003
0.003
0.003
0.004
0.004
0.004
0.004
0.00}
0.003
N02
(PPM)
0.004
0.0
0.002
y O.lOli
0.072
0.228
0.290
0.395
0.464
0.169
0.046
0.040
0.041
0.039
0.03o
0.035
0.033
0.030
0.029
0.026
0.026
0.027
0.027
concentration: 3 |
NO
(PPM)
0.004
0.004
0.004
0.004
0.004
0.003
0.004
0.003
0.002
0.002
0.001
0.001
0.002
0.002
0.004
0.004
0.003
0.003
0.003
0.002
0.001
0.003
0.003
DAY 2,
N02
(PPM)
0.029
0.029
0.030
0.030
0.032
0.032
0.033
0.033
0.03J
0.033
0.032
0.033
0.033
0.033
0.032
0.033
0.033
0.032
0.030
0.027
0.02'J
0.024
0.025
NOX
(PPM)
0.005
0.592
, 0.581
*J 0.655fe/
0.647
0.635
0.632
0.584
0.540
0.174
0.048
0.040
0.041
0.041
0.039
0.038
0.03b
0.054
0.034
0.031
0.031
0.031
0.030
>vȣ-
8-27-77
NOX
(PPM)
0.032
0.032
0.033
0.034
0.036
0.035
0.037
0.036
0.035
0.035
0.033
0.033
0.034
0.034
0.036
0.037
0.037
0.036
0.034
0.029
0.026
0.027
0.028
I-P-S CN-5
(UG/M3) (K-CN/CMi)
a
372.4
14.000
116.9 11.000
59.8
11.000
49 X SUNSHINt
I-P-S CN-5
(UG/M3) (K-CN/CM3)
6.600
6.0 17.000
SR
(L/M1N)
0.001
0.003
0.001
0.005
0.101
0.340
0.613
0.613
0. 780
0.677
0.816
0.837
0.673
0.6M3
0.754
0.485
O.I 1)2
0.027
0.0
0.0
0.0
0.0
0.0
CU-SK
(LANG)
0.01
O.OB
0.29
0.78
1.63
23. 22
32.08
5b.72
70.16
116.16
157.86
207.11
256.05
296.19
335.64
378.78
405.52
415. 2J
416.64
416.64
<»16.64
416.64
H16.64
ItMH
CtLSlUS
19.0
19.2
16.8
lb.2
18.2
19.6
21.4
21.4
23.1
23.9
25,0
26.2
26.8
27.4
28.3
26.2
27.3
25.7
23.5
22.2
22. 7
22.4
21.9
Sft
(L/M1N)
0.0
0.0
0.0
0.0
0.001
0.007
O.OVI
0.238
0.348
0.762
1.049
0.803
0.889
0.500
0.784
0.446
0.504
0.255
0.04S
0.0
0.6
0.0
0.0
CU-SR ItMP
(LANG) CELSIUS
0.0
0.0
0.0
0.0
0.01
0.11
1.19
7.80
22.91
47.20
96.20
157.22
206.07
256.38
2H8.54
333.00
360.21
388.51
402.15
404.40
404.40
404.40
404.40
20.9
It. 9
18.V
10. J
17.9
17.7
18.5
20.4
22.9
25
27
2tt
29
26
.3
.7
.2
.1
.7
29.b
29.4
29.«
29.4
2S.4
25.1
2i.6
22.4
-------
CHAMBEH NU. 2
OAK 1. B-26-/7
HUN 23 J
11ME
(1ST)
0.63
1.30
3.13
6.47
6.30
8.97
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
18.10
19.30
20.30
21.30
22.30
23.30
OiUMt
(PPM)
0.002
0.0
0.0
0.0
0.173
0.300
0.323
0.360
0.423
0.507
0.540
0.546
0.556
0.552
0.517
0.474
0.433
0.401
0.372
0.346
0.321
NO
(PPM)
0.003
0.560
0.566
0.545^'
0.019
0.016
0.013
0.009
0.007
0.006
0.006
0.005
O.OOS
0.004
O.OOS
0.005
O.OOS
0.004
0.004
0.003
0.003
NU2
(PPM)
0.001
0.0
0.005
0.090t'
0.477
0.362
0.364
0.334
0.313
0.293
0.262
0.233
0.209
0.163
0.164
0.151
0.140
0.131
0.120
0.122
0.120
NOX
(PPM)
0.004
0.560
0.571
0.635
0.497
0.396
0.377
0.343
0.320
0.299
0.268
0.230
0.214
0.167
0.169
0.156
O.l^S
0.135
0.132
0.125
0.123
55 X SUNSHINE
1-P-S CN-5
(UL/M3) (K-CN/CM3)
RH SHUU UIAMBIH S1UUV
USEPA CONIKACI NO. 68-02-2437
76.0 23.000
36.6 110.000
4.6 135.000
aj Target initial concentration: 5 |>|>u£.
bj Data are insufficient tu puralt correction tor interference.
OAT 2, 8-27-/7
49 X SUNSHINE
1IME
(ESI)
0.30
1.30
2.30
3. JO
4.30
5.30
6.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
16.30
19.30
20.30
21.30
22.30
OZONE
(PPM)
0.298
0.274
0.250
0.224
0.200
0.176
0.155
0.141
0.153
0.201
0.331
0.454
0.563
0.597
0.623
O.b49
0.640
0.644
0.620
O.r>95
0.5/3
0.552
0.533
ttu
(PPM)
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.003
0.002
0.002
0.001
0.002
0.002
0.003
0.004
0.004
0.003
0.003
0.003
0.002
0.002
0.003
0.003
N02
(PPM)
0.118
0.116
O.U6
0.117
0.116
0.115
0.117
0.119
0.121
0.121
0.122
0.120
0.120
0.115
0.112
0.106
0.103
0.097
0.009
0.003
0.076
0.073
0.070
NUX
(PPM)
0.122
0.120
0.120
0.121
0.120
0.119
0.121
0.122
0.121
0.123
0.123
0.122
0.122
0.110
0.116
0.112
0.106
0.100
0.092
0.005
0.07H
0.076
0.075
I-P-S CN-5
(UG/M3) (K-CN/CM3)
50.000
0.0 107.000
SN
U/MIN)
0.001
0.003
0.002
0.101
0.613
0.613
0.780
0.677
0.616
O.H37
0.673
0.643
0.754
0.465
0.162
0.027
0.0
0.0
0.0
0.0
0.0
CU-SK
(LANG)
0.04
0.11
0.32
3.69
36.33
62.98
78.12
123.07
166.22
215.65
262.91
302.75
343.33
363.73
407.38
415.51
416.64
416.64
416.64
416.64
416.64
UMP
CELSIUS
19.0
19.2
16.2
l«.2
21.4
21.4
23.1
23.9
25.0
26.2
26.8
27.4
20.3
20.2
27.3
25.7
23.5
22.2
22.7
22.4
21.9
3K
(L/MIN)
0.0
0.0
0.0
0.0
o.ooi
0.007
0.091
0.238
0.340
0.782
1.049
0.803
0.809
0.500
0.764
0.446
0.504
0.255
0.043
0.0
0.0
0.0
0.0
CU-SN IEMP
(LANG) CELSIUS
0.0
0.0
o.o
0.0
0.02
0.19
2.12
10.22
26.48
55.18
106.90
165.41
215.14
261.40
296.59
J37.55
365.35
391.11
402.59
404.40
404.40
404.40
404.40
20.9
19.9
10.9
10.3
17.9
17./
10.5
20.4
22.9
25.3
27./
20.2
29.1
20.7
29.5
2V.4
29.8
29.4
27.4
25.1
23.6
22.4
21.6
-------
CHAMBEK UO. 3
DAY I. U-26-/7
RUN 23 » C
55 X SUNSHINt
Hfl SMUG CHAHbtM SIUUY
UStPA CUtllHACI NO. 68-02-2437
NJ
i—'
O
IIMt
(EST)
0.70
1.6}
J.47
6.60
7.13
8.47
9.47
10.47
11.47
12.47
13.4/
11.47
15.17
16.47
17.47
lb.«7
19.47
20.47
at. 47
22.47
23.47
OZONE
(PPM)
0.041
0.0
0.0
0.0
0.0
0.004
0.490
0.702
0.656
0.604
0.561
0.519
0.48}
0.453
0.42S
0.407
0.387
0.370
0.354
0.139
0.322
NO
(PPM)
0.002
0.561
0.54ft
0.536^'
0.489
0.161
0.007
0.0
o.o
0.0
0.001
0.003
0.002
O.OOJ
0.004
0.003
0.004
0.004
0.004
0.003
0.003
N02
(PPM)
0.006
0.0
0.048
0.124^'
0.172
0.442
0.258
0.0!>7
0.038
0.042
0.041
0.037
0.036
0.032
0.031
0.030
0.028
0.026
0.025
0.027
0.027
a/ Targui initial concentration: i fpwC;
MIX T-P-S CN-5
(PPM) (DC/Ml) (K.CN/CM3)
0.008
0.561
0.596
0.660J1/
0.661
0.603
0.266
0.057
0.038 232.8
0.042 12.000
0.042
0.040
0.038 91.9 8.800
0.035
0.03S
0.033
0-.033 40.0
0.031 20.000
0.030
0.030
0.030
ux|>i-rluciil tiuployi-d uwliient
0.033
0.033
0.034
0.034
0.034
0.034
0.033
0.033
0.031
0.030
0.027
0.026
0.025
P. Oi5
49 X SUNSHINE
NOX T-P-S CN-5
(HHM) (UC/M3) (K-CN/CM3)
0.029
0.031
0.033
0.035
0.037
0.039
0.040
0.040 10.100
0.038
0.034
0.034
0.034
0.034
0.037
0.038
0.037
U.037
0.035
0.032
0.029
0.027
0.028 4.4
0.037 26.000
SH
U/MIN)
0.001
0.003
0.002
0.101
0.340
0.613
0.780
0.677
0.818
O.HJ7
0.673
0.643
0.754
0.485
0.182
0.0<>7
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.04
0.17
0.36
5.69
9.55
44.59
86.06
129.97
174.57
224.18
269.76
309.31
351.02
388.68
409.23
415.78
416.64
416.64
416.64
416.64
416.64
ItMP
CELSIUS
19.0
19.2
18.2
18.2
19.6
21.4
23.1
23.9
25.0
26.2
26.8
27.4
26.3
28.2
27.3
25.7
23.5
22.2
22.7
22.4
21.9
SH
U/MIN)
0.0
0.0
0.0
0.0
0.001
0.007
0.091
0.23H
0.348
0.782
1.049
o.aol
0.889
0.500
0.784
0.446
0.504
0.255
0.043
0.0
0.0
o.o
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.03
0.26
3.05
12.65
30.03
63.15
117.60
US. 60
224.21
266. 5B
304.59
342.10
370.49
393.71
403.03
404.40
404.40
404.40
404.40
11 MP
CtLSlUS
20.9
19.9
16.9
18.3
17.9
11.1
IB. 5
20.4
22.9
25.1
27.7
28.2
29.1
28.7
29.5
29.4
29.8
29.4
27.4
25.1
23.6
22.4
21.6
-------
CHAMOtH NU. 4
DA» It B-26-/7
KUN 23 I
55 X SUNSHINt
HI1 SMOG CHAHUCK S1UUY
USEPA CONIKACI NO. 60-02-2437
TIME
(CST)
1.97
3.61
4.47
4. 60
7.JJ
a. 63
9.63
10.63
11.63
1.2.63
13.63
14.63
IS. 63
16.63
17.63
16.63
19.63
20.63
21.63
21.63
23.63
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.274
0.357
0.394
0.444
0.510
0.532
0.535
0.548
0.530
0.406
0.446
0.407
0.378
0.352
0.32B
0,305
NU
(PPM)
0.555
0.542 ,
0.531^'
0.553
0.33B
0.017
0.010
0.006
0.007
0.005
0.006
0 . 00'..
0.005
0.005
0.006
0.005
0.005
0.004
0.004
0.003
0.004
NU2
(PPM)
0.032
0.047.,
0.054^'
0.030
0.290
0.425
0.352
0.320
0.312
0.209
0.260
0.231
0.209
0.104
0.169
0.154
0.145
0.139
0.133
0.131
0.127
NOX I-P-S
(PPM) (UG/M3)
0.567
O'5*9..,
0.585fe>
0.583
0.636
0.442
0.362
0.336 103.1
0.319
0.294 90.6
0.266
0.236
0.214 26.3
0.109
0.175
0.159
0.150
0.143 0.0
0.137
0.134
0.131
CN-5
(K-CN/CN3)
50.000
88.000
105. 000
to a/ Target Initial concentration: 5 |>paC; uxucrluuiit employed uubl (irlor purification.
l~1 l>/ Data are lusuf fie lent to permit correction tor interference.
PA» 2, 0-27-77
49 X SUNSHINE
I IMC
(1ST)
0.63
1.63
2.63
3.63
4.63
5.63
6.63
7.63
6.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
18.63
19.63
20.63
21.63
22.63
U20NE.
(PPM)
0.263
0.261
0.241
0.219
0.197
0.177
0.159
0.151
0.170
0.241
0.369
0.478
0.572
0.569
0.623
0.634
0.634
0.623
0.597
0.571
0.550
0.532
0.512
NU
(PPM)
0.004
0.004
0.004
0.004
0.004
0.004
0.003
0.003
0.002
0.001
0.002
0.001
0.002
0.003
0.004
0.003
0.003
0.003
0.002
0.002
0.002
0.003
0.003
N02
(PPM)
0.123
0.122
0.121
0.121
0.120
0.121
0.120
0.121
0.123
0.125
0.123
0.121
0.121
0.115
0.113
0.106
0.103
0.096
0.009
0.083
0.070
0.074
0.072
NUX
(PPM)
0.127
0.126
0.125
0.125
0.124
0.125
0.123
0.124
0.125
0.126
0.125
0.122
0.123
0.116
0.117
0.112
0.106
0.099
0.091
0.005
0.060
0.077
0.075
I-P-S CN-5
(UG/M3) (K-CN/CM3)
112.000
03.000
0.0
SR
U/MIN)
0.001
0.002
0.002
0.002
0.340
0.613
0.700
0.677
0.618
0.837
0.673
0.645
0.754
0.485
0.162
0.027
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.23
0.38
0.48
0.52
13.63
50.47
93.56
136.47
182.42
232.22
276.24
315.46
358.26
393.33
410.90
416.04
416.64
416.64
416.64
416.64
416.64
IIMP
CUSIUS
19.2
18.2
17.6
17.6
19.6
21.4
23.1
23.9
25.0
26.2
26.0
27.4
28.3
20.2
27.3
25.7
23.5
22.2
22.7
22.4
21.9
Stt
(L/MIN)
0.0
0.0
0.0
0.0
0.001
0.007
0.091
0.238
0.348
0.782
1.049
O.H03
0.809
0.500
0.784
0.446
0.504
0.255
0.043
0.0
0.0
0.0
0.0
CU-SH IIMP
(LANG) CtLSlUS
0.0
0.0
0.0
0.0
0.04
0.32
3.92
14.94
33.37
70.66
127.67
161.31
232.74
271.38
312.11
346.36
3/5.33
396.16
403.44
404.40
404.40
404.40
404.40
20.9
19.9
18.9
18.3
17.9
17.7
18.5
20.4
22.9
25.3
27.7
20.2
29.1
28.
29.5
29.4
29.6
29.4
27.4
25.1
23.6
22.4
21.6
-------
li»» 1. '/-
1
i.i.;i ,''j : L.I 4:>ii
II I.I
(tsn
0.11
2.11
3.47
S.li
o.ll
7.11
rt.ll
**. I i
10.11
11.11
12.11
11.11
14.11
1 S . 1 1
1 <• . 1 i
I/. 11
It*. 1 i
I'/. 11
20. 1 1
21.11
22.11
2i.ll
ii/.i'il
(r.v.)
o.a
O.J
O.il
O.J
.1. I;
0.0
li.Oil'l
o.loi
II . J1,^
'1 . S9 I
i/.itr/
O.i'H
o . m
y.«."**j
0.2/4
0.2S1
0.217
«.2ll
') . 1 9 "/
". 1 7S
W.IS4
0.11-4
a/ Consider tills
1 1 HI:
(IM)
O.-l i
l.ll
2.11
1.11
4.11
S.li
O.li
7.11
tt.ll
9.1 i
1 i> . 1 1
11.11
12.11
11.11
14.11
IS. 11
I...I i
17. 11
1 >* . 1 1
I'M J
20.I i
21.11
22.11
21.11
Illu II
(PIM)
0 . 1 1 S
0.09n
0.084
0.0/1
0.062
II . O'j 1
o.o 'is
U.U-4'4
" . >'to /
O.il'/
o.i'.'S
O.t'H /
O.^'/'j
0.2H',
O.,!"ll
0 . 2'/ 1
U.2I-.S
I'. 2/0
o.2oi
0..-SI
o.t'-H
W.214
{1 . (.'^fo
o.22i>
III
(IV I/
u . v.O^
U. ll>t>
.1.1 OoS
0.1H4
...I'll
O.MS
0.06li
O.ull
0 . 00 7
U.OO'I
V.OII4
(I.IIUi
O.M01
II.I>1>1
O.UU2
O.OH1
O.OO'I
0 . 0 U 1
II.UUl
II . OH i
o.u
0.0
value to be
till
(IT.D
0.0
O.OOii
0.001
0.002
O.l'll i
U. II 111
O.OUi
O.jol
0.1/02
o. 1*02
o.ooi
O.IMIt
tt.ll 1)1
O.OIII
U.OUI
o. J02
U . UU'I
U . l.ll/4j
«.«••' 7
ii.i/i)/
0.007
W.i/ 07
0 . o w /
O.iiOS
.;,,,,
(I-IM)
O.OUt!
0.0
' O.II-4Ui'
O.lll'/
II . U 1 9
0 . OSu
O.U'-I
0.111
O.H'IH
i) . Ot'S
0 . (/ 1 H
o.ol/
O.OI/
0 . 0 1 •>
O.Olo
0.011
11.012
0 . II 1 2
O.OII
O.ull
O.OII
O.OII
MIX
(I'l'f-)
U.IKM
0. loo
0.20<> 2'
0.2lt'l
0.200
0.201
0.190
u.124
O.O'.S
0.029
U.022
o.Ot'O
U.019
O.JIM
O.Olo
0.017
O.Olo
0.014
0.014
0.014
0.011
O.'UI
')?. 'i. Ul
I -sill
(PI 1)
o.u
o.o
0.0
.soo
.soo
.soo
.soo
.'->00
.soo
.SJti
.Ibl
. I9S
.1S6
.129
.118
.026
.OOri
0.9'>l|
11.874
0.790
0 . o / u
O.SIO
the Inierfc-rciici.— corrected Initial
UAr 2, 9-
HII2
(I'PM)
O.OII
0.012
o.oii
0 . 0 14
O.OI..
O.OI/
O.Olo
O.lUr!
0.02S
0.021
0.021
0.019
0 . U 1 9
0 . 0 1 a
0.01 it
0 . II 1 (I
o.oi/
b . 0 1 o
I) . O 1 -I
O.OII
II . II 1 0
II . II U '/
ll.dO''
ll.OUCl
1-77
MUX
(I'I'M)
» . 0 1 1
J.OI2
0.014
O.Olo
0.019
0.020
0.021
o.O, 'S
0.027
O.I'2S
0.1-22
0.020
u.02u
O.OI'/
U.Ut-'O
0.020
O.Ui^l
u.u?2
.1.021
u . 0 1 o
0.017
O.Olo
U.l)lo
O.UI i
MO X S
1-bUL
(PPM)
0.14S
0.2IH
IhMllld.
Si 12
(I'I'll)
0.0
0.0
0.0
0.0
0.0
0 . 0 1 U
0.274
.OS6
.486
.SOO
. 1S2
.2S4
.2 IS
.2211
.21*0
.187
.Ii4
.OS6
0.9S2
0.819
O./l 7
O.S^H
concent cut Ion.
jiiaium
.Sl)2
(I'PM)
0.141
tni:>H
( PPH )
0.0
o.o
o.o
1.SOO
1 .SOO
1 . SOO
l.lil
0 . 4S2
0.107
o.o
0.0
0.010
0.0
O.o
o.o
0.0
0.0
0.0
0.0
(.lllSH
(PPM)
K|| L.UII, InAiiolK SlUdY
UUlt'A Uliilhktl »l). 6b-02-2'O7
I-P-:, LN-S
(r-r.ii/tMS)
u.o
2S.OOO
IS. 700
Sb.l
4.000
I-P-S LN-S
(UC/M1) (K-CW/CM1)
2.7
0.0
0.0
BO.000
/'I. 000
I.OSO
O.S10
Sff
(L/Hiro
o.o
0.0
o.o
0.001
0.044
olbM
0.909
I.171
0.667
1.191
O.S79
0.786
O.SI6
0.0
0.0
0.0
0.0
0.0
SK
(L/MJN)
0.0
0.0
0.0
0.0
0.0
0.002
0.088
0.116
0.614
O.OB4
1.076
1.141
1.072
1.201
0.9S4
0.748
O.S08
0.1 76
0.012
0.0
0.0
0.0
0.0
0.0
CU-SH UMP
(L*NG) CIlSIUS
0.0
0.0
0.0
0.02
0.91
8.SO
11.40
71.SI
128.11
194.18
211.98
278.10
144.90
426.10
4S4.92
466.19
467.64
467.64
467.64
467.64
46/.64
22.1
19.S
18.a
17.6
18.2
21.6
24.2
26.2
29.0
29.6
II.i
II.t
12.2
12.0
10.9
28.7
2S.I
24.7
22.6
22.1
21.9
CU-Sk ItMP
(LANG) CLLS1US
0.0
0.0
0.0
0.0
0.0
0.02
0.81
8.02
10. IS
69.10
121.HI
188.92
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0.002
0.002
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0.004
0.002
0.001
0.00?
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O.OuO
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O.VOl
u.uot
O.HOI
0.001
0.002
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O.'JOI^
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0.021
0.02'j
U.02S
0.024
0.021
O.U22
0.021
0.022
0.021
Chu lucectereacc-corructeJ
KAr 2, 9-
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(I'P-I)
0.021
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O.U2r.
0.02/
0.020
0.0r:'»
0.012
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0.010
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0.027
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0.71?
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0.0
0.0
0.0
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0.0
0.0
0.111
0. /I2
1.149
1.121
I.Onl
1.021
O.nOl
O./bl
O.Ho7
O.ttOl
O.'j9'j
0.474
0.151
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0.0
0.0
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0.1H7
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0.0
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HULPA (.UK (KALI Mil. 1.8-
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(UG/Hi) (H-t(l/CMl)
1 /H.i
11 .000
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22.000
202.6
9.&00
2.800
21.1
Initial concentration.
80 X
l-SUt
(PPM)
SIlflSHlHI
SU2
(PPM)
CHISH
(PPM)
I-P-S CN-'j
(UG/Mi) (K-CN/CHi)
0.0
110.000
2.8 120.000
0.0 0.//0
2.8
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0.0
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0.0
0.0
0.0
0.0
0.001
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0.111
0.05J
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1.171
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O.rio7
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0.«.96
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22. J
20. S
18. 8
18.2
17.6
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21.6
24.2
26.2
27. a
2'».0
29.6
11.1
11. 1
12.2
12.0
10.9
28.7
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24.7
22.6
22.1
21.9
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21.1
21.1
21.1
20.7
20.4
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20.4
21.6
24.7
27.1
29. b
11. 1
11.8
12.8
11.4
11.1
12. 9
11.6
29.7
27.8
26.7
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10.11
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19.11
20.11
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0.002
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0.0
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0.047
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0,604
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0.122
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O.Obh
0.017
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0.119
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0.101
0.099
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1ICU
(LSI)
1.10
o. 10
7.10
8. JO
9.10
10.10
11.10
12.10
11.10
14. JO
15. )0
16. )fa
17.10
lu.JO
I9.JO
20; 10
21.10
22. JO
21. iO
a/ Kxperl
U^UllL
(PPM)
0.04o
0.2t)'l
0.282
0.258
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C.c'V4
0. Jl/
0.1)4
0 . I'l 4
0.1J9
0.2''5
u.275
0.264
u.251
0.245
0.215
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(PPM)
0.017
0.005
0.010
0.011
0.011
0.01)
0.011
0.012
o.ou
0.010
0.006
'i.ooi
0.002
0.0
O.oOO
0.000
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0.050
0.044
0.t)4M
0.047
0.047
0 0*-* 1
0 0^ i
0.05)
0.055
0.050
0.040
0.04U
0.0'I2
0.0-Jl
O.O'IO
0.040
•eat employed imblent air with
Injection, Hit
II ML
(1 SO
U.JO
I.Jo
2.iO
J.iO
4.10
5.10
6.10
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1). JO
9. JO
10. J<»
1 . J"
2. Jo
J. JO
'1.10
5 . Ju
ii. J<»
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Irt. jo
IV. JO
(J/lllit
(PPli)
0.225
0.217
0.212
0.205
0.199
0.194
0.186
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0 . 1 / 1>
o. lo?
o . t'25
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0, J'I2
0. JVM
0.449
o.-1/tt
0.4;»»i
0.4/0
O.iSI
d.<»*;/
Initial concentrations
Nil
(Pl'il)
0.001
0.0
u.uOO
0.002
O.OOl
o.ooo
0.002
0.002
0 . ll u i
o.oo/
O.OII
0.0| |
0.01 I
O.ol f
0 . >' 1 0
o.ol |
0.012
O.ol |
0 . (1 0 H
O.doS
OA\f ±. 9.
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(PPM)
O.OJ/
0.017
0.0)7
O.Ola
0.01'J
O.rtl'l
0.014
0.0 J5
0 . (i JV
0.0"!
O.O'lo
0.0'JO
O.u'ji
0.0'JM
O.ti'J'J
0 . 055
O.il'jb
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0 . o ^ '->
O.ll'll
I'l.llpLllt - 95 i jlliililllliL
I.OX PHIIC Cl4>'>
(PPM) (PP'IJ (K-LN/CHS)
O.U74 0.717 H.JOO
0.048 0.525
O.OS4 0.141
0.057 0.244
O.O59
0.064
U.0b4
U.Obb 0.410
0.069
0.060
0.054
0.049
0.045
O . 0 4 1
0.040
0.040
no prior purification; due to an operational proklen during reactant
arc not clearly defined.
-I1-/7
02 X SUNSH1NL
NIK PKUP CN-5
(PPM) (PPM) (K-CU/CMJ)
0.0)8
0.0)7
i). 017
0.018
0.016
0.0)4
O.OJo
0 . ft J /
0.042
0.050 0.0
0.05/
O.Ool
0.064 0.0
0.06o 0.0
0.0o5 0.0
o.ilbd 0.0
0.067 0.0
0.06J (1.0
ii.O'ji 0.0
0.04O 0.0
6d-02-24)7
3H
(L/M1N)
0.001
0.0/2
0.265
0.6)6
O.BB4
I.07M
i.iaa
1.20/
1.112
0.968
0.725
0.440
0.150
0.001
0.0
0.0
0.0
0.0
0.001
SK
(L/MIN)
0.001
O.OOS
0.002
0.002
0.002
O.OOJ
0.064
0.280
0.600
0,056
1.055
1.161
1.179
1.094
O.V22
0.696
0.40/
0.146
0.006
0.0
CU-SR
(LANG)
O.Ob
1.78
9.9J
H. 15
75.97
112.50
199.16
270.79
141.86
406. B2
460.5}
499.04
520.56
526. at)
526.92
526.92
526.9,!
526.92
5?6.94
CU-Sft
(LANG)
0.02
0.11
0.28
0.40
0.52
0.65
I.9J
9.66
12.22
/2. tt6
127. «9
19}. 1 J
261.20
112.41
194.96
446.21
482.76
502.49
508.71
508. 9«
It HP
CELSIUS
12.}
12.)
15.2
18.1
20.9
22.1
21.2
24.1
24.8
24.8
24.8
25.2
2). 7
20.1
17.4
Ib.)
15.)
14. b
ii. a
ItMP
CLLblUS
11.0
11.1
11.)
12.7
12.2
11.8
12.0
14.8
16.)
21.9
21.B
24.9
26.1
27.1
27.1
27.4
27.1
25.9
22.9
21.9
-------
NU.
1<
AY i, 9-
12-/7
M>H tt : I'Kurti.t
11 Ml
(1ST)
1.47
2.47
3.47
4.47
5.63
6.47
'.47
8.47
9.14?
10.47
I 1.47
12.47
1 3.47
14.47
15.4?
16.47
17.47
IH.4/
19.47
20.47
21.4?
22.47
23. 4/
LUHUL
(PCS)
0.002
0.0
0.0
U.O
0.0
0.002
0.023
0.175
0.150
o.u'M
O.U73
0 .97i
0.9/8
0.9'(5
O.rtOS
O.b41
0.111 1
0.7U9
0 . / 6 '*
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mi
(PCM)
0.004
0. /52
0.727
O.t>59
0 . 55 |
0.56S
0. loO
0.037
0.011
0.012
o.ul?
O.Oll
0.010
0.010
0.005
0.004
0.00,?
0.001
0.001
0.000
NII2
(PP«>
0.04/
0.202
0.211
0.250
0.359
0.470
0.597
0.64B
0.542
0.40*
0.299
0.21*'
0.228
0.2uU
0.194
0.105
0.175
0.10/
O.|o3
O.|6b
mix
(P>M)
0.051
0.9S1)
0.939
0.910
0.910
O.bi5
0.75?
u.6rtt
0.557
0.4^0
0.311
0 .^sti
0.218
G.21U
U.I 99
0 . 1 d'*
O.I //
0.1 ott
0.164
O.ltiO
hll jM(lt. tllAMDi K
UStt'A CUNIHAll Hll. 6»-02-24i/
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(PPM)
cn-5
754
,753
0.759
0.669
0.570
o!273
0.59U
0.950
0° a/ tuperiMent. eM|>loyed ambient air with no prior purification.
OAY 2, 9-ii-77
1 (ML
USD
0.47
1.17
2, '17
3.M/
4.47
5.47
6.47
7.47
t).47
9.47
10. 4/
11.47
12.47
13.47
1 4 . 1| 7
1 •>.'(?
lh.47
17.47
10.47
19. 4/
U/Li,iL
II'PI-U
0 . / 35
0.721
U.7IO
0.<>95
o.6tm
O.u/4
O.i>59
U.649
O.oW
0.044
0.6b2
0. 74U
O.P15
O.B72
0.909
0.92l»
O.'Jott
o,n«2
O.O49
O.dl3
NU
(PPM)
0.001
0.001
O.uOl
0.002
0.001
0.001
0.002
0.00,.'
0.003
0.006
0.010
O.UU9
0.009
0.009
O.oon
().()» 9
0.010
U.OOH
il.UI'7
O.OU5
KII2
(PPMJ
0 . 1 5u
0.152
0.140
ft. 146
0 . 1 4'1
0.142
O.I 4U
0 . 1 36
0.139
O.I4t.'
0.140
O.llo
0.131
0.122
O.ll 1
0.11/0
0.0 V2
O.OoU
0.0/2
0.0o4
KlIX
(PPM)
U.157
U.153
0.149
0.140
0 . 1 45
0 . 1 '1 S
0.141
0.1 3«
0. 1 4^
II. 1 411
O.I5C
0. 145
u. 140
0.131
0.119
0.109
0.102
0.066
U.0/9
U.069
H2 X SUnSMINl
PKOP CN-5
(PPM) (n-tN/ti
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SK
U/M1N)
0.001
0.001
0.001
0.002
0.002
0.07?
0.2H5
0.6 56
0.1181
1.078
1.166
1.207
1.132
0.96B
0./25
0.446
0.150
0.001
0.0
0.0
0.0
0.0
0.001
CU-SK
(LANG)
0.09
0.15
0.21
0.30
0.44
2.51
12.84
19.80
an. 99
143.50
£11.26
283.10
353.40
416.70
467.92
503. 61
522.09
526.89
526.92
526.92
526.92
526.92
526.95
I LHP
CtlblUS
12. J
12.0
11.7
11. a
• 2.2
12. i
l^>,2
• 6.1
20.9
22. i
2J.2
24.3
21.6
24. B
24.8
25.2
2i.7
20.1
17.1
16.3
is. 3
11.6
13.6
SK
(L/MII4)
0.001
0.003
0.002
0.002
0.002
O.OOi
0.064
o.^ao
0.600
O.B56
1.055
1.161
1.179
1.094
0.922
0.696
0.4&7
0.116
0.066
0.0
CU-SK JIMP
(LANG) CtLSlUS
0.03
0.11
0.30
0.42
0.54
O.fett
2.50
12.52
JH.34
at .62
13B.b5
205.00
275.23
343.57
404.36
453.31
486.92
503.98
50B.79
506.90
13.0
IS.l
13.3
J2.7
12.2
11.6
12.0
14.6
ltt.3
21.9
23. b
24.9
26.1
27.1
27.3
27.4
27.1
25.9
22.9
21.9
-------
CHAMRfK NO. <|
DAY I, 9-12-77
to
KUII ? / : PKOHLNl -'
a/
95 X SUtiSHINl
HH SHUf. CHAMItbK SlUl>It
USIPA CdNlRAtl NO. 68-02-2417
IlMt
(F.SI)
1.63
a. 6i
3.63
4.63
5.30
6.63
7.63
a. 63
9.63
10.63
11.63
12.63
11.63
14.63
15. hi
16.63
J7.61
IB. 63
19.63
20.63
21.63
22.63
23.63
u/um
(PPM l
0.002
0.0
0.0
0.0
0.005
0.0/7
0.118
0.7H8
0.411
0.943
0.963
0.968
0.953
0.915
O.B5S
O.H29
O.B05
0.78H
0.71.9
0.753
Nil
(PPM)
0.004
0.387
0.374
0.300
0.193
0.039
0.010
0.009
0.008
0.010
o.oon
0.009
0.009
0.009
0.004
0.004
0.1702
0.001
0.001
o.oon
NIV
(PPM)
0.043
0.100
0.103
0.152
0.2»3
0.156
0.30H
0.2.f7
O.I 9«
0.196
O.IB9
0.176
0.170
0.159
0.115
0.136 •
0.13V
0.124
0.120
O.I1H
NOX
(PPM)
0.047
0.4B7
0.477
0.460
0.456
0.397
0.3IH
0.235
0.207
0.206
0.197
0.165
0.179
0.167
0.14V
0.141
0.131
0.125
V.122
0.118
CHOP
(PPM)
0.697
0.711
0.671
0.5H6
0.454
0.216
0.072
CN-5
(K-CN/CMS)
0.295
0.620
a/ Experiment eaployed avblent air with no prior purification.
0*\f g, V-IJ-//
H2 X SUNSMIMt
nut
(CSt)
0.63
1.63
2.63
J.63
'1.63
S.i.3
6.63
7.63
0.63
9.M
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
18.63
19.63
tunnt
(PPill
0.736
0.722
0.710
0.6''6
0.6H'I
0.6/1
0.657
0.647
0.634
0.633
O.o50
0.69U
0.7'«'»
0./H1
O.HOI
O.h03
0.766
0. 760
0. 734
0.710
t4U
(PPM)
0.001
0.001
0.000
0.001
0.001
0.001
0.00?
o.no^
0.003
O.U06
0.000
0.007
0.007
0.007
0.007
O.OOH
O.OOfl
U.OIII
U.007
O.U05
NO?
(PPM)
0.114
0.112
0.110
0.107
0.103
0.102
0.101
O.IUJ
0.104
0.107
O.IOn
0.105
O.ldl
O.O1"!
O.<"'i«
o.o n>
0.06''
0.01,1
O.U'jl
0.0"'»
tinx
(PPM)
0.115
0.113
0.110
O.IOP
0.104
•1.104
0.102
0.105
0.107
0.113
0.114
O.I !<•
o.ioe
0.101
U.O'M
o.ns,'
0.077
O.OOH
(1.061
0.054
PKOP
(PPM)
n.o
0.0
0.0
0.0
0.0
0.0
0.0
0.0
(1.0
(1.0
o.o
tN-5
(K-CN/CM3)
SH
(L/M1N)
0.001
0.001
0.001
0.002
0.002
0.072
0.2H5
0.636
O.flHI
I.O/H
i.ina
1.207
1.132
0.968
0.725
0.448
0.150
0.001
0.0
0.0
0.0
0.0
0.001
CM-SR
(LANG)
0.10
0.16
0.22
0.32
0.40
3.20
15.57
45.94
93.48
153. H5
222.69
294.68
364.27
425.99
474. HH
507.91
523.53
526.90
526.92
Mb. 92
526.92
526.92
526.96
UMP
CtLSIUS
12.3
12.0
11.7
II. 8
12.2
12.3
15.2
18.3
20.9
22. J
23.2
24.3
24.8
24.8
24.8
25.2
23.7
20.1
17.4
16.3
15.3
14.6
13. «
SK
(L/MIN)
0.001
0.003
0.002
0.002
0.002
0.003
0.064
0.2«0
0.600
0.85H
1 . 05S
1.163
1.179
1.094
0.922
0.696
0.407
0.146
0.006
0.0
CU-SR
(LANG)
0.04
0.17
0.12
0.44
0.56
0.71
3.20
15.20
44.10
«9.8S
148. 7B
216. 16
286.55
354.0?
413.21
459. 9
-------
CHAMBER NO. I
DAY I, 9-18-77
RUN ft I COS
77 X SUNSHINE
RTI SMUG CHAMBER STUDY
USEPA CONIRACI HO. 68-02-24J7
TIME
(E3T)
0.11
1.13
2.13
4. IS
5.13
6.1}
T.li
7.85
8.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
10.13
14.13
20.13
21.13
22.13
23.13
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.001
0.001
0.002
0.002
0.002
0.002
o.ooi
0.002
0.001
0.001
0.0
0.0
0.0
0.0
0.0
0.0
NO
(PPM)
0.009
0.160 a/
0.159
0.157
0.155
0.159
0.162
0.161
0.159
0.151
0.153
0.150
0,151
0.148
0.14Z
0.136
0.136
0.12A
0.123
0.122
N02
(PPM)
0.006
0.044a/
0.006
0.047
0.016
0.043
0.036
0.035
0.032
0.014
0.057
0.039
0.041
0.042
0.042
0.041
0.042 '
0.042
0.014
0.016
NO* 1
(PPM)
0.015
0.204 »/
0.204
0.204
0.203
0.202
0.200
0.196
0.191
0.188
0.190
0.189
0.192
0.191
0.184
0.177
0.178
0.170
0.157
0.158
r-3UL
PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS
PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S
(UG/M3)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CN-5
(K-CN/CM3)
0.0
0.0
0.0
8.100
1.100
0.0
0.0
SR
(L/MIM)
0.0
0.0
0.001
0.001
0.004
0.045
0.238
0.238
0.567
0. ?«i
1.005
0.921
1.193
1.078
0.701
0.668
0.198
0.10B
0.005
0.0
0.0
0.0
0.0
0.0
CU-SR
(LANG)
0.0
0.0
0.01
0.07
0.15
0.71
4.92
15.20
21.76
57.47
106. 18
165. H2
223.21
29J.69
155.61
197.43
435.40
457.02
462.70
4h2.96
462.96
462.96
462.96
462.96
ItMP
CELSIUS
21.4
20. 8
20.8
19.7
20.0
20.2
20.4
20.4
22.0
25.1
27.2
28.1
29.1
29.6
29.1
29.1
29.1
26.9
25.1
21. U
21. 2
21.4
21 .7
21.4
NJ
K)
O
at Consider this to he the interference-corrected Initial concentration.
DAY 2, 9-19-77
74 X SUNSHINE
TIME
(EST)
0.11
1.13
2.13
3.13
4.13
5.13
6.13
7.13
8.13
9.13
10.13
11.13
12.11
13.13
14.13
15.13
16.13
17.13
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.004
0.005
0.006
0.007
0.004
0.007
0.006
0.003
NO
(PPM)
0.121
0.122
0.122
0.121
0.121
0.118
0.120
0.119
0.109
0.104
0.099
0.094
0.087
0.075
0.073
0.069
0.065
N02
(PI'M)
0.015
0.015
0.017
0.016
0.041
0.042
0.041
0.049
0.054
0.051
0.050
0.051
0.051
0.051
0.055
0.053
0.055
NOX
(PPM)
0.156
0.157
6.159
0.159
0.162
0.160
0.161
0.169
0. 163
0.157
0.148
0.146
0.119
0.128
0.128
0.122
0.120
T-SUL
(PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS
(PPM)
.500
,500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S CN-5
(UG/M3) (K-CN/CMJ)
0.0 0.0
0.0
O.H40
0.470
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.001
0.002
0.04.J
0.228
0.513
0.721
0,994
1.032
0.697
0.644
O.H04
0.667
0.431
0. I 18
CU-SH UMP
(LANG) CELSIUS
0.0
0.0
0.0
0.0
0.01
0.08
0.52
1.54
20.44
52.84
98.23
Ib8.I 1
217.48
258.88
298.77
305.94
3H4.12
407.54
20.9
20.6
20.2
20.0
20.1
20. 4
20.4
21 ,4
2J.2
24.7
26.;
28.4
2«,9
29. J
29.6
28.4
27.7
26.1
-------
ro
CHAMUER HI). 2
DAY 1. 9-18-77
RUN 29 I COS
R11 V4QG CHMttlR'SlUW
U3EPA CONTRACT NO. bB-
77 X SUNSHINE
TIME
(ESI)
0.10
1.10
J.47
4.10
5. JO
6. JO
7. JO
7.86
a. jo
9. JO
10.30
11. JO
12. JO
13. JO
14. JO
IS. JO
16.30
17. JO
18.30
19. JO
20. JO
21. JO
22. JO
2J.JO
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.003
O.OOb
0.007
0.008
0.009
0.011
0.010
O.OIt
0.006
0.003
0.0
0.0
0.0
0.0
0.0
o.o
NO
(PPM)
0.008
0.079
0.077a/
0.076
0.075
0.074
0.070
0.069
0.065
0.061
0.055
0.056
0.051
0.051
0.040
0.042
O.OJ6
0.035
0.036
0.029
0.029
N02
(PPM)
0.007
0.020
0.021 a/
0.024
0.027
O.OJ2
0.034
0.032
0.034
0.034
0.035
0.037
0.040
O.oat
0.045
0.047
0.048
0.049
0.049
0.042
0.042
NOX 1
(PPM)
0.015
0.098
0.098 a/
0.100
0.102
0.106
0.105
0.101
0.099
0.094
0.090
0.093
0.092
0.092
0.093
0.089
0.064
0.085
0.085
0.071
0.071
I-SUL
(PPM)
.500
.500
.500
.500
.500
.500
.500
.500
,500
.500
COS
PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S
(UO/MJ)
0.0
6.3
0.0
0.0
o.o
0.0
0.0
0.0
CN-5
(K-CN/CMJ)
0.0
0.0
0.0
5.600
0.560
O.J50
O.JOO
•/ Interference-corrected Initial (NO). (N02]( and [NOX1 ate 0.071. 0.037. and 0.108 ppn.
0»V 2, 9-19-77
74 X SUNSHINE
TIME
(ESI)
O.JO
1.30
2. JO
3.30
4. JO
5.30
6.10
7.30
8. JO
9.30
10.30
II. JO
12.30
13. JO
14.30
15. JO
16. JO
17. JO
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.004
0.009
0.015
0.019
0.024
0.025
0.026
0.028
0.026
0.016
NO
(PPM)
0.029
0.031
0.031
0.032
0.031
0.030
0.034
0.036
0.037
0.036
0.035
0.032
0.027
0.02J
0.021
0.0(9
0.013
N02
(PPM)
0.042
0.042
0.044
0.045
0.046
0.050
0.051
0.051
0.046
0.041
O.OJ9
0.037
0.040
0.036
0.040
0.041
0.045
NOX
(PPM)
0.071
0.073
0.075
0.077
0.079
0.080
0.085
0.087
0.083
0.077
0.074
0.06V
0.067
0.060
0.060
0.060
0.050
r-sut
(PPM)
,500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS
(PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S CN-5
(UC/M3) (K-CN/CMJ)
o.o
0.0
0.0
0.0
0.0
SR
(L/M1N)
0.0
0.0
0.0
0.001
0.004
0.045
0.238
0.2J8
0.567
0.78J
1.005
0.921
I.I9J
1.076
0.701
0.66A
0.396
0.108
0.005
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANK)
0.0
0.0
0.06
0.08
0.19
1.17
7.J4
I5.6J
27.55
6S.45
116.43
175.22
2J5. J7
304.06
362.76
404.24
4J9.46
458.12
462.75
462.96
462.96
462.96
462.96
462.96
IEMP
CELSIUS
21.4
20.0
20.2
19.7
20.0
20.2
20.4
20.4
22.0
25.1
27.2
28.1
29. J
29.6
29.1
29.1
29.1
26.9
25.1
23.8
23.2
21.9
21.7
21.4
SR
(L/MIN)
0.0
0.0
0,0
0.0
0.001
0.002
0.04S
0.22B
0.51 J
0.721
0.994
1.032
0.697
0.644
0.804
0.667
0.411
O.I 16
CU-3R HMP
(LANG) CtLSIUS
0.0
0.0
0.0
0.0
0.02
0.10
0.95
6.86
25.67
60.20
108.J7
168.70
221.59
265.45
J06.9/
J52.75
JBfl.52
408. 7
-------
Is)
N>
CHAMBER NO. 3
DAV I, 9-18-77
RUN 29 '. COS
77 X SUNSHINE
R11 SMOG CHAMBtK STUDY
USEPA CONTRACr NO. 6A-02-2437
TIME
(1ST)
0.47
1.17
2.60
0,91
5.47
6.47
7.17
7.95
6.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
l«.«7
19.47
20.47
at. 47
22.47
25.47
ozone
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
NO
(PPU)
0.009
0.780a/
0.752"
0.738
0.727
0.723
0.747
0.760
0.797
0.606
0.827
0.620
0.849
0.674
0.871
0.830
o.ajo
0.795
0.764
0,751
0.7JI
NU2 NUX T-SUt COS
(PPM) (PPM) (PPM) (PPM)
0.009 0.016
0.395 a, h/
0.42057^
0.039B/
0.431E/
0.427B/
0.363
0.315
0.289
0.264
0.250
0.236
0.235
0.225
0.221
0.237
o.22a
0.246
0.242
.175 a.b/
. 1 72 5T
.176B/
.157 BY
.150^
.110
.095
.065
.070
.077
.058
.084
.099
.091
.071
.058
.041
.026
0.247 0.996
0.256 0.9B7
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
I-P-S
(UG/MS)
3.4
2.8
.0.0
0.0
0.0
0.0
0.0
0.0
CN-5
(K-CN/CM3)
0.0
0.0
0.0
6. 100
1 .100
0.0
0.0
fc •*#•»» V 9 V V « f -? | V * f. •J** V ^ ~ 13 I • J V V i JV V
a/ Interference-corrected initial (NO), fN>2|, nl)<| INOX) are 0.787, 0,3<>4, and 1.181 p\m.
b/ Instnmcnt was overranpcd; data suspect.
DM 2, 9-W-77
74 X SUNSHINt
MMl
(tSI)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
6.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
OZONE
(PCM)
0.0
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
• o.o
0.0
0.0
MO
(PPM)
0.714
0.701
0.69J
0.697
0.661
0.661
0.653
0.655
0.646
0.669
0.657
0.666
0.667
0.662
0.664
0.656
0.641
NU2
(PPM)
0.264
0.270
0.293
0.2B7
0.305
0.313
0.305
0.305
0.264
0.239
0.216
0.224
0.206
0,197
0.193
0.198
0.197
NOX
(PPM)
0.978
0.971
0.986
0.983
0.986
0.974
0.958
0.960
0.910
0.906
0.874
0.690
0.873
0.859
0.657
O.B54
0.637
t-SUL
(PHM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.5UO
.500
.500
.500
.500
.500
.500
.500
COS
I PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
I-P-S CN-5
(UG/M3) (K-CN/CM3)
0.0
0.0
0.0
0.0
0.0
SH
(L/MIN)
0.0
0.0
0.001
0.001
0.004
0.045
0.216
0.235
0.567
0.783
1.005
0.921
i.m
1.07b
0.701
0.668
0.39B
0.10R
0.005
0.0
0.0
0.0
0,0
0,0
CU-SR
(LANG)
0.0
0.0
0.05
0.09
0.2i
1.6J
9.77
16.63
33.33
73.44
126.66
1S4.61
2«7. 5U
315.86
369.93
411.06
443.52
459.22
at>^,80
462.96
462.96
462.96
462.96
'162.96
HMH
CtLSlUS
21.4
20.8
20.8
19.7
• 20.0
20.2
20.4
20.4
22.0
25.1
27.2
2H.I
29.1
29.6
29.1
29.1
29.1
26.9
25.1
23. B
23.2
21 .<>
21.7
21 .1
SH
(L/M1N)
0.0
0.0
0.0
0.0
0.001
0.002
0.04J
0.228
0.513
0. /2l
0.994
1.052
0.697
0.644
0.804
0.667
0.4})
o.nn
CO-SH
(LANG)
0.0
0.0
0.0
0.0
O.Oi
0. \t
1.39
9. 19
JO. 91
67. 55
I1H.5I
179.22
231.70
272.02
315.17
3S9.55
392.91
409. 95
IfMP
CtLSlUS
20. 4
20.6
20.2
20.0
20.1
20. J
20.4
21.4
23.2
24. 7
2b.7
2H.4
2S.9
c'9.3
29.6
2«.4
27.7
26.1
-------
10
N>
CO
CHAMBER NO. 4
DA» I, 9-18-77
RUN 29 | COS
77 X SUNSHINE
RII SMOG CHAMBER STUDY
UStPA CONTRACT NO. 68-02-2437
TIME
(ESI)
0.61
1.63
3.13
4.63
$.63
6.63
7.61
7.97
8.63
9.63
10.61
11.63
12.63
13.63
14.63
IS. 63
16.63
17.63
16.63
19.63
20.63
21.63
22.63
23.63
OZONE
(PPM)
0.0
0.*
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
«.«
0.
0.
0.
0.
0.
0.0
0.0
0.0
NO N02
(PPM) (PPM)
0.391 a/ O.lOO
0.378
0.372
0.366
0.364
0.366
0.370
0.165
0.362
0.156
0.355
0.357
.110
.118
.!!•»
.124
.102
.092
.091
.090
.090
.089
.093
0.361 0.069
0.355 0.092
0.317 0.094
0.316 0.066
0.326 0.094
0.325 . 0.095
0.313 0.004
0.304 0.091
HUX T-SUL COS
(PPM) (PPM) (PPM)
a/ 0.491 a/
0.486
O.«9|
0.465
0.««7
0.468
0.462
0.456
0.452
0.449
0.445
0.450
0.450
0.446
0.411
0.425
0.422
0.420
0.197
0.195
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S
(UG/M1)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
M
CN-5
(K-CN/CMJ)
0.0
0.0
0.0
0.0
0.220
0.0
0.0
a/ Interference-corrected initial [NT)), (N021, and (NOX) are 0.381, 0.093, and 0.474
0*V 2, 9-19-77
74 X SUNSHINE
TIME
(EST)
0.63
1.63
2.63
1.63
4.63
5.61
6.61
7.63
8.63
9.63
10.63
11.61
12.61
11.63
14.61
15.63
16.61
17.61
OZUNC
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.001
0.001
0.001
0.001
0.001
0.0
0.0
NO
(PPM)
0.301
0.296
0.299
0.301
0.298
0.292
0.267
0.281
0.274
0.270
0.261
0.262
0.246
0.241
0.216
0.212
0.227
0.219
N02
(PPM)
0.093
0.094
0.100
0.096
0.104
0.105
0.107
0.110
0.094
0.101
0.094
O.IU1
0.100
0.092
0.099
O.IVI
0.101
0.098
NOX
(PPM) .
0.394
0.190
0.399
0.396
0.402
0.197
0.195
0.192
0.166
0.171
0.155
0.161
0.148
0.111
0.117
0.111
0.12B
0.117
T-SUl
(PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS
(PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S CN-5
(UG/M1) (K-CN/CM1)
0.0
0.0
0.0
0.0
0.0
3H
(L/MIN)
0.0
0.0
0.0
0.001
0.004
0.045
0.218
0.216
0.567
0.763
1.005
0.921
1.191
1.076
0.701
0.668
0.198
o.ioa
0.005
0.0
0.0
0.0
0.0
0.0
CU-SR
(LANG)
0.0
0.0
O.Ob
0.10
0.27
2.06
13.06
16. 91
16.77
80.96
116.11
191.45
259.00
126.21
176.66
417.47
447.14
460.26
462. 65
462.96
462.96
462.96
462.96
462.96
ItMP
CELSIUS
21.4
20. B
20.2
19.7
20.0
20.2
20.4
20.4
22.0
25.1
27.2
2B.I
29.1
29.6
29.1
29.1
29.1
26.9
25.1
21. H
21.2
21.9
21.7
21.4
SK
(L/MIN)
0.0
0.0
0.0
0.0
0.001
0.002
0.041
0.228
0.511
0.721
0.994
1.012
0.697
0.644
0.604
0.667
0.411
0.118
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.04
0.14
i.ni
II. 18
15.81
74.47
128.05
IB9.I1
23H.39
27B.20
122.89
165. 9S
197,05
411.08
ft HP
CELSIUS
20.9
20.6
20.2
20.0
20.1
20.1
20.4
21.4
21.2
24.7
26.7
2B.4
28.9
29.1
29.6
2H.4
2/.7
26.1
-------
CHAMBEH NO. 1
DAY I, 9-21-77
RUN 30 t CS2
HTI SMOU CHAMBEH STUDY
USEPA CONTRACT NO. 68-02-2437
64 X SUNSHINE
TIME
(LST).
0.13
1.30
2.30
1.13
4.13
5.13
6.13
7.13
a. 13
9.13
10.13
11.13
12.13
13.13
14.13
IS. 13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.004
0.014
0.024
0.032
0.040
0.044
0.046
0.052
0.050
O.Oa^
0.027
0.01S
0.010
O.OOb
0.005
0.003
NO
(PPM)
0.004
0.162
0.16Z
0.162
0.160 a/
0.161 ~
0.150
0.146
0.109
0.083
0.068
0.056
0.048
0.038
0.031
0.030
0.024
0.016
0.008
0.004
0.002
0.002
0.00?
0.001
H02
(PPM)
0.001
0.0
0.037
0.041
0.042
0.043
0.043
0.055
0.084
0.103
0. 14
0. 18
0. 17
0. 13
0. 12
0. 10
0.113
0.115
0.114
0.10U
0.103
0.099
0.096
0.095
NOX T-SUL
(PPM) (PPM)
0.005
0.162
0.199
0.203
a/ 0.202 a/
0.204"
0.201
0.201
0.19J
0.186
0.182
0.174
0.165
0.151
0.144
0.139
0.136
0.131
0.122
0.111
0.105
0.101
0.098
0.096
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS SU2 CS2
(PPM) (PPM) (PPM)
.500
.500
.500
.500
.500
0.216 .500
0.289 .500
0.356 .500
0.409 .500
0.471 .500
0.519 .500
0.547 .500
0.536 .500
0.551 .500
0.5J8 .500
0.549 0.010 .500
0.542 0.010 .500
0.535 0.010 .500
I-P-S
(UG/MJ)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CN-5
SR
(K-CN/CM3ML/MIN)
78.000
180.000
67.000
90.000
54.000
1.700
0.0
0.0
0.0
0.0
0.0
0.0
0.045
0.255
O.bl5
0.759
0.99J
1.102
1.079
0.962
0.733
0.626
0.349
0.097
0.001
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.35
4.69
22.02
5'l.82
102.19
16,?. 62
22«.56
242.38
34B.32
391.46
426,06
445.84
U50.91
450.96
150.96
H50.96
150.96
1150.96
TtMP
CELSIUS
19.2
19.9
19.5
16.9
!«.»
18.4
17.9
19.1
20.9
22.4
23.8
24.8
25.4
25.7
25.9
26.0
25. fl
24.4
21.1
19.2
17.8
16.6
16.8
15.;
a/ Consider this value to be the interference-corrected initial concentration.
PAY 2. 9-pa-77
68 X SUNSHINE
TIME
(EST)
0.13
1.13
2.13
J.I 3
4.13
5.13
6.13
7.13
8.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
OZONt
(PPM)
0.002
0.001
0.0
0.0
0.0
0.0
0.0
0.025
0.071
0.101
0.125
0.166
0.204
0.244
0.273
0.295
0.290
NU
(PPM)
0.001
0.000
0.0
0.000
0.001
0.001
0.000
0.008
0.009
0.009
0.009
0.007
0.006
0.005
0.005
0.006
0.005
NU2
(PPM)
0.091
0.090
0.088
O.flbb
0.005
0.084
0.083
0.072
0.065
0.056
0.053
0.048
0.041
0.037
0.032
0.027
0.024
NUX
(PPM)
0.092
0.090
0.088
0.096
0.086
0.085
0.083
0.080
0.074
0.065
0.062
0.055
0.049
0.042
0.037
0.033
0.02"
r-SUL
(PPM)
1.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
CUS
(PPM)
0.514
O.S20
0.522
0.522
0.522
0.535
0.591
0.707
0.756
O.B36
0.93?
0.981
1.04/1
1.127
1.145
SU2
(PPM)
0.010
0.010
0.075
0.100
0.1
-------
N>
10
CHAMBER HO. 2
DM I, 9-21-77
WH JO s CS2
64 X SUNSHINE
RTI SMOG CHAMBER STUDY
USER* CONTRACT NO. 68-02-24J7
TIME
(EST)
0.30
I.SJ
2. 80
J.JO
4. JO
5. JO
6. JO
7. JO
8. JO
9. JO
10. JO
II. JO
12. JO
IJ.JO
14.30
IS. JO
16. JO
17.30
18. JO
19.30
20. JO
21. JO
22. JO
23.30
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.007
0,050
0.094
0.134
0.177
0.227
0.27S
0.309
0.330
0.333
0.3IS
0.283
0.249
0.230
0.212
0.202
0.193
NO
(PPM)
0.004
.081
.080
.079
.079 a/
.079 ~
.077
.043
0.02J
O.OID
0.016
0.012
0.011
o.ooa
0.007
0.006
0.008
0.008
0.006
0.002
0.001
0.001
0.001
0.000
N02 NUX T-3UL COS S02 CS2 T-P-S CN-5 SK CU-SH ItMP
(PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (UG/MJ) (K-CN/CMJ) U/MIN) (L»NG) CELSIUS
0.005 0.009 0.0 0.0 |9.2
0.002 0.083 0.0 0.0 19.9
0.019 0.099 0.0 0.0 |9. S
0.021 0.100 0.0 0.0 16.9
0.02U/ 0.100 a/ 0.0 0.0 18.0
0.023 0.102 .500 .500 0.0 0.0 18.4
0.027 0,104 .500 .500 0.0 0.0«5 0.81 J7.9
0.061 0.104 .500 .500 0.0 120.000 0.255 7.29 19.1
0.074 0.097 .500 .500 0.0 fcH.OOO 0.515 27.27 20.9
0.07J 0.091 .500 0.234 .500 67.000 0.759 62.56 22.4
0.071 0.087 .500 0.319 .500 0.0 0.9SJ 1|»>.JI 23.8
0.067 O.OBO .500 0.405 .500 1.102 I7i. «6 24.8
0.061 0.072 .500 0.501 • .500 0.0 105.000 1,079 2J9.56 25.4
0.052 0.060 .500 0.588 .500 0.962 302.20 25.7
0.046 0.054 .500 0.671 .500 41.000 0.7JJ J55.79 2b.9
0.041 0.047 11.4 0.626 397.85 26.0
0.035 0.042 .500 0.756 .500 O.J49 430.42 25.8
0.025 0.033 .500 0.765 .500 0.097 446. 8J 24.4
0.016 0.022 .500 ' 0.740 .500 0.001 ISO. 92 21.1
0.010 0.012 .500 0.724 .500 0.0 450.96 19.2
0.008 0.009 0.0 0.0 450.96 17.8
0.008 0.009 .500 0.725 0.0 .500 1.000 0.0 450.96 lb.6
0.007 0.008 .500 0.722 0.0 .500 0.0 450.96 16. fl
0.006 0.006 .509 0.706 0.0 .500 0.0 450.96 J5.7
a/ Consider this value to be the interference-corrected initial concentration.
DAY 2, 9-22-77
68 » SUNSHINE
UMt
(ESI)
O.JO
1.30
2.30
J.JO
4.30
5. JO
6.30
7. JO
8.30
9.30
10. JO
II. JO
12. JO
IJ.JO
14. JO
15.30
16.30
OlUNt
(P»M)
0.186
0.179
0.172
0.166
0.163
0.157
V.I52
0.145
0.142
0.151
0.178
0.224
0.263
0.294
0.319
0.333
0.327
MJ N02
(PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
.007
.007
.006
.006
.006
.006
.005
0.0 0.006
0.002 0.009
0.004 <
>.OIO
0.006 0.011
0.007 0.012
0.006 O.OIJ
0.005 0.015
0.005 0.015
0.006 0.015
0.006 0.015
NUX T-SUL
(PPM) (PPM)
0.007 1.500
0.007
0.006
0.006
0.006
0.006
0.005
0.006
0.011
0.014
0.017
0.019
0.019
0.020
0.020
0.021
0.021
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
COS
(PPM)
0.693
0.703
0.703
0.703
0.699
0.697
0.602
0.706
0.717
0.777
0.8J9
0.908
0.952
0.999
1.061
1.071
302 CS2
(PPM) (PPM)
0.0 1.500
0.010
0.010
0.067
0.091
0.105
0.101
O.I J9
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.SCO
I-P-S CN-5 SH
(UG/MJ) (K-CN/CMJ) (L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0 0.0
0.052
0.0 0.293
0.52J
O.BOO
0.952
1.066
0.9J9
7.5 27.000 0.912
0.746
0.5JJ
0.0 27.000 O.J27
CIl-SP.
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.9H
«. 59
50.11
66.46
III. If
I7b. J9
238.06
29
387.77
110.05
TEMP
CELSIUS
15.1
13.9
12.9
12.3
\f.\
11. fl
12. 1
14.6
17.6
19. a
22.1
23. 7
24.2
24./
25.0
24.9
24. S
-------
ro
CHAMOEK NO. 3
OAT l, 9-21-77
RUN JO 1 C32
64 X SUNSHINE
RTI SMOG CMAMbEH STUDY
USEPA CONTRACT NU. 6H-02-24J7
TIME
(CST)
0.37
1.77
1.17
4.47
5.47
6.17
7.47
8.47
9./I7
10.47
11.47
13. '47
13.47
14.4?
15.47
16.47
17.47
16.47
19.47
20.47
21.47
22.47
23,47
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
HO
(PPM)
o.oos
0.762 a/
0.760-
0.751
0.739
0.726
0.710
0.608
0.669
0.674
0.659
0.642
0.621
0.601
0.604
0.612
0.5/9
O.S71
0.565
O.SS6
0.546
O.S38
0.528
NU2
(PPM)
0.009
0.19ia/
0.216"
0.227
0.238
0.249
0.251
0.249
0.245
0.232
0.238
0.224
0.21B
0.215
0.208
0.212
0.211
0.222
0.221
0.221
0.230
0.231
0.233
NOX T-SUL C03 S02 CS2 T-P-S CN-5 SH CU-SR TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (IJG/MJ) (K-CN/CM3) (L/MIN) (LANG) CELSIUS
0.014 0.0 0.0 19.2
0.975i,/ 0.0 0.0 19.9
0.976" 0.0 0.0 18.9
0.978 0.0 0.0 18.4
0.977 .500 .500 0.0 n.o 18.4
0.975 .500 .500 0.0 0.045 1.27 17.9
0.961 .500 .500 0.0 90.000 0.255 9.69 19.1
0.937 .500 .500 0.0 91.000 0.515 32.52 20.9
0.914 .500 .500 66.000 0.759 70.30 22.4
0.906 .500 .500 0.0 0.193 122. «4 25.8
0.897 .500 .500 1.102 1BS.10 24.8
0.867 .500 .500 0.0 41.000 1.079 £50. 57 25.4
O.B39 .500 .500 0.9b2 312.01 25.7
9.815 .500 .500 2B.OOO 0.733 363.27 25.9
0.812 .500 0.223 .500 0.0 0.626 404.23 26.0
0.824 .500 0.257 .500 0.349 413.98 25.8
0.789 .500 0.239 .500 0.097 447.81 24.4
0.793 .500 0.234 .500 0.001 450.93 21.1
0.786 .500 0.223 .500 0.0 450.96 19.2
0.777 0.0 0,0 450.96 17.8
0.776 .500 0.265 0.010 .500 1.300 0.0 (150.96 16. b
0.769 .500 0.271 0.010 .500 0.0 450.96 16. ft
0.761 .500 0.24ft 0.010 .500 0.0 M50.96 15.7
a/ Consider this value to be the interference-corrected initial concentration.
DAY 2, 9-22-77
66 X SUNSHINE
TIME
(EST)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
U/UME
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NU
(PPM)
0.517
0.511
0.504
0.498
0.49J
0.486
0.481
0.463
0.440
0.426
0.420
0.406
0.39<)
0.389
0.375
0.373
0.360
N02
(PPM)
0.234
0.239
0.244
0.245
0.250
0.254
0.257
0.257
0.249
0.225
0.210
0.215
0.210
0.214
0.204
0.205
0.199
NOX
(PPM)
0.751
0.750
0.748
0.743
0.741
0.742
0.738
0.720
0.689
0.651
0.638
0.621
0.609
0.603
0.579
0.578
0.559
f-SUL
(PPM)
1.500-
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
CUS
(PPM)
0.232
0.257
0.253
0.251
0.2SO
0.246
0.2SJ
0.329
0.352
0.38S
0.417
0.44?
0.461
0.484
0.519
0.526
302
(PPM)
0.010
0.010
0.010
0.065
0.094
0.094
0.106
0.121
0.132
CS2
PPM)
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
T-P-S CN-5 SR
(UG/MJ) (K-CN/CM3) (L/M1M)
0.0
0.0
0.0
0.0
0.0
0.0 0.0
o.osa
63.000 0.293
0.523
0.800
0.952
1 .066
0.939
0.0 18.500 0.91?
0.746
0.511
3.3 2B.OOO 0.327
CU-SK
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
1.47
11.18
35.45
7'l.64
126. 9J
187.26
247. 6
-------
CHAMBER NO. 4
0»Y I, 9-21-77
RUN 10 t cs2
64 X SUNSHINE
Rll SMUG CHAMBER STUDY
USEPA CONTRACT NU. 68-02-2437
TIME
(EST)
0.97
1.98
3.63
a. 63
5.63
6.63
7.61
6. 63
9.6J
10.63
11.63
13.63
13.63
14.63
15.63
16.63
17.63
18.61
19.63
20.63
21.63
33.63
23.61
UZONE
(PPM)
0.0
».o
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.003
0.004
0,005
o.oos
0.005
0.005
0.003
0.001
0.0
0.0
0.0
0.0
0.0
0.0
NU
(PPM)
0.396
0.3»7«/
0.381
0.378
0.376
0.369
0.347
0.310
0.280
0.245
0.221
0.200
0.186
0.176
0.171
0.164
0.152
0.150
0.146
0.144
0.143
0.141
0.138
N02
(PPM)
0.0
0.099 a/
O.|04~
0.107
0.110
0.115
0.131
0.150
0.174
0.189
0.203
0.205
o.aoi
0.201
0.204
0.206
0.197
0.201
O.|9fl
0.197
0.199
0.196
0.193
NOX
(PPM)
0.396
0.486 a/
0.485"
0.465
0.486
0.484
0.478
0.460
0.455
0.434
0.424
0.406
0.388
0.376
0.375
0.370
0.349
0.351
0.344
0.341
0.342
0.337
0.331
T-SUL
(PPM)
0.596
1.500
I.SOO
1.500
1.500
1.500
1.500
1.500
I.SOO
1.500
1.500
1.500
1.500
1.500
1.500
1.500
1.500
COS S02 CS2
(PPM) (PPM) (PPM)
0.327
0.243
0.336
0.333
0.395
0.423
0.432
0.435
0.439
0.439 0.010
0.438 0.010
0.443 0.010
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.SOO
I-P-S
(UG/M3)
0.0
0.0
0.0
0.0
0.0
4.3
0.0
cn-5
SR
(K-CN/CH3HL/M1N)
150.000
105.000
64.000
83.000
68.000
1.800
0.0
0.0
0.0
0.0
0.0
0.045
0.255
0.515
0.759
0.993
1.102
1.079
0.962
0.733
0.626
0.349
0.097
0.001
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
1.70
12.34
37.47
77.59
111. 98
195.68
260.93
321.24
370.31
410.24
437.33
44B.75
450. 11
450.96
450.96
450.96
450.96
450.96
TEMP
CELSIUS
19.2
19.9
18.9
16.4
16.4
17.9
19.1
20.9
22.4
23.6
24.6
25.4
25.7
25.9
26.0
25.6
24.4
21.1
19.2
17. B
16.6
16. 8
15.7
l-o
10
a/ Consider this value to be the interference-corrected initial concentration.
DAY 2. 9-22-77
68 X SUNSHINE
Tint
(ESI)
0.63
1.63
2.63
3.63
4.63
5.63
6.63
7.63
8.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.006
0.013
0.019
0.035
0.0)4
0.038
0.047
0.048
0.040
0.041
no
(PPM)
0.136
0.136
0.135
0.135
0.133
0.134
0.130
0.110
0.095
0.086
0.077
0.065
0.055
0.0'IB
0.036
0.034
0.026
NU2
(PPM)
0.193
0.190
0.189
0.187
0.107
O.lHb
O.l«5
0.190
O.lfltt
0.176
0.179
0.179
0.100
0.174
0.176
0.170
0.167
NOX
(PPM)
0.329
0.32$
0.324
0.322
0.320
0.320
0.315
0.300
0.283
0.2<>4
0.256
0.244
0.235
0.222
0.214
0.204
0.191
T-SUL
(PPM)
1.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
CUS
(PPM)
0.407
0.430
0.427
0.425
0.425
0.425
0.446
0.541
0.572
0.6|fl
0.677
0.6V8
0.737
0.76H
0.601
0.820
SU2
(PPM)
0.010
0.010
0.074
0.095
0.131
0.133
0.150
0.163
0.166
CS2
(PPM)
1.500
.500
.500
.500
.500
.500
.500
.500
.SOO
.SOO
.500
.500
.500
.500
.500
.500
T-P-S CN-5 SH
(UG/MS) (K-CN/CM3)(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0 0.0
0.052
100.000 0.293
0.523
0.800
0.952
1.066
0.939
3.9 59.500 0.932
0.7«6
O.S3J
0.0 41.000 0.327
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
1.97
l'l.
-------
CHAMBER NO. I
0»V I, 9-23-77
RUN 31 I M2S
SI X SUNSHINE
Rll SMIll, LHAMIIL'R SlUOr
USEPA CONTRACT NO. 66-02-2437
N5
10
oo
IlMt
(CST)
0.13
1.13
2.11
3.13
1.13
5.13
6.13
7.13
a. 12
9.10
to. 10
11.06
12.13
13.13
11.13
IS. 13
16.13
17.13
18. 12
19.12
20.10
21.10
22.10
23. OB
OZONt
(PPM)
0.000
0.0
0.0
0.0
0.0
0.0
0.000
0.0
0.000
0.001
0.001
0.001
u.ooi
0.0
o.o
0.0
0.0
0.0
0.0
0.001
0.001
I4O
(PPM)
0.001
0.001
0.163
0.16| a/
0.170 -
0.191
0.202
0.209
0.210
0.218
0.221
0.B
O.H51
1.04B
0.848
0.822
0.596
0.322
0.063
0.001
0.0
0.0
0.0
0.0
0.0
CU-SR
(LANG)
0.01
O.Ob
0.07
O.li
0.19
0.2S
0.66
5.04
22.08
54.16
98.99
151.47
205.51
266. 81
317.51
J65.07
196.69
4|h. IS
420.49
420.54
4ao,S4
420.54
420.54
420.51
1LMP
CELSIUS
12.6
12.2
.9
.6
.5
.8
.9
14.0
IH.4
21.7
2S.4
24.3
25.6
**. 1 S
24. Ib
S7.02
102. 72
160. HO
221.87
2BI.27
128.51
161. 1 1
Ittl .60
184. «4
104.84
HMP
CLLS1US
15.1
14.4
11.9
11.5
13.2
12.9
13.3
14.9
1 '.6
19.2
22.6
24.6
25.9
26.7
27.3
27.4
26.1
24.9
21. /
20.7
-------
to
ts>
CHAMIIEH Ml). 2
D»Y \, 9-21-M
RUN II I H23
51 X SUNSHINE
RT1 SMOG CHAMBER STUDY
U31PA CONTRACT NO. 68-02-2417
IINE
(1ST)
O.JO
1.10
2.10
J.10
4.10
5.10
6.10
7.10
6.28
9.27
10.27
11.10
12.10
11.10
14.10
15.10
16.10
17.10
16.28
19.26
20.27
21.27
22.27
21.25
OZONE
HO
(PPM) (PPM)
0.000
0.0
0.001
0.003 •
0.0 0.082
0.0 0.062s/
0.0 0.09|
0.0
0.000
0.000
0.000
0.001
0.001
0.001
0.0
0.0
.10}
.111
.116
.120
.126
.126
.112
.111
.117
0.0 0.115
0.0 O.li9
0.0 0.116
o.o 0.111
0.0 0.111
0.001 0.129
0.001 0.126
N02
(PPM)
0.001
0.001
0.022
0.021 a/
0.012"
0.001
0.002
0.002
0.004
0.001
o.ooi
0.001
0.002
0.001
0.001
0.004
0.005
0.005
0.006
0.006
0.007
NOX
(PPM)
0.004
0.006
0.104
0.101 a/
0.101
0.107
0.111
0.118
0.124
0.128
0.111
0.114
0,115
0.116
0.11H
0.141
0.141
O.I 18
0.117
0.115
0.115
T-SUL
(PPM)
0.0
0.0
0.0
1.500
1.500
1.500
1.500
I.SOO
1.500
1.500
1.500
1.500
1.500
1.500
1.500
1.500
1.500
S02 H2S
(PPM) ^ (PPM)
0.0 0.0
0.0 0.0
0.0 0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.122
0.115
0.157
0.140
O.|9|
0.172
0.140
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
F-P-S
(ur,/Hjj
4.6
0.0
1.4
0.0
0.0
0.0
0.0
CN-5
(H-CN/CMJ)
0.0
72.000
125.000
110.000
125.000
a/ Consider this value to be the iiiterfercucc-correctcJ initial concentration.
0»r 2. 9-24-77
16 X SUNSHINt
502
(PHM)
TIME
(CST)
0.23
1.21
2.22
J.22
4.22
5.20
6.10
7.10
6.10
9.10
10.10
11.10
12.10
11.10
14.10
15.10
16.10
17.10
16.10
020NE
(PPM)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.0
o.o
0.0
0.000
0.001
0.002
0.002
0.002
0.002
0.001
0.001
0.0
NO
(PPM)
O.U7
0.127
0.125
0.125
0.124
0.122
0.121
0.122
0.125
0.126
0.122
0.120
0.111
0.106
0.099
0.092
0.085
0.081
0.078
N02
(PPM)
O.OOo
0.006
0.007
0.006
0.006
0.005
0.005
0.004
0.004
0.006
0.011
0.020
0.021
0.025
0.010
0.029
0.012
0.014
O.Oil
NOX
(PHM)
0.111
0.111
0.1)2
0.111
0.110
0.127
0.126
0.126
0.129
0.112
0.115
0.140
0.114
0.112
0.129
0.121
0.117
0 . 1 1 5
0.112
T-SUL
(PPM)
0.910
0.644
0.791
0.716
0.667
0.641
0.591
0.505
0.505
0.471
0.415
0.409
0.198
0.170
0.182
0.144
0.117
0.29d
0.228
0.194
0.187
0.181
H2S
U'PH)
1.158
1.078
1.016
0.947
0.881
0.825
0.770
0.694
0.618
0.516
0.415
0.129
0.228
0.125
O.OB5
0.061
T-P-S
(UG/lll)
CN-5
(K-CN/CM1)
0.0 0.0
11.7 47.000
SH
(L/M1N)
0.001
0.0
0.001
0.001
0.001
0.001
0.046
0.251
0.525
0.7JO
0.898
0.811
1.048
0.818
0.822
0.596
0.122
O.OflJ
0.001
0.0
0.0
0.0
0.0
0.0
CU-SH
(L*NG)
0.02
O.Ob
O.U8
0.11
0.20
0.26
1.1 I
7.6i
21.12
61. hi
108.15
162. 41
216.20
275.48
J25.90
171. IS
101.97
416.99
•20.50
420.54
420.51
420. Sa
420. 5a
420. 5«
TEMP
CtLSIUS
12.6
12.2
.9
.6
.5
.8
.9
14.0
18.4
21.7
21.1
24. J
25.6
25.7
26.0
26.1
2S.9
24.1
21.4
19.1
17.8
17.2
16.7
IS. 8
8.1
19.10
2.100
SR
(L/M1N)
0.0
0.0
o.o
0.0
0.0
0.001
0.010
0.097
0.211
0.516
0.711
0.9S4
1.062
0.97H
0.614
0.611
U. Jo'i
0.062
0.0
0.0
CU-SR IEMP
(LANK) CtLSIUS
0.0
0.0
0.0
0.0
0.0
0.01
0.60
1.61
11.40
29.61
6U.49
II?.«5
171.64
211.84
289.57
114.7h
366. M
162.2a
38'l.flu
1B4.H4
15.1
14.4
11.9
13.5
11.2
12.9
II. 1
14.9
17.6
19.2
22.6
24.6
25.9
26.7
27.1
27.1
26.1
21.9
21.7
-------
u>
o
CHAMBER NO. 3
DAY 1, <»-21-77
RUN 31 ( H2S
51 X SUNSMINt
HI I SMUG CHAMBER STUDY
USEPA CONTRAC1 Nil. 68-02-2417
TIHt
(ESI)
0.47
1.47
2.47
1.47
4.47
5.47
6.47
7.47
8. 45
9.4}
10.41
11.61
12.47
11.47
14.47
15.47
16.47
17.47
18.45
19,45
20.41
21.4}
22.43
21.42
OIOHi
(PPM)
0.000
0.0
0.0
0.0
o.o
0.0
0.000
0.000
0.001
0.001
0.001
0.002
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.000
NU
(PPM)
0.004
0.005
0.751
0.741 a/
0.755
0.814
0.880
0,901
0.89}
0.910
0.905
0.917
0,905
0.905
0.895
0.901
0.874
0.854
0.812
0.818
0.802
N02
(PPM)
0.004
0.005
0.212
0.211a/
0.184
0.102
0.011
0.010
0.011
0.001
0.009
0.008
0.007
0.012
0.02J
0.029
0.047
0.062
0.071
O.OB5
0.089
nox
(PPM)
0.009 1
0.010 1
0.965
0.954 a/
0.919
0.917
0.913
0.911
0.907
0.9|4
0.911
0.925
0.912
0.917
0.918
0.912
0.921
0.916
0.901
0.901
0.891
I-SUL
tPPM)
>.o
>.o
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
S02
(PPM)
0.0 (
0.0 (
0.0
0.147
0.155
0.147
0.119
0.126
0.150
0.209
0.257
0.290
0.129
0.374
0.176 "
0.350
0.292
H2S
»'PM)
>.o
1.0
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
,T-P-S
(UG/MD
0.0
2.8
0.0
4.6
4.6
5.1
3.6
CN-5
(K-CN/CM3)
0.0
91.000
105.000
98.000
110.000
are insufficient to penalt correction for interference.
DAY 2, 9-24-77
TIME
(EST)
0.40
1.40
2.18
1.18
4.18
5.17
6.47
7.47
8.47
9.47
10.47
11.47
12.47
11.47
14.47
15.47
16.47
17.47
18.47
19.47
UZIME
(PPM)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.0
0.0
0.000
0.000
o.ooo
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NU
(PPM)
0.790
0.774
0.759
0.750
0.740
0.724
0.708
0.70]
0.698
0.701
0.694
0.682
0.671
0.655
0.650
0.611
0.620
0.617
0.604
N02
(PPM)
0.101
0.109
0.121
0.124
0.131
0.115
0.146
0.116
0.130
0.106
0.092
0.091
0.089
0.091
0.086
0.092
0.091
0.09B
0.100
HOX
(PPM)
0.891
0.881
0.879
0.874
0.870
0.859
0.8'jl
0.818
.0 . 828
0.808
0.786
0.771
0.761
0.747
0.716
0.721
0.711
0.716
0.709
T-SUL
(PPM)
0.846
0.79}
0.716
0.687
0.641
0.597
0.552
0.529
0,487
0.471
0.441
0.198
0.418
0.416
0.411
0.404
0.186
0.154
0.287
16 X SUNSHINE
302
(PPM)
0.257
0.252
0.244
0.225
H2S
(PPM)
0.945
0.878
0.816
0.756
0.701
0.650
0.595
0.541
0.481
0.404
0.294
0.097
0.067
0.050
I-P-S
(UG/MD
CN-5
(K-CN/CMI)
0.0 0.0
14.8 21.000
SH
U/MIN)
0.001
0.0
0.001
0.001
0.00)
0.001
0.0
13. S
14. •»
17.6
19.2
22. h
24.6
25. V
26.7
27.3
27.4
2b.l
24.')
il.l
20.7
-------
CHAMBER NO. 4
0*V 1, 9-21-77
RUN 31 I H2S
SI X SUNSHINE
NT I SMOG CHAMBER SlUOt
UStH* CONTRACT NO. 68-
TIME
(EST)
0.63
1.63
2.63
3.63
4.63
5.63
6.63
7.63
a. 62
9.60
10.60
11. 80
12.63
13.63
14.63
15.63
16.63
17.63
18.62
19.62
20.60
21.60
22.60
23.58
OZONE
(PPM)
0.001
0.0
0.0
0.0
0.0
0.0
0.0
0.000
0.001
0.001
0.001
0.002
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.000
NO
(PPM)
0.002
0.003
0.389
0.385 a/
0.405
0.450
0.473
0.476
0.480
0.486
0.488
0.493
0.492
0.491
0.488
0.486
0.475
0.466
0.458
0.453
0.447
N02
(PPM)
0.004
0.003
0.103 ,
0.104 a/
0.073
0.024
0.005
0.003
0.007
0.004
0.004
0.004
0.001
0.001
0.005
o.ooa
0.014
0.020
0.023
0.025
0.031
NUX
(PPM)
O.OOS
0.006
0.492
0.489 a/
0.478
0.474
0.478
0.481
0.488
0.491
0.491
0.497
0.493
0.492
0.493
0.494
0.489
0.486
0.481
0.476
0.478
r-SUL
(PPM)
D.O
5.0
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.375
S02
(PPM)
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.068
0.064
0.171
0.189
O.|9tt
0.239
0.262
0.249
0.202
H2S
(PPM)
D.O
0.0
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.500
.496
T-P-S
(UG/M3)
2.9
^.8
0.0
0.0
0.0
0.0
0.0
CN-S
(K-CN/CM3)
0.0
90.000
95.000
105.000
98.000
a/ Data are insufficient to permit correction for interference.
OAr 2, 9-24-77
TIHC
(EST)
0.57
1.57
2.55
3.55
4.55
5.53
6.63
7.63
8.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
18.63
19.63
OZONE
(PPM)
0.000
0.000
0.000
0.000
o.ooo
0.000
0.0
0.0
0.0
0.000
0.000
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NO
(PPM)
0.142
0.435
0.43|
0.427
0.422
0.414
0.409
0.408
0.407
0.406
0.398
0.387
0.379
0.370
0.360
0.348
0.345
0.336
0.332
N02
(PPM)
0.033
0,035
0.030
0.03«
0.039
0.042
0.044
0.039
0.036
0.035
0.042
0.048
0.050
O.OSO
0.053
0.055
0.055
0.066
0.055
NOX
(PPM)
0.474
0.471
0.407
0.465
0.461
0.456
0.453
0.448
0.443
0.441
0.440
0.4J5
0.429
0.420
0.414
0.404
0.400
0.402
0.3A7
T-SUL
(PPM)
O.HI1
0.763
0.710
0.669
0.62B
0.589
0.543
0.517
0.481
0.450
0.423
0.411
0.411
0.393
0.396
0.362
0.343
0.301
0.228
36 X SUNSHINE
3(12
(PPM)
0.200
0.191
0.18ft
H2S
(PPM)
•
0.967
0.917
o.a/i
0.818
0.768
0.720
0.664
0.607
0.536
0.448
0.3«0
0.251
0.114
O.OH3
0.073
I-P-S
(UG/M3)
CN-5
(K-CM/CM3)
0.0 0.0
10.5 32.000
SR
U/MIN)
0.001
0.0
0.001
0.001
0.001
o.oot
0.046
0.254
0.525
0.730
O.«9fl
0.8)1
1.048
0.848
0.622
0.596
0.322
0.083
0.001
0.0
0.0
0.0
0.0
0.0
CU-SR
(LANG)
0.04
0,06
0.10
0.16
0.22
0.2B
2.04
12.66
37.83
76.08
125.93
187.37
236.95
292.27
342.17
382.95
408.35
416.64
420.52
420.54
420.54
420.54
420.54
420.54
IEMP
CELSIUS
12.6
12.2
11.9
11.6
11.5
II. 8
11.9
14.0
16.4
21.7
23.3
24. J
25.6
25.7
26.0
26.3
25.9
24.3
21.4
19.1
17.8
17.2
16.7
15.8
0.0
2.000
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.001
0.030
0.097
0.211
0.516
0.733
0.954
1.062
0.97B
0.614
0.61 1
0.345
0.062
0.0
0.0
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.03
1.19
5.53
15.66
39.84
79.01
131.34
192.66
?5i.2l
S0r>.69
346. 86
J7 J.46
3H3.«6
3au.hu
ifl'I.HH
TEMP
CELSIUS
15.1
14.4
13.9
13.5
13.2
12.9
IJ.J
14.9
17.6
19.2
22.6
24.6
25.9
26.7
27.3
27.4
26.1
^a.9
21. /
20.7
-------
CMAMhfK nil. |
DA* I, 9-28-77
RU?« 12 : Clli-3-Ull
64 * SIINSHIIU.
((II 3Mill, (.IIAI-IIH R Sillily
ustPA cMUTiMtr no. 68-02-2117
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13
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13
13
13
13
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o.o
0.0
u.o
o.o
0.0
0.0
0.001
0.0/6
0.555
0.402
0.481
O.ibO
0.323
0.2V5
0.267
0.229
0. OS
0. IVj
0. 126
0 . 1 1 5
0.093
0.0 7S
O.OS6
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(I'P.'I)
0.006
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0.012
O.I'jQ
0.159s/
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0.129
0.0lri
0.006
O.OO'j
O.OOS
0.005
O.OOS
0.005
0.004
0.005
0.007
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0.006
0.006
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0.401
0.37'l
0. 468
0.561
0.3S4
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0.136
0.119
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0. 501
0.290
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0.001
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O.OIJ
0.01 J
O.OI.J
0.011
O.OM
o.on
o.oio
0.011
o.oiu
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0. 160
O.I Jl
O.I 111
0.144
o.iai
0.07J
0.010
1-P-S CN-'j
(IH./H.I) (K-CN/tMJ)
0.690
0.0
'ii. 4 in. ooo
4H.i? J9.000
11.7
ac'.h i.«"o
b.HOO
16.0
b. JOO
SH
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.016
O.?bl
O.WB
O.bbH
O.U6U
0.710
I.OHH
1.098
0.71H
O.bSO
0.11 J
0.071
0.071
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
1.16
Lit
£9.42
61. 74
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a/ Intcrfereiice-correctod initial (NO), (M12)> a"1'
I>AY ?, 10- 4-77
arc 0.062, 0.020, ami 0.082 p|w.
lit
SUNSHIML
ii ML
(LSI)
0.
i .
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4.
5.
6.
7.
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9.
10.
11.
12.
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0.
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0.
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0.
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0.
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0.
SUL 5112
I'M) (I'PM)
597
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166
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161
ISO
5b2
I'l 9
1 \t>
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104
2/t'
2*"
<•*<'!
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I-I'-S CH-5
(IIU/MJ) (K-CW/C.M1)
'I. I
5.2
0.0
I'j.OOO
SK
(L/MIN)
0.001
0.001
0.0
0.0
0.0
0.0
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N)
W
00
CHA.mi 1' .*
DAY 1, 10
-*l-/7
HI I bill!, CHAI
IISI PA CHNIKAI
PUN J.I : L2ll'i-S-H 71 X
I IMC
(ESI)
0.97
1 .61
2.10
1.11
4.5$
5.72
6. no
7.47
8. '17
9.47
10. '17
11.47
12.47
11. hi
14.47
15.47
16.47
17.47
17. 9/
IH.flO
19.47
20. JO
21.47
22.61
21.11
OIUUI
(I'I'H)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.011
0.012
0.041
0.072
0.144
0.240
0.282
0.111
0.11 1
0.2/1
0 . 25 I
0.226
0.214
0.202
0. Itt'l
0.172
0. I6H
HO
(I'I'M)
0.001
0,021
O.«02
0.7H|a/
0.762
0.709
O.TI7
O.I7H
O.IDI
0.067
rt.O/n
0.042
0 . 0 1 1
O.U07
0.006
0.001
0.002
O.W04
0.002
0.002
O.OOJ
U.002
o.ooj
it.0i>2
ti(>2
(PHU
0.0'«
0.5 III
O.'tlt/
I) . 't 1 1
0. IVI
0.295
0.250
0.218
0.2(lo
ft 1 9 *4
0. lr'()
O.lrti
O.I I't
0.174
0. 1 1 !>
a/ Interference-corrected initial (NDJ,
L)AV 2/ 10
II Mi.
(LSI)
0.11
l.ll
2.11
1.90
4.97
5.47
6.47
7.47
8.61
9.47
10.47
11.47
12.47
11.47
14.47
15.47
16.47
17.47
(l^i l.ll
(CPU)
0.160
0.154
0 . 1 4 /
0.1 lo
0. Ill
0.129
0.12-1
0.119
0.126
0.151
0.214
O.c'liO
0.454
6.4UI
0 . 4 I :>
0.447
II.'4'V
(III
(IT I)
0.002
0.002
O.tlOJ
0.002
0.002
0. H'l?
0 . OU|
J.002
0. ul)S
0. Ul''4
O.uo'l
(1. 004
o. nu«
O.U-M
W. ilO,"
0. .104
II . .Mlf1
Ml 12
(PP*)
O.H.9
0 . 1 n /
0 . 1 1.6
i) . 1 o 5
0. l"r-
0 . | (i 1
0. |5'»
O.I Ml
0 . U. 1
ii . 1 •• 1
<> . 1 >> 1
.) . I i./f
0 . 1 6 >
.1.1. .2
ii. 1 '"'
.1. ICl
n . I " I
mix
(»'!•«)
0.010
0.021
0.802
I/ 0.994
0.9/0
0.9'IH
0.914
0. 7H9
0.649
0.611
O.SttH
0.519
0.425
O.ihl
11.100
0.254
0.220
0.2D9
0. 196
l). 192
O.I H6
0 . 1 II 1
0.177
II . 1 75
(ND21, and
- 4-77
IlUX
(I'PH)
0.171
0.1 6'»
0.169
0.167
II. ll.'l
0 . 1 1. J
.) . 1 n 0
0.11.2
U.I 66
l). 16'i
0.1 <>5
0.166
II . 1 6 /
U . 1 t.S
U . ll>'l
O.K.')
'i. 1*. 4
l-sut
(PPH)
0.0
.500
.500
a/ .500
.500
.500
.145
0.869
0.662
0.551
O.'llH
0.189
0.142
0.104
0.274
0.211
0.118
0.010
0.010
(NOX1 are 0.
76 X
1-aiiL
(PPM)
SUNSHINt
sn2 I-P-S
(PI'M) (UC./HJ)
0.0
0.0
0.0
0.0
0.165 141.5
0.166 |07.|
0.120 l.'t.O
0.240
0.244 h'».l
0.221
^
0.202 51.1
0.171
0.095
0.010
fl . 0 1 0
758, 0.2.10. and 0.988 pfw
SUNKHIMI
S(I2 I-P-S
(PPM) (IHi/M.1)
f*.l>
4.4
«.9
CN-5
(K-CN/CH1)
7.100
19.0UO
19.000
14.000
16.000
12.000
LN-5
(K-tN/tMl)
0.0
6.000
6.HOO
0.0
SH
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.016
0.281
0.5/8
0.558
0.464
0.710
t .088
1 .098
0.718
0.650
O.SI1
0.0/1
0.071
0.0
0.0
0.0
0.0
0.0
0.0
SH
(L/MIN)
0.001
0.001
0.001
0.0
0.0
0.0
0.026
0.246
0.565
0.800
0.98M
1.105
0.99.1
0. /02
0.751
0.511
0. S24
0.059
CU-SM
a«t«;)
0.0
0.0
0.0
0.0
0.0
0.0
1.7)
10. OB
15.12
69.44
100.26
115.61
189.50
265.60
110.21
151.19
180.89
192.84
194.97
195.10
195.10
195.10
195.10
195.10
195 . 1 0
CU-SH
(L*U(.)
0.01
0.07
0.11
0.18
0.18
0. 18
0.9|
fl.hrt
17.86
/2.96
126.26
188.84
251.98
101.16
i'16.86
185.21
4 1 0 . 66
'122.62
UMP
CtLSlUS
14.6
14.7
14.7
15.0
16.2
17.1
17.1
17.4
16.7
15.6
15.6
12.1
12.6
12.2
8.9
7.1
sfq
CtLSlUS
5.2
4.6
4.9
3.6
1.1
2.6
2.8
6.4
11.8
14.7
16.2
17.4
17.9
17.8
18.0
18. 1
18.2
16.1
-------
tllAi-itifK ill). <|
DAY i, ID- i-//
win 33 : L2H5-S-M
73 X iiUNSHINt
Nil SM(IG CHAMBtH S1UDT
USff'A riinlHAU Nil. 68-02-2437
1 1 Ml
(tSl)
1.13
2. 41
3.47
4.97
5.97
6.13
6.97
7.«.3
A. 63
9.63
10.97
11.63
12.63
13.97
14.63
15. BO
16. 72
18.13
18.97
20.47
Oltl.U
(f'l'.l)
0.0
0.0
0.0
0.0
0.0
0.0
0.005
O.OH6
0.171
0.200
0.232
0.294
0.346
0.361
0.364
0.350
0.311
0.294
0.2/2
III!
(ITU)
0.004
0.024
0.39ft
l'.392a/
0.3H7
0.340
0.133
0.02ft
0.013
o.oon
O.OOH
d.007
0.006
0.003
0.003
0.003
O.OU3
0.002
0.003
n8, O.J29, ajxl 0.497 pp«.
0»v -'. 10- «-//
I if.I
US?)
5.80
0.63
7.63
H.HO
9.63
10.
1
.63
.63
12.63
13.63
14.63
15.63
16.63
I 7.63
U.19U
O.|tl4
0.179
0.|H|
0.200
U.305
O.lB'i
0.403
0.411
li. 4 1 4
Mil
(»'!'. i)
0.002
0.002
o.oo/i
0.005
0.004
O.U04
O.UH3
0.00?
U.HU2
•i.iUM
SJ(I2
(ITU)
O.I 49
o!|49
0.1 5H
0.150
0.147
0. |49
0 . I -I /
0. |4i>
('. t -i 'j
0.1-12
UUX
(I'fM)
0.150
0.151
0.154
0.155
0.153
O.l'il
U.153
O.I S«l
O.I4H
0 .1 'I 7
i). I'15
76 X
I-SUL
(I'PM)
Si 12
(CHI)
I-H-S CN-5
(IJK/M3) (K-CN/CM3)
0.200
5. 7
0.0
4.0
4.600
5. /»0
0.0
SM
(L/H1N)
0.0
0.026
0.2'46
0.565
O.HOti
0.968
1.105
0.993
0.702
0.751
0.513
0.32H
0.059
CU-SH ttMP
(LANG) CLLSIUS
0.16
1.16
11.04
43.62
«0.64
115.75
199.45
261.52
310.10
354.07
390.13
415.77
423.19
2.6
2.B
6.4
II. a
l«.7
16.2
17.4
17.9
17.8
in.o
IH.l
IH.2
16.3
-------
CHAMBER NU. |
OAT I. 10- 5-77
RUN 34 I (CH3S>2
99 X SUNSHINE
RT1 SNUG CHAMBER STUDY
UStPA CONTRACT NO, 68-02-2437
N>
*-
O
TIME
(tST)
o.ao
i.eo
2.30
J.27
4.40
5.IJ
6.13
7.13
a. n
9.30
10.63
11.63
12.13
13.13
14.30
IS. 13
!<>. |3
17.13
16.13
16.63
19.47
20.13
21.13
22.13
23.47
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.004
0.080
0.100
0.107
o.ne
0.129
0.129
0.121
0.10S
0.069
0.062
0.071
0.064
0.054
0.046
0.037
NO
(PPM)
0.002
0.149
0.155
0.156
0.154
0.057
0.024
0.010
0.007
0.006
0.011
0.009
0.006
0.006
0.004
0.002
0.001
0.002
0.002
0.002
0.001
0.0
0.0
a/ Consider this value to be
TIME
(LSI)
0.47
1.47
2.97
3.97
4.97
5.97
6.80
7.47
6.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
OZOflfc
(PPM)
0.033
0.027
0.021
0.016
0.014
0.011
0.006
0.007
0.007
0.015
0.029
0.043
0.074
0.104
0.114
0.114
0.105
NO
(PPM)
0.0
0.0
0.0
0.0
0.000
o.o
0.002
0.002
0.002
0.002
0.002
0.004
0.007
0.007
0.006
o.ooa
0.005
N02
(PPM)
0.003
0.0
a/ 0.035a/
0.040"
0.040
0.102
0.066
0.029
0.012
0.013
0.011
0.010
0.011
0.011
0.009
0.010
0.012
0.010
0.009
0.006
0.006
0.006
0.006
NUX
(PPM)
0.005
0.149
0.190 a/
0.196
0.193
0.156
0.091
0.040
0.019
0.021
0.022
0.019
0.019
0.016
0.014
0.013
0.013
0.012
0.012
0.010
0.008
0.006
0.006
the interference-corrected
DAY 2. 10-
N02
(PPM)
0.006
0.006
0.006
0.006
0.006
0.007
0.006
0.007
0.007
0.006
0.009
0.010
0.011
0.011
0.013
0.012
0.011
6-77
I4UX
(PPM)
0.006
0.006
0.006
0.006
0.007
0.007
0.007
0.009
0.009
0.010
0.011
0.014
0.018
0.016
0.021
0.019
0.017
T-3UL
(PPM)
0.0
1.500
1.500
1.500
1.500
1.500
0.659
0.752
0.542
0.525
0.492
0.446
0.423
0.397
0.329
0.2)0
initial
29 X
I-SUL
(PPH)
0.135
0.118
0.099
302 T-P-S
(PPH) (UG/M3)
0.0
0.0
0.0 0.0
0.0
0.065
0.379 502.4
0.662
0.606 230.9
0.432
0.421 127.9
0.392
0.354
0.327 148.9
0.312
0.260
65.4
.
concentration.
SUNSHINE
S02 T-P-S
(PPM) (UG/M3)
8.9
J.6
O.OB3
0.074
0.059
0.0
PAN
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
PAN
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CN-5
(K-CN/CM3)
0.0
23.000
27.000
24.000
2.600
1.200
CN-5
(K-CN/CMi)
0.0
1.000
0.0
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.027
0.256
0.556
0.7T9
O.V60
1.067
1.056
0.947
0.785
0.561
0.291
0.052
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SR
(L/MIN)
0.0
0.0
0.001
0.0
0.0
0.0
0.040
0.155
0.407
0.663
O.b4l
0.926
0.979
0.637
0.417
0.276
0.191
0.035
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.21
3.62
21.32
64.36
131.37
195.01
226.94
289.45
353.01
390.36
421.9)
437.50
440.22
440.22
440.22
440.22
440.22
440.22
400.22
Ctl-SR
(LANG)
0.0
0.0
0.06
0.06
0.06
0.06
1.98
6.63
14.93
41.35
HO. 18
115.64
171.62
227.69
264.19
2flfl.ll
304.01
314.25
TtMP
CELSIUS
5.1
4.5
3.9
3.4
2.9
2.6
2.6
5.4
9.9
14.2
17.3
16.9
19.8
20.4
20.8
20.3
20.7
ia.7
14.8
14. »
12.6
11.3
10.3
9.4
6.7
TtMP
CELSIUS
8.2
7.8
7.5
7.3
7.2
7.5
7.6
10.3
13.4
16.8
18.7
20.4
21.9
22.6
22.8
21.6
19.8
18.7
-------
CHAMBER NU. 2
DAY If 10- 5-77
RUN 14 : (CH3S)2
Rtl SMOG CHAMBER STUDY
USLPA CONTRACT NO. 68-02-2437
99 X SUNSHINE
I IMC
(CST)
0.97
2!47
3.47
4.63
5.30
6.30
7.30
6.30
9.47
10.00
II. 80
12.30
13.30
14.47
15.30
16.30
17.30
18.30
18.80
19.63
20.30
21.30
22.30
23.63
UZQNC
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.002
0.020
0.042
0.079
0.104
0.112
0.109
0.096
0.063
0.076
0.069
0.064
0.055
0.049
0.043
NO
(PPM)
0.004
0.070
N02
(PPM)
0.004
0.0
.074a/ 0.0»7a/
.073
.073
.013
.012
.010
.011
0.011
0.010
0.010
0.008
0.005
0.004
0.002
0.001
0.002
0.003
0.002
0.000
0.0
0.0
a/ Consider this value to be
TIME
(tST)
0.63
1.63
2.13
5.13
4.13
5.13
6.13
7.63
8.30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
UZONE
(PPM)
0.037
0.033
0.032
0.027
0.024
0.021
0.019
0.015
0.016
0.023.
0.036
0.052
0.067
0.117
0.124
0.125
0.116
riu
(PPM)
0.0
0.0
0.0
0.0
o.o
0.0
0.000
0.001
0.003
0.002
0.002
0.005
0.000
0.007
0.000
0.007
0.005
0.010
0.017
0.050
0.020
o.oio
0.006
0.006
0.000
0.009
0.009
0.009
O.OOB
0.009
0.010
0.010
0.008
0.006
0.007
0.006
0.006
NUX
(PPM)
O.OOB
0.070
0.09|a/
0.091
0.009
0.062
0.039
0.020
0.017
0.019
0.016
0.016
0.016
0.015
0.012
0.011
0.011
0.012
0.011
0.011
0.007
0.006
0.006
the inter fcreiKc-correcterl
DAY 2, 10-
N02
(PPM)
0.005
0.005
0.005
0.005
0.005
0.006
0.006
0.005
0.007
o.ooa
0.008
0.009
0.011
0.012
0.012
0.012
0.011
6-77
NUX
(PPM)
0.005
0.005
0.005
0.005
0.005
0.006
0.006
0.006
0.010
0.010
0.010
0.014
0.019
0.019
0.020
0.018
0.017
T-3UL
(PPM)
0.0
.500
.500
.500
.500
.500
.500
.362
.094
0.636
0.601
0.547
0.469
0.457
0.420
0.276
Initial
29 X
T-SUL.
(PPM)
0.095
0.081
0.058
S02 T-P-S
(PPM) (UG/H3)
0.0
0.0
0.0
0.0 0.0
0.0
0.010
0.192 156.7
0.387
0.514 177.4
0.497
0.484 107.6
0.439
0.393
0.365 107.8
0.333
0.267
concentration.
SUNSHINE
S02 F-P-S
(PPM) (UG/M3)
t
0.0
0.0
0.010
0.010
0.010
4.S
PAN
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0
o.o
0.0
o.o
0.0
o.o
0.0
0.0
0.0
PAN
(PPM)
0.0
0.0
o.o
0.0
o.o
0.0
0.0
0.0
0.0
0.0
o.o
o.o
0.0
0.0
CN-5
(K-CN/CM3)
0.0
18.500
19.000
22.000
2.100
1.200
CN-5
(K-CN/CH3)
0.0
0.690
0.0
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.027
0.256
0.556
0.779
0.960
1.067
1.056
0.917
0.785
0.561
0.291
0.052
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SH
(L/MIN)
0.0
0.0
0.001
0.0
0.0
0.0
0.040
0.155
0.407
0.66)
0.511
0.926
0.979
0.6J7
0.417
0.276
O.|9|
0.035
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.19
6.23
26.99
72.11
143.16
205.90
237.71
299.11
361.02
396. OB
021.88
438.04
440.22
440.22
440.22
440.22
440.22
440.22
440.22
CU-SR
(LANG)
0.0
0.0
0.01
0.06
0.06
0.06
0.37
6.32
19.09
4A.lt
85.70
125.09
101.60
234.19
26B.45
290.93
305.96
ill. 61
TEMP
CELSIUS
5.1
4.5
3.9
3.4
2.9
i. 6
2.t>
5.4
9.9
14.2
17.3
18.9
19.6
20.4
20.8
20.3
20.7
18.7
1«.8
14.8
12.6
11.3
10.3
9.4
B.7
HMP
CELSIUS
6.2
7.6
7.5
7.3
7.2
7.5
7.6
10.3
13.4
16.8
18.7
20.4
21.9
22.6
22.8
21.6
19.8
18.7
-------
CHAHBLK 140. 3
PAY I, 10- 5-77
RUN 14 I (CH1S12
RTI SMOG CHAMBER STUDY
USCPA CONTRACT NO. 68-02-2017
99 X SUNSHINt
TIME
(EST)
0.47
1.11
2,77
1.87
4.60
5.47
6.47
7.47
8.47
9.61
10.97
11.97
12.47
11.47
14.63
15.47
16.47
17.47
IB. 47
18.97
19.80
20.47
21.47
22.47
23.80
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.003
0.054
0.056
0.104
0.221
0.267
0.376
0.385
0.370
0.347
0.314
0.282
0.269
0.251
0.239
0.223
0.209
0.194
NU
(PPM)
0.006
0.794
N02
(PPM)
0.004
0.0
0.784 a/ O.|9ba/
0.764
0.743
0.129
0.014
0.044
0.024
0.011
0.009
0.008
0.007
0.005
0.003
O.OOl
0.002
0.002
0.003
0.001
0.0
0.0
0.0
a/ Consider this value to be
TIME
(EST)
0.80
1.80
2.30
J.JO
4.30
5. JO
6.30
7.13
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
OZONE
(PPM)
0.183
0.173
0.167
0.159
0.150
0.143
0.114
0.126
0.115
0.115
0.121
0.114
0.166
0.194
O.|97
0.19M
0.180
NO
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.000
0.001
0.003
0.002
0.002
0.005
0.008
0.007
0.007
0.007
0.004
0.215
0.229
0.612
0.445
0.2****
0.214
0.117
0.096
0.045
0.031
0.026
0.024
0.024
0.026
0.022
0.021
0.021
0.021
0.020
0.020
NOX
(PPM)
0.010
0.794
0.980 a/
0.979
0.972
0.742
0.478
0.143
0.216
0.146
O.I OS
0.053
0.018
0.011
0.028
0.025
0.028
0.024
0.024
0.021
0.021
0.020
0.020
the interference-corrected
DAY 2. 10-
N02
(PPM)
0.019
0.019
0.019
0.019
0.019
0.020
0.020
0.020
0.021
0.021
0.024
0.025
0.027
0.029
0.029
0.02B
0.027
6-77
NOX
(PPM)
0.019
0.019
0.019
0.019
0.019
0.020
0.020
0.020
0.024
0.025
0.026
0.030
0.014
0.036
0.036
0.034
0.012
T-SUL
(PPM)
0.0
0.0
I.SOO
1.500
1.500
1.096
0.765
0.685
0.655
0.506
0.492
0.465
0.466
0.421
0.398
0.292
S02 T-P-S
(PPM) (UG/M3)
0,0
0.0
0.0
0.0 0.0
0,0
0.707
0.6S8 276.3
0.564
0.543 146.3
0.422
0,411 174.6
0.163
0.159
0.145 68.2
0.129
0.248
90.3
PAN
(PPM)
0,0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CN-5
(K-CN/CM1)
0.0
22.000
23.000
24.000
1.600
1.600
initial concentration.
29 X
T-SUL
(PPM)
0.072
0.062
0.055
SUNSHINE
S02 I-P-S
(PPM) (UG/M3)
0.0
4.7
0.010
0.010
0.010
3.0
PAN
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0
0.0
0.0
o.o
CN-5
(K-CN/CM3)
0.0
0.750
0.0
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.027
0.256
0.556
0.779
0.960
1.067
1.056
0.947
0.785
0.561
0.291
0.052
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SR
(L/MIN)
0.0
0.0
0.001
0.0
0.0
0.0
0.040
0.155
0.407
0.663
0.541
0.926
0.979
0.637
0.417
0.2/6
0.191
0.035
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.76
8.84
32.66
71.79
152.95
216.78
208.48
30B.77
168.55
401.60
427. «5
43B.57
440.22
440.22
440.22
440.22
440.22
440.22
440.22
CU-SH
(LANK)
0.0
0.0
0.02
0.06
0.06
0.06
0./6
3.67
2J.24
54. H8
91.22
I1M.53
191.59
240.60
272.70
293.74
307.9J
3M.97
ItMP
CELSIUS
5.1
4.S
1.9
3.4
2.9
«f.6
2.6
5.4
9.9
14.2
17.1
18.9
19.8
20.4
20.8
20.3
20.7
18.7
14. «
14.8
12.6
11.3
10.3
9.4
8.7
ItMP
CELSIUS
8.2
7.8
7.5
7.3
7.2
7.5
7.6
10.1
13.4
16. ft
18.7
20.4
21.9
22.6
22.8
21.6
19. B
18.7
-------
CHAMBER NO. 4
DAY 1, 10- 5-77
RUN 11 S (CH3S)2
RU SMUG CHAMBER STUDY
USEPA CUNTRACT NO. 68-02-2437
99 X SUNSHINE
to
*-
u>
TIME
2
NO
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.003
0.002
0.003
0.008
0.006
0.010
0.008
0.006
0.003
NU2
(PPM)
0.010
0.009
0.009
0.010
0.010
0.010
0.011
0.011
0.015
0.016
0.010
0.01A
0.019
0.010
0.017
NOX
(PPM)
0.010
0.009
0.009
0.010
0.010
0.010
0.014
0.015
0.016
0.024
0.026
0.028
0.027
0.024
0.021
T-SUL
(PPM)
0.010
0.010
0.010
802 T-P-S
(PPM) (UG/M3)
0.0
0.0
0.010
0.010
0.010
3.2
PAN
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CN-5
(K-CN/CM3)
0.0
0.010
0.0
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.027
0.256
0.556
0.779
0.960
1.067
1.056
0.947
0.765
0.561
0.291
0.052
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SR
(L/MIN)
0.0
0.001
0.0
0.0
0.0
0.040
0.155
0.407
0.663
0.541
•0.926
0.979
0.637
0.417
0.276
0.191
0.0 IS
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
1.02
11.30
42.67
67.73
97.08
163.00
258.62
317.66
376.56
385,96
430.64
439.06
440.22
440.22
440.22
440.22
440.22
440.22
440.22
CU-SR
(LAMG)
0.0
0.03
0.06
0.06
0.06
1.19
5.25
27.14
61.24
96.41
143.42
200.99
246. HO
276.70
296.39
309.74
115.10
TEMP
CELSIUS
5.1
4.5
1.9
3.4
2.9
2.6
2.6
S.4
9.9
l«.2
17.3
18.9
19.8
20.4
20.6
20.3
20.7
18.7
14.8
12.6
12.6
11.3
10.3
9.4
8.7
TEMP
CELSIUS
8.2
7.5
7.3
7.2
7.5
7.6
10.3
13.4
16. A
18.7
20.4
21.9
22. 6
22. B
21.6
19.8
18.7
-------
CHAMBER NU. |
OA» 1, 10- 7-77
RUN 3b : (C2H5S)2
34 X SUNSHINE
RTI SMOG CHAMBER STUDY
USEPA CONTRACT NU. 66-02-2437
1 IMC
(EST)
0.11
1.13
3.07
J.91
0.30
5.13
6.13
7.13
a. 13
9.13
10.13
11.13
12.1)
13.13
14.13
IS. 13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
OZONE
(PPM)
0.0
• .•
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.000
0.037
0.078
0.118
0.155
0.163
0.169
O.I6S
0.168
0.146
0.125
0.106
0.091
0.071
0.060
NO
(PPM)
0.003
0.001
0.153
0.159
0.159
0.155
O.I5«a/
0.026-
0.016
0.006
0.005
0.004
0.004
0.004
0.002
0.003
0.003
0.003
0.004
0.004
0.004
0.004
0.003
0.002
N02
(PPM)
0.002
0.002
0.0
0.036
0.036
0.017
0.0i7 a/
0.132-'
'0.076
0.066
0.070
0.075
0.079
0.078
O.OBO
o.oeo
0.076
0.077
0.075
0.072
0.072
0.070
0.071
0.069
NOX
(PPH)
0.004
0.003
0.1S3
0.197
0.197
0.192
0.191 a/
0.14B-7
0.094
0.076
0.075
0.079
0.063
0.062
0.082
0.063
0.081
0.060
0.079
0.076
0.076
0.074
0.073
0.070
T-SUL
(PPM)
0.0
0.0
l.SOO
1.500
1.500
1.313
0.669
0.722
0.703
0.690
0.661
0.635
0.594
0.559
0.511
0.406
0.246
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.168
0.409
0.551
0.549
0.552
0.533
0.513
0.474
0.414
0.326
0.203
,
I-P-S
(UG/M3)
f.O
lot. e
50.6
28.0
17.9
6.7
PAN
(PPM)
0.001
0.0
0,000
0.027
0.044
0.051
0.047
0.045
0.044
0.036
0.040
0.042
0.040
0.035
0.032
0.037
0.037
CN-5
(K-CN/CM3)
1.300
41.000
56.000
2.100
1.700
ivj a/ Data Insufficient to permit correction for interference.
*" DAY 2, 10- 6-77
29 X SUNSHINE
TIME
(EST)
0.13
1.13
2. 13
J.U
4.13
5.13
6.13
7.13
6.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
OZOHE
O'PM)
0.047
0.035
0.026
0.020
0.015
0.011
0.006
0.007
0.006
0.015
0.027
0.042
0.054
0.055
0.054
0.047
0.041
NO
(PPM)
0.001
0.001
0.002
0.001
0.002
0.002
0.002
0.002
0.001
0.0
0,0
0.0
0.0
0.000
0.0
0.000
0.000
NU2
(PPM)
0.068
0.067
0.066
0.067
0.066
0.065
0.063
0.064
0.064
0.06.5
0.067
0.068
0.0/0
0.070
0.069
0.071
0.070
NOX T-SUL
(PPM) (PPM)
0.069
0.060
0.068
0.068
0.066
0.067
0.065
0.066
0.065
0.063
0.067
0.06A
0.070
0.071
0.069
0.071
0.070
3O2 f-P-S PAN
(PPM) (UU/M3) (PPM)
0.034
0.034
0.033
0.031
0.032
0.031
0.0 0.029
0.030
0.031
0.033
0.036
0.0 0.04S
0.046
O.OSO
0.049
20.3 0.046
CN-5
(K-CN/CM3)
0.0
5.700
2.600
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.033
0.202
0.431
0.646
0.930
0.9<>5
0.965
0.886
0.509
0.411
0.163
0.027
0.0
0.0
0.001
0.002
0.003
0.003
CU-3H
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.26
3.56
1 7.16
«S. 00
BS.97
I«2.2B
201.90
260. 25
110.57
340.35
363.07
J71.79
373.20
373.20
373.21
373.27
373. <»0
373. SB
TEMP
CELSIUS
14.6
12.6
12.1
• 12.1
11.7
10. 8
10. 8
12.6
11.5
16.5
11.1
19.6
20.5
20.6
20.5
20.6
19.6
17.3
15.1
14.6
13.6
13.3
14.1
13.9
SR
(L/MIN)
0.003
0.002
0.003
0.003
O.OOJ
0.003
0,006
0.049
0.150
0.250
0.355
0.319
0.133
0.092
0.052
0.034
0.036
CU-SR HMP
(LANt) CELSIUS
0.02
0.20
0.12
0.50
0.66
0.86
l.OB
l.flfl
5.61
15.39
31.21
52.23
69.9a
77.5B
82.79
K5.77
87.H2
13.7
13.6
1J.4
11.4
13.6
13.6
13.3
13.4
13.9
15.1
| 6./I
17.4
1«.0
17.9
it. e
16.2
16.1
-------
N>
Si
CHAMBER NO. 2
DAY I, 10- 7-77
RUN 35 I (C2M5S)2
34 X SUNSHINE
RTI SMOG CHAMBER STUDY
USEPA CONTRACT NO. 68-02-24)7
TIME
USD
0.30
1.30
1.27
4.13
4.47
5.30
6.30
7.30
a. 30
9.30
10.30
11.10
12.30
13.30
14.30
15.30
16.30
17.30
18.30
19.30
20.30
21.30
22.30
23.30
OZONE MO
(PPM) (PPM)
0.0 0.002
0.0 0.001
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.001
0.002
0.031
O.OS3
0.077
0.095
0.104
0.102
0.093
.074
.075
.075
.074
.072 a/
.017"
.015
.013
.008
.005
.004
.004
.002
.002
.001
.003
o.oao 0.004
0.066 0.005
0.055 0.005
0.046 0.004
0.038 0.002
0.011 0.002
N02
(PPH)
0.003
0.003
0.0
0.020
0.019
0.020
0,020 a/
0.041
0.025
0.020
0.024
0.029
0.034
0.036
0.040
0.040
0.039
0.036
0.017
0.016
0.016
0.015
0.035
0.035
NOX
(PPM)
0.006
0.004
0.074
0.095
0.094
0.094
0.093 a/
0.058
0.040
0.033
0.032
0.034
0.038
0.040
0.042
0.042
0.042
0.041
0.041
0.041
0.041
0.039
0.037
0.036
T-SUL
(PPM)
0.0
0.0
.500
.500
.500
.500
.311
1.076
0.876
0.837
0.813
0.778
0.741
0.698
0.676
0.622
0.497
0.242
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.089
0.195
0.425
0.566
0.611
0.614
0.600
0.568
0.553
0.507
0.397
0.200
T-P-S
(UU/M3)
0.0
77.3
18.6
17.5
7.7
4.3
v
PAN
(PPM)
0.0
0.0
0.000
O.OOb
0.017
0.023
0.027
0.040
0.030
0.040
0.026
0.028
0,024
0.023
o.oia
0,018
0.015
0.017
CN-5
(K-CN/CM3)
3.500
32.500
41.000
1.400
0.950
a/ Itata Insufficient to permit correction for Interference.
OA» 2, 10- 8-77
29 X SUNSHINE
tint
(EST)
0.10
I.JO
2.30
3.30
4.30
5.30
6.30
7.30
8.30
9.30
10.10
1 1.30
12.10
11.10
14.30
15.30
16.30
OZONE
(PPM)
0.024
0.019
0.015
O.Olt
0.000
0.006
0.005
0.004
0.006
0.012
0.023
0.0 3'l
0.043
0.044
0.045
0.042
0.017
NO
(PPM)
0.001
0.001
0.001
0.002
o.ooi
0.002
0,001
0.00]
0.001
0.0
o.o
0.0
0.0
0.0
0.0
0.000
0.000
N02
(PPM)
0.036
0.034
0.035
0.033
0.034
0.034
0.034
0.034
0.035
0.036
O.O'IO
0.042
0.045
0.04h
0.045
0.046
0.046
NOX
(PPM)
0.037
0.03S
0.036
0.015
0.035
0.036
0.035
0.035
0.036
0.036
0.040
0.012
0.045
0.0'I6
0.045
0.016
0.046
f-SUL S02 T-P-S PAN
(PPM) (PPM) (UG/M3) (PPM)
0.019
0.022
0.020
0.024
0.018
0.026
1.1 0.022
0.017
0.017
0.018
0.026
0.013
0.0 0.033
0.034
O.OSJ
0,0)6
0.0 O.OJ5
CN-5
(K-CN/CM3)
0.0
2.950
3. 100
SR
(L/M1N)
0.0
0.0
0.0
0.0
0.0
0.0
0.031
0.202
0.431
0.646
0.930
0.995
0.985
o.ana
0.509
0.411
0.163
0.027
0.0
0.0
0.001
0.002
0.003
0.003
CU-SR
(LANG)
0.0
0.0
0,0
0.0
0.0
0.0
0.59
5.62
21.86
51. 59
95.46
152. »3
211.95
269.30
315.76
344.54
364.73
372.07
37J.20
373.20
373.22
373.29 •
373. 4J
373.61
IEMP
CELSIUS
14.6
12.6
12.4
11.7
11.7
10.8
10.8
12.6
l«.b
16.5
18.4
19.6
20.3
20.6
20.5
20.6
19.6
17.3
15.1
14.6
13.6
13.3
14.1
13.9
SH
(L/MIN)
0.003
0.002
0.003
0.003
0.003
0,003
0.008
0.049
0.150
0.250
0.355
0.319
0.133
0.092
0.052
0.034
0.036
CO-SH TEMP
(LANG) CELSIUS
0.05
0.22
0.35
0.53
0.71
0.89
1. 16
2.18
7.14
17.9*
34.83
55.«8
71.27
78.52
83.12
86.11
B8.19
13.7
13.6
13.4
13.4
13.6
11.6
13.3
13.4
13.9
IS.I
16.4
17.4
18.0
17.9
16.8
16.2
16.1
-------
CHAMBER NO. 3
DAY 1, 10- 7-77
RUN 35 I (C2M5S)2
34 X SUNSHINE
Rll SMOG CHAMBER STUDY
USEPA CON1RAC1 NO. 68-02-2437
rt Me
(EST)
0.47
1.47
2.57
3.5J
4.63
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.«7
14.47
J5.47
16.47
17.47
18.47
19.47
20.47
21.47
22.47
23.47
UZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.034
0.06S
0.122
0.215
0.154
0.460
0.531
0.5S9
0.560
0.540
0.505
0.463
0.426
0.396
0.370
0.345
0.322
W)
(PPM)
0.002
0.001
0.796
0.797
0.778
0.763
0.736 a/
0.033"
0.031
0.022
0.009
0.005
0.003
0.003
0.002
0.002
0.003
0.004
0.004
0.005
0.005
0.004
0.003
0.002
NU2
(PPM)
0.004
0.005
0.0
0.186
0.202
0.214
0.229 a/
0.732-
0.603
0.521
0.4M6
0.372
0.323
0.306
0.296 -
0.283
0.267
0.25B
0.250
0.246
0.239
0.235
0.232
0.226
NUX
(PPM)
0.006
0.004
0.798
0.983
0.981
0.977
0.965 a/
0.765-7
0.634
O.b'13
0.'I55
0.376
0.326
0.308
0.298
0.285
0.270
0.262
0.254
0.250
0.243
0.236
0.234
0.210
T-SUL
(PPM)
0.0
0.0
1.500
1.500
1.500
1.500
0.867
0.735
0.689
0.650
0.644
0.618
0.593
0.569
O.S55
0.505
0.394
0.206
502
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.729
0.636
0.605
0.563
0.558
0.529
0.508
0.467
0.475
0.430
0.330
0.179
T-P-3
(UG/H3)
0.0
231 .8
71.0
60.1
47.0
34.7
PAN
(PPM)
0.0
0.0
0.0
0.102
0.154
0.176
0.198
0.200
0.194
0.196
0.177
0.166
0.150
0.141
0.113
0.126
CN-5
(K-CN/CM3)
2.950
27.000
23.000
2.700
1.000
a/ Data insufficient to permit correction for interference.
DAY ?. JO- 8-77
29 X SUNSHINE
TIME
(EST)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
I3.«7
14.47
15.47
16.47
OZONE
(PPM)
0.29V
0.276
0.256
0.236
0.216
0.200
0.182
0.167
0.156
0.152
0.166
0.185
0.200
0.197
0.191
0.179
0.167
NU
(PPM)
0.002
0.003
0.003
0.00)
0.002
0.003
0.003
0.002
0.001
0.0
0.0
0.0
0.0
0.0
o.ooo
0.001
o.ooi
N02
(PPM)
0.223
0.221
0.2J9
0.215
0.213
0.210
0.209
0.208
0.209
0.212
0-.217
0.218
0.210
0.216
0.213
0.210
0.211
NUX
(PPM)
0.225
0.224
0.222
0.218
0.215
0.213
0.212
0.210
0.210
0.212
0.217
0.218
0.218
0.216
.0.214
0.212
0.212
T-SUL
(PPM)
SU2
(PPM)
T-P-S
(UG/MJ)
0.0
•
0.0
0.0
PAN
(PPM)
0.131
0.120
0.131
0.134
0.125
0.122
0.121
0.118
0.122
0.127
0.141
0.142
0.148
0.143
0.135
0.136
0.142
CN-5
(K-CN/CM3)
0.0
10.700
2.600
3H
(L/M1N)
0.0
0.0
0.0
0.0
0.0
0.0
0.01)
0.202
0.411
0.646
0.930
0.995
0.985
0.888
0.509
O.otl
0.16)
0.027
0.0
0.0
0.001
0.002
0.00}
0.003
CU-SK
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.9J
7.66
26. £5
58.18
104.95
162.58
222.00
278.16
320. 9S
118.71
366.40
372.34
373.20
371.20
373.23
371.32
373.46
373.64
IEMP
CELSIUS
14.6
12.6
12.0
12.4
11.7
10.6
10.8
12.6
14.5
16.5
18.4
19.6
20.3
20.6
20.5
20.6
19,6
17. J
15.1
14.6
13.6
13.3
14.1
13.9
5K
(L/MIN)
0.003
0.002
0.001
0.003
0.003
0.003
0.008
0,049
O.ISO
0.250
0.355
0.319
0.133
0.092
0.052
0.034
0.036
CU-SH IEMP
(LANG) CELSIUS
0.06
0.24
0.1"
0.56
0.74
0.92
1.25
2.ea
8.67
20.49
16.45
5B.74
72.63
79.45
83.85
86.46
88.56
13.7
13.6
13.4
I3J6
J3.6
13.1
13.4
13.9
15.1
16.4
17.4
18.0
17.9
16.6
16.2
16.1
-------
CHAMBEH NO. 4
DAY I. 10- 7-17
RUN 35 t (C2H5S)2
34 X SUNSHINE
fill SMOG CHAMBER StUOV
USfPA CONIHACT NO. 68-02-3117
*-
-vj
TIME
(ESI)
0.63
1.63
a. 73
3.73
4.60
S.63
6.63
7.63
6.63
9.63
10.63
11.63
12.63
13.63
14.63
IS. 63
16.63
17.63
16.63
19.63
20.63
21.63
22.63
23.63
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.023
o.oai
0.144
0.231
0.314
0.303
0.444
0.470
0.472
0.450
0.416
0.385
0.362
0.340
0.320
0.300
0.261
NO
(PPM)
o.oot
0.000
0.440
0,452
0.446
0.440
0.422 a/
0.012"
o.ooa
0.004
0.004
0.004
0.005
0.003
0.004
0.003
0.003
0.004
0.004
O.OOS
0.004
0.004
0.003
0.002
N02
(PPM)
0.002
0.002
0.0
0.096
0.099
0.101
O.llSa/
0.329-
0.291
0.282
0.275
0.272
0.271
0.263
0.254
0.2*5
0.233
0.227
0.222
0.217
0.213
0.209
0.20S
0.200
NUX
CPPM)
0.003
0.002
0.440
0.549
0.515
O.S41
0.538 a/
O.J40
0.299
0.286
0.279
0.27S
0.276
0.266
0.257
0.246
0.235
0.230
0.225
0.221
0.216
0.212
0.207
0.202
1-SUL
(PPM)
0.0
0.0
1.500
1.500
1.500
1.500
0.805
0.673
0.636
0.572
0.531
0.469
0.456
0.423
0.393
0.302
0.170
0.064
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.651
0.562
0.542
0.473
0.435
0.395
0.365
0.336
0.312
0.241
0.123
0.049
t-P-S
(UC/M3)
6.1
161.9
43.9
53.6
27.9
16.7
PAN
(PPM)
0.0
0.0
0.030
0.125
0.171
O.IP6
0.191
0.187
0.183
0.172
0.175
0.162
0.151
0.140
0.133
0.122
0.12"
0.120
0.124
CN-5
(K-CN/CM3)
1.400
23.000
25.000
2.400
0.900
a/ flora insufficient to penult correction for Interference.
OAT 2, 10- 8-77
29 X SUNSHINE
TIME
(ESI)
0.63
1.63
2.63
3.63
4.63
5.63
6.63
7.63
8.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
OJUNE
(PPM)
0.261
0.230
0.224
0.205
0.187
0.173
0.157
0.145
0.136
0.134
0.149
0.165
0.172
0.166
0.156
0.146
0.133
NO
(PPM)
0.003
0.002
0.002
0.002
0.002
0.003
0.002
0.001
0.001
0.0
0.0
0.0
0.0
o.o
0.000
0.001
0.001
N02
(PPM>-
0.197
0.192
0.190
O.I«7
0.183
0.180
0.179
0.176
0.176
0.178
0.181
0.161
0.181
0.181
0.179
0.178
0.178
NOX T-SUL
(PPM) (PPM)
0.200
0.194
0.192
0.169
0.185
0.163
0.161
0.177
0.177
0.178
O.IAI
0.181
0.181
0.161
U.lflO
0.179
O.I71)
802 I-P-S PAN
(PPM) (UG/M3) (PPM)
0.125
0.115
0.116
0.122
0.118
0.118
0.0 0.110
0.111
0.109
0.111
0.126
0.12V
3.0 0.133
0.125
0.128
0.118
0.0 0.122
CN-5
(K-CN/CM3)
0.0
4,600
2.SOO
SH
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.033
0.202
0.43)
0.646
0.930
0.995
0.965
0.888
0.509
0.411
0.163
0.027
0.0
0.0
0.001
0.002
0.003
0.003
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
1.25
9.62
30.39
64.36
113.87
172.13
231.45
266.89
325. «4
352.68
367.96
372.60
373.20
373.20
373.24
373.33
373.49
373.67
?EMP
CELSIUS
14.6
12.6
12.0
12.4
11.7
10.8
10.8
12.6
1«.S
16.5
18.4
19.6
20.3
20.6
20.5
20.6
19.6
17.3
15.1
14.6
13.6
13.3
14.1
13.9
SR
(L/MIN)
0.003
0.002
0.003
0.003
0.003
0.003
0.008
0.049
0.150
0.250
0.355
0.319
0.133
0.092
0.052
0.034
0.036
CU-SH IEMP
(LANG) CELSIUS
0.11
0.26
0.41
0.59
0.77
0.95
1.32
3.35
10.11
22.89
41.86
61.60
73.91
no.34
8«.3b
66.79
88.90
13.7
13.6
13.4
13.4
13.6
13.6
13.3
13.4
13.9
15.1
16.4
17.4
16.0
17.9
16.6
16.?
16.1
-------
CHAMBER NU. I
DAY 1, 10-10-77
RUN 36 I CHS-S-C2H5
Rll SMOG CHAMBER STUDY
USER* CONTRACT NO. 68-02-2437
ro
**
00
TIME
(E3T)
0.13
1.13
3.07
3.97
4.47
S.13
6.13
6.60
7,47
a. 13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
a/ Data
ttZONE.
(PPM)
0.005
0.0
0.000
0.000
0.000
0.000
o.ooo
0.0
0.003
0.038
0.166
0.185
0.167
0.159
0.158
0.156
0.153
0.145
0.124
0.102
0.064
0.069
0.056
0.046
0.036
NO
(PPM)
O.OOS
0.003
0.147
0.160
0.156
0.1SS
0.150a/
0.145"
0.103
0.032
0.008
0.008
0.007
0.005
0.005
0.004
0.004
0.009
0.013
.015
.018
.020
.018
.020
0.016
N02
(PPM)
0.003
0.004
0.0
0.036
0.039
0.036
0.039a/
0.042-'
0.075
0.117
0.063
0.043
0.043
0.044
0.046
0.046
0.044
0.045
0.044
0.043
0.043
0.041
0.043
0.041
0.041
NOX
(PPM)
0.008
0.007
0.147
0.197
0.195
O.|9|
O.|89a/
0.187"
0.179
0.149
0.071
0.051
0.050
0.048
0.050
0.050
0.048
0.054
0.056
0.058
0.060
0.061
0.061
U.061
0.057
T-SUL
(PPM)
0.963
0.956
0.943
1.118
1.109
1.064
0.935
0.673
0.466
0.427
0.391
0.363
0.329
0.320
0.292
0.256
0.248
0.218
are insufficient to permit correction for interference
DAY 2, 10-1
TIME
(EST)
0.13
1.13
2.13
3.13
4.13
5.13
6.13
7.13
a. 13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
OZONE
(PPM)
0.027
0.022
0.016
0.012
o.ooa
0.006
0.004
0.004
0.009
o.oia
0.039
0.087
0.119
0.146
0.148
0.144
0.135
NU
(PPM)
0.015
0.013
0.013
0.010
o.ooa
0.007
0.006
0.006
0.006
0.006
0.007
0.006
0.005
0.003
0.004
0.00}
0.005
NU2
(PPM)
0.040
0.039
0.037
0.035
.038
.037
.036
.035
.038
.040
.039
0.042
0.042
0.043
0.0"!
0.04L
0.042
1-77
NOX
(PPM)
0.055
0.052
0.050
0.045
0.047
0.044
0.043
0.041
0.044
0.046
0.046
0.048
0.047
0.046
0.045
0.044
0.047
55 X
T-SUL
(PPM)
0.212
0.159
0.153
0.146
0.135
0.121
0.117
0.113
76 X SUNSHINE
SO2
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
SUNSHINE
302
(PPM)
0.0
0.0
0.010
0.010
0.010
0.01V
0.010
0.010
1-P-S
(UG/M3)
0.0
73.2
24.6
8.0
I-P-S
(UG/M3)
0.0
0.0
0.0
PAN
(PPM)
0.0
0.0
0.001
0.0
0.004
0.011
0.019
0.018
0.019
0.020
0.020
0.021
0.021
0.020
0.020
0.020
0.017
0.017
0.016
0.017
PAN
0.019
0.015
O.OJ7
0.018
0.018
0.014
0.017
0.021
0.022
0.017
0.020
0.020
0.019
0.019
0.021
0.022
CN-5
(K-CN/CMS)
0.0
23.000
31.000
12.500
2.400
CN-5
(K-CN/CM3)
0.0
1.600
0.2SO
SH
U/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.018
0.018
0.202
0.507
0.606
0.716
0.956
0.944
0.78A
0.744
0.547
0.236
0.020
0.0
0.0
0.002
0.001
0.001
0.001
SR
U/MIN)
0.002
0.001
0.0
0.0
0.0
0.0
0.023
0.231
0.250
0.582
0.885
0.749
0.7S4
0.450
0.363
0.205
0.097
0.018
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.14
O.H6
0. 7fl
17.15
48.36
65.66
130.52
187.78
243.21
290.14
333.25
363.64
376.12
377.16
377.16
3//.I7
377.29
377.35
377.41
CU-SR
(LANG)
0.02
0.13
0.18
0.18
0.18
0.18
0.36
3.36
17.37
14.96
72.24
124.28
169.26
212.1 3
2JB.45
259.00
2/0. «6
275.66
TEMP
CELSIUS
9.9
6.5
5.0
5.0
4.2
3.7
3.4
3.4
6.2
10.5
12.4
13.2
14.7
14.9
15.9
16.8
17.1
16.9
14.1
11.5
10.7
11. 1
10.9
10.4
9.8
IEMP
ULSlUS
10. 1
9.8
8.8
7.6
7.0
0.2
6.1
6.4
11.6
14.7
16.9
18.0
18.6
18.6
18.6
18.5
18.1
17. 2
-------
CHAMBER NU. 2
DAY 1, 10-10-77
RUN 36 I CH3-3-C2H5
76 X SUNSHINE
RU SMOG CHAMBER STUDY
USEPA CONTRACT NU. 66-02-2437
TIME.
(EST)
0.30
I.JO
3.2?
4.30
4.63
5.10
6. JO
6.97
7.63
a. 30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
10.30
19.30
20.30
21.30
22.30
23.30
a/ Itata
OZONE
(PPM)
0.0
0.0
0.000
0.000
0.000
0.000
0.000
0.002
0.011
0.055
0.138
0.136
0.131
0.131
0.134
0.134
0.134
0.124
0.105
0.085
0.068
0.056
0.0«6
0.037
0.029
NU
(PPM)
0.003
0.001
0.078
0.080
0.080
0.079
0.078a/
0.070
0.040
0.016
0.008
0.008
0.007
0.006
0.006
0.006
O.OOb
0.010
0.014
0.018
0.020
0.021
0.022
0.021
0.017
N02
(PPM)
.003
.006
.0
.022
.022
0.023
0.021a/
0.028
0.050
0.052
0.024
0.019
0.022
0.022
0.025
0.026
0.029
0.029
0.026
0.025
0.026
0.025
0.024
0.021
0.025
NOX
(PPM)
0.006
0.007
0.078
0.102
0.102
0.102
0.099 a/
0.098
0.090
0.068
0.033
0.027
0.029
0.028
0.032
0.032
0.035
0.040
0.040
0.044
0.045
0.046
0.045
0.045
0.042
T-3UL
(PPM)
0.975
0.977
0.962
0.954
1.15!
1.144
1.090
0.984
0.805
0.627
0.597
0.561
0.536
0.501
0.485
0.466
0.409
0.395
0.365
0.350
0.343
0.333
0.326
902
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
T-P-S PAN
•(UG/M3) (PPM)
0.0
0.0
0.001
0.0
0.0
0.0
31.5
0.014
0.016
0.024
0.015
0.019
8.8 0.019
6.0 0.014
0.011
0.012
0.011
0.011
0.0(4
0.011
0.011
CN-5
(K-CN/CMS)
0.0
16.000
22.000
11.500
1.700
are insufficient to permit correction for interference.
DAY 2, 10-1
IIHC
(tST)
0.30
1.30
2.30
3.30
4.30
5.30
6.10
7.30
a. 30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
It. JO
17.30
UZONt
(PPM)
0.023
0.018
0.014
0.011
0.007
0.006
0.004
0.004
0.010
0.022
0.045
0.090
0.118
0.136
0.137
0.13%
0.126
NO
(PPM)
0.014
0.013
0.014
0.012
0.013
0.009
0.007
0.007
0.006
0.007
0.008
0.007
0.006
0.005
0.004
0.004
0.005
N02
(PPM)
0.022
0.023
0.022
0.022
0.022
0.023
0.023
0.022
0.023
0.025
0.025
0.031
0.031
0.032
0.032
0.031
0.030
1-77
NOX
(PPM)
0.036
Oi036
0.036
0.034
0.035
0.032
0.031
0.029
0.029
0.032
0.033
0.036
0.036
0.037
0.036
0.036
0.035
55 X
T-SUL
(PPM)
0.317
0.312
0.308
0.276
0.281
0.2*5
0.278
0.273
0.336
0.2B5
0.275
0.261
0.24R
0.237
0.228
0.223
SUNSHINE
SU2
(PPM)
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
I-P-S PAN
(UG/M3) (PPM)
0.014
0.009
0.010
0.014
0.0 0.012
0.014
0.015
0.016
0.016
0.017
0.0 0.016
0.018
0.016
0.011
0.020
0.0 0.014
CN-5
(K-CN/CMi)
0.0
1.200
0.250
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.018
0.018
0.202
0.507
0.60H
0.716
0.956
0.944
0.788
0.744
0.547
0.236
0.020
0.0
0.0
0.002
0.001
0.001
0.001
SR
(L/MIN)
0.002
0.001
0.0
0.0
0.0
0.0
0.023
0.231
0.250
0.5S2
0.6H5
0.719
0.754
0.450
0.363
0.205
0.097
O.Olfl
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.32
1.05
8.72
22.33
54.56
92.99
140.27
197.41
251.24
297.73
33H.03
366.05
376.32
377.16
377.16
377.20
.377.30
377.36
377.42
CU-SR
(LANG)
0.04
O.l«
0.18
0.18
0.18
0.18
0.59
S.72
19.92
40.90
at. 27
131.42
176.95
216.72
242.15
261.09
271.45
275.84
TEMP
CELSIUS
9.9
8.5
5.0
4.2
4.2
3.7
3,4
3.4
6.2
10.5
12.4
13.2
14.7
14.9
15.9
16.8
17.1
16.9
14.1
11. S
10.7
11.1
10.9
10.0
9.8
IEMP
CELSIUS
10. 1
9.8
8.8
7.6
7.0
6.2
6.1
».4
11.6
14.7
16. 9
lfl.0
in. 6
18.6
l«.6
10.5
19.1
n,z
-------
CHAMBER NO. J
DAY 1, 10-19-77
RUM 36 I CH3-S-C2H5
to
cn
O
TIME
(EST)
0.47
1.47
2.60
1.50
4. BO
5.17
6.47
7.11
7.80
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
18.47
19.47
20.47
21.47
22.47
23.47
a/ Data
OZONE
(PPM)
0.0
0.0
0.9
0.000
0.000
0.000
0.001
0.001
0.001
0.020
O.J97
0.292
0.407
0.4|7
0.016
0.424
0.426
0.413
0.382
0.358
0.341
0.327
0.313
0.298
0.285
NO
(PPM)
.001
.003
.768
.an
.790
.772
.74da/
0.692~
0.506
0.192
0.019
0.005
0.003
0.0
0.001
0.000
0.001
0.006
0.011
0.013
0.014
0.015
0.016
0.015
0.014
H02
(PPM)
0.006
0.005
0.0
0.211
0.226
0.234
0.245a/
0.207"
0.428
0.611
0.495
0.297
0.213
0.232
0.227
0.224
0.222
0.216
0.211
0.206
0.203
0.200
0.197
0.194
0.192
NUX
(PPM)
0.007
0.008
0.768
1.024
1.016
1.005
0.993a/
0.979"
0.936
0.802
0.514
0.302
0.237
0.232
0.228
0.221
0.224
0.222
0.222
0.219
0.217
0.215
0.213
0.209
0.206
T-SUL
(PPM)
0.962
0.976
0.965
1.162
1.132
0.997
0.735
0.393
0.010
0.010
0.0
are insufficient to permit correction for interference
DAY 2, 10-
T1ME
(ESI)
0.47
1.47
2.47
1.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
l«.«7
15.47
16.47
17.47
OZONE
(PPM)
0.273
0.261
0.2SI
0.239
0.231
0.222
0.215
0.206
0.203
0.207
0.236
0.311
0.354
0.384
0.389
0.388
0.376
NO
(PPM)
0.011
0.010
0.007
0.006
0.006
0.004
0.001
0.001
0.002
0.002
0.004
0.005
0.003
0.001
0.001
0.003
0.005
N02
(PPM)
0.190
0.186
0.186
0.185
0.180
0.180
0.176
O.T'b
0.175
0.176
0.176
0.179
0.179
0.178
0.174
0.169
0.164
1-77
NOX
(PPM)
0.201
0.197
0.193
0.191
0.186
O.IB'I
0.178
0.177
0.177
0.178
0.180
0.164
0.182
0.179
0.175
0.172
0.169
55 X
T-SUL
(PPM)
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
76 X SUNSHINE
302
(PPM)
0.0
0.0
0.0
0.0
0.010
0.010
0.079
RU SMOG CHAHHtR STUDY
USEPA CUUIRACT NO. 66-02-2437
0.010
0.010
0.0
SUNSHINE
so2
(PPM)
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
I-P-S
(UG/H1)
0.0
141.9
12.0
I-P-S
(UG/M3)
0.0
0.0
0.0
PAN
(PPM)
0.0
0.001
0.0
o.ooo
O.OOJ
0.046
o.oeo
0.109
0.11)
0.1 OS
0.095
0.09J
0.062
0.075
0.071
0.071
0.072
0.067
0.069
0.069
PAN
(PPM)
0.072
0.068
0.066
0.070
0.070
0.071
0.075
0.076
0.073
O.ORO
0.076
0.079
0.076
0.075
0.060
CN-5
(K-CN/CM3)
0.0
22.000
31.000
11.000
4.000
CN-5
(K-CN/CMJ)
0.0
I .600
0.0
SR
U/MIN)
0.0
0.0
0.0
0.0
0.0
o.o
0.018
0.202
0.202
0.507
0.60H
0.716
0.956
0.944
0. J8H
0.744
0.547
0.236
0.020
0.0
0.0
0.002
0.001
0.001
0.001
SH
(L/MIN)
0,002
0.001
0.0
0.0
o.o
0.0
0.023
0.231
0.2SO
0.5B2
0.885
0.719
0.75«
0.450
0.363
0.205
0.097
O.OIH
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.51
2.66
10.78
27.50
60.77
100.29
150.02
207.04
259. 2B
305.32
344.41
368.45
376.52
377.16
377.16
377.22
377.31
377.37
377.41
CU-SR
(LANG)
0.06
0.15
0.18
o.ie
0.18
0.1B
0.83
8.07
22.47
46.83
90.30
139.50
IHI.b'i
221.31
245.86
263.18
272.43
276.03
TEMP
CELSIUS
9.9
8.5
6.8
5.0
4.2
3.7
3.4
fo.2
6.2
10.5
12.4
13.2
14.7
14.9
15.9
16.8
17.1
16.9
14.1
11.5
10.7
11.1
10.9
10.1
9.8
TEMP
CELSIUS
10.1
9.8
6.8
7.6
7.0
6.2
6.1
8.4
11 .6
14.7
16.9
18.0
18.6
16.6
18.6
18.5
18.1
17.2
-------
CHAMBER NU. 4
DAY i. 10-10-77
RUN 36 l CH3-3-C2H5
76 X SUNSHINE
RTI SMOK CHAMHEK S1UOY .4
USEPA CONTRACT NU. 6B-02-2437
TIME
(EST)
0.63
1.63
2.07
3.00
4.97
5.63
6.63
7.30
7.97
0.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
16.63
19.63
20.63
21.63
22.63
23.63
a/ Data
OZONE
(PPM)
0.0
0.0
0.000
0.000
0.000
0.000
0.001
0.001
0.007
0.076
0.265
0.274
0.270
0.264
0.262
0.263
0.260
0.244
0.216
0.196
0.179
0.165
0.1S1
0.137
0.125
NU
(PPM)
0.002
0.001
0.394
0.419
0.411
0.406
0.394a/
0.340
0.177
0.040
0.000
O.ooa
0.004
0.001
0.001
0.003
0.002
0.000
0.012
0.013
0.015
0.015
0.016
0.014
0.013
NO2
(PPM)
0.004
0.004
0.0
0.106
0.103
0.107
0.1 09a/
0.152"
0.2/0
0.316
0.171
0.119
0.110
0.119
0.116
0.116
0.116
0.112
0.106
0.106
0.106
0.10$
0.104
0.102
0.103
NUX
(PPM)
0.005
0.005
0.394
0.525
0.514
0.513
O.S03a/
0."92
0.447
0.356
0.179
0.122
0.122
0.120
0.117
0.118
0.110
0.120
0.120
0.119
0.121
0.120
0.120
0.116
0.116
I-SUL
(PPM)
0.963
0.957
0.945
1.142
1.099
0.956
0.719
0.356
0.243
0.010
O.OIO
0.010
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.054
O.OIO
0.0
0.0
T-P-S PAN
(UC/M3) (PPM)
0.0
0.0
0.0
0.0
0.000
79.2 0.036
0.062
0.062
0.060
0.059
0.054
25.3 0.051
19.9 0.046
0.043
0.042
0.040
0.040
0.040
0.040
0.036
CN-5
(K-CN/CMi)
0.0
17.500
29.000
11.500
2.600
are Insufficient to permit correction for interference.
DAV 2, 10-11-77
TIME
(LSI)
0.63
1.63
2.63
3.63
4.63
5.63
6.63
7.63
0.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
OZONE
(PPM)
0.115
0.104
0.096
0.006
0.001
0.074
0.069
0.064
0.066
0.000
0.123
0.106
0.228
0.247
0.251
0.247
0.234
NO
(PPM)
0.011
0.007
0.006
0.006
0.006
0.004
0.001
0.0
0.002
0.002
0.005
0.005
0.001
0.001
0.002
0.003
0.003
N02
(PPM)
0.102
0.100
0.097
0.097
0.095
0.096
0.093
0.09S
0.094
0.094
0.097
0.097
0.097
0.097
0.094
0.093
0.091
NOX
(PPM)
0.113
0.107
0.103
0.103
0.101
0.100
0.094
0.095
0.096
0.096
0.102
0.101
0.096
0.096
0.097
0.096
0.094
55 X
T-SUL
(PPM)
0.0
0.0
0.0
O.OIO
0.010
0.010
0.010
o.oio
0.0
SUNSHINE
S02
(PPM)
0.0
0.0
0.0
O.OIO
O.OIO
0.0
0.0
o.oio
0.0
I-P-S PAN
(UG/M3) (PPM)
0.038
0.038
0.035
0.038
0.0 0.041
0.040
0.042
0.053
0.042
0.056
0.0 0.050
0.044
0.049
0.047
0.043
0.0
CN-5
(K-CN/CMJ)
0.0
2.300
0.0
SR
(l/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.018
0.202
0,202
0.507
0.606
0.716
0.956
0.944
0.788
0.744
0.547
0.2J6
0.0«?0
0.0
0.0
0.002
0.001
0.001
0.001
SH
(L/MINI
0.002
0.001
0.0
0.0
0.0
o.o
0.023
0.231
O.«">0
0.56?
0.8A5
0.749
0.754
0.450
0.363
0.205
0.097
O.OIB
CU-SR
(LANG)
0.0
0.0
.0
.0
.0
.0
.66
.72
12.84
32.36
66.60
107.16
159.20
216.10
266.85
312.46
349.66
370.72
376.72
377.16
377.16
377.23
377. J2
377.36
377.14
CU-SH
(LANG)
0.08
0.16
O.IH
0.16
O.IA
0.18
I.OS
1".29
2«.d7
5?.«2
98.79
146.75
I9I.B8
225.63
249. 31
265.15
27J.37
27h.20
IEMP
CELSIUS
9.9
8.5
6.8
5.0
4.2
3.7
3.4
6.2
6.2
10.5
12.4
II. 2
l«.7
14.9
15.9
16.8
17.1
16.9
14.1
II. 5
10.7
11.1
10.9
10.4
9.8
HMP
CfLSlOS
10. 1
9.8
8.6
7.6
7.0
6.2
6.1
8.4
11.6
l«.7
16.9
1«.0
16.6
16.6
16.6
18.5
16.1
17.2
-------
CHAMBEH NO. |
DAY I, 10*15-77
RUN 17 I C2H5-S-C2H5 100 X SUNSHINE
RTI SMOG CHAMBER STUDY
USEPA CONTRACT NO. 68-02*24)7
T1MC
(EST)
O.li
l.tl
2.61
1.<>1
4.47
5. 47
6.1)
7. IS
7.80
0.47
9.11
10.11
11.11
12.11
11.11
14.11
IS. 11
16.11
17.11
10.11
19.11
20.11
21.1)
22.1)
2J.I1
OZONE
(PPM) (1
0.0
0.0
0.
0.
0.
0.
0.
0.
0.001
0.018
0.00)
0.225
0.110
0.111
0.114
0.117
0.115
0.125
0.104
0.274
0.2S2
0.214
0.220
0.204 C
0.190 C
NO
PPM)
.002
.021
.4)5
.415 •/
.429"
.422
.418
.19«
.120
.167
.061
.021
.011
.010
.010
.000
.000
.008
.008
.007
.002
.0
.0
.0
.0
N02
(PPM)
0.00)
0.0
0.0
0.072 a/
0.097-
0.094
0.104
0.115
O.IOI
0.204
0.117
0.215
0.102
0.170
0.171
0.172
0.160
0.161
0.1*9
0.151
0.151
O.lSO
O.l«6
0.140
0.142
NUX
(PPM)
0.005 (
0.021 (
0.415
0.507a/
0.526"
0.516
0.522
0.509
0.501
0.4SI
0.170
0.256
0.195
O.IOO
0.18)
0.180
0.176
0.171
0.167
0.161
0.155
0.150
0.148
0.146
0.142
r-sui
IPPM)
J.010
>.009
.079
.865
.071
.057
.067
.040
.702
.651
.500
.115
.210
.159
.1)7
.100
.07)
.062
.05)
302
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
T-P-S
(UC/M1)
o.o
10.8
61.5
14.0
1.0
PAN
(PPM)
0.0
o.o
0.0
0.001
0.001
0.020
0.047
0.071
0.070
0.074
0.072
0.067
0.062
0.0t2
0.062
0.071
0.069
0.075
0.085
0.088
CH-5
(K-CN/CM1)
1.600
27.000
8.600
1.400
2.100
SH
(t/MIN)
0.006
0.00?
0.006
0.006
0.005
0.004
0.022
0.243
0.24)
0.406
0.698
0.864
I. 010
1.012
0.927
0.751
0.514
0.2)1
d.024
0.0
0.0
0.001
0.005
0.009
0.008
CU-SR
(LANC)
0.05
0.41
1.01
1.17
1.64
1.91
2.21
5.26
15.02
29. J9
47.74
90.92
14J.90
204.51
264.57
118.02
162.01
190.68
401.01
404.20
404.28
404.29
404. )8
404.71
405.24
TEMP
CELSIUS
4.4
).a
i.l
2.2
2.0
1.)
1.6
4.0
4.0
/.9
11.4
14.2
16.
17.
18.
18.
18.
18.
15.
11.
9.
6.)
8.1
8.6
10. I
in
10
a/ Interl'erence-corrcctal initial (HO], (N02), aid |NOX] are 0.418, 0.091, aitJ 0.509 |i|m.
DAY 2. 10-16-77
17 . SUNSHINE
UML
(EST)
O.I)
1.1)
2.1)
).l)
4.1)
5.1)
6.1)
7.1)
8.1)
9.1)
10.1)
11. 1)
12.1)
D.I)
14.1)
15.1)
16.1)
17.1)
OZONE
(PPM)
0.174
0.159
0.144
0.1)0
0.110
0.107
0.095
0.004
0.079
0.075
0.074
0.076
0.074
0.077
0.004
0.080
0.004
NO
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.004
0.00)
0.00)
0.004
0.004
0.005
0.001
0.004
0.004
0.006
NO2
(PPM)
0.142
0.141
0.140
0.140
0.116
O.DS
0.1)4
0.1)4
0.1)1
0.1)0
O.I))
0.112
0.1)1
0.129
o.n
-------
to
Cn
CHAMBER NO. 2
DAY li 10-15-77
RUN 37 t C2H5-S-C2H5 100 X
SUNSHINE
RT1 SMOG CHAMBER STUDY
"SEP* CONTRACT NO. 68-02-2437
TIME
(EST)
0.30
1.30
2.47
3.00
4.63
5.63
6.30
7.30
7.9/
8.63
9.30
10.30
11.30
12. JO
13.30
14.30
15.30
16.30
17.30
IS. 30
19.10
20.30
21.30
22.30
23.30
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.010
0.044
O.I4S
0.242
0.327
0.399
0.4S7
0.4S4
0.402
0.457
0.427
0.404
0.382
0.371
0.354
0.336
NO
(PPM)
0.001
0.024
0.807
0.796 a/
0.772"
0.761
0.754
0.706
0.586
0.369
0.169
0.057
0.026
0.010
0.006
0.005
0.004
0.006
0.003
0.002
0.001
0.0
0.0
0.0
0.0
N02
(PPM)
0.005
0.0
0.0
0.234 a/
0.254
0.261
0.267
0.292
0.361
0.525
0.619
0.573
0.468
0.384
0.325
0.293
0.276
0.261
0.252
0.216
0.241
0.236
0.233
0.2*9
0.228
NOX
(PPM)
0.006
0.024
0.807
1.030 a/
1.026
1.022
1.021
0.998
0.967
0.894
0.788
0.630
0.494
0.394
0.331
0.298
0.280
0.267
0.255
0.248
0.2a2
0.236
0.233
0.229
0.22B
T-SUL
(PPM)
0.010
0.854
0.831
0.836
0.831
0.836
0.795
0.714
0.565
0.425
0.274
0.191
0.154
0.143
0.112
0.086
0.083
0.066
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.097
0.118
0.115
0.115
0.086
0.010
0.065
0.051
I-P-S PAN
(UG/M3) (PPM)
0.0
0.0
14.5 0.0
0.0
0.0
61.4 0.020
0.048
0.066
27.0 0.095
0.110
0.119
0.117
0.114
0.110
0.0 0.101
0.100
0.114
0.121
0.129
0.133
CN-5
(K-CN/CMJ)
2.0SO
20.000
26.000
56.000
3.300
SK
(L/MIN)
0.006
0,007
0.006
0.006
0.005
0.004
0.022
0.241
0.243
0.406
0.698
0.664
1.010
1.012
0.927
0.751
0.514
0.233
0.024
0.0
0.0
0.001
0.005
0.009
0.008
CU-SR
(LANG)
0.11
0.49
0.9S
1.28
1.69
1.95
2.44
7.73
17. SO
33.29
54.66
99.73
154.20
214.84
274.03
326.48
367.27
393.05
403.27
404.28
404.28
404.30
404.43
404.60
405.32
UMP
CELSIUS
4.4
3.8
1.1
2.2
2.0
1.3
1.6
4.0
4.0
7.9
11.4
14.2
16.9
17. 6
18.2
16.7
18.9
16.)
15.4
11.6
9.9
e.j
8.1
0.6
10. t
a/ Interference-corrected initial (NO], [NT)21. and [NOX| are 0.780, 0.252. ami 1.032 ppm.
DAY 2, 10-16-77
17 X SUNSHINE
TIME
(EST)
0.30
1.30
2.30
3.30
4.30
5.30
6.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14,30
15.30
16.30
17.30
OZONE
(PPM)
0.322
0.307
0.293
0.279
0.262
0.250
0.236
0.227
0.219
0.213
0.211
0.205
0.198
0.198
0.200
0.195
0.194
NO
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.003
0.002
0.002
0.003
0.003
0.005
0.004
0.003
0.004
0.007
N02
(PPM)
0.222
0.221
0.219
0.216
0.215
0.211
0.205
0.206
0.206
0.204
0.206
0.202
0.199
0.202
0.200
0.195
O.|9b
NOX
(PPM)
0.222
0.221
0.219
0.216
0.215
0.211
0.207
0.209
0.208
0.207
0.209
0.205
0.204
0.206
0.204
O.I9B
0.201
I-SUL
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
302
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0
0.0
T-P-S PAN
(UG/M3) (PPM)
0.141
0.139
0.142
0.143
0.144
0.136
2.0 0.125
0.134
0.137
0.136
0.136
2.3 0.136
0.138
0.138
0.139
0.137
2.5 0.136
CN-5
(K-CN/CM3)
0.0
0.250
0.0
SR
(l/MIN)
0.007
0.005
0.004
0.003
0.004
0.004
0.026
0.090
0.159
0.164
0.301
0.109
0.3S3
0.502
0.220
0.3)6
0. I8S
0.028
CU-SR TEMP
(LANG) CELSIUS
0.13
0.51
0.79
1.01
1.21
1.45
2.12
4.92
11.56
21.19
33.50
48.10
59.03
82.90
107.94
123.26
140.79
149.06
12.4
12.1
11.6
II.)
II. 2
10.6
9.8
10.4
11.0
JO.9
10.6
9.3
9.0
9.4
10.I
10.6
M.)
10.2
-------
CHAMBEH NO. 3
DAY tr 10-15-77
RUN 37 t C2H5-S-C2H5 100 X SUNSHINE
RTI SMUG CHAMBER STUDY
USER* CONTRACT NO. 68-02-2417
TIME
(EST)
0.47
1.47
3.0J
4.30
s.ao
6.47
7.«7
8.13
e.ao
9.17
10. HI
11.47
12.47
13.47
14.47
15.47
16.47
17.47
IB. 47
1<».47
20.47
21.47
22.47
23.47
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.007
0.037
0.065
0.128
0.146
0.146
0.151
0.156
0.162
0.162
0.152
O.IJ5
0.110
0.091
0.075
0.061
0.050
0.040
NO 1
(PPM) f|
0.004
0.025
0.080
o.oee »/
o.oaa~
0.086
0.064
0.036
0.026
0.019
0.01B
0.017
0.016
0.014
0.014
0.014
0.014
0.014
0.013
o.ooa
0.006
0.003
0.0
0.0
«02
>PH)
.005
.0
.0
.015 a/
.020"
.021
.036
.050
.039
.031
.032
.040
.048
.052
.052
.055
.055
.051
.050
.050
.048
.047
.048
.046
NOX 1
(PPM)
0.009 <
0.025
0.088
O.lOia/
0.108
0.107
0.100
0.066
0.065
0.050
0.050
O.OS7
0.064 (
0.066 (
0.066 (
0.069 (
0.069 (
0.065 (
0.063 <
0.058 (
0.054 (
0.050 (
0.048
0.046
r-sut
[PPM)
).010
.887
.878
.883
.841
.770
.670
.597
.514
.469
(.437
>.4I1
1.380
>.352
).333
).307
>.264
>.243
1.227
1.2)8
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
T-P-S
(UG/M3)
0.0
11.6
24.4
0.0
0.0
PAN
(PPM)
0.001
0.0
0.0
0.000
0.001
0.014
0.013
0.016
0.023
0.025
0.026
0.032
0.033
0.030
0.025
0.031
0.037
0.038
0.044
0.048
CN-5
(K-CN/CM1)
2.150
16.000
3.100
9.100
2.600
SR
(L/HIN)
0.006
0.007
0.006
0.005
0.004
0.022
0.243
O.a06
0.106
0.698
0.864
1.010
1.012
0.927
0.751
0.514
0.233
0.024
0.0
0.0
0.001
0.005
0.009
0.008
CU-SR
(LANG)
0.17
0.56
1.15
1.59
1.99
2.66
10.21
21.11
37.43
61.98
108. 54
164.50
225.16
283.46
334.14
372.51
395.43
403.52
404.28
404.28
404.3!
404.48
404.89
405.40
TEMP
CELSIUS
4.4
3.8
2.2
2.0
1.3
1.6
4.0
7.9
7.9
11.4
14.2
16.9
I/. 6
18.2
18.7
IB. 9
18.3
15.4
11.6
9.9
8.3
8.1
8.6
10. 1
M a/ Interference-corrected initial INO|. [N02|, and INt^l arc 0.073, 0.033, and 0.106 pf«.
DAY 2, 10-16-77
17 X SUNSHINE
TIME
(EST)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
OZONE
(PPM)
0.031
0.021
0.015
0.009
0.005
0.0
0.0
0.0
0.001
0.010
0.020
0.021
0.022
0.029
0.035
0.034
0.037
NO r
(PPM) (1
0.001 <
0.002 1
0.004
0.005
0.006
0.007
0.010
o.oio •
0.011
0.010
0.010
0.011
0.011
0.010
0.009
0.012
0.012 <
102
»PM)
1.046
>.045
.046
.046
.048
.046
.046
.047
.044
.049
.Obi
.053
.054
.051
.058
.056
.057
UUX
(PPM)
0.047
0.047
0.050
0.051
O.OS4
0.053
0.056
.057
.055
.058
.061
.064
.065
0.064
0.068
0.067
0.069
T-SUL
(PPM)
0.213
0.212
0.208
0.200
0.191
0.177
0.166
0.156
302 T-P-S
(PPM) (UG/M3)
0.0 0.0
0.0
0.0
0.0
0.0
0.0 0.0
0.0
0.0
0.0
PAN
(PPM)
0.050
0.052
0.051
0.054
0.038
0.043
0.038
0.037
0.052
0.047
0.055
0.053
0.060
0.060
0.058
0.058
CN-5
(K-CN/CMJ)
0.0
0.250
-------
CHAMBER NO. 4
DAY I, 10-15-77
RUN 37 | C2H5-S-C2H5 100 X SUNSHINE
RTI SMItC CHAMBER STUDY
USEPA CONTRACT NO. 611-02-24)7
TIME
(EST)
0.61
1.63
2.80
4.10
5.<»7
6.61
7.61
8.10
8.97
9.63
10.63
11.63
12.61
11.63
14.61
IS. 61
16.6}
17.61
18.61
19.63
20.61
21.61
22.6)
23.61
OZONE
(PPM.)
0.0
0.0
0.0
0.0
0.0
0.0
0.006
0.018
0.109
0.191
0.211
0.225
0.224
0.226
0.227
0.22)
0.213
0.197
0.179
O.I6S
0.1SO
0.1)7
0.124
O.lll
NO
(PPM)
0.001
0.022
0.167
0.168 a/
0.166
0.165
0.117
O.OS4
0.027
0.019
0.017
0.016
0.014
0.012
0.01)
0.01)
0.01)
0.012
0.011
0.009
0.005
0.00!
0.000
0.0
N02
(PPM)
0.004
0.0
0.0
0.040 a/
0.041
0.041
o.oao
0.119
0.107
0.080
0.070
0.073
0.078
0.078
0.077
0.076
0.074
0.073
0.070
0.067
0.067
0.066
0.065
0.065
NUX
(PPM)
0.005
0.022
0.167
0.208 a/
0.209
0.208
0.197
0.173
0.134
0.099
0.087
0.089
0.092
0.090
0.090
0.089
0.087
0.08%
0.081
0.076
0.072
0.067
0.065
0.065
T-SUL
(PPM)
0.010
0.877
0.861
0.861
0.800
0.71)
0.598
0.)95
0.)42
0.311
.280
.254
.225
.217
.189
SU2
(PPM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0
T-P-S PAN
(UG/H)) (PPM)
0.0
0.001
0.0
10.8 0.0
0.0
0.008
25.2 0.02)
0.029
0.018
0.0 0.048
0.041
0.042
0.038
0.0)5
0.035
0.0 0.0)1
0.034
0.047
0.041
0.051
0.056
CN-5
(K-CN/CM3)
4.850
17.500
4.200
3.100
1.400
SR
(L/MIN)
0.006
0.007
0.006
0.005
0.004
0.022
0.243
0.406
0.406
0.698
0.864
1.010
1.012
0.927
0.751
0.5(4
0.21)
0.024
0.0
0.0
0.001
0.005
0.009
0.008
CU-SR
(LANG)
0.2)
0.62
1.07
1.53
2.0)
2.87
12.55
25.25
41.57
68.68
116.84
174.20
2)4.87
292,38
341.35
377.45
397.67
403.75
404.28
404.28
404.32
404.53
404.98
105.48
TtM»'
CELSIUS
4.4
).«
1.1
2.0
1.1
1.6
4.0
7.9
7.9
11.4
14.2
16.9
17.6
18.2
18.7
18.9
18.3
15.4
11.6
9.9
8.3
H.I
8.6
10. 1
N>
tn
en
a/ Interference-corrected initial [NO], (Nf)2), and JKDX) arc 0.1 S3. 0.057, ant 0.210 ppn.
DAY 2, 10-16-77
17 X SUNSHINE
TIMt
(EST)
0.63
1.6)
2.63
3.6)
4.63
5.63
6.63
7.6)
8.6)
9.6)
10.6)
11.6)
12.6)
l).63
14.6)
15.63
16.63
17.63
OZONE
(PPM)
0.100
0.090
0.082
0.074
0.066
0.059
0.052
0.047
0.047
0.050
0.054
0.054
0.056
0.061
0.064
0.064
0.064
NO
(PPM)
0.0
0.001
0.002
0.003
0.006
0.006
0.008
0.008
0.007
0.009
0.008
0.009
0.009
0.009
0.008
0.009
0.011
N02
(PPM)
0.065
0.064
0.062
0.064
0.064
0.062
0.062
0.064
0.063
0.064
0.064
0.064
0.066
0.063
0.066
0.065
0.064
HOX
(PPM)
0.065
0.065
0.064
0.067
0.070
0.068
0.070
0.07)
. 0.070
0.072
0.072
0.073
0.075
0.073
0.075
0.073
0.075
T-SUL
(PPM)
0.126
0.12B
0.126
0.121
0.110
0.105
0.099
0.094
SU2
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
f-p-S PAN
(UG/M3) (PPM)
0.055
0.054
0.051
0.050
0.052
0.047
0.0 0.044
0.053
0.053
0.060
0.060
3.4 0.06|
0.062
0.057
0.060
0.056
0.0 0.059
CN-5
(K-CN/CM3)
0.0
0.210
0.200
SR
(L/MIN)
0.007
0.005
0.004
0.003
0.004
0.004
0.028
0.090
0.1^9
0.164
0.301
0.109
0.353
0.502
0.220
0.33A
0.185
0.028
CU-SR
(LANG) CELSIUS
0.26
0.6|
0.87
1.07
1.29
1.53
2.68
6.70
14.71
24.44
3V.«6
50.26
66.02
92.64
112.30
129.96
104.45
149.62
12.4
12.1
11.8
II.
II.
10,
9.B
10.4
11.0
10.9
10.8
9.3
9.0
9.4
10.I
10.6
II . J
1*1.2
-------
CHAMBEH Nil. |
DAY I, 10-17-77
RUN 38 : L4H4S
98 X SUNSHINt
KI1 SMOG CUAMHIR SIIIOY
UStP* CIINtKAtT NO. 6B-O
t/i
0\
HUE
(CSI)
0.13
1.13
2. HO
3.13
4.13
5.13
6.13
7.13
A. 13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
UZUNl
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.010
O.U26
0.055
O.OBtt
0.115
0.124
0.100
0.07B
0.060
0.047
0.039
0.033
0.027
0.024
0.020
lit)
(PPH)
0.002
0.001
0.157
0.15Ba/
0.155-
0.152
0.149
0.135
0.10|
0.0(,2
0.032
0.017
0.009
0.005
0.00/1
0.004
0.004
0.004
0.003
0.003
0.003
U.004
0.003
NO2
(PPM)
0.001
0.001
0.0
0.042
0.04<>
0.0«2
0.051
0.0/7
0.093
0.090
0.067
0.042
0.022
0.014
0.014
0.012
0.012
0.012
0.012
0.013
0.012
0.012
IJOX
(PPM)
0.003
0.002
0.157
I 0.200 a/
0.197 U
0.194
0.191
0.186
0.17B
0.155
0.122
O.OB4
0 . 0', 1
0.027
O.OIA
O.OIH
0.017
0.016
0.016
0.015
0.017
O.U16
0.016
I-SUL
(PPM)
0.0
0.0
0.924
0.922
0.921
0.909
0.906
0.900
0.886
O.B43
0.766
0.710
0.637
0.55B
0.498
0.468
0.441
0.407
0.361
0.329
0.294
0.296
0.285
0.276
SU2 I-P-S
(PPM) (UG/H3)
0.0
o.O
0.0
0.0 0.0
0.0
0.0
0.0
0.0 3.0
0.0
O.OIO
O.OIO 14.1
O.OIO
O.OIO
O.OIO
0.066 ?.'\.\
0.078
14.7
PAN
(PPH)
0.0
0.0
0.003
0.004
0.002
0.006
0.001
0.002
0.007
0.005
0.004
0.003
CN-5
(K-CN/CM3)
0.0
1.500
14.000
8,600
9.100
10.000
2.100
a/ Consider this value to lie the Interference-corrected initial concentration,
DAY 2, |o-|H-77
9<« X SUNSHINE.
I1ML
(ESf)
0.13
1.13
2.13
3.13
4.13
5.13
6.13
7.13
8.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
IB. 13
19.13
20.13
21.13
22.13
24.13
UiWtl
(PPH)
0.016
0.014
0.012
0.009
0.007
0.006
O.OU5
0.004
0.007
0.015
0.024
0.035
G.0'15
0.052
0.055
0.055
0.051
0.044
0.036
0.027
H . 02 1
u . u 1 5
U.UI2
0.009
(P
0
0
0
III)
PM)
.004
.004
.004
0.002
0
0
1)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.003
.ooa
.003
.003
.004
.003
.004
.003
.OO'I
.003
.003
.003
.003
.002
.001
.001
.0(1,?
.003
O.IK)}
0.001
N(>2 NIJX I
(PPM)
0.013
0.013
0.012
0.012
0.013
0.013
0.013
0.012
0.012
o.o id
0.013
0.015
O.Olo
0.015
0 . 0 1 •>
0.015
0.013
0.013
0.013
0.012
O.OIf-
0 . 0 | c'
0 . II 1 J
0 . 0 1 ,'
(PPM)
0
0
0
0
0
0
u
0
0
0
(I
0
0
0
0
1)
0
0
0
»
0
u
0
.016
. 0.1 /
.015
.014
.016
.015
.016
.015
.016
.015
.017
.OIR
.020
.018
.018
.OIH
.0|t>
.015
.014
.013
.0|4
,014
,0|6
-SOL
(PPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.271
.264
.25B
.255
.253
.244
.243
.241
.241
.243
.244
.243
.225
.100
.169
.151
SU2 t-P-S
PAN
(PPM) (UU/M3) (PPH)
0
0
0
0
0
0
0.0 0
0
0
0
0.0 0
0
o.oio
O.OIO 0.0
o.oio
.005
.001
.004
.005
.001
.007
.002
.006
.004
.007
. 00»,
.001
CN-5
(K-CH/CH3)
0.0
6.000
1 .100
0.01 3
SH
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.014
0.2a2
0.503
0.749
0.940
1.047
1.058
0.967
0.785
0.534
0.245
0.024
0.0
0.0
0.0
0.0
0.001
0.002
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.11
2.57
IB. OH
50.18
96.61
153. H5
216.75
279.52
336.12
361 .26
4) 1 .05
424.03
425.28
425.28
425.28
425.28
425.29
425.35
IIMP
CELSIUS
4.6
4.2
3.2
2.2
2.2
2.1
1.8
3.7
6.7
8.1
9.1
9.9
10.3
11.'
12.4
12.7
12.4
10.0
5.6
3.5
2.2
1.0
0.3
-O.I
SR
(I./MIN)
0.002
0.001
0.001
0.0
0.0
0.0
0.01 3
0.
-------
CMAMnf.H HO. t
DAY 5, 10-IV-/7
RUN 5tt i CIM'IS
79 X SUNSHINE
11 ME
USD
0.11
1.15
a. is
5.15
4.15
5.15
0.15
7.15
6.15
9.15
10.15
11.15
12.15
15.15
M.I5
IS. 15
16.15
U2UNI
(PPM)
0.007
0.005
0.00
(PPM)
0.012
0.012
0.012
0.012
0.012
0.010
0.011
O.OHl
0.012
0.010
0.012
0.012
0.012
0.014
0.015
0.012
0.015
Ml IX
(I'I'M)
0.015
0.015
0.011
0.015
0.012
0.011
O.OJ2
n.Oll
0.014
0.015
0.014
0.015
0.015
0.014
0.015
0.012
0.015
T-SUL
(PPM)
0.125
0.094
0.105
0.097
0.090
0.089
0.082
0.075
SI 12
(PPM)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
I-P-S
(UG/MJ)
HI I SMUG CHAMntK STUDY
USEPA CONIHALI Nil. 68-02-2417
PAGl 5
PAN CW-5
(PPM) (K-CN/CMi)
0.200
S.700
1.400
SH
(I./MIN)
0.002
0.0
0.0
0.001
0.001
0.001
0.011
0.175
0.448
0.708
O.HB7
0.974
O.H05
0./50
0.671
0.49S
0.217
CU-SH
(LANG)
0.02
o.ia
0.12
0.15
0.19
0.2S
0.59
2.51
14.85
45.74
87. 62
141.52
198.6?
24h.25
289.57
J28.46
55b.99
It HP
CH.SIUS
15.4
12.2
9.4
7.8
7.2
6.7
A.I
7.0
11.4
15.4
16.2
17.4
17.6
17.7
17.7
17.1
16.9
ts>
KEY:
3AHUAD
NUHOiR
4
UH1J3
(PPM) OZONE
(PPM) NITROGEN OXIDE
(PPM) NITROGEN DIOXIDE
(PPM) TOTAL NITROGEN OXIDES
CELSIUS TEMPERATURE (DRY IIULH)
(L/M1N) TOTAL SOLAR RADIATION
(LANG) CUMULAUVE TOTAL SOL AH RADIATION
(PPM) TOTAL SULFUR
(PPM) SULFUR DIOXIDE
(UG/M3) TOIAl PAHTICULATE SULFUR
(PPM) PERQXVACETYL NITRATE
(K-CU/CM5) CONDENSATION NUCLEI ( POP=b )
-------
CMAMOFH NO. £
DAY I, 10-17-77
RUN 30 : C4H4S
98 X SUNSHINE
HI I SMUP. CMAHHfM SIUOY
USEPA CUNfHAtT NO. 68-02-2437
11 Ml
(CSI)
O.JO
I.JO
2.30
3. 80
4.30
S.JO
6.30
7.30
6.30
9.30
10.30
11.30
12.30
13.30
14.30
IS. 30
16.30
17.30
IB. 30
19. JO
20.30
21.30
22.30
23.30
UlUUL
(PPM)
0.001
0.001
0.0
0.0
0.0
0.0
0.001
0.007
0.027
0.067
0.112
0.107
0.066
0.073
0.063
0.054
0.044
0.034
0.026
0.02'l
0.020
0.01 7
0.014
ir
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
no
I'M)
.002
.001
.079a/
,080"~
.077
.076
.074
.059
.037
.017
.008
.005
.006
.005
.005
.006
.006
.004
.005
.004
.003
.004
.004
NII2
(PI'M)
0.002
0.002
0.026 a/
0.025-
0.024
0.025
0.026
O.OJB
0.051
0.045
0.020
0.007
0.007
0.009
o.oon
o.oott
0.0l>7
0.000
0.007
0.007
o.oot*
0.007
O.OU7
NIJX
(PPM)
0.004
0.003
0.105 a/
0.105
0.101
0.101
0.100
0.097
O.OH8
0.062
0.026
0.012
0.013
0.014
0.013
0.014
0.013
0.012
0.0)2
0.011
0.012
o.on
0.012
I-SUL
(PPM)
0.0
0.0
0.922
0.927
0.916
0.909
0.912
0.907
O.BH5"
0.835
0.765
0.701
0.647
0.619
0.506
0.580
0.551
0.508
0.455
0.425
0.402
0.384
0.354
0.363
SU2
(PPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.010
.010
.010
.010
.071
.078
.096
I-P-S P
AN
(UC/M3) (PPM)
0.0
15.2 0.
0.
14.6 0.
0.
0.
0.
5.5 0.
0.
0.
0.
0
001
001
noi
0
000
0
0
002
001
CN-S
(K-CN/CMJ)
0.0
0.430
10.HOO
6.SOO
7.400
6.600
2.100
SH
(L/M1N)
0.0
0.0
0.0
0.0
0.0
0.0
0.014
0.222
0.503
0.749
0.940
1.047
1.056
0.967
0.76S
O.S34
0.245
0.024
0.0
0.0
0.0
0.0
0.001
0.002
UI-SR (IMP
(LANG) CELSIUS
0.0
0.0
0.0
0.0
0.0
0.0
0.25
4.64
23.21
57.82
106.20
164.S3
227.54
289.19
344.13
386.71
413.55
424.27
425.28
425.28
425.28
425.28
42S.30
425.37
4.6
4.2
3.2
2.2
2.2
2.1
1.8
3.7
6.7
8.1
9.1
9.9
10.3
11.7
12.4
12.7
12.4
10.0
5.6
3.5
2.2
1.0
0.3
-0.1
ro
Cn
00
a/ Consider this value to be the interference-corrected initial concentration.
DAY 2, 10-16-77
92 Z SUNSHINt
I IMC
(tSI)
0.30
1.30
2.30
3.30
4.30
5.30
6.30
7.3«
B.30
9.30
10.30
11.30
12.30
13. 10
14.30
15.30
16.30
17.30
10.30
IV. 30
20.30
21.30
22.30
23.30
IIZlKlL
(I'P t)
0.012
O.CIO
0.007
0.006
0.005
0.004
0.003
0.004
0.009
0.017
O.Uc'.l
0.040
0.050
0.05o
0.060
o.o«.o
q.OSb
0.05"
0.0 IS
0.03M
0.03'(
U.030
0 . OS 1
O.Ocfi
NO
(PPM)
0.005
0.001
0.004
0.003
0.004
0.00,?
0.003
0.003
0.003
0.004
0.003
0.003
0.001
0.004
0.003
0.004
0.003
0.003
0.001
u.ooi
0.01)2
0.003
0.002
0.001
NO?
(PPM)
O.OOtt
O.OOli
o.oott
o.nutt
o.oon
O.OOH
o.oon
O.noH
0.0 OH
0.007
0.010
0.01 1
0.013
0.012
o.on
0.012
0 . 0 U1
O.«l
0 . n I o
o.nlu
NDX
(PPM)
0.0|
I) . 0 1 5
0.012
o.oi i
U . 0 1 2
o.nid
tl . 0 1 f
II. Ill 1
I -Sill.
(PI'M)
0.356
0.354
0.347
0.345
0.342
0.336
0.333
0.331
0.331
0.329
11.329
0.319
0.301
0.270
0.250
0.,>3S
0.c".2
C.f'19
0 . 2 1 /
O..V3
S02
(I'PM)
I-P-S PAN
(UI1/M3) (PPM)
0.002
0.001
0.0
0.001
0.0
0.001
U.O 0.001
0.0
0.002
•> . <> o.o
CN-5
(K-CN/CMi)
0.0
0.071
o.oio
0.0
4. 150
0.580
SH
(L/MIN)
0.002
0.001
0.001
0.0
0.0
0.0
0.013
0.269
0.4H1
0.736
0.925
0.966
0.9H8
O.H65
0.700
0.495
0.160
0.013
0.0
0.0
0.001
0.004
0.003
0.001
CU-SR HMP
(LANG) CELSIUS
0.04
0.14
0.20
0.24
0.24
0.24
0.47
5.86
25.82
59.27
106.83
163.07
221.42
278.49
327.42
365.73
369.40
396. 15
396.90
396.90
396.9^
397.03
397.25
397.40
-0.4
-0.9
-1.3
-1.6
-I .9
-2.1
-1.9
O.I
5.2
10.9
15.0
16.9
18.2
18.9
19.1
19.2
17.2
16.2
13.7
12.5
12.1
|4!5
14.0
-------
CHAHHEK MJ. £
DA» 3, 10-19-77
HUN 3« I C4H4S
79 X SUNSHINE
HHt
((.ST)
0.50
1.50
2.50
5.50
1.50
5.50
6.50
7.10
fl.iO
9.30
10.30
11.30
12.30
I3.3U
14.30
15.30
16.30
U/OMt
(PPH)
0.025
0.021
0.01 /
0.011
0.010
0.007
W.OOb
0.004
0.009
0.023
0.03B
0.053
0.066
0.072
0.07b
0.081
0.0/7
HU
(PPM)
0.00)
0.001
O.UOI
0.001
0.001
0.001
0.001
0.001
0.003
0.002
0.001
0.000
0.001
0.0
0.0
0.001
0.001
ND2
(PPM)
O.OIU
0.009
0.009
0.009
0.009
0.009
o.oov
O.OOH
0.009
0.010
0.011
0.011
0.012
0.013
0.015
0.012
0.015
MUX
(PPH)
0.011
0.010
0.010
0.010
0.010
0.011
0.010
0.009
0.012
0.012
0.012
0.012
0.013
0.013
0.013
0.013
0.014
I-SUL
(PPM)
O.IB4
0.130
0.126
0.176
0.118
0.115
0.110
0.100
S02
(PPM)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
T-P-S
(UG/M3)
Nil SMOG CHAMHLK STUDY
IIStPA CONIRACI NO. 6B-02-24J7
PACE 5
PAN CN-5
(PPM) (K-CN/CM5)
0.0
5.300
0.950
SR
(L/MIN)
0.002
0.0
0.0
0.001
0.001
0.001
0.011
0.173
0.448
0.708
o.ae;
0.974
0.605
0.730
0.671
0.495
0.217
CU-SR
(LANG)
0.04
0.12
0.12
0.14
0.20
0.26
0.50
4.07
19.40
50.96
96.67
151.45
206. fll
2b3.6B
296.42
335.51
358.21
IEMP
CELSIUS
13.4
12.2
9.4
7. B
7.2
6.7
6.1
7.0
11.4
15.4
16.2
17.4
17.6
17.7
17.7
17.1
16.9
N>
Ul
VO
KtY:
SARUAD
HIIHIUR
44201
42601
4?602
42605
<«!IOI
65501
651UO
42269
41401
12169
44501
51114
NAMt
*»»«.
U2ONK
NO
NO2
NIIX
It HP
SH
CU-SR
I-SIIL
S(J2
r-p-s
PAN
CN-5
UNIIS
(PPM)
(PPM)
(PPM)
(PPM)
CELSIUS
U/MIN)
(LANG)
(PPM)
(PPM)
(UG/M3)
(PPM)
(K-CN/CM5)
DtSCHIPUON
UZONt
Nl IMOGEN DIOXIDE
IOIAL NIINOGEN (IKIOES
ItMPEHATUME (UHY HULB)
IOIAL SOLAR RADIAIKIN
COMULAUve IOIAL SOLAR RADIATION
IUIAL SULFUR
SULFUR DIOXIDE
TOIAL PAKTICULAIt SULfUR
PEHOXYACEtYL NIIRAIE
CONDENSATION NUCLEI ( POP=S )
-------
CHAMIIfli NO. 3
DAY I, 18-I7-/7
RUN J» : C4M4S
98 I SUNSMINf
Kri S««UG CHAMhtK SlUDY
USM'» CONTRACT ML 68-02-2457
I1HE
(tST)
0.47
1.47
2.40
5.40
4.47
5.47
6.47
7.47
0.47
9.47
10.47
11.47
12.47
15.47
14.47
15.47
16.47
17.47
10.47
19.47
20.47
21.47
22.47
21. 4/
cuunt
(PPM)
0.002
0.002
0.0
0.0
o.o
0.0
0.0
0.0
o.o
0.001
0.001
0.002
O.OU2
0.002
0.002
0.002
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
no
(PPM)
0.001
0.001
O.tOI
0.70fta/
0./66
0.747
0.727
0.709
0.600
0.665
0.652
0.596
0.565
0.529
0.497
0.477
0.465
0.455
0.444
0.455
0.427
0.420
0.4I6
0.412
H02
(PPH)
0.002
0.002
0.0
0.2l4a/
0.225
0.250
0.247
0.255
0.25U
0.261
0.264
0.275
0.205
0.290
0.291)
0.291
0.204
0.2112
0.201
0.2/9
0.270
0.277
0.200
0.2/7
I4DX
(PI»'O
0.004
0.005
0.001
1.002 a/
0.991J
0.905
0.974
0.964
0.446
0.924
0.696
0.071
0.046
0.019
0.787
0.760
0.749
0.757
0.725
0.712
0.705
0.697
0.697
0.600
^ a/ Interference-corrected initial {!*»), lff)zj, ami |(>
O
riMt
«S1)
0.47
1.47
2.47
1.47
1.47
5.47
6.47
7.47
0.47
9.47
10.47
11.47
12.47
13. 4/
14.47
15.47
16.47
17.47
10.47
19.47
20.47
21.47
22.47
25.47
T-SIIL
IPPM)
0.0
0.0
0.0
0.809
0.876
0.075
0.876
0.875
0.857
0.025
0.024
0.770
0.750
0.695
0.669
0.654
0.610
0.574
0.540
0.522
0.500
0.497
0.490
0.405
DX) arc
SII2 I-P-S
(PPM) (Uli/MJ)
0.0
0.0
0.0
0.0 0.0
0.0
0.0
0.0
0.0 0.0
0.0.
0.010
0.010 0.4
0.010
0.010
0.010
0.010 11.4
0.050
7.1
0.802, 0.215, ami 1.01? Pl*.
PAN
(PPM)
0.0
0.0
0.0
0.000
0.000
0.0
0.0
0.0
0.001
0.0
0.0
CN-5
(K-CH/CM1)
0.225
5.050
21.000
15.500
12.500
9.100
1.000
OAT 2, IO-18-//
Ll/Clllt
U'PMJ
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.002
0.004
O.UO'I
0.006
0.007
o.ooi
0.007
O.A05
0.005
0.0
0.0
0.0
0.0
0.0
o.u
0.0
11(1
O'PM)
0.400
fl!40|
0.5«>4
0.508
0.182
0.5/7
0.5/4
0.571
0. 158
0.515
0.3IS
0.200
0 . ,.'(, |
0.2-10
0.220
0.219
0.215
0.207
0.2H7
0.201;
0.20S
0.20<.
0.«'06
lr./'H6
Nf)2
U'PHl
0.264
0.2/0
0.279
0.276
0.276
0.2/5
0.2/5
0.2/0
0.251
0.251
U.752
0.24*
0.2"''
0.2'lrt
0.215
0.240
0.25/
0.25'i
0.252
0 . 22o
0.224
0.21''
0.220
0.2I*
mix
U'PM)
11.677
0..676
0.675
0.664
0.65«
0.652
0.6'|9
0.60)
0.609
0.574
0.517
0.52«
0.510
11.48*
0.475
0.'159
0.4SO
0 . '< 4 1
0.419
0.415
11.42*
0.425
•I. 4, '6
n.422
42 X
T-SUl
IPP«>
0.476
0.475
0.471
0.469
0.464
0.460
0.«55
O.U1H
0.425
0.414
0.407
0.104
0.597
0.5*4
U.5/4
n.i/l
0.564
0.555
0.107
0.2H5
0.262
0.24|
<> ,i">l
0.248
SUNSHINE
sii2 r-c-s
(tlti/M))
0.0
4.0
0.010
0.072
0.010 0.0
0.010
CAN
(PPW)
0.002
0.0
o.ooi
0.0
O.OOI
0.0
0.000
0.002
0.0
0.002
0.002
0.005
CM-5
IH-CN/CMJ)
0.0
2.000
0.620
SH
U/M1N)
0.0
0.0
0.0
0.0
0.0
0.0
0.014
0.222
0.505
0.749
0.940
1,047
1.050
0.967
0.705
0.554
0.245
0.024
0.0
0.0
0.0
0.0
0.001
0.002
SH
CO-SR HMP
(LANG) CttSiUS
0.0
0.0
0.0
0.0
0.0
0.0
0.59
7.10
20.54
65.46
115.79
175.21
250.54
299.25
552.14
592.16
416.05
424.52
425.20
425.28
425.28
425.20
425.11
425.40
4.6
4.2
5.2
2.2
2.2
2.1
1.8
1.7
6.7
8.1
9.1
9.9
10.5
11.7
12.4
12.7
12.4
10.0
5.6
5.5
2.2
1.0
0.5
-O.I
CU-SH UMP
(LANb) CIL51US
0.002
0.001
O.OOI
0.0
0.0
0.0
0.015
0.269
0.401
0.716
0.925
0.966
0.9HO
0.6«>5
0.700
0.495
0.160
0.011
0.0
0.0
O.OOI
0.004
0.005
O.OOI
0.06
0.15
0.21
0.24
0.24
0.24
0.61
0.6|
50.72
66.70
116.26
172.92
251.50
207.11
154.56
170. 7B
591.05
596.49
196.90
196.90
196.91
597.07
597.28
59/.4I
-0.4
-0.9
-1.1
-1.6
-1.9
-2.1
-1.9
O.I
5.2
10.9
15.0
16.9
10.2
10.9
19.1
19.2
17.2
16.2
15.7
12.5
12.1
M.2
14.5
14.0
-------
r«). 3
HI I SHOli CIIAKIIIEH STUDY
USEPA COMTKACI NO. 68-02-2437
HUH 3» S
Tint
(LSI)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
6.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
OZOru
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.005
0.009
0.013
0.016
0.010
0.014
0.019
0.015
0.007
NO
(PPM)
0.207
0.207
0.206
0.203
0.201
0.202
0.200
0.194
0.179
0.157
0.134
0.117
0.095
0.092
0.085
0.079
0.071
\
nng
(PPM)
0.211
0.209
0.202
0.196
0.194
0.189
0.186
0.181
0.16(1
o.ioo
0.162
O.lol
0.1/3
0.163
0.159
O.lb«
0.1 'j9
C4H4S
NIIX
(PPM)
0.4|6
0.416
O.'IOS
0.399
0.396
0.39|
0.3H6
0.375
0.347
0.317
0.296
0.280
0.266
0.254
0.244
0.237
0.230
79 X SUNSHINE
I-SUL
(PPM)
0.241
0.232
0.216
0.199
0.201
0.202
0.187
0.199
0.197
0.186
0.177
S02
(PPM)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
O.OS3
pAiif: 3
I-P-S PAH CN-S
(UG/M3) (PPM) (H-CN/CM3)
35.000
2.100
1.600
3R
(L/H1N)
0.002
0.0
0.0
0.001
0.001
0.001
0.011
0.173
0.448
0.708
O.Hft?
0.974
0.803
0.730
0.671
0.495
0.217
CU-SR
(LANG)
0.06
0.12
0.12
0.15
0.21
0.27
0.61
5.64
23.97
58.19
105.71
141.39
215.00
261.13
303.26
J3B.56
360.42
UHP
CtLSIUS
13.4
12.2
9.4
7.6
7.2
6.
6.
7.
11.
15.
16.
17.
17.
17.
17.
17.
16.9
ro
ON
KtYl
SAkll»l>
NUMHC H
44201
4^601
42602
42603
62101
63301
63300
42269
42401
12169
44301
31114
NAME
AHHK.
ll/OIJt
NO
NU2
N(IX
ItMP
5K
CU-SK
r-sut
SU2
I-P-S
PAN
CN--i
UNITS
(PPM)
(PPM)
(PPM)
(PPM)
CELSIUS
(L/MIN)
(LANG)
(PPM)
(PPM)
O/G/M3)
(PPM)
(K-CN/CM3)
OtSCHIPlHIN
OZONE
MI IMOGEN (IXIDE
NlIMOGEN DIOXIOE
IUIAL NIIHOf.EN UXIUtS
IEHPEHAIUHE (DRY BULH)
IOIAL SOLAN RADIATION
CUMULAIIvt IOIAL SOLAR HAOIAIIUN
tOIAL SULFUR
SULFUR DIOXIDE
KIIAL PA«riCUL*I£ SULFUR
PEHOXYACtTYL NIIRAR
CONDENSATION NUCLEI ( PDP^S )
-------
CHAMHtK MM. «
OAY I, IU-I7-/7
RUN 18 : C4H4S
96 X SUNSHINE
HI I S^IIC CHAMHtK SfUOY
USEPA CUMlKACf NO. 6A-02-2417
NJ
IIME
(LSI)
0.61
1.61
2.61
1.57
4.6)
5.61
6.61
7.61
8.61
9.61
10.61
11.61
12.61
11.61
14.61
IS. 6)
16.61
17.61
lit. 61
19.61
20.6}
21.6}
22.6}
21.61
OlUNE
(CPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.002
0.005
0.008
0.011
0.016
0.017
O.OIS
0.005
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Ml
(PPM)
0.001
0.0
a. 198
0.405a/
0.198-
O.)9|
O.V»|
0.1/1
0.149
0.11}
0.266
0.215
0.175
0.145
0.121
0.109
0.098
0.09]
0.090
0.09|
0.090
0.09|
0.09|
o.o9^
NO2
(PP1)
0.002
0.002
0.0
O.I 04 a/
o.iii/-'
0.110
O.llS
0.120
0.110
0.150
0.1/1
0.199
0.209
0.211
0.209
0.205
G.20'l
0.20J
0.201
0.197
0.19}
0.191
O.IHh
D.I 05
NIIX
(PPM)
0.002
0.002
0.19fl
0.509 ,/
0.505J
0.501
0.496
0.49|
0.4/9
0.46)
0.419
0.414
0.184
0.158
0.112
0.111
0.302
0.296
0.291
0.2B8
0.284
0.2a2
0.2/8
0.2/6
l-SUL
(PPM)
0.0
0.0
0.0
0.859
0.917
0.914
0.896
0.908
0.889
0.851
0.8*02
0.770
0.717
0.6/7
0.617
0.625
0.59}
0.54}
0.515
0.496
0.4H)
0.471
0.460
0.451
302 I-P-S
(PPM) (Uf./MJ)
0.0
.0
.0
.0 0.0
.0
.0
.0
0.0 0.0
0.0
0.010
0.010 10.4
0.010
0.010
0.010
0.010 10.6
0.060
10.1
PAN
(PPM)
0.0
0.001
0.0
0.002
0.002
0.0
0.000
0.001
0.001
0.0
CM-5
(K-CN/CM1)
0.0
2.450
16.000
10.000
11.000
9.100
1.800
a/ Consider this value to be the interference-corrected Initial concentration.
OAr 2, 10-18-77
92 X SUNSHINE
line
(ESI)
0.61
1.61
2.6}
1.6}
4.61
5.ol
6.61
7.6}
6.6}
".61
10. Dl
11.61
12.61
D.61
14.61
15.6}
16.6}
17.6)
18.6)
|9.6i
20.6)
21.61
22.1.1
21.61
lUUUt
(PP.-1)
0.0
0.0
O.I)
O.rt
0.0
0.0
0.0
0.007
0.012
0.021
O.Oli
0.050
0.066
0.077
O.Ohl
O.OHI
0.069
0 . OS 1
0.04|
0.0),'
0.025
0.019
0.016
0.01 (
(Ml
(PPM)
0.092
0.09|
0.090
0.090
O.OH9
O.OH9
0.000
0.095
O.OB9
0.0/7
0.052
0.017
o.o,;?
0.019
0.015
0.0|<>
0.006
O.OUJ
0.00}
O.OU3
o.oo'i
W.ilO'l
0.002
0.001
til 12
(PPM)
O.lrti
o.ioo
0.1/6
O.l/i
0.1/2
0. Ihll
O.li.i
0.150
0. 1 4"
O.I2/
0. 1 il
0.1 111
0. I'M'
n.ni
0.101
O.OVi
0.09t'
O.i'ltl
p. <>«.<<
O.Pol
0.055
0.0'jt
0.0 -r»
O . 0 "« 11
IIOX
(PPM)
0.2/5
0.270
0.266
0.262
0.261
0.256
0.252
0.2'I5
0.221
U.204
O.l«l
O.I6/
U.14/
II . 1 JO
0.116
0.107
0.0 '*«
|>.OM(>
0.071
i).Ub4
II.05H
11.1156
il. "SI
il.0'|9
I-SUL
• (PPM)
0.450
0.44}
0.415
0.414
0.410
0.421
0.416
0.407
0.186
0.17/
0 . 16<>
0 . 152
O.lil
0.313
0.287
0.297
0.2H/
0 . «*5H
0.250
0.219
SU2 I-P-S PAN
(PPM) (Uti/MJ) (PPM)
0.0
0.001
0.001
0.000
0.001
0.001
0 . 0 0.0
0.0
0.001
0.0
0.002
H.I 0.004
0.010
0.010
O.Hh/
0.010 0.0
0 . 052
CN-5
(K-lN/CMi)
0.0
2.200
O.HIO
SH
(L/MIN)
0.0
0.0
0.0
0.0
0,0
0.0
0.014
0.222
0.501
0.719
0.940
I.04/
1.058
0.967
0.785
0.514
0.2«S
0.024
0.0
0.0
0.0
0.0
0.001
0.002
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.51
9.21
11.17
72.65
124.81
185.26
248.49
108.55
159.67
197.28
418.40
424.75
425.28
425.28
425.28
425.28
425.12
425.41
IEHP
CttSIUS
4.6
4.2
1.2
2.2
2.2
2.1
1.8
1.7
6.7
8.1
9.1
9.9
10.1
11.7
12.4
12.7
12.4
10.0
5.6
1.5
2.2
1.0
0.1
-0.1
SK
(L/MIN)
0.002
0.001
0.001
0.0
0.0
0.0
a. oiJ
0.269
Q.afil
0.716
0.925
0.966
0.9R8
0.»65
0.700
0.095
0.160.
0.011
0.0
0.0
0.001
0.00"
0.00*
0.001
CU-SH
(LANG)
0.08
0.16
0.22
0.24
0.24
0.24
O./l
It. »9
15.14
71. «4
125.14
182.19
240.99
295.62
}4l.2«
1/5.51
192,57
196.61
196.90
196.90
196.94
19/.I1
197.11
197.42
UNP
CELSIUS
-0.4
-0.9
-1.1
-1.6
-1.9
-2.1
-1.9
0.1
5.2
10.9
15.0
16.9
18.2
1».9
19.1
19.2
17.2
16.2
11. /
12.5
12.1
M.2
14.5
H.O
-------
CHAMBER NO. <4
DAY 1, JO-19-77
RUN 3» I C4ICIS
79 X SUNSHINE
Rtl SMOG CHAMHt.M STUDY
USEPA CUN1RACI NO. 68-02-2437
PAGE 3
lIMt
tesTj
0.63
1.63
2.63
3.63
1.63
5.63
6.63
7.63
B. 63
9.63
10.63
11.63
12.63
13.63
14.63
15.03
16.63
OlONf
(PPM)
0.010
0.007
0.006
0.004
0.003
0.002
0.00
-------
CHAMHKH MO. |
DAY I, 10-20-7?
RUM 19 I ICHD2C4H2S 100 X SUHSltINt
HI I SMUG CMAHHf.K STUDY
USER* CONTRACT NO. 6H-02-2417
NJ
0>
-P-
TIME
(EST)
0.11
1.13
2.67
3.97
4.a7
5.13
6.11
7.11
e.u
9.11
10.11
li.ti
12.13
11.11
14.11
IS. 11
16.11
17.11
IB. 11
I'.ll
20.13
21.11
22.11
21.11
OZCJHE
(HP.*)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.003
0.010
0.041
0.108
0.092
0.0/5
0.066
0.061
O.OSO
0.040
0.030
0.022
0.016
0.011
0.006
0.005
HI)
(PPM)
0.001
0.002
O.I4B
0.158 a/
0.158"
O.ISfl
0.149
0.127
O.OB|
0.016
0.013
O.OIQ
0.010
0.009
0.009
0.011
0.012
0.012
O.OI|
0.011
0.011
0.014
0.012
Nf)2
(PPM)
0.0
0.0
0.0
0.032 b/
O.Oil ~
0.029
0.029
0.047
0.072
O.Odl
O.OSB
O.OS1
0.049
0.045
O.O'II
0.019
0.035
0.034
0.032
0.012
0.031
0.032
0.032
NO* I-SUL
OM'M) (PPM)
0.003 0.0
0.002 0.0
0.118 0.618
0.642
0.189 a/ 0.774
0.190
O.IB4
O.I7R
0.174
O.IS3
0.120
0.071
0.061
0.059
0.055
O.OS1
0.050
0.047
0.046
0.043
0.043
0.045
.766
.747
.744
.710
.696
.658
.614
.573
.552
.513
.512
.487
.453
.176
.104
.262
.22B
0.046
0.044
SO2 1-P-S
(PCM) (Of./MJ)
0.0
0.0
0.0
0.0
0.0 0.0
0.0
0.0 0.0
0.010
0.010
0.115 5.7
0.170
0.17« 4.9
0.200
0.217
0.221 3.1
0.221 0.0
0.200
0.119
O.OR5
0.059
PAN
(PPM)
0.019
0.024
0.0?4
0.020
0.017
0.016
f.W-5
(K-CM/CMJ)
2.950
1.900
6.600
10.500
12.000
13.500
11.000
2.050
aj Data insufficient to permit correction for interference.
E/ Interference-corrected initial (NT)?! is 0.048 pn».
DAY r, 10-21-77
'85 X SUNSHINt
TIME:
(CST)
0.13
1.13
2.13
1.13
4.13
S.I3
6.13
7.13
8.11
"Ml
10.11
11.11
12.11
13.13
14.13
I5.I3
16.13
U/UIIK
(PCM)
0.002
0.001
0.001
0.001
0.0
0.0
0.0
0.0
0.004
0.007
0.012
0.025
0.036
0.040
0.045
0.041?
0.045
Wt
(PPM)
0.011
0.01?
0.012
0.012
0.011
o.on
0.011
0.011
0.013
0.012
0.011
0.011
0.010
0.00ft
0.006
0.006
0.005
Nil?
(PPM)
0.031
0.031
0.030
0.030
0.029
0.030
0.011
0.030
0.030
0.010
O.Oli
O.Oil
0.029
0.020
0.026
0.02'>
0.02S
NIIX
(PPM)
0.044
0.041
0.042
0.042
0.041
0.041
0.041
0.041
0.043
0.042
0.042
0.04£
0.039
O.Olt.
0.032
0.031
0.010
I-SUL
(PPH)
0.150
0.146
0.154
0.171
0.191
0.199
0.196
0.210
0.204
0.203
0.193
S02
(PPM)
0.0
0.0
0.010
0.010
0.010
0.010
O.OHO
0.09/
O.IOB
O.IIS
0.116
T-P-S PAN
(UG/M1) (PPM)
0.017
0.017
0.0 0.017
0.018
0.017
0.016
0.0|5
o.O 0.015
0.013
0.012
0.0 0.012
CII-5
(K-Ctl/CMl)
0.200
S.OOO
5.700
2.400
SH
(l/MIN)
0.0
0.0
0.0
0.0
0.0
o.o
0.011
0.161
0.442
0.701
0.875
0.972
0.982
0.874
0.709
0.472
O.J97
0.01 J
0.0
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.09
2. 10
IS. IS
41.69
87.10
140.16
19B.76
256. B4
107.99
348.68
174.66
185.24
185.92
IBS. 92
185.92
Ifl5.<»2
185.92
185.92
.IIHP
CELSIUS
a. 9
2.1
1.7
l.i
0.9
0.7
0.8
2.7
7.9
11. 0
15.?
16. 6
17.0
17.7
18.2
18.1
17.5
11.7
10.0
7.9
6.4
5.4
4.4
1.6
SR
(l/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.170
0.410
0.692
0.901
0.920
0.725
0.722
0.661
0.417
0.109
CU-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.08
I.9J
14.00
40.00
fll.95
I1A.I6
1^1.81
215.31
278.17
316.03
118.96
UMP
CELSIUS
2.9
2.1
1.6
0.9
0.5
0.0
-0.2
1. 7
6.5
11.4
15.1
16.5
17.2
17.7
18.2
18.5
17.6
-------
CHAMBEH WO. 2
DAY I. 10-20-J7
RUN 39 s (cn3)2C4H2s too * SUNSHINE
HTI SMOG CHAMBER STUDY
USEPA CONIRACI Nil. 68-02-2437
NJ
TIME.
(ESI)
0.30
1.30
2.97
3.13
4.63
5.30
6.30
7.30
A. 30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
18.30
19.30
20.30
21.30
22.30
23.30
n/ Dnta
OiONt
(PPM)
0.0
0.0
0.0
6.0
0.0
0.0
0.0
0.006
0.020
0.0to5
0.079
0.06B
0.062
0.058
0.053
0.046
0.038
0.030
0.023
0.014
0.013
0.009
0.006
insufficient
NO
(PPM)
0.007
0.005
0.075
O.Oflla/
0.083
0.080
0.078
0.063
0.03A
0.016
0.011
0.01?
0.013
0.011
0.011
0.012
0.014
0.013
0.013
0.013
0.015
0.015
0.015
to ncrNit
N02
(PPM)
0.001
0.0
0.0
O.OI9b/
0.019-
0.017
0.016
0.026
0.037
0.034
0.027
0.027
0.025
0.023
0.022
0.021
0.019
0.018
0.017
0.015
O.OI/
0.017
O.Olo
correction
NUX
(PPM)
0.008
0.005
0.075
0.100 a/
0.101
0.097
0.094
0.090
0.075
0.050
U.03H
0.039
0.038
0.034
0.032
0.013
0.03J
0.032
0.030
0.026
0.031
0.032
0.031
t-SUL
(PPM)
0.0
0.0
0.0
0.738
0.803
0.795
0.799
0.79S
0.782
0.760
0.744
0.724
0.694
0.681
0.672
0.650
0.629
0.593
0.504
0.434
0.395
0.365
0.343
0.326
SU2
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.115
0.114
0.135
0.162
0.185
0.191
0.192
0.174
0.105
0.010
0.010
T-P-S PAN
(UG/M3) (PPM)
0.0
0.0
2.7
3.3
0.012
2.8 0.011
0.0 0.010
0.009
0.011
0.01?
0.011
0.011
0.011
0.011
CN-S
(K-CN/CMi)
0.200
1.600
4.000
5.700
5.700
4.800
1.300
for interference.
b/ Interference-corrected initial fNT^l is 0.035 ppn.
PAY 2, 10-21-77
TIME
(EST)
0.30
1.30
2.30
3.30
4.30
5.30
6.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14.30
15.10
1*. 10
IWlNt
(PPM)
0.004
0.004
0.001
0.001
0.0
0.0
0.0
0.0
0.006
0.009
0.014
0.027
0.036
0.039
0.042
0.042
0.039
NO
(PPM)
0.016
0.015
0.014
0.014
0.013
0.012
0.014
0.014
0.014
0.014
0.012
0.012
0.010
0.010
0.008
0.007
0.007
IJ(»2
(PPM)
0.015
0.015
0.016
O.OI')
O.OIS
0.016
0 . 0 1 5
0.01f>
0.016
O.OI/
0.020
0.020
0,01''
o.oia
0.017
0.017
O.OIS
HOX
(PPM)
0.031
0.010
0.030
0.029
0.029
0.02B
0.029
0.029
0.030
0.031
0.032
0.032
0.029
0.02B
0.0,'S
0.02"
0.022
85 -X
T-SUL
(PPM)
0.319
0.306
0.299
0.294
0.289
0.281
0.293
P. 291
0.300
0.110
0.325
0.319
0.31S
0.327
0.321
0 . 1 1 H
0.307
SUNSHINE
SO2
(PPM)
0.0
0.0
0.010
0.010
0.010
0.010
0.066
O.OB1
0.098
0.109
0.112
I-P-S PAD
(UG/M3) (PPM)
0.011
0.011
0.011
O.OU
0.012
0.0
0.012
0.011
0.012
O.OI 1
O.Otl
0.0 0.010
0.010
0.009
o.o 0.009
CN-S
(K-CN/CM3)
0.200
1.400
5.000
2.000
s«
(L/HIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.011
0.184
0.442
0.701
0.875
0.972
0.962
0.874
0.709
0.472
0.197
0.013
0.0
0.0
0.0
0.0
0.0
0.0
CU-SH
(LANG)
0.0
e.o
0.0
0.0
0.0
0.0
0.20
3.97
19.66
50.84
96.03
150.28
208.78
265. 7S
315.22
353.50
376.87
385.37
385.92
3«5.92
385.92
385.92
385.92
3*5.92
TEMP
CELSIUS
2.9
2.3
1.7
1.3
0.9
0.7
0.8
2.7
7.9
13.0
15.2
16.6
17.0
17.7
18.2
18.1
17. S
13.7
10.0
7.9
6.4
5.4
4.4
3.6
sn
(L/MIN)
0.0
0.0
o.o
0.0
0.0
0.0
0,010
0.170
O.«10
0.692
0.901
0.920
0.725
0,722
0.6h3
0,41 7
0.149
CU-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.18
3.6ti
18.18
47.06
93.14
147.54
199.23
242,68
284.93
320.29
340. 4«
TEMP
CELSIUS
2.9
2.1
1.6
0.9
O.S
0.0
-0.2
1.7
6.5
11.4
15.1
16.5
17.2
17.7
18.2
18. S
1 7.6
-------
CHAMBER NO. 3
DAY |, 10-20-77
RUN 39 t (C»I3)2C4H2S 100 X SUNSHINC
RTI SMUG CMAMHCH STUDY
USEPA CONTRACI NO. 68-02-2437
K5
TIME
(EST)
0.47
1.47
2.47
3.30
3.47
4.80
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
18.47
|9,U/
20.47
21.47
22.47
23.47
OZONE
(PPM)
0.0
.0
.0
.0
.0
.0
.0
0.0
0.0
0.0
0.001
0.004
0.020
0.055
0.097
0.121
0.144
0.121
0.079
0.048
0.031
0.019
0.012
0.008
0.005
MO
(PPM)
0.009
0.006
0.787
0.831
0.868 a/
0.813"
0.829
0.802
0.775
0.710
0.590
0.185
0.206
0.096
0.047
0.027
0.017
0.013
0.011
0.009
0.008
0.009
0.010
0.011
0.010
IIO2
(PPM)
0.001
0.0
0.0
0.147
O.I97I)/
0.216
0.221
0.230
0.248
0.2/9
0.344
0.465
0.535
0.533
0.492
0.434
0.380
0.332
0.278
0.236
0.213
0.202
0.197
0.192
0.189
a/ Interference-corrected initial [M>] is
F/ Data insufficient to pendt correction
NDX
(PPM)
0.010
0.006
0.787
0.978
.065 b/
.060
.051
.032
.023
0.989
0.934
0.850
0.741
0.631
0.539
0.461
0.397
0.345
0.288
0.245
0.222
0.211
0.206
0.203
0.199
T-SIIL
(PPM)
0.0
0.0
0.0
0.0
0.825
0.867
0.856
0.864
0.850
0.813
0.728
0.662
0.579
0.549
0.548
0.559
0.544
0.521
0.464
0.346
0.257
0.208
8(12 1 -P-S
(PPM) (UG/M3)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0
.0
.0
.0
.0
.0
.0 0.0
.0
.0 0.0
.010
.010
.188 27.4
.263
.347 34.8
.401
.I'll
.434 23.7
.415 0.0
.366
.261
.182
.145
PAN
(PPM)
0
0
0
0
0
0
0
0
0
.009
.019
.028
.035
.036
.040
.042
.041
.039
CN-5
(K-CN/CM3)
0.225
28.000
29.000
31.000
29.000
27.000
1.050
0.830 pp«-
for interference.
DAY 2, 10-21-77
11 HE
(CSI)
0.47
1.47
2.47
3.47
4,47
5.47
6.47
7.47
8.47
<».47
10.47
11.47
12.47
13.47
14.17
15.47
16,17
17. PO
UJUNE
NU
(PPM) (PPM)
0.002
0.002
0.001
0.001
0.0
0.0
0.0
0.009
0.023
0.058
0.114
0.209
0.25
-------
CHAMHEH NO. 4
DAY I, 10-20-/7
RUN 39 ! (CH312C4H2S
KU SMUG CHAMBER STUDY
USEPA CONTRACT NU. 68-02-24)7
100 Z SUNSMINt
IIME
(CST)
0.63
1.63
2.70
3.57
3.77
4.97
5.63
6.63
7.63
6.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
17.63
18.63
19.63
20.63
21.63
22.63
23.63
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.004
0.027
0.008
0.123
0.252
0.238
0.226
0.209
0.188
0.166
0.147
0.132
0.119
0.106
0.094
NO
(PPM)
0.005
0.003
0.364
0.388
0.4l6a/
0.410-
0.407
0.397
0.302
0.332
0.227
0.107
0.039
0.006
0.008
0.004 •
0.005
0.006
0.008
0.007
0.007
0.007
0.009
0.008
0.008
N02
(PPM)
0.0
0.0
0.0
0.027
O.lOib/
0.105-
0.103
O.IOJ
0.114
0.14-4
0.211
0.26/
0.253
0.189
0.147
0.143
0.137
0.132
0.1 25
0.123
0.120
0.119
O.ll/
0.117
O.I 16
a/ Interference-corrected initial [NO] is
E/ Data
insufficient
to permit
correction
NUX
(PPM)
0.005
0.003
0.364
0.415
0.5|9b/
0.515
0.510
0.500
0.495
0.476
0.438
0.373
0.292
0.195
0.155
0.147
0.142
0.139
0.134
0.129
0.126
0.126
0.126
0.125
0.125
0.390 ppm.
1-SUL
(PPM)
0.0
0.0
0.0
0.776
0.781
0.813
0.611
0.616
0.603
0.776
0.725
0.652
0.587
0.550
0.533
0.542
0.521
0.488
0.427
0.300
0.207
0.171
SO2 . I-P-S
(PPH) (UG/hi)
0.0
0.0
0.0
0.0
0.0
0.0 0.0
0.0
0.0 0.0
0.010
0.114
0.171 16.6
0.223
0.317 25.0
0.383
0.4|5
0.406 16.1
0.385 0.0
0.330
0.217
0.139
0.096
PAN
(PPM)
0.010
0.022
0.056
0.050
0.055
0.050
0.050
0.052
CN-5
(K-CN/CM3)
0.225
17.000
25.000
24.000
25.000
17.500
2.300
for interference.
DAY 2, 10-21-77
IIMI
(1ST)
0.63
1.63
2.63
3.1.3
4.63
5.63
6.63
7.63
8.63
9.63
10.63
ll.'.i
12.63
13.63
14.63
15.61
16.6}
UZOIIt
(PPM)
0.044
0.076
0.069
0.062
0.055
0.050
0.043
0.037
0.037
0.040
0,076
0.130
0.192
0 . 2 1 J
0.238
0.248
0.23H
NU
(PPM)
0.000
0.008
O.OJ7
0.006
0.006
0.006
0.005
0.006
0.000
o.oon
0.000
0.006
0.005
0.005
0.003
0.003
0.002
NO2
(PPM)
0.115
0.115
0. 1«
0. 14
0. 13
0. 12
0. II
0. 11
0. II
0. 13
0. 10
0. 10
0.104
0.103
o.ova
O.O'M
O.OH7
NUX
(P»'H)
0.123
0.122
0.121
0.120
0.119
O.I IB
0.116
0.117
0.119
0.121
0.118
0.116
0.109
0.107
o.ini
0.096
0.08')
85 X
1-SUL
(PPM)
0.010
0.010
0.010
0.010
0.010
0.069
0.005
0.090
0.105
0.090
0.113
0.105
SUNSHINE
802 I-P-S
(PPM) (UG/MJ)
0.0
0.0 0.0
0.010
o.oto
0.010
0.010
0.010
0.058
0.010 4.4
0.06H
0 . 1) 1 0
ft. 0|(1 0.0
PAH
(PPM)
0.054
0.054
0.046
0.054
0.056
0.05S
0.053
0.051
0.049
0.047
0.045
0.041
O.OJ9
0.056
tN-5
(K-CN/CM3)
0.^00
<>.300
/".9f>0
i r.03
SR
U/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
O.OIt
0.184
0.442
0.701
0.875
0.972
0.902
0.874
0.709
0.472
0.197
0.013
0.0
0.0
0.0
0.0
0.0
0.0
SR
(L/MIN)
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.170
. 0.410
0.692
0.901
0.920
0.725
0.722
0.663
0.417
O.|4'»
0.010
CU-SR
(LANU)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.4?
7.62
28.41
64. 72
113.35
169.52
220.22
283.06
329.26
362.84
380.77
305.63
385.92
385.92
385.92
305.92
385.92
3flS.92
CU-SK
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.38
7.03
26.30
61.56
110. 9H
165.76
2t».58
256.97
298.06
32«.54
343. 4J
346. 76
UMP
CELSIUS
2.9
2.3
1.7
1.3
J.3
0.9
0.7
0.6
2.7
7.9
13.0
15.2
16.6
17.0
17.7
18.2
16.1
17.5
13.7
10.0
7.9
6.4
5.4
1.1
3.6
II MM
CELSIUS
?.9
2.1
1 .6
0.9
0.5
0.0
-0.2
1.7
6.5
11.4
15. J
16.5
17.2
17. 7
16.2
ltt.5
17.6
13. «
-------
LHA'llll I. (III. I
OAY |, l\i-d,!-ll
KIIN 4U : i-LH3-l4H3S 100 X SUNSH1M
RFl SMIlt; CHAMhLH SIHOY
USM'A CIIHIKACI Ml). bfl-02-2437
JO
0\
00
II ME
((.SI)
0.15
1.13
5.80
5.32
6.15
7.13
P. 11
9.13
10.11
11.13
12.13
13.11
10.13
15.15
16.13
17.13
10.11
19.13
20.15
21.15
22.15
23.13
ll/UNt
(PP 1)
0.0
0.0
o.o
0.0
0.0
0.0
0.004
0.052
O.O//
0.052
0.052
0.059
0.064
0.067
0.064
0.052
O.Oil
0.02c(
0.020
0.012
0.007
0.006
mi
(PPM)
0.0
0.001
0.13/a/
U.14|~
0.110
0.156
0.115
0.05<»
O.O28
0.021
0.01 7
0.015
0.010
0.00«
O.OOJ
0.007
0.005
O.OO'I
o.ooa
0.005
0.005
0.006
li
r;
(Pi
0
0
0
0
0
0
n
0
0
i)
0
0
n
0
0
0
0
0
0
0
0
0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
a/ Interference-corrected initial
b~/ Data
IIMt
(tSI)
0.13
1.13
2.13
3.13
4.13
5.13
6.15
7.15
11.11
9.11
10.13
11.13
12.13
13.15
14.13
15.15
lb.13
1/.I5
IB. 11
insufficient
(J/UML
(PI'-II
O.OO'I
o.ooi
0.0
0.0
0.0
O.n
0.0
0.0
O.Ol'/
0.014
0.021
O.O'll
0.091
0.101
0.106
0.100
0.091
to permit
(> «
»n
iiU
(I'P.I)
0.006
0.006
0.006
O.l'OS
0.004
0.002
li. 00 J
O.OOt,
0.005
0. u('«>
o.o(;s
0.005
0.005
C.Oi'5
0. 0«l«
y.'His
i, .mi j
12
'MJ
II
0
I) b/
0 ~
n
0
0
02 /
ncii
oil
Old
020
022
020
02(1
021
Olti
on
01 1)
OH)
OH)
Ol/
(NO] is
correction
i \f * * '•
c
fin2
u
0
0
0
0
II
0
0
I)
0
0
0
n
0
0
ii
0
(i
V
•
•
•
m
.
.
w
9
m
m
f
f
•
m
m
f
••')
Olb
nib
019
Olb
nl 1
HI /
n in
ui /
ii 1 (i
n 1 1,
020
Odii
cVS
025
IV 1
02.1
02 4
UIIX
(PP'I)
0.0
0.001
0 . 1 i / b/
II. Ml ~
0.139
0.156
0.115
O.OH5
0.050
0.052
0.054
0.015
0.052
0.02"
0.020
• 0.02B
0.025
0.022
0.021
0.024
0.024
0,023
0.089 ppM.
I-SUL
(PPM)
0.0
0.0
0.691
0.693
0.6B'I
0.669
0.657
0.604
0.511
0.510
0.506
0.4«6
(1 . 4 7 5
O.H55
0.416
0.124
0.251
SII2 I-P-S
(f'PM) (U(,/M3)
0.0
0.0
0.0
0.0 0.0
0.0
0.0 0.0
0.0)0
0.010
0.122 16.0 -
0.175
0.222 14.5
0.263
0.2H4 15.0
0.291
0.264 ' 7.4
0.19H
0.141
PAD
(PPM)
0
(I
0
0
0
0
0
0
0
0
0
0
0
0
.0
.om
.007
.010
.010
.010
.010
.OOP
.008
.008
.006
.005
.007
.006
CN-5
(K-CN/CM1)
0.0
16.0110
7.200
12.000
12.000
12.000
9.600
2.000
for interference.
mix
(PI'M)
0.024
0.022
0.024
0.021
0.021
0.020
0.021
u . (i 2 3
0.021
0.024.
0.1-20
O.Oil
0 .Old
o.o in
O.HC''
O.o, '8
o.o,'/
PO X
I-SOL
(PPM)
0.0)0
0.010
0.010
O.OHI
0.104
0.119
0.167
0.1511
0.) 7ft
0. I'*''
0.2DO
SUNSH1UI
SU2 I-P-S
(PI'H) (UG/MD
o.om o.o
0.0
0.0)0
0 . 0 1 (I
0.010
(1.079 1.9
O.OHfl
fl. 09o
O.I 01.
0 . 1 1 "
0. 1 lo
1.0
PAH
(PPM)
0
0
0
0
0
0
(I
0
(I
()
0
.009
.one
.1109
.009
.009
.009
.009
.008
.0(0
.0(18
.007
CN-5
(h-CN/CM$)
o.u
1 .hOO
1 .800
o., v>o
SH
(I./HIN)
0.0
0.0
0.0
0.0
0.012
0.200
0.365
0.596
O.H24
0.95H
0.956
O.B19
0.6ft 1
0.4S5
0.185
0.009
0.0
0.0
0.0
0.0
0.0
0.0
SH
U/MIN(
0.0
0.0
0.0
0.0
0.0
0.0
O.Oil
0.141
0.404
0.601
0. /Hh
O.H59
0.87 J
0.706
0.511
0.161
0.114
0.010
0.0
CII-SX
(LANG)
0.0
0.0
0.0
0.0
0.09
2.?fl
15.57
19.27
/6.8I
127.29
184.76
241.20
290.95
130.11
155.52
165.05
365.52
365.52
365.52
165.52
165.52
165.52
CU-SW
(LANG)
0.0
0.0
0.0
0.0
0.0
0.0
0.09
1.76
12.27
18.05
75.55
121. 2B
I7't.9i
22h.OI
266. flS
296. 15
116. 19
122.22
322.74
I IMP
CtLSIUS
3.7
3.0
1.9
0.9
0.7
2.3
7.0
12.5
16.9
19.9
21.5
22.5
22.9
21.0
21.9
16.9
12.4
10.7
9.4
8.2
7.1
6./
HMP
CtLSIUS
b.t
5.7
5.1
4.9
4.4
4.2
4.1
5.4
11.6
|4.9
17.7
19.1
20.6
21.1
21.1
20.5
19.2
17.2
IS.l
-------
CHAK.nt-K nil. 2
OAY |, 10-22-77
HIIN 'to : 3-CH3-C4H3S ion x sunsitltit
NT I SMUG CMAMHtK SI HOY
USfcPA ION IK AC I Nil. 6B-02-2457
fo
ON
lint
(LSI)
0.30
1.30
3.b7
4.98
5.63
6.50
7.30
8.50
9.30
10. 10
11.30
12.30
13.30
14. 30
l'>. 50
16.30
1 /. 50
18.50
19.10
20.30
21.30
22.30
23. 50
MZUUL
(PIM)
0.0
U.O
0.0
0.0
U.(l
0.0
n.o
0.004
0.029
O.I3S
0.1 '10
0.149
O.I6b
O.lfc/
0. 97
0. VI
0. /It
0. S2
0. 5->
0.117
0.1 II I
O.U9I
0.0 /M
.III
(PPM)
VI. 00|
O.OOb
0.215
0.2IP3/
0.217
0.216
0.209
0.177
0.095
0.02u
O.OIIP
O.OOq
0.003
0.005
0.00,?
0.002
0.002
O.OOl
0.001
0.002
O.OOJ
0.005
0.005
11(12
(PP">
O.O
o.o
0.0
0. on li a/
O.OOo
O.OUb
O.OOl.
0.052
O.Orto
0.062
0.049
0.0b3
O.ObO
0.0'JI
O.U4/
O.DMS
0.041
0.039
0.037
0.037
0 . 0 JO
0.03b
0.0 Jb
mix
(P»'M)
0.001
0.005
0.21 3
0.2e!ha/
0.225
0.222
0.216
0.209
0,1/9
ii. OH 7
O.Obf
O.Ob'
O.OS4
0.0b4
0.000
U.0'17
0.043
0.040
0.059
0.039
11.039
0.037
0.03'i
l-SOl
(PPM)
o.o
0.0
0.644
0.64)
0.645
O.b34
0.62b
0.609
O.Sbl
0.4bl
0.142
0.4411
0.44S
0.429
0.412
0.3HO
0.36(1
0.2S6
0.1/7
SII2 I-P-S
(PPM) (UG/H3)
O.H
0.0
0.0
0.0
0.0 0.0
0.0
0.0 0.0
0.010
O.OIO
O.IS6 28.9
0.2M
0.305 10.4
0.121
0.520 26,6
0.312
0.3lb
0 . 2 7 '1 4.9
0.194
0.117
PAN
(PPH)
0.000
0.006
0.017
0.014
0.016
0.016
0.015
0.016
CN-b
(K-CH/CMJ)
0.0
16.000
IO.HOO
15.bOO
H.bOO
H.bOO
B.SOO
l.HOO
a/ Interference-corrected initial {NO}, [ND2|, find |NOX| arc 0.164, 0.045, aixl 0.20!) ppw.
OAv f.
HO \ SHUSH I Ml
11 ML
USD
0. 30
1.30
2.30
3.50
4.30
5. 50
6. 30
7.30
B. 30
9. JO
10.511
1 1. 50
1 2 . 5 u
1 i. 30
14.50
T..30
10.30
1 7. lo
IK. 4"
Ultl'H
(PI
«.
0.
'/.
0.
0.
0.
0.
'>.
0.
0.
0.
0.
0.
II.
u.
o.
'1.
0 .
M)
Ot.H
01.2
0',2
0'IM
059
03S
•J29
02 J
U25
•)i'i
U'jM
ll'i.l
1 Jo
H.'l
IIUI
I'M
!>(•
In/
Ill)
(PITi)
O.OOq
O.Odl
U. O.||
0.0
0.0
0.0
O.OOl
o.»ioi
O.HI'2
0.005
o.oos
O.OOO
O.OOS
(.. 1)11'.,
I) .11(1 '1
ii. dog
• '.llt'b
" . :ui-i
wit?
(PPM)
o.ni'i
0.0 3b
O.dio
O.ll in
0.0 J'i
0.0 i'>
O.OSl.
0.05).
0.0 io
0 . (i .J /
0.0 J"
O.ll >"
0 . 0 J /
li.Oio
u. Ii 3 i
(i . n ',,'.
II. 0,"'
II .llr".
IUIX
(PP'U
O.llJ1'
0.03/
0.03/
0.036
0.0 Jb
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CHAMHtK HU. 2
DAY 1, 11-11-77
HUM 13 : PKlU'tMf
RII SMOG CHAMHtH STUDY
UStt'A CUNFHACI Nil. 68-02-2137
100 X SIINSH1NL
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CHAMIILK NO. i
DAY \, 11-11-77
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UStPA CONIK AC 1 rill. 6H-02-2437
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CHAMHtH fill. 4
DAY I, 11-11-77
RUN 41 t PHIJPlM.
HI I SMUG CHAMHtR SIUOY
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CHAMHLH 'Hi. I
HAY i, H-13-/7
HUM i»4 : PKIII'INt
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319.74
119.80
ItMP
CtLSIUS
-2.2
-i.9
1.9
5.6
6.7
I./
0.0
I.«AV I, 11-14-77
to
oo
tn
89 X SUNSMINt
lint
(1 SI)
0.10
1.10
2.10
1.10
4.10
•j.10
6.10
7.10
H. 10
9.10
10.10
11.10
12.10
11.1"
14.10
15*10
10. 50
17. 10
oinriL
(I'pn)
0.170
0.169
o.t<>r
0.161
0.159
0.157
0.152
0. ISO
O.I«I7
O.|4|
O.I3/
0.131
0.115
0.137
O.liH
0.139
<> . 1 16
IKI
(PPM)
0.006
0.005
0.006
0.005
0.004
O.Ool
O.QO
0.003
0.00?
0.002
0.001
0.001
0.00^
'Hi/
(PPM)
0.0/0
0.0/0
0.0/0
o.o/^
o.n/'i
0.07u
0.07b
o.on
0.0/h
0.0 79
n.O'io
0.0'U
0 . 0 >ll
ft.O'V
O.OHI
0.082
o.nrto
mix
(PPM)
0.075
0.075
0.075
0.077
0.078
0.0f»
0.078
0.078
0.079
0.081
O.OH2
0.084
0.081
0.084
0.082
0.081
0.0«
-------
CH AMUCK Nil. 3
OAV I, 11-13-77
HUM 44 :
HU SMUG CHAMHfM STUDY
IJStPA CONTRACT NU. 66-02-2137
100 X SUNSHINt
N)
1 1 M{
(LSI)
2.47
3.13
4.62
5.73
6.60
7.47
B.47
9.47
10.47
1 1 .47
12.47
13.47
14.47
IS. '47
16.47
17.47
IB. 47
19.47
20.47
21 .47
22.47
23.47
UlilNf.
(I'PM)
0.000
0.001
0.001
o.ooo
0.0
o.o
0.000
0.003
0.012
0.046
0.139
0.239
0.299
0.310
0.297
0.271
0.251
0.236
0.226
0.219
0.213
0.207
I1IJ
(PP*)
0.0
0.0
0. 39 A
0.398
0.36A
0.364
0.362
0.3U2
0.197
0.063
0.029
0.009
0.006
0.003
0.001
0.000
0.004
O.OOS
0.006
0.007
0.006
O.OOS
ND2
(PP4)
0.002
0.001
0.0
0.097
0.103
0.103
0.123
O.I 74
0.266
0.3S3
0.3ol
0.301
0.22S
0. 74
0. '14
0. 24
0. 13
0. II
O.I US
O.IOS
O.I OS
0. 106
III)*
(PPM)
0.002
0.001
0.39ft
0.495
0.491
0.4B6
0.4HS
0.476
0.464
0.436
0.369
0.310
0.231
O.I 77
0.145
0.124
0. 17
0. 16
0. 12
0. 12
0. 12
0. 13
PHUP
(PPM)
0.667
0.637
0.616
0.602
0.592
0.592
0.5BO
0.509
0.435
0.354
0.236
PAN
(PPM)
0.0
0.000
0.001
O.OOS
0.013
0.027
0.044
O.OSh
0.061
O.OS8
0.057
0.057
0 . 056
0.057
0.057
0.056
CH-5
(K-CN/CM3)
0.0
0.0
0.210
0.210
0.320
0.260
0.2SO
t
DAY 2, 11-14-77
89 X SUNSHINt
II ML'
(1ST)
0.47
!.«/
2.47
J.47
4.47
S.47
6.47
7.47
B.47
9.47
10.47
11.47
12.47
13.47
14.47
IS. 47
16.47
17.47
0/UNC
(PP
O.IOH
0.
0.
0.
0.
o.
0.
0.
0.
0.
0.
o.
1 1
12
1 i
IS
IS
IS
IS
17
IS
IS
19
0.122
0. 122
O.I.M
0.122
0.121
NIJX
(f'HH)
0. 13
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
(>.
Ib
17
16
16
IB
16
16
20
16
Ifi
21
0.124
11.123
0.123
0 . 1 2 'I
H.12'1
PROP PAN
(PPM) (TPM)
0.057
0.057
0.057
0.057
0.058
O.OSH
O.OSR
O.G60
0.059
0.060
0.060
O.OSM
CO- 5
(H-CH/CM3)
0.0
0.0
0.0
SR
(L/M1N)
0.0
0.0
0.0
0.001
0.004
0.209
O.SOA
0.606
0.774
0.662
O.B62
0. 766
O.V»J
0.363
0.106
0.001
0.0
0.0
0.0
0.001
0.001
0.001
SH
(L/M|N)
0.001
0.001
0.002
0.003
0.002
0.0
0.003
0.202
0.26S
O.S30
O.S49
O.B2I
0.633
0.739
O.S71
0.346
0.091
0.0
CU-SH
(LANG)
0.0
0.0
0.0
0.04
0.25
6.19
27.17
60.41
101. SI
ISO. 43
202. IS
2SI.22
292.48
321.70
336.23
339.63
3J9.66
339.66
339.66
339.69
339. 7S
339.81
CU-SH
(L»NG)
0.03
0.09
O.IH
0.32
0.4B
O.S4
O.l>2
6.42
20.31
43.69
76.02
1 16.63
166.23
213. S6
255.16
261. M
294.77
297.66
HMP
CELSIUS
-2.2
-3.9
3.9
S.6
6.7
1.7
0.0
HMP
CILSIUS
-1.7
-3.9
-6.1
3.9
6.3
10.0
-------
CHAMIILK NO. 4
DAY I. ll-JJ-77
RUN OK ; PKUPLtll
100 I SUMSHINt
RTI SMIIti CIIAMIUR SlUOY
USEPA CONIKALI Nil. 68-02-2437
00
I IMC
(LSI)
2.63
3.30
1.30
5.40
6.97
7.63
8.63
9.63
10.63
1 1.63
12.63
13.63
14.63
15.63
16.63
17.63
Id. 61
19.61
20.61
21.63
22.63
23. hi
II ML
(tST)
0.63
l.ol
2.63
3.61
4.63
5.63
6.bl
7. hi
B. 63
9.61
10. (.1
11. bl
12.63
13.61
14. bl
15.63
16. bi
U/LINL
(PPM)
0.000
0.001
0.001
0.001
0.0
0.0
0.0
0.000
0.001
0.005
0.009
O.Olo
0.018
0.013
0.004
0.0
0.0
0.0
0.0
0.0
0.0
0.0
II/.U.1L
(PPM)
0.0
0.0
0.000
0.000
o.OOu
0.001
n . 00 1
O.OOH
O.Ult.
0.031
0.036
0.069
0.09<>
0.125
0. 11H
0.12''
0 . 1 0 '1
NO
(PPM)
0.0
0.0
0.792
0.7/6
0. 742
0.72H
0.690
O.o2l
0.513
0.422
0.313
0.232
0.165
0.159
0.139
0.1)2
0.111
0.110
0.1 10
0.110
0.128
0.127
Mil
(PPM)
0.124
0.121
0.121
0.121
0.119
0.116
0.113
0.121
0. 121
P. 115
O..IH9
0.067
0.04!
0.027
0.016
0.007
O.OOS
W12
(PPM)
0.001
0.0
0.0
0.205
0.229
0.241
0.269
0.319
0.392
0.4/1
0.548
0.590
0.607
0.6U6
0.606
0.594
0.583
0.5//
0.564
0.502
0.55/
0.551
DAY 2, 11
H(I2
(PPM)
0.550
0.54D
0.512
0.51V
0.519
0.515
0.513
0.519
0.501
o.4m<
fl.nii
0.4/1
0.4'jt
0.121
0. 1
-------
CHAMBER NO. I
0»V I. M-18-77 a/
RUN 46 I THIOPHENES 100 X SUNSHINE.
RT1 SMOG CHAMHfH STUDY
USEP4 CONTRACT NO. bH-02-24S7
ro
OO
00
TIME
(EST)
0.13
1.13
2.63
4.13
5.68
6.13
7.13
a. 13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.002
0.008
0.043
0.091
0.127
0.104
0.084
0.067
0.054
0.044
0.0)7
0.034
0.029
0.027
0.024
a/ 2-Mcthylthio|>liene
NO
(PPM)
0.0
0.001
0.252
0.24/b/
0.241"
0.237
0.235
0.209
0.128
0.047
0.016
0.005
0.002
0.003
0.004
0.002
0.002
0.002
0.006
0.008
0.009
0.009
N02
(PPM)
0.001
0.001
0.0
0.051
0.052
0.051
0.053
0.06H
0.124
0.144
0.104
0.064
0.052
0.051
0.050
0.047
0.047
0.048
0.047
0.045
0.046
0.045
b/ Interference-corrected initial |l*>]
DAY 2, 1
TIME
(ESI)
0.13
1.13
2.13
3,15
4.13
5.13
6.13
7.13
A. 13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
OZUNE
(PPH)
0.022
0.019
0.017
0.015
0.014
0.013
0.012
0.010
0.010
0.016
0.020
0.026
0.036
0.050
0.061
0.065
0.061
NO
(PPM)
0.006
0.006
0.005
0.005
0.003
0.004
0.003
0.004
0.004
0.004
0.004
0.002
0.002
0.001
0.001
0.001
0.001
N02
(PPM)
0.045
0.041
0.045
0.044
0.044
0.043
0.043
0.043
0.042
0.042
0.039
0.037
0.036
0.035
0.034
0.033
0.032
NUX
(PPM)
0.001
0.002
0.252
b/ 0.298
" 0.292
0.288
0.288
0.277
0.252
0.191
0.120
0.069
0.054
0.054
0.054
0.049
0.049
0.050
0.053
0.053
0.055
0.054
, JN02J. ail
1-19-77
NUX
(PPM)
0.051
0.050
0.050
0.049
0.047
0.047
0.046
0.047
0.046
0.045
0.043
0.039
0.038
0.036
0.035
0.034
0.033
I-SUL
(PPM)
b/ 0.574
0.562
0.553
0.550
0.538
0.473
0.367
0.264
0.190
0.149
0.122
0.109
0.082
0.068
0.061
0.062
cl INfy are
99 X
1-SUL
(PPM)
0.010
0.010
0.010
0.010
0.047
0.010
0.010
0.010
0.010
S02
(PCM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0
O.Z38, 0.060,
SUNSHINE
S02
(PPM)
0.0
0.0
0.010
0.010
o.oto
0.010
0.010
0.010
0.010
PAN
(PPM)
0.0
0.0
0.000
0.006
0.015
0.024
0.027
0.027
0.027
0.025
0.025
0.024
0.02S
and 0.298
PAN
(PPM)
0.024
0.024
0.02)
0.022
0.022
0.020
0.018
0.018
0.017
0.021
0.022
0.020
0.020
0.01ft
O.OIS
0.017
0.016
CN-5
(K-CN/CM5)
0.540
0.540
44.000
60.000
60.000
58.000
54.000
44.000
p|MI.
CN-5
(K-CN/CM3)
0.430
0.620
0.950
1.200
1 .BOO
1. 700
SH
(L/MIN)
0.0
0.0
0.0
0.001
0.0
0.001
0.093
0.551
0.569
0.7JJ
O.H24
0.821
0.734
0.567
0.336
O.OH2
0.0
0.0
0.0
0.0
0.0
0.001
0.001
CU-SH
(LANG)
0.0
0.0
0.0
0.01
0.06
0.07
0.85
fl.28
30.00
6S.42
110.11
159.55
20«. 29
2M.02
283.249.bil
279.56
29S.H7
UMP
CELSIUS
1.1
1.1
2.2
10.0
14.1
15.0
-------
CHAMBER NO. 2
DAY I. 11-18-77 a/
RUN 46 I TMIOPMENE3- 100 X SUNSHINE
RII SMUG CHAMBER STUDY
USEPA CONTRACT NO. 68-02-2437
TIME
(EST)
0.30
1.30
3.25
4.30
5.55
6.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
18.30
19.30
20.30
21.30
22.30
23.30
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.004
0.017
0.074
0.133
0.163
0.157
0.146
0.135
0.117
0.104
0.094
0.086
0.079
0.076
0.071
NO
(PPM)
0.000
0.0
0.295
0.291 b/
0.287
0.294
0.276
0.238
0.128
0.039
0.012
0.003
0.0
0.002
0.002
0.001
0.001
0.001
0.007
0.008
0.007
0.007
N02
(PPM)
0.002
0.0
0.0
0.033b/
0.030
0.029
0.033
0.062
0.134
0.132
0.085
0.062
0.059
0.057
0.056
0.054
0.053
0.052
0.051
0.050
0.051
0.051
NOX
(PPM)
0.002
0.0
0.295
0.324 b/
0.317
0.313
0.309
0.300
0.262
0.171
0.097
0.065
0.059
0.059
0.058
0.055
0.054
0.053
0.058
0.058
0.058
0.058
T-3UL
(PPM)
0.503
0.486
0.481
0.481
0.455
0.380
0.272
0.205
0.176
0.153
0.132
0.114
0.010
0.010
0.010
0.010
SU2
(PPM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.106
0.113
0.101
0.085
0.010
0.010
0.010
0.010
0.0
PAN
(PPM)
0.000
•0.0
0.008
0.018
0.027
0.030
0.030
0.028
0.028
0.028
0.026
0.027
CN-5
(K-CN/CM3)
0.0
0.0
17.000
29,000
30.000
34.000
33.000
29.000
a/ 2-Methxlthiophcne
2o EX Interference-corrected initial [NI)|, [N021, and
^ PAY 2, 11-19-77
are 0.242, 0.066 and 0.308 ppm.
99 X SUNSHINE
TIME
(CST)
0.30
1.30
2.30
3.30
4.30
5.30
6.30
7.30
0. 30
9.30
10.30
11.30
12.30
13.30
1«.30
15.30
16.30
OZONE
(PPM)
0.066
0.064
0.059
0.056
0.053
0.051
0.049
0.046
0.044
0.043
0.048
0.063
0.083
0.105
0.120
0.126
0.120
NO
(PPM)
0.005
0.004
0.004
0.004
0.003
0.003
0.002
0.003
0.003
0.003
0.003
0.002
0.001
0.001
0.001
0.60I
0.001
(102
(PPM)
0.048
0.0«9
0.048
0.048
0.047
0.047
0.016
0.045
0.046
0.045
0.0 to
0.0 "40
0.045
0.0.«>a
TEMP
CELSIUS
1.1
I.I
2.2
10.0
11.4
15.0
-------
N>
^O
O
CHAMBER NO. J
DAY I, 11-18-77 _/
RUN 46 ! IH10PHENES 100 X SUNSHINt
RTI SMUG CHAMBER STUDY
USEPA CONTRACT NO. 68-02-24J7
TIME
(EST)
0.47
OZONE
NO
(PPM) (PPM)
0.0 0.0
1.47 0.0 0.0
3.78
s!l8
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
17.47
18.47
19.47
20.47
21.47
22.47
23.47
0.0 0.261
0.0 0.2S7b/
0.0 0.250"
0.0 0.24S
0.001 0.238
0.004 0.199
0.010 0.128
0.029
0.056
0.084
0.104
0.107
0.094
0.076
0.064
.066
.032
.017
.007
.005
.004
.003
.003
0.054 0.003
0.047 0.008
0.044 0.006
0.038 0.010
0.035 0.008
N02
(PPM)
0.001
0.001
0.0
0.047b/
0.045-
0.050
0.056
0.085
0.131
O.|55
0.151
0.132
0.114
0.102
0.092
0.085
0.080
0.076
0.073
0.071
0.066
0.066
NOX
(PPM)
0.001
0.001
0.261
0.304b/
0.295-
0.295
0.294
0.264
0.259
0.221
0.183
0.149
0.121
0.107
0.096
0.088
0.083
0.079
0.081
0.079
0.078
0.076
I-SUL
(PPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.381
.370
.364
.357
.360
.330
.283
.223
.155
.126
.090
.066
.010
.010
.010
.010
.0
S02
(PPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0
.0
.0
.0
.0
.0
.010
.010
.010
.010
.010
.010
.010
.010
.010
.0
.0
PAN
(PPM)
0.000
0.0
0.003
0.008
0.016
0.022
0.028
0.033
0.034
0.033
0.032
0.033
0.031
0.032
CN-5
(K-CN/CM3)
0
0
22
29
36
32
33
31
.0
.590
.000
.000
.000
.000
.000
.000
a/ 2, S-Dimethylthiopheiie
§/ Interference-corrected Initial |NO|, |N02I- and |N°xl are 0.246, 0.064, and 0.310 ppm.
DAY 2, 11-19-77
99 X SUNSHINE
UML
(EST)
0.47
1.47
2.47
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
16.47
OZONE
(PPM)
0.032
0.029
0.027
0.024
0.023
0.021
0.019
0.018
0.019
0.031
0.040
0.052
0.076
0.103
0.122
0.126
0.120
NO
(PPM)
0.006
0.006
0.006
0.004
0.003
0,004
0.002
0.003
0.003
0.003
0.001
0.001
0.001
0.002
0.001
0.001
0.001
N02
(PPM)
0.066
0.065
0.06
0.12
0.15
'I. 7b
21.12
49. 12
86.27
130.88
|7fl.O*
22J.OI
260.41
285.72
297.29
UMH
CUS1US
1.1
1 .1
2.2
10.0
1"."
15.0
-------
CHAMBLR NO. «
0»V I, tt-lB-77 ,,
RUN 46 : TMIOPHCNtS 100 X SUNSHINE
Ntl SMOG CHAMBER STUDY
USEPA CONTRACT NO. 68-02-2437
TIME
(EST)
0.63
1.61
4. 80
6.6)
7.63
6.63
9.63
10.63
11.63
12.63
13.63
14.63
IS. 63
16.63
17.63
ia.63
19.6)
20.63
21.63
22.63
23.63
UZONt NO
(PPM) (PPH)
0.0 0.000
.0 0.0
.0 0.249b/
.0 0.2)9-
.0 0.236
.001
.003
.006
.014
.026
.035
.037
.032
.015
0.001
0.0
0.0
0.0
o.o
0.0
0.0
.229
.202
.152
.100
.065
.045
.034
.026
.016
.007
.007
.008
.012
.014
.015
.015
N02
(PPM)
0.001
0.0
O.OSSb/
0.061 ~
0.064
0.064
0.084
0.113
0.141
0.1«7
0.141
0.131
0.127
0.128
0.134
0.133
9.132
0.129
0.125
0.124
0.123
NOX
O'PM)
0.001
0.0
0.304 b/
0.300 ~
0.300
0.293
0.2A6
0.265
0.241
0.212
0.186
0.165
O.IS3
0.144
O.Hl
0.140
0.140
0.141
0.139
0.139
0.138
T-SUL
(PPM)
0.764
0.746
0.743
0.741
0.729
0.671
0.614
0.556
0.503
0.«57
0.421
0.403
0.369
0.349
0.358
0.340
0.335
0.329
0.322
S02
(PPM)
0.0
0.0
0.0
0.0
0.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0
0.0
PAN
(PPM)
0.0
0.0
0.000
0.001
0.003
0.003
0.003
CN-5
(K-CN/CM3)
0.540
17.000
18.500
32.000
27.000
«/ Thioplicne
E/ Interference-corrected initial |NT>1, fN02), and [NO*] are 0.248, 0.060. and 0.308
DAY 2, 11-19-77
99 X SUNSHINE
TIME
(EST)
0.63
1.63
2.6)
3.63
4.6)
5.63
6.63
7.63
8.63
9.63
10.63
11.63
12.63
13.63
14.63
15.63
16.63
OZONE
NO
(PPM) (PPM)
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
o.
0.
0.
0.
0.
0.
0.
0
0
0
0
0
0
.014
.014
.013
.014
.014
.014
0 0.015
008 0.025
017 0.033
026 0.031
036 0.020
060 0.011
062 0.007
095 0.004
097 0.002
087 0.001
073 0.001
N02
(PPM)
0.120
0.117
0.115
0.113
0.111
O.lll
0.107
0.093
0.075
0.063
0.057
0.051
0.040
0.031
0.023
0.021
0.021
NUX
(PPM)
0.134
0.131
0.126
0.127
0.125
0.125
0.122
0.118
0.108
0.095
0.077
0.062
0.047
0.035
0.025
0.022
0.022
T-SUL
(PPH)
0.320
Q.315
0.312
0.308
0.306
0.299
0.296
0.294
0.286
0.263
0.241
0.221
0.216
0.186
0.164
0.147
0.132
S02
(PPM)
0
0
0
0
0
0
0
0
0
.0
.010
.010
.010
.010
.010
.010
.010
.010
PAN
(PPH)
0.003
0.003
0.003
0.003
0.003
0.002
0.002
0.002
0.003
0.003
0.003
0.004
0.004
0.005
0.005
0.005
CN-5
(K-CN/CM3)
12
29
29
4
25
11
.400
.000
.000
.800
.000
.500
SR
(L/M1N)
0.0
0.0
0.001
0.001
0.093
0.351
O.S69
0.733
O.B24
0.824
0.734
0.567
0.336
O.OR2
0.0
0.0
0.0
0.0
0.0
0.001
0.001
tU-SR
(LANG)
0.0
0.0
0.05
0.10
3.64
18.21
17.07
B7.41
13«. 8i
184.27
230.31
268.03
293.32
303.88
305.70
305.70
305.70
305.70
305.70
305.74
305.80
TIMP
CKS1US
6.7
6.1
6.1
12.2
15.0
14.4
8.9
2.2
SR
(L/MIN)
0.0
0.001
0.001
0.0
0.0
0.0
0.001
0.162
o.3<»8
0.5'«4
0.704
0.7«tt
0.7«5
0.708
0.528
0.302
0.070
CU-SR
(LANG)
0.0
0.0«
0. 10
0.12
0.12
0.12
0.16
6.30
24.9«
54. i«
93.03
138.45
16S.6I
229.80
26S.4B
288.62
297.97
IfMP
CELSIUS
I.I
I.I
2.2
10.0
11.4
15.0
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-79-227
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
ATMOSPHERIC CHEMISTRY OF SELECTED SULFUR-CONTAINING
COMPOUNDS
Outdoor Smog Chamber Study - Phase 1
5. REPORT DATE
December 1970
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
J. E. Sickles, II and R. S. Wright
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
1NE625B EA-41 (FY-78)
27709
11. CONTRACT /OR ANT NO. I
68-02-2437
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 9/76 - 2/78
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The chemical behavior of hydrogen sulfide, carbonyl sulfide, carbon disulfide,
methanethiol, ethanethiol, methyl sulfide, ethylsulfide, methyl-disulfide,
ethyldisulfide, methylethylsulfide, thiophene, 2-methylthiophene, 3-raethylthiophene,
2,5-dimethyl-thiophene and propane (used as a control) was investigated under
atmospheric conditions in outdoor smog chambers. Target initial concentrations of
2.0 ppm carbon of a test compound and 0.1, 0.2, 0.5 and 1.0 ppm NO were investigated
simultaneously in four identical smog chambers. A total of twenty 2-day four-chamber
runs, or eighty 2-day experiments invovling irradiated sulfur species-NO or propene-
NO systems was conducted.
x The results of experiments conducted with each compound were analyzed by
examining the influence of initial conditions on the following selected reaction
parameters: the time to NO-NO^ crossover; maximum concentration of 0», N02, PAN,
S0_, particulate sulfur, and condensation nuclei; nitrogen mass balance; time to
one-half consumption of the test species; and second-day net ozone concentration.
Subsequently, selected reaction parameters were compared across test compounds.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air pollution
Sulfur inorganic compounds
Sulfur organic compounds
Ozone
Nitrogen oxides
Test chambers
Photochemical reactions
13E
07B
07C
03B
07E
13. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
305
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
292
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