United States
Environmental Protection
Agency
Office of
Research and
Development
Environmental Sciences Research
Laboratory
Research Triangle Park, North Carolina 27711
EPA-600/7-78-029
March 1378
ATMOSPHERIC CHEMISTRY OF
POTENTIAL EMISSIONS FROM
FUEL CONVERSION FACILITIES
A Smog Chamber Study
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
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The nine series are:
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2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
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This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
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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
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essary environmental data and,control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-029
March 1978
ATMOSPHERIC CHEMISTRY OF POTENTIAL EMISSIONS
FROM FUEL CONVERSION FACILITIES
A Smog Chamber Study
by
J. E. Sickles, II
L. A. Ripperton
W. C. Eaton
R. S. Wright
Research Triangle Institute
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2258
Project Officers
Joseph J. Bufalini
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
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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.
ii
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ABSTRACT
The atmospheric chemistry of chemical species that may be emitted from
fuel conversion facilities was studied in smog chambers. One hundred and
six bag experiments and 20 smog chamber experiments were performed. A screen-
ing program was conducted using 125-liter Teflon bags as reactors to assess
the ozone-forming potential of 17 compounds, which were candidates for smog
chamber testing. From these 17 compounds, 6 compounds and a control species,
propylene, were selected for testing in the presence of nitrogen oxides in
four outdoor smog chambers. The test compounds were: furan, pyrrole, thio-
phene, methanethiol, methyl sulfide, and methyl disulfide. Multiple-day
exposures were performed, and both static and transport conditions were
simulated. In addition to ozone, sulfur dioxide was produced as a secondary
pollutant by the photooxidation of the sulfur-containing species.
The effect of dilution on both ozone and sulfur dioxide production was
examined. The behavior of the test compounds was compared to that of a
surrogate urban mix. Under the proper conditions, the six test compounds were
found to produce net ozone levels in excess of 0.08 ppm on the second and
third days in both static and dilution experiments. The atmospheric behavior
of these compounds should be considered in detail if substantial anthropogenic
emissions, such as may occur at fuel conversion facilities, are anticipated.
This report was submitted in fulfillment of Task B of Contract No.
68-02-2258 by the Research Triangle Institute under the sponsorship of the
U. S. Environmental Protection Agency. This report covers the period June 30,
1975, to June 30, 1977, and work was completed as of May 6, 1977.
iii
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CONTENTS
Abstract iii
Figures vli
Tables viil
Acknowledgments x
1. Introduction 1
2. Summary and Conclusions 4
3. Recommendations 9
4. Experimental. 13
Overview 13
Apparatus 15
Teflon bag reactors 15
Air supply ...... 16
Injection system 18
Sampling system. 18
Bag characterization experiments 18
RTI Smog Chamber Facility 21
Subsystems comprising the smog chamber facility 21
Chamber characterization 29
Reagents 34
Measurement methods 34
Bag studies 34
Chamber studies 37
Ozone, ..,,.,,..,.. , 37
Oxidant. ...,...., ,.,,.ซ.,. 37
Nitrogen oxides (NO, N02, and NOX) . 38
Nitrogen dioxide ,..,.,..... 39
Sulfur dioxide ,.,......,._, 39
Individual hydrocarbons ,..,....,. 39
Formaldehyde ...,..,,,.,., 41
Solar radiation. .,,.,.,,...,,, 41
Environmental variables. ..,,...., 41
Procedure , 41
Bag Studies f ...,.,.. 42
Ozone-forming potential , 42
Dark stability , , 43
Light stability , 43
Dark phase reactivity with ozone 44
Dark phase reactivity with NOX .,..,., 44
Smog chamber studies 44
Static experiments ....,.., 45
Dilution experiments ..,,., ... 45
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5. Results and Discussion 47
Choice of compounds for study 47
Bag studies 48
Ozone-forming potential 48
Substituted methyl groups 53
Heterocyclics. 56
Sulfur-containing compounds 57
Selection of compounds for subsequent bag and
chamber studies 58
Dark stability 58
Light stability 60
Bark phase reactivity with ozone 63
Dark phase reactivity with NOX 66
Overview of bag studies 69
Chamber studies. . . 71
First-day behavior 77
NO-N02 crossover times . 77
Ozone formation 78
NOX conversion 78
Sulfur dioxide formation 80
First-day dilution effects 84
Second- and third-day effects 85
Ozone formation 86
Sulfur dioxide formation 89
References 92
Appendixes 96
A. Environmental conditions for irradiated bag and chamber studies . . 96
B. Results of bag studies 98
C. Hydrocarbon analyses from chamber runs. . 114
D. Detailed data sheets 116
E. Concentration profiles 181
vi
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FIGURES
Number
1 Air Supply 17
2 A 27-cubic meter Teflon outdoor smog chamber .... 22
3 System diagram, RTI smog chambers 23
4 Air purification unit, RTI smog chamber 24
5 Reactant injection system, RTI smog chambers .... 26
6 Heated stainless steel manifold for volatilizing
liquid test compounds prior to injection into a
smog-chamber ..... 27
7 Sampling system, RTI smog chambers 28
8 Hypothetical representation of Ozone Maxima as a
function of initial nitrogen oxides and hydrocarbon
concentrations 50
9 Concentration profiles for first day (7-13-76) of
thiophene-NO static smog chamber experiment .... 82
X
10 Concentration profiles for first day (7-28-76) of
methyl disulfide-NO static smog chamber experiment. 82
X
11 Concentration profiles for first day (7-28-76) of
methyl sulfide-NO static smog chamber experiment. . 83
X
12 Concentration profiles for first day (7-28-76) of
propylene-NO static smog chamber experiment .... 83
X
13 Ozone concentration profiles for three-day thio-
phene-NO runs conducted in RTI outdoor smog
chamber No. 2 90
14 Sulfur dioxide concentration profiles for three-day
thiophene-NO runs conducted in RTI outdoor smog
chamber No. Z 90
vii
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TABLES
Number
1 Experimental Program 14
2 Bag Characterization Studies 20
3 Preinjection Hydrocarbon Analyses (ppmC) 31
A Chamber Characterization Experiments 33
5 Reagents 35
6 Measurement Methods 36
7 Summary of Selected Results of Ozone-forming
Studies Conducted in Bags at Low Initial
HC/NO Ratios 51
x>
8 Summary of Selected Results of Ozone-forming
Studies Conducted in Bags at High Initial
HC/NO Ratios 52
x
9 Comparison of Maximum Ozone Concentrations Achieved
in Bags at Low and High HC/NO Ratios 54
X
10 Summary of Dark Stability Results 59
11 Summary of Light Stability Results 62
12 Summary of Results of Dark Reactivity Experiments
With Ozone 64
13 Summary of Results of Dark Reactivity Experiments
With NO 68
X
14 Summary of Test Compound Half-lives Expressed
in Hours 70
15 Summary of Selected Smog Chamber ResultsDay 1. . . 73
16 Summary of Selected Smog Chamber ResultsDay 2. . . 74
17 Summary of Selected Smog Chamber ResultsDay 3. . . 75
viii
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18 Comparison of Ozone Formation in Bag and Chamber
Studies 79
19 Net Ozone Produced in Both Static and Dilution
Chamber Runs 87
ix
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ACKNOWLEDGMENTS
This project was conducted by the Research Triangle Institute under
Task B of Contract Number 68-02-2258 for the U.S. Environmental Protection
Agency. The support of this agency is gratefully acknowledged as is the
advice and guidance of the EPA personnel who contributed to the project:
Dr. Basil Dimitriades, who initiated the project, and Dr. J. J. Bufalini,
who served as Project Officer.
Several people in the Environmental Measurements Department of the
Research Triangle Institute contributed substantially to this project.
Mr. Cliff Decker was Laboratory Supervisor for the project. Mr. Dennis
Ewald and Mr. Dave Dayton conducted day-to-day chamber operations, data
reduction, and data verification. Messrs. Bob Denyszyn and Peter Grohse
developed the gas chromatographic procedures used and, along with Mr. David
Hardison, conducted all the GC analyses. Mrs. Ann Turner conducted the
wet chemical determinations. Mrs. Sandra Burt transferred the data into
a computer-compatible format and implemented the computer-generated
concentration-time profiles.
We gratefully acknowledge these individuals for their efforts in
bringing this project to a successful conclusion.
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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 emissions.
Contaminants such as mineral matter and sulfur-, nitrogen-, and oxygen-contain-
ing compounds are removed and transformed during the processing 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 emissions may include not only the
commonly considered pollutants such as SO , NO , CO, and hydrocarbons, but
X jt
other compounds not previously considered from either the toxic or ozone-
generative viewpoint. It is, therefore, necessary that the impact of
synthetic-fuels processing on air quality be considered.
The literature survey, conducted as the first task of this contract and
published as a companion document (ref. 1), addressed atmospheric emissions
from coal gasification, coal liquefaction, shale oil production, and petroleum
refining. The survey findings indicate that the same or similar chemical
species are expected to be emitted from each of the four fuel-conversion
operations. Compounds identified as potential emissions from fuel-conversion
facilities are summarized as follows:
1. Sulfur-containing compounds will include S0_, H_S, thiols
(mercaptans), sulfides, and thiophenes.
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2. Nitrogen-containing compounds will include NO, N02> NH3>
HCN, and heteorocyclic species such as pyrroles and
pyridines.
3. Organic compounds will include primarily volatile hydro-
carbons up to C-_. Aromatic emissions such as benzene,
toluene, and xylenes are anticipated. Other organics
such as aldehydes, ketones, phenols, and polycyclic
organic matter (POM) are expected.
For details concerning the fuel-conversion operations, chemical species,
concentrations, and emission rates, the literature survey should be con-
sulted (ref. 1).
The purpose of the task described in the present document was to study,
by smog chamber simulation, the atmospheric chemistry associated with emissions
from production and refining operations related to coal gasification, coal
liquefaction, shale oil production, and petroleum refining. Since the impact
on the air quality of both rural and urban areas of emissions from such
operations may be very great, it is necessary to characterize their potential
for air pollution and photochemical oxidant formation. A major objective was
to examine the ozone-producing potential of selected chemical species and
nitrogen oxides exposed to natural sunlight irradiation at ambient temperatures,
The approach devised consisted of the following four steps:
1. Identify and select several candidate compounds that are
likely to be emitted from fuel conversion processes for
experimental evaluation in smog chambers. Choose candidate
compounds from the literature survey (ref. 1), focusing on
those compounds or families of compounds whose ambient air
chemistries have not been thoroughly investigated.
2. Devise and conduct a screening program using 125-1 Teflon
bag reactors exposed to natural sunlight irradiation at
ambient temperatures to assess relative reactivity based on
ozone production of the selected candidate materials in the
presence of nitrogen oxides.
*Registered trademark of the E.I. DuPont De Nemours and Company, Inc.
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Based on the screening tests select compounds for investiga-
tion under static and simulated transport conditions in the
four outdoor smog chambers comprising the RTI Smog Chamber
Facility.
Conduct 3-day smog chamber tests on the selected compounds in
the presence of NO . Choose test conditions which employ
X
natural sunlight irradiation at ambient temperatures and which
simulate both static (stagnant) and transport (dilution) atmos-
pheric conditions.
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SECTION 2
SUMMARY AND CONCLUSIONS
The atmospheric chemistry of 17 compounds was investigated in this study.
One hundred and six bag experiments and 20 smog chamber experiments were performed.
Many of the compounds were identified as potential air pollutants from produc-
tion and reiining operations related to coal gasification, coal liquefaction,
shale oil production, and petroleum refining. The compounds selected for
testing were: furan, pyrrole, thiophene, methanethiol, methyl sulfide, methyl
disulfide, carbonyl sulfide, cyclopentadiene, 2-methyl furan, 2,5-dimethyl
furan, 2-methyl thiophene, toluene, ethylbenzene, orthp-xylene, meta-xylene,
para-xylene, and propylene. Propylene was included as a control.
Screening tests were performed to assess the ozone-forming potential
of each of the above compounds. These experiments were conducted by irradi-
ating air mixtures of the compound and nitrogen oxides in 125-1 Teflon bag
reactors under natural sunlight at ambient temperatures. Each compound was
tested at two initial HC/NO ratios, 5 and 20. Target initial concentrations
were 10 ppmC of the compound and 2.0 and 0.5 ppm of NO . The National
Jt
Ambient Air Quality Standard (NAAQS) for photochemical oxidant, 0.08 ppm,
was exceeded in at least one of the two test conditions for every compound
tested except carbonyl sulfide and methanethiol. In addition, sulfur
dioxide was observed as a product of photooxidation of each of the sulfur-
containing compounds.
The following six compounds were chosen for additional bag studies
and also for multiple-day smog chamber experiments: furan, pyrrole, thio-
phene, methanethiol, methyl sulfide, and methyl disulfide. As in the
screening tests, propylene was chosen as a control compound for many of
the bag and chamber experiments.
The stability of air mixtures of each of the six test compounds was
evaluated in 125-1 bag reactors both in the dark and under irradiation.
All six test compounds were relatively stable in the dark, with half-lives
of 3 days or longer. Exposure to sunlight enhanced the decay rates of
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each tested compound except methyl sulfide. Pyrrole and methyl disulfide
exhibited half-lives of less than 1 day. Considerable quantities of S0_
were observed as a product of irradiated air-methyl disulfide mixtures.
The dark phase reactivity of each of the six test compounds in the
presence of CL was investigated in bags. Pyrrole and furan reacted rapidly
with 0_. The rate constant determined for pyrrole was approximately the
same as that determined for propylene. Among the sulfur-containing compounds,
thiophene was the most reactive with 0_, and the alkyl sulfides were con-
siderably less reactive.
Dark phase reactivity bag studies for each of the six test compounds
were also conducted in the presence of NO . These experiments indicated
that the test compounds were relatively unreactive with NO in the dark.
2ฃ
Although the decay rate of pyrrole was enhanced somewhat by the presence of
N0_, half-lives for the test compounds were longer than 1 day. The NO decay
ฃ A
rate was increased by a factor of three in the presence of furan. In general,
however, nitrogen oxides behavior was not appreciably changed by the presence
of the other five test compounds.
The behavior of the six test compounds in the ozone-potential screening
tests indicated that each compound can participate in atmospheric photo-
oxidation reactions. Many chemical reactions may contribute to the removal
of the test compounds from the atmosphere, and the additional bag studies
were conducted to determine the qualitative importance of four alternate
pathways. Comparison of the findings indicated photooxidation to be a major
pathway.
Multiple-day experiments in the four outdoor smog chambers comprising
the RTI Smog Chamber Facility were conducted with furan, pyrrole, thiophene,
methanethiol, methyl sulfide, methyl disulfide and the control hydrocarbon,
propylene. Target initial conditions for these tests were 5.0 ppmC of the
test compound and 1.0 ppm NO (20% N09). The design of the chamber facility
X ฃ
provided for irradiation with natural sunlight at ambient temperature and
also allowed the simulation of both static and transport (dilution) atmos-
pheric conditions. Three test compounds were studied simultaneously, with
one in each of the first three chambers; these results were compared with
results of the control compound in the fourth chamber. Comparisons of these
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results were also made with results of runs conducted on other days with a.
simulated urban mix.
On the first day of a static run, thiophene was the slowest of the
test compounds to reach N0-N02 crossover and required over 5 hours past
dawn. The other test compounds required less than 3 hours. The ordering
of the times to reach the maximum [0_] for the test compounds roughly dupli-
cated that for the times to NO-NO, crossover. Thiophene, the slowest
compound to crossover, achieved [CL] after 1500 EST, whereas the other
j fllฃLX
five compounds reached TO-] by 1000.
With each of the test compounds, except the slow-reacting thiophene,
NO was consumed more quickly than with propylene. Consumption of N0x was
very rapid in the alkyl sulfide runs; within an hour of the [0,^]^^, the
NO- concentration had dropped to low levels, and approximately 90 percent
of the initial NO had b^en consumed.
x
Each of the sulfur-containing species tested in the chambers produced
S0? as a product of photooxidation on the first day of a static run. Substan-
tial amounts of S0? were produced by the alkyl sulfides, whereas thiophene
produced the smallest quantities of SO, of the sulfur-containing compounds
tested in the chambers. Sulfur dioxide was detected as a reaction product
simultaneously with the onset of NO oxidation. Concentration profiles
indicate that the largest increase in [SO-] occurred between the time of
N0-N00 crossover and the time of [0-] , with the [S00] occurring at
ฃ 3 max * max
approximately the same time as the [0,1
ff 3Jmax
First, second, and third day behavior were compared using net ozone
values (AO. ป [0,,] - [0,] . ). The open-chain sulfur species produced
j j HLฃl3C J TuJLil
not only A0ป values of 0.4 to 0.7 ppm on the first day of static runs, but
also considerable amounts of ozone on the second and third days. Thiophene,
in contrast to the other test compounds, produced more ozone in static runs
on both the second and third days than on the first day. In two static
experiments with thiophene, a fivefold increase in A03 was observed from the
first to the second day.
Each of the sulfur-containing compounds produced considerable quantities
of SO- on the first day of a static run, whereas only thiophene produced
significant levels on the second and third days. Of the compounds tested
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in the chambers, only the slow-reacting sulfur compound thiophene produced
significant quantities of both 0 and SO- in multiple-day irradiations.
These findings suggest that, under stagnant conditions, large anthropogenic
emissions of thiophene may reduce local air quality by increasing ambient
levels of both <} and SCL.
In dilution runs the chamber contents were diluted with purified air
at a fixed rate starting at 0800 EST on the first day. The dilution rate
was chosen so that after 24 hours of operation, 95 percent of the original
chamber contents would be replaced by purified air. Dilution was terminated
24 hours after initiation, and the remaining 2 days of the run were conducted
in the static mode. Under dilution conditions thiophene produced a first-day
[0_] level over five times greater than the value achieved in the corres-
j THrtX
ponding static run. Among the test compounds, however, this was the exception,
and in general, dilution resulted in a slight reduction of the first day
Under dilution conditions, first day A0_ levels were larger than the
levels produced on the second and third days. This may suggest a decrease
in ozone production on subsequent days downwind from sources of the tested
compounds .
Second and third day AO, levels in dilution experiments were generally
less than those in static runs. They were never reduced in proportion to
the extent of dilution: A0_ levels were generally reduced by less than 40
percent after 95 percent dilution. This finding demonstrates the nonlinear
behavior of ozone formation in air parcels which experience dilution.
Dilution reduced [S0_] values achieved on the first day by the
2 max J J
sulfur-containing species in comparison with static runs. Net SO levels
on the second and third days were reduced essentially to zero by dilution.
The pronounced reductions of S02 levels achieved on each day of the multiple-
day dilution runs reflects reactant-limited behavior on the resulting S0ซ
formation. This may be contrasted with the nonlinear precursor-product
relationship for ozone formation*.
The test compounds with the exception of the control, propylene,
produced A0_ levels in excess of the NAAQS of 0.08 ppm on the second and
third days in both static and dilution experiments. The atmospheric behavior
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of these compounds should, therefore, be considered in detail if significant
anthropogenic sources, such as fuel conversion facilities, are to be con-
structed.
The results of this study suggest that, on a carbon basis, organosulfur
compounds have similar ozone-generative potential as hydrocarbons normally
recognized as ozone precursors. The experimental concentrations employed in
this study were significantly higher than those anticipated in the atmosphere.
If the demonstrated analogy between the ozone-generative potential of organo-
sulfur compounds and hydrocarbons at high concentrations can be extrapolated
to lower concentration levels, then these compounds should be considered as
members of the nonmethane hydrocarbon class of oxidant precursors. On this
basis it seems reasonable to assume that nonmethane hydrocarbon standards
and control strategies aimed at oxidant control would maintain their current
degree of effectiveness if the organosulfur species are included in the
category of nonmethane hydrocarbons.
This research has also shown that organosulfur compounds in the presence
of NO and sunlight are precursors of S00. Organosulfur compounds, there-
Jป 4b
fore, should be considered in the development of future standards and con-
trol strategies for SO- and sulfates.
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SECTION 3
RECOMMENDATIONS
Fuel conversion technology is in the early stages of its development.
The identity and emission rates of organics emitted by fuel conversion pro-
cesses are, therefore, poorly defined. Current estimates are based on
engineering process flow diagrams, design material balances, and pilot plant
results. Empirical emissions data are needed to supplement and verify current
estimates. Large field programs encompassing both source sampling and
ambient air monitoring should be mounted to identify and quantify emissions
from pilot-, demonstration-, and commercial-size fuel conversion facilities.
Research projects are currently underway to identify various emissions from
laboratory-scale units. The Research Triangle Institute through EPA Grant
No. 1394 (Pollutants from Synthetic Fuels Production) is conducting such a
project with a small coal gasifier. Future atmospheric chemistry studies of
emissions from such facilities should be coordinated closely with the above
investigations.
This investigation has identified research areas which can be explored
by smog chambers and by more fundamental chemical studies. The photochemistry
of many of the test compounds is poorly defined over the range of wavelengths
incident on the earth's surface: fundamental work is needed in this area.
The hydroxyl radical is believed to be the dominant reactive species in
photochemical smog reactions; other reactive species include ozone and atomic
oxygen. Rate and mechanistic studies of the interactions of these reactive
species with the test compounds are needed to provide a better understanding
of the occurring chemistry and to allow computer simulation for predictive
modeling.
This research has demonstrated the feasibility of using outdoor smog
chambers to explore the atmospheric chemistry of selected chemical species.
The feasibility of using small bag reactors for screening or special studies
has also been demonstrated. The approach for future smog chamber investigations-
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of potential emissions from fuel conversion facilities should be similar to
that employed in the current study.
1. Use bag reactors to screen candidate compounds for subsequent
smog chamber testing based on some criterion such as ozone-
generative potential. Bag reactors can also be used for special
stability or reactivity experiments.
2. Investigate the atmospheric chemistry of the selected compounds
over multiple-day exposures in large outdoor smog chambers. Such
experiments would be conducted with air-mixtures of the selected
compound in the presence of nitrogen oxides. Results from these
experiments could be used to define such first-day features as
production surfaces for secondary pollutants such as ozone or in
some cases S09. These experiments could be used to explore the
effects of repeated diurnal cycles on ozone or SO,, production.
3. Extend the experimental conditions employed in smog chambers to
reflect more closely the chemical systems into which these compounds
may be introduced. Experiments should be designed to explore the
interaction of potentially emitted test species with other compounds.
The following studies would be useful in this regard.
(a) Explore the effects of adding the test compound to mixtures
of a control hydrocarbon and NO . Two reference hydrocarbons
A
could be used: a reactive hydrocarbon such as propylene or
butene and a less reactive species such as propane or butane.
Results of standard runs conducted simultaneously in both the
presence and absence of the test compound could be compared
to determine the presence or extent of synergistic behavior.
This type of study should precede further studies described
below.
(b) Emissions from fuel conversion facilities will include species
unique to the industry in addition to more commonly encountered
compounds. One or more surrogate mixtures of fuel conversion
emissions' compounds could be examined in smog chambers. Control
strategies could be tested by varying the initial HC and NO
A
concentrations, their ratio, or the relative amounts of the
various species comprising the surrogate mixture.
10
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(c) With the ever increasing demand for energy, it is unlikely
that future fuel conversion facilities will be located in
areas totally remote from urban centers. Emissions are,
therefore, expected to become mixed with urban plumes after
one or more days of transport. This scenario could be
simulated by injecting a surrogate fuel conversion emissions
mixture into smog chambers on the second day of experiments
with a surrogate urban mix.
4. Investigate aerosol formation and behavior during the photooxidation
of organic sulfur species. It is recognized that the introduction
of SCL into a photochemically reactive HC-NO system will result
ฃ. X
in aerosol generation. Photochemically reactive systems of NO
A
and sulfur-containing organic species were shown in the current
study to generate S0_. Simultaneous aerosol generation is also
anticipated and should be examined.
The previous paragraphs have described in broad terms the types of
studies that should be considered, based on the findings of this research.
The specific recommendations which follow are suggested for consideration
in the next phase of this research program.
1. Focus on one class of compounds such as sulfur-containing species.
2. Employ detection techniques specific for the class of compounds
to be tested. Such a technique for sulfur species is gas chroma-
tography with flame photometric detection.
3 . Conduct smog chamber experiments with compounds selected from the
following list of candidates. Although starred species were smog
chamber test compounds in the present study, they may warrant
additional investigation.
H2S *(CH3S)2
COS
-------
Conduct screening and special studies with selected compounds in
bag reactors using the procedures developed in the current study.
Conduct smog chamber studies designed to address the key issues
of ozone formation and SO, formation over multiple-day exposures.
In addition, several of the candidate compounds may contribute to
natural sulfur emissions, and these smog chamber studies may provide
incidental data which can be used to elucidate the role of chemical
or photochemical processes in the natural sulfur cycle.
Injection, sampling, or analytical difficulties prevented verifi-
cation of initial injected concentrations of methanethiol; this
should be resolved.
PAN determinations should be conducted to elucidate the NO consump-
Ji
tive mechanism which occurs during the photooxidation of the open
chain sulfur species.
It is anticipated that the ultimate fate of sulfur-containing
species in the atmosphere will be sulfate formation. Filter samples
for subsequent X-ray fluorescent (XRF) analyses should be taken
periodically during smog chamber runs. These data will allow the
estimation of a sulfur balance and the fraction of sulfur in the
particulate (and gas) phase.
12
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SECTION 4
EXPERIMENTAL
OVERVIEW
This subsection describes the experimental design and also provides a
general overview of the experiments conducted in this study. Table 1
identifies the compounds examined and provides a brief summary of the ex-
perimental program. Details concerning the apparatus, reagents, measure-
ments, and procedures are provided in subsequent subsections.
The selection of compounds for experimental evaluation was based on the
literature survey (ref. 1). The compounds listed in the first column of
Table 1 were selected as candidates for smog chamber evaluation. The ex-
perimental program consisted of two phases: (1) screening studies aimed at
selecting compounds for smog chamber evaluation and (2) the smog chamber
studies.
The screening program was designed to assess the relative reactivity
based on ozone production of the candidate compounds. Ozone-forming potential
was evaluated in 125-1 Teflon bag reactors for mixtures of each compound
and NO (20% NO-) at nominal initial HC/NO ratios of 5 and 20. Target
X ^ Ji
initial concentrations of 10 ppmC of the candidate compound and either 2.0
or 0.5 ppm of NO were employed. Up to 10 bags could be tested simultaneously
X
under identical environmental conditions for any 1-day exposure. This allowed
fast and efficient screening of compounds for subsequent study in smog
chambers. This program was also employed to identify incompatibilities be-
tween the subject compound and Teflon film, which should be considered prior
to examination of the compound in the smog chamber facility.
Based on the results of the bag experiments, six compounds were selected
for further examination in smog chambers (see Table 1). These compounds,
however, were first subjected to additional experiments conducted in bag
reactors. These experiments addressed the following points:
13
-------
Table 1. EXPERIMENTAL PROGRAM
Type of Experiment Conducted
Compound Formula
Compound Name
Furan
Pyrrole
Thiophene
Methanethlol
Methyl sulfide
Methyl disulfide
Carbonyl sulfide
Cyclopentadiene
2-Methylfuran
2,5-Dimethylfuran
2-Methylthiophene
Toluene
Ethylbenzene
ortho-Xylene
meta-Xylene
para-Xylene
Propylenel'
C4H40
C4H5N
C4H4S
CH3-SH
CH3-S-CH3
CH3-S-S-CH3
COS
C5H6
C5H60
C6H80
C5H6S
C7H8
C8H10
/
A/Propylene was employed as a control hydrocarbon in the smog chamber tests.
-------
1. Dark phase stability of the selected compound in clean air,
2. Stability of the selected compound in clean air during and
after 1 day of exposure to natural irradiation,
3. Dark phase reactivity of the selected compound and ozone in
clean air,
4. Dark phase reactivity of the selected compound and NO in
A
clean air.
Three-day smog chamber tests were conducted using the six compounds
indicated in Table 1. These tests were conducted in the four outdoor smog
chambers comprising the RTI Smog Chamber Facility. Target initial concen-
trations of 5 ppmC of the subject compound and 1 ppm of NO (20 percent NO-)
A *
were employed. Three test compounds were studied simultaneously with one in
each of the first three chambers. Propylene was employed in the fourth
chamber as a control. Test conditions were used, which simulated static and
transport atmospheric conditions.
APPARATUS
Two types of reactors were employed in this investigation: Teflon bag
reactors and large, outdoor smog chambers. This equipment is described in
the following paragraphs.
Teflon Bag Reactors
Clear plastic bags have been employed as photochemical reactors for out-
door irradiation in several studies (refs. 2, 3, 4). Bag reactors are economical
and simple to fabricate. Reactor contents experience no dilution by sampling;
therefore, measured concentrations require no correction for dilution.
The role of surface-mediated reactions in smog chamber investigations
is unclear (ref. 5). Bufalini (ref. 6) has observed "memory" or "dirty
chamber" effects for NO in glass, aluminum, and Teflon chambers. The ex-
A
cellent gas-phase nitrogen balance observed by Gay and Bufalini (ref. 7)
in a Teflon bag suggests a reduced heterogeneous component for the Teflon
surface as compared to glass. Although the level of trace contaminants varies
from batch to batch, Teflon film may exhibit among the lowest levels of trace
contaminant off-gassing of the materials commonly employed in photochemical
smog studies (ref. 8). Teflon film also exhibits a reduced heterogeneous
15
-------
ozone-destructive potential. These considerations lead to the choice of
Teflon film as the wall material for the RTI outdoor smog chambers (ref. 9).
In view of the above points, Teflon film was also selected as the material of
construction for the bag reactors in this study.
Twenty 125-1 bags were fabricated from 0.05-mm (2 mil) thick fluorinated
ethylenepropylene (FEP), Type A Teflon film. This material exhibits excellent
light transmission in both the ultraviolet and visible regions of the solar
spectrum incident on the earth's surface (ref. 10). Bag dimensions were
approximately 0.9 m by 1.1 m, and the surface-to-volume ratio for each in-
flated bag was approximately 16 m~" . The configuration of an inflated bag
resembled that of a plump pillow.
After fabrication, the bags were "conditioned" in an attempt to lower the
bag reactivity and reduce possible contamination by wall off-gassing. This
was conducted by filling each bag with ozonized air to a concentration greater
than 5 ppm, storing in the dark for one day, and flushing with clean air from
the air supply.
A metal framework with a horizontal flexible "clothesline" was constructed
to support 10 to 12 bags for simultaneous outdoor irradiations. The bag
support was located in a grassy area within 10 to 15 m of the laboratory which
housed the instruments and air supply system. The supporting line was about 9
m in length, oriented east to west, and configured at approximately 2 m from
the ground. Each bag was suspended by two of its corners from the line. The
bags were carried from the outdoor bag support into the laboratory for chemical
analyses and then returned to the line. The length of time required for each
battery of measurements was typically 15 to 20 minutes.
Air Supply
The air supply for this study is illustrated in Figure 1. Commercially
supplied compressed breathing grade air was purified before use by catalytic
* t
oxidation, Purafil scrubbing, and drying with Drierite.
The desired volume of air, 125 1, was introduced into each bag through
its gas connection by a timed fill at a known flow rate. Flow rate from
Registered trademark of H.E. Burroughs and Associates.
Registered trademark of the W. A. Hammond Drierite Company.
16
-------
BREATHING GRADE AIR
CATALYTIC
HC OXIDATION
UNIT
-*
6.4mm 00
COPPER
TUBING
COOLING COIL
I t
i 03 GENERATOR
ROTAMETER
METERING
VALVE
TO BAG
Figure 1. Air supply.
-------
the air supply was monitored continually with a rotameter during each
timed fill.
The catalyst bed was charged with 120 g of 0.5% Pd on 3.2 mm alumina
spheres and was operated at 260ฐ C. For these conditions the catalyst should
oxidize 99.99+ percent of the hydrocarbons in the cylinder air (ref. 4).
Analyses of C^ to C.,. hydrocarbons in the air from the air supply showed a
maximum of 0.6 ppb (V/V) with a minimum detectable concentration (MDC) of 0.1
ppb (V/V). Methane concentration was below the MDC of 50 ppb.
A gas scrubber containing 500 g of Purafil was used to remove any NO
w w 2ฃ
contaminants. A measured zero NO concentration (MDC:0.001 ppm) from the air
x
supply was observed throughout the experimental program.
A gas scrubber containing 500 g of Drierite was used to remove water
desorbed from the Purafil by the passing air.
Injection System
Pollutants were injected sequentially into each bag through its gas
connection. Nitric oxide and nitrogen dioxide were injected by timed in-
jections from commercially prepared (Scott Research Laboratories)
certified cylinders containing 52.2 ppm NO in nitrogen and 52.3 ppm NO-
in nitrogen. Test hydrocarbon compounds were introduced into the bags
by syringe injections of the pure gas or pure liquid.
Ozone for the decay studies was introduced during the air fill by timed
activation of an ultraviolet ozone generator, which had been installed in the
air supply line for this purpose.
Sampling System
The chemical analyses conducted in the bag studies involved instrumental
methods. In most of the experiments a 1-ra long, 3.2-mm OD Teflon sampling
tube was used to manually connect a bag with each of the instruments in turn.
Ozone, NO , and HC analyzers were employed. An SO- analyzer was used if the
X *
test compound contained sulfur. These instruments are described in a later
section.
Bag Characterization Experiments
Three types of chamber characterization experiments have been conducted:
clean air irradiations, 0- decays, and NO oxidations. The results of these
experiments are presented in Table 2 and are discussed below.
18
-------
The purpose of clean air irradiations is to determine the amount of ozone
formed when purified air is irradiated in smog chambers. The ozone results
from photochemical processes involving trace levels of nitrogen oxides and
organics. These trace contaminants either remain in the air after purifi-
cation or desorb from the walls of the reactor. Ozone levels of 0.013 and
0.034 ppm were formed during clean air irradiations conducted in bags (see
Table 2). These results compare favorably with the values of 0.009, 0.033,
and 0.034 ppm reported recently in a similar study (ref. 4), which also
employed Teflon bag reactors.
Ozone can disappear inside a chamber by reacting 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 reactivity. Based on
this measure, Teflon bag reactors have been observed to be among the least
reactive of current smog chambers with dark phase ozone half-lives of 45 to
150 hours and half-lives of 9 to 16 hours under exposure to natural irradia-
tion (ref. 4). The reduced half-lives for irradiated conditions may be
attributed mainly to secondary reactions following ozone photolysis. Dark
phase half-life measurements were conducted for selected bags in the current
study and yielded values of from 70 to 92 hours (see Table 2). These results
are consistent with the previously referenced work and emphasize the reduced
heterogeneous ozone-destructive potential of Teflon film.
The oxidation of NO should proceed in the dark by the third-order thermal
reaction, NO + NO 4- 0- -ป 2 NO-. In the absence of reactive organic species,
the above thermal reaction should be the major pathway for NO disappearance.
Loss rates of NO under irradiation in excess of the thermal rate may be
attributed to participation of organic contaminants in the normal photo-
chemical NO-oxidation reactions. Dimitriades has suggested that the rate of
NO loss under irradiated conditions provides a highly sensitive measure of
chamber contamination levels (ref. 10). Nitric oxide oxidation experiments
were conducted by injecting 80% NO and 20% N02 into bags containing 125 1
of purified air. The bags were then either stored in the dark or exposed to
sunlight. The apparent second order rate constants for NO disappearance were
determined from the slope of [NO] vs. time plots. Ratios of experimentally
2 -1 1
determined rate constants to the established value (1.77 x 10 ppm hr
19
-------
Table 2. BAG CHARACTERIZATION STUDIES
EXPERIMENT RESULTS
Clean Air Irradiation Date l^lmax17
6-8-76
6-9-76
Ozone Decay (Dark) Date
6-3 to 6-4-76
6-3 to 6-4-76
6-3 to 6-4-76
8-5-76
NO Oxidations (Light and Dark) Date
6-2-76
6-8-76
6-9-76
6-17-76
8-6-76
0.013
0.034
fn 1 I/
I03jinitial-
0.666
1.220
1.183
1.258
^initial17
1.380
1.626
1.732
1.062
0.943.
'l/^7
76
75
70
92
Exposure3-/ kexPt/kthemA7
L 0.97
L 0.83
L 0.86
D 1.56
D 1.22
Concentration units: ppm.
u
21
Ozone half lives, t1/9, are expressed in hours.
_. i/ *
"L" signifies that the bag was exposed to natural sunlight during the experiment; "D" signifies that
the bag was stored In the dark during the experiment.
'kexpt is the rate constant calculated from the data assuming a second order reaction; ktner,,i is the
established rate constant for the thermal oxidation of NO at 300ฐ K (1.77 x 10~2 ppm~l hr~l [ref. Ill)
-------
[ref. 11]) are presented in Table 2. These ratios range from 0.83 to
1.56 and suggest a low background reactivity for the bags in this study.
RTI Smog Chamber Facility
The Research Triangle Institute Smog Chamber Facility consists of four
3 1
smog chambers (volume: 27 m ; surface to volume ratio: 1.9 m ) Figure 2
illustrates the general design. The chambers are located outdoors, and
irradiation is provided by natural sunlight. The walls are 0.13 mm thick (5
mil) FEP Teflon film supported by aluminum frames. The floors are 0.25 mm
(10 mil) thick FEP Teflon film laid over a reflective layer of aluminum foil,
which serves to raise the light intensity within the chambers and thus com-
pensate for transmission losses through the walls. Mixing in each chamber is
provided by a 0.45-m diameter aluminum fan blade on a shaft driven by a 185-W
(1/4 hp) motor using a belt-pulley system.
Subsystems Comprising the Smog Chamber Facility
In addition to the chambers proper, provisions were made for purifica-
tion, reactant injection, and sample collection with subsequent instrumental
and wet chemical analyses. The overall system is illustrated in Figure 3.
Air purification unitDetails 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 meteoro-
logical tower. This air is then drawn through each chamber and exhausted at
j _i
flow rates up to 0.34 m min by three two-stage diaphragm pumps. Purging
3 -1
may also be accomplished at higher flow rates, up to 2.3 m min , by opening
a manway in the floor and allowing the tower blower to force air through each
chamber.
After purging with ambient air, the chambers are sealed, and air is
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: 200-475ฐ C),
4. Air cooler,
21
-------
3.05 m
E
CM
CV1
f
ALUMINIUM FRAME
INLET, OUTLETS,
STIRRER MOTOR,
SAMPLING OUTLETS
Figure 2. A 27-cubic meter Teflon outdoor smog chamber.
22
-------
WET CHEM.
SAMPLER
AMBIENT
AIR -
INTAKE
WET CHEM.
SAMPLER
NJ
AIR
PURIFICATION
SYSTEM
AIR
PURIFICATION
SYSTEM
INSTRUMENTED
6AS ANALYSIS
INSTRUMENTATION LAB
Figure 3. System diagram, RTI smog chambers.
-------
AMBIENT AIR
INTAKE
FILTER
CATALYST
COLUMN
DESSICANT
COLUMN
^
VซT
FILTER
HUMIDIFIER
PURIFILL COLUMN
TO DRAIN
1 COOLING UNIT
tCOOLING WATER
Figure 4. Air purification unit, RTI smog chamber.
-------
5. Purafil column (containing 6.5 kg of Purafil for NO and 0- removal),
6. Humidifier.
Solenoid-driven valving allows 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 and dilution operation.
The purification or "cleanup" operation requires 8 to 12 hours at a flow rate
3 1
of approximately 0.28 m 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.
3 -1
Flow rates for this operational mode are between 0.0085 and 0.058 m min .
3 -1
A flow rate recirculating through the purification unit of 0.058 m min was
employed to simulate 95 percent dilution over 24 hours. Of course, the purifi-
cation unit was not employed (zero flow rate) to simulate static conditions.
Injection systemA schematic of the reactant injection system is seen in
Figure 5. There are three injection manifolds from cylinders of compressed
gases. The flow rates are controlled by calibrated manual needle valves, and
the quantity of each injection is controlled by timed, manual operation of the
appropriate solenoid valves. Nitric oxide and NO- are injected sequentially
from a single Teflon manifold. Hydrocarbons (propylene in this study) are
injected from a copper manifold. Ozone may be added by injecting oxygen from
a third manifold through an 0. generator at each chamber; this feature is
employed in 0_ decay experiments. After the reactants have been injected,
each of the manifolds is flushed with nitrogen.
Pure gases such as methanethiol are introduced via syringe injection
through a N?-purged 1-m long, 4.8-mm ID TFE Teflon tube located under each
chamber. This Teflon tube is also used for periodic grab sampling. Pure
liquid compounds are injected as liquids from a precision gas-tight syringe
with subsequent volatilization in a heated, stainless steel injection mani-
fold. A schematic of the heated injection manifold is presented in Figure 6.
Nitrogen is used as a purge gas to sweep the injected compound into the
chamber.
Sampling SystemThe sampling system is illustrated in Figure 7. Automatic.
sampling from each chamber occurs at 10-minute intervals four times per hour.
25
-------
U V. OZONE OCNERATOH
AMP TRANSFORMER
CUftY-VAFOR IAUP
ro
-EXHAUST
Figure 5. Reactant injection system, RTI smog chambers.
-------
VOLATILIZED COMPOUND
+ N2 PURGE GAS
INTO CHAMBER
CHAMBER FLOOR
STAINLESS STEEL ENCASED
CHROMEL-ALUMEL
THERMOCOUPLE
Q
CONNECTION TO
THERMOCOUPLE
READOUT
HEATING TAPE POWER LINE
(TO VARIABLE VOLTAGE
POWER SUPPLY)
N2PURGE
GAS IN
GAS TIGHT SYRINGE
CONTAINING LIQUID
TEST COMPOUND
ฃ!I I'M'I'M'I'N
{<3 5cm l>]
Figure 6. Heated stainless steel manifold for volatilizing liquid
test compounds prior to injection into a smog-chamber.
-------
AMBIENT AIR (tower)
CHAMBER
I
to
CO
INSTRUMEsrTATION LAB.
TFE TEFLON TUBING
'54
MANUAL CONTROL
Figure 7. Sampling system, RTI smog chambers.
-------
An automatic timer activates the appropriate sampling solenoid valves and pro-
vides for a 10-minute sample from each chamber once per hour. During the re-
maining 20 minutes the operator is free to calibrate instruments, analyze bag
samples, or allow the timer to automatically sample ambient air from the 10-m
meteorological tower.
The sampled air must travel through 4.8-mm ID Teflon tubing for distances
of 48 m from the most distant and 26 m from the nearest chamber to the lab-
oratory. The sample is drawn at a flow rate of 0.005 m rnin" (5 1pm) by a
Metal-Bellows MB-41 pump and is delivered to a glass manifold in the
laboratory from which the instruments draw their samples. These instruments
include an 0_ analyzer, an N0-N09-N0 analyzer, and an SO, analyzer
3 -1
having a total volumetric flow requirement of 0.003 m min (3 1pm).
In addition to the automated sampling system described above, a 1-m
long, 4.8-mm ID Teflon tube is located under each chamber for periodic manual
grab sampling. Wet bubbler samples for oxidant, NO-, and CH20 determinations
are collected at this location. Samples for subsequent hydrocarbon analyses
are also collected at this point in 10-1 Teflon bags. These samples are drawn
through the 1-m long sampling tube with a Metal-Bellows MB-41 pump and ex-
hausted into the Teflon bags. Typically, grab samples are collected manually
twice a day from each chamber (at 0900 and 1600 EST).
Chamber Characterization
Operating characteristics of the chambers comprising the RTI Smog Chamber
Facility are documented in the following paragraphs. These points are reported
to provide a basis for assessing the performance of the RTI chambers and to
allow comparison with other chambers.
MixingAs noted earlier, mixing in each chamber is provided by a fan
designed for that purpose. Unless specified otherwise, the fan operates
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 in excess of 4.0 m sec near the moving fan blade.
If a smog chamber can be assumed to be an agitator-stirred tank, then a
recently published relationship can be used to estimate the time required for
29
-------
complete mixing (ref. 12). This procedure indicates that mixing should be 90
percent complete within 24 seconds after injection of a pollutant.
Purification systemThe air purification system routinely reduces the
NO content of the purified air to a measured zero (MDC: 0.001 ppm). The
catalytic hydrocarbon oxidation system typically reduces C2 to CIQ hydrocar-
bons measured by gas chromatography to less than 50 ppbC (MDC: 0.1 ppb
[V/V]). Typical "postcleanup" hydrocarbon levels are shown in Table 3 for
each chamber.
Dilutior. The target recirculation flow rate through the purification
3 1
unit employed in this study was 0.058 m min . This corresponds to 95 per-
cent dilution in 24 hours and may be interpreted to mean that, after 24 hours
of operation at this flow rate, 95 percent of an unreactive material initially
present would be removed by the purification unit. A manual control valve
(V108 in Figure 4) is used to set the recirculation flow rate through the
purification unit. The valve setting is established manually prior to each
run in which dilution is to be employed. Based on CO measurements, the target
flow rate is expected to be achieved within +20 percent.
Chamber tightnessExchange of chamber contents with the ambient atmos-
phere 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. The sampling flow rate of
3 -1
0.005 m min for 10 minutes per hour corresponds to a dilution of 4.4 per-
cent in 24 hours. Under static conditions, overall 24-hour exchange rates in-
cluding the contribution due to sampling are expected to range from 15 to
35 percent based on the 24 percent maximum value recently reported (ref. 13)
for chambers of similar construction. Leak tests using CO and Freon 12 as
tracers have indicated that exchange rates generally fall within the expected
range. The reported data have not been corrected for dilution.
Sample line lossesThe most distant chamber is 48 m from the instru-
ments in the laboratory. When NO, N0ซป and 0_ are present in the chamber,
during periods of irradiation, a small reduction of NO and 0ป and a
slight increase in N02 may occur due to reaction in the dark sample line
(ref. 14). 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.
30
-------
Table 3. PRETNJECTION HYDROCARBON ANALYSES (ppmC)
^\Chamb e r
Compound ^\.
Ethane /Ethylene
Propane
Propylene
Acetylene
n Butane
1 Butene
Butene
i Butane
i Pentane
Cyclopentane
Toluene
SUM
1
4-23-76
0.034
OAAI
.UU1
OAAT
. UUi
OAm
. UU1.
OAAQ
. UUo
I/
Om n
. UJLU
0.056
to. 1
8-3-76 8-24-76
0.004 0.008
Onm
.UUI
Onm A AAO
. UUI U . UUi
OAA1 A AA*>
. UUJL U. UUi
OAA/i
. UU**
OAAA A AA1*
. UUH U UU J
0.016 0.017
No. 2
4-23-76^ 8-3-76 8-24-76
0.010 0.012
OAA1 A AAO
.UUi U.UUi
OAA1
. UUI
OAA1 A AAT
. UUฑ U.UUJ.
OAAT A AA^
.UUJ U.UUj
OA1 1
. UJ.J.
OAA1
.UUI
OAAT A nni
. UU J U . UU J
0.032 0.021
No. 3
4-23-76 8-3-76
0.050 0.005
OAAO
. UU/
OAA*5 A AAO
. UU J U.UU/
.UUi U.UU1
OAAQ A AA1
.UUo U.UU1
OAA1
. UU J
OAAT
0.065 0.013
8-24-76
0.016
OAAO
. UUz
OAAQ
. UU J
OAA1
.UUI
OAA9
.UUi
OAA1
. UUJ
0.027
No. 4
4-23-76 8-3-76
0.005 0.011
OAA9
. UUi
OAA1
. UUi
OAA1
. UUi
OAA9
. UUZ
OAA7
. UU/
0.007 0.023
8-24-76
0.007
OAAO
. UUi
Onm
Onm
. UUi
Onm
. UU j
OAAO
. UUi
0.016
Entries denoted by blanks," ", represent either nondetected concentrations or concentrations detected at
less than 0.001 ppmC.
21
Analysis not available.
-------
The sampled air volume must pass through a considerable length of
sampling line (26 to 48 m) and a pump before it is delivered to the instru-
ments for analysis. Sample modification is therefore expected. Experiments
were conducted to quantify these changes for 0_, NO, and N02. The losses were
typically less than 5 percent; therefore no corrections were made to the data.
Grab samples for subsequent hydrocarbon analyses were collected at each
chamber, were drawn through a 1-ra long, 0.0048-m ID Teflon tube with a Metal-
Bellows MB-41 pump, and were exhausted into 10-1 Teflon bags. An in-line
MnO scrubber, which was employed in a previous study (ref. 9) in an attempt
to remove 0_ and stabilize hydrocarbon concentrations, was not used in this
study. This measure was taken in view of a recent study (ref. 15), which
indicated that Mn02 is effective in oxidizing thiols to disulfides.
Characterization experimentsThree types of chamber characterization
experiments have been conducted: clean air irradiations, 0,, decays, and NO
oxidations. The results of these experiments are presented in Table 4.
Similar characterization experiments were conducted for Teflon bag reactors;
these results were discussed earlier.
The levels of background ozone formed in clean air irradiations con-
ducted in the RTI smog chambers range from 0..04 to 0.14 ppm. The results
of multiple-day experiments presented in Table 4 indicate that on the first
day ozone levels near 0.08 ppm were achieved. The second- and third-day
ozone concentrations slightly exceed the first-day levels. These background
ozone levels compare favorably with the value of 0.14 ppm reported for the
outdoor UNC facility (ref. 13) and the value of 0.10 ppm reported for the
indoor Bureau of Mines chamber (ref. 10).
Examination of the ozone half-lives reported in Table 4 for the four RTI
chambers indicates consistent behavior from chamber to chamber. Dark phase
half-lives range from 18 to 37 hours, and light phase values range from 9 to
11 hours. These half-lives are greater than the values summarized recently
for 10 indoor chambers (ref. 4). Although the ozone half-lives in the RTI
facility are somewhat less than the values discussed earlier for Teflon bag
reactors, the above comparisons indicate that the RTI chambers have a low
reactivity with ozone.
Experimentally determined rate constants for NO oxidation have been
divided by the established value for the second order thermal reaction
32
-------
Table 4. CHAMBER CHARACTERIZATION EXPERIMENTS
EXPERIMENT
Clean Air Irradiations
Ozone Decays
(Light and Dark)
NO Oxidations
(Light and Dark)
CHAMBER
RESULTS
4-6-76^-' 4-7-76 4-8-76 4-23-76^ 4-24-76
1
2
3
4
3/ 4/
I03'max Time'
0.065 1538
0.075 1558
[0-] Time [Oj Time [0,1 Time 10,J Time
3 max l 3 max 3 max 3 max
0.094
0.115
8-1-75
1
2
3
4
1
2
3
4
lฐ3' initial ll/2
0.600
0.621
0.609
0.650
^initial1'
0.540
0.569
0.538
0.575
(light)^
9.8
10.4
10.8
9.5
7-11-75
1538 0.080
1558 0.109
0.101
1538 0.040
1558 0.073
0.073
8-1-75
~ 1*V initial
0.829
0.825
0.823
0.835
k /k . (light)-'
expt therm *
2.
0.
2.
2.
44
94
18
01
t1/2 (dark)-'
21.8
27.5
23.1
30.3
8-3
1708 0.
1518 0.
1728 0.
1838 0.
139 1508
074 1518
113 1528
116 1838
4-25 to 4-26-76
^initial
0.735
0.726
0.563
0.523
to 8-4-76
IN01 initial kexpt/ktherm
0.588
0.675
0.520
0.622
1.63
1.37
2.15
1.61
t1/2 (dark)17
25.4
37.1
18.4
24.4
(dark)!"/
A three-day experiment.
Concentration units: ppm.
Ozone half-lives, t, .,, are expressed in hours.
7/
Experiment was conducted from 0100 until 0530 EST.
fcexpt is the rate constant calculated from the
data assuming a second order reaction; Athena la
the established rate constant for the thermal
oxidation of NO at 300" K (1.77 x 10~2 ppsT1 hr-1
[ref. 11]); experiment was conducted from 0700
until 1330 EST.
27
A two-day experiment.
-EST.
- Experiment was conducted from 0900 until 1530 EST.
8/
Experiment was conducted 2100 until 0330 EST.
Experiment was conducted from 1900 until 0340 EST.
-------
(1.77 x 10~2 ppnf1 hr'1 [ref. 11]). These ratios are presented in Table 4
and range from 0.9 to 2.5. They may be compared to the values of 4.0
for the Bureau of Mines chamber (ref. 10) and to values of 4.8 and 3.0
for the outdoor UNC facility (ref. 13). These comparisons emphasize the
low background reactivity exhibited by the RTI Smog Chamber Facility.
REAGENTS
The reagents used in this study are listed in Table 5. Other
information including boiling point, purity, injection mode, and supplier
is also provided.
The single component gas and liquid reagents employed in this study were
acquired from commercial suppliers with stated purities generally better than
95 percent. Dicyclopentadiene was "cracked" fay distillation to cyclopentadiene
(ref. 16) prior to injection. The other reagents were used without further
purification.
Analyses of the gas mixtures reported by suppliers were confirmed in our
laboratory. One of the propylene tanks, 294 ppm (V/V), was prepared at RTI by
blending 99% propylene gas (Phillips Petroleum Company) with hydrocarbon-free
air (Airco). The concentration was determined by gas chromatographic com-
parison with commercially supplied (Scott Research Laboratories) calibration
mixtures of propylene and air.
Nitrogen used as a purge gas in bag and chamber studies was Matheson
"Oxygen Free" grade. Air for the bag studies was delivered from the air
supply. This catalytic air cleanup system was described in the "Apparatus"
subsection. Air for the chamber studies was supplied from air purification
systems, also described in the "Apparatus" subsection.
MEASUREMENT METHODS
The measurement methods employed in the bag and chamber studies are
described below. A summary of these methods is presented in Table 6.
Bag Studies
Instrumental methods of chemical analysis were employed in the bag
studies. Ozone, NO, NO-, and the reactant hydrocarbon analyses were conducted
routinely; sulfur dioxide was also measured if the reactant compound
contained sulfur. These data are reported in Appendix B. A description
of each analytical method is provided in the next subsection.
34
-------
Table 5. REAGENTS
Reagent
Furan
Pyrrole
Thiophene
Methanethiol
Methyl sulfide
Methyl disulfide
Dicyclopentadiene
2-Methylfuran
2 , 5-Dimethylf uran
2-Methylthiophene
Toluene
ortho-Xylene
meta-Xylene
para-Xylene
Ethylbenzene
Carbonyl sulfide
Propylene
Propylene
Nitric oxide (bag study)
Nitric oxide (chamber)
Nitrogen dioxide (bag study)
Nitrogen dioxide (chamber)
Nitrogen (Oxygen Free)
c'
(.32)
131
83-85
(7.6)
38
109
170
63-66
92-94
113
(110.6)
(144.4)
138-139
(138)
136
(-48)
(-47)
(-47)
C-152)
(-152)
(21.1)
(21.1)
(-195.8)
Purity^/
99"*"
98
NS^
99.5
98
NS
95
90
99
95
99
NS
NS
NS
99
97.5
205+4 ppm
(V/V) ia
air
294 ppm
(V/V) in
air
52.2+1
ppm in N.
220 ppm
in N2
52.3+1
ppm in N.
115 ppm
in N2
99.998
Injection
Model/
VL.L
VL.L
VL.L
G
VL.L
VL.L
L
L
L
L
L
L
L
L
L
G
GM
GM
GM
GM
GM
GM
Purge
Gas
Supplier
Aldrich Chemical Company
Aldrich Chemical Company
J. T. Baker Chemical Co.
Matheson Gas Products
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrj.ch Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Fisher Scientific
Eastman Organic Chemicals
Eastman Organic Chemicals
Eastman Organic Chemicals
Aldrich Chemical Company
Matheson Gas Products
Scott Research Laboratories
RTI Blend
Scott Research Laboratories
Matheaon Gas Products
Scott Research Laboratories
Matheson Gas Products
Matheson Gas Products
Designated by supplier as a measure of purity; values in parentheses taken from
Handbook of Chemistry and Physics (ref. 17).
-'AS designated by supplier.
3/Injection mode: VL - Volatilization of liquid via heated injection manifold with
~~ M purge gas (see Figure 6); L Direct syringe injection of liquid into 125 liter
tlflon bag; G - Direct syringe injection of gaa into N.-purged line or Teflon bag;
GM Injection of ppm level gas phase mixture via smog chamber injection system
(see Figure 5).
-''NS Not specified by supplier.
-^Dicyclopentadiene was "cracked" by distillation to give cyclopentadiene of b.p.
42.0* C; cyclopentadiene was injected.
35
-------
Table 6. MEASUREMENT METHODS
MEASURED QUANTITY
03
Oxidant
NO
N02
NO
X
N02
SO,
Individual HC
3/
Solar Radiation
4/
% Possible Minutes Sunshine
4/
Daily Maximum Temperature
METHOD
Chemiluminescent
NBKI (Wet Bubbler)
Chemiluminescent
Chemiluminescent
Chemi lumines cen t
Saltzman
(Wet Bubbler)
Pulsed Fluorescent
Gas Chromatography/
Flame lonization
Chromo tropic Acid
(Wet Bubbler)
Pyranometer
MANUFACTURER RANGE
Bendix Model 8002 0-1 ppm
0-1 ppm
TECO Model 14B 0-10 ppm
TECO Model 14B 0-10 ppm
TECO Model 14B 0-10 ppm
0-5 ppm
TECO Model 43 0-5 ppm
Perkin Elmer Model 900 >0.05 .
ppm (V/V)-^
01 ppm
Eppley Model 2 0-2 Langleys
MDCฑ'
0.001 ppm
0.001 ppm
0.001 ppm
0.001 ppm
0.001 ppm
0.005 ppm
0.002 ppm
0.05 5/
ppm (V/V)-
0.015 ppm
STUDY-'
B,C
C
B,C
B,C
B,C
C
B,C
B,C
C
B,C
B.C
B,C
u>
Minimum detectable concentration.
2 / i
Identifies the study in which each measurement method was employed: bag studies are designated by "B",
and chamber studies are designated by "C".
ป/
Data collected by the U.S. Environmental Protection Agency, Division of Meteorology, Research Triangle
Park, North Carolina.
Data collected by U.S. Weather Service at the Raleigh-Durham Airport (ref. 18).
This value is for direct injection of a 1 mfc volume of sample.
-------
Chamber Studies
Both instrumental and manual analytical techniques were employed in the
chamber studies. Analytical C>3, NO, N02, and S02 data from automated instru-
ments were recorded from each chamber for 10 minutes per hour. These data are
reported in Appendix D as a single value for each chamber once per hour. The
reported concentrations were reduced from strip chart recordings at times
eight minutes into each 10-minute sampling period.
Oxidant, N02ป and formaldehyde were determined by wet chemical tech-
niques. Samples were collected twice daily from each chamber at 0900 and 1600
EST. Individual hydrocarbon concentrations were determined by gas chroma-
tographic analyses of grab samples collected at 0500 and 1300 EST on the first
day. Generally, by the second day the concentration of the compound of
interest had been reduced to nondetectable levels (<0.05 ppm [V/V]). There-
fore, hydrocarbon samples were not collected on the second and third days of a
three-day run. Hydrocarbon analyses from chamber runs are reported in
Appendix C.
Ozone
Ozone was monitored with a Bendix Model 8002 Ozone Analyzer. The principle
of this operation employs the chemiluminescent gas-phase reaction between
ozone and ethylene. The instrument operates in the continuous mode with a
range of 0 to 1 ppm and an MDC of 0.001 ppm. Calibration was performed using
a stable ultraviolet light ozone generator. The output of the 0- generator
was determined by gas-phase titration of 0_ with known NO concentrations
from certified standard mixtures of NO in nitrogen (ref. 19). A recent
intercomparison of our NO calibration cylinder with four other certified
calibration cylinders indicates the [NO] in our cylinder to be low by 6.5
percent. The reported ozone data have not been corrected, and a correction
factor (multiplier) of 1.065 would be required to account for the above
difference.
Oxidant
For chamber studies, photochemical oxidant concentrations were measured
by the NBKI technique (refs. 19,20). This involved passing a known volume of
chamber air through two all-glass midget impingers in series; each contained a
37
-------
1% neutral-buffered potassium iodide solution. These solutions were sub-
sequently analyzed with a Bausch and Lomb Spectronic 100 spectrophotometer.
Sampling times were usually 10 minutes at flow rates of 600 to 700 ml min .
Flow rate was controlled by a calibrated hypodermic needle protected from
overspray by a dessicant cartridge and glass wool trap. The reported data
have not been corrected for responses to sulfur dioxide, nitrogen dioxide,
peroxyacyl nitrates or other oxidizing species. The equimolar negative
interference by SO, is readily apparent in the first-day data from chamber
runs with sulfur-containing species which produce considerable amounts of
SO-. In the reported data, the time assigned to a measurement of a
chamber is the automated instrument sampling period for that chamber
which is closest to the beginning of the bubbler sampling period.
Nitrogen Oxides (NO, NO,, and NO )
ฃ Jv
Nitrogen oxides were monitored with a TECO Model 14B NO-NO analyzer.
fL
The principle of operation employs the chemiluminescent gas-phase reaction
between NO and 0_. Two modes of operation are required to determine both NO
and NO,. Nitric oxide is measured first using the reaction of NO and 0,. The
determination of NO,, however, requires catalytic reduction of NO, to NO prior
to the reaction of NO with ozone. After reduction of NO to NO, the signal
from the total NO in the sample is taken to be the NO concentration. Electronic
2ฃ
subtraction of the original NO signal from the NO signal gives the NO- concen-
A. Z.
tration. The instrument operates in two intervals within a 90-second cycle
corresponding to the two modes of operation: NO concentration is updated at the
end on the first interval and NO- and NO concentrations are updated at the end
^ A
of the next interval. The analyzer has a range of 0 to 10 ppm and an MDC of
0.001 ppm. Calibration of NO and NO was performed by dilution of a certified
J\
cylinder of NO in nitrogen. Calibration of NO, was performed by using the NO,
* ฃ,
produced from the gas-phase titration of known NO concentrations with 07 from
the calibrated ozone generator. As was noted in the earlier discussion of
the ozone calibration procedure, the [NO] in our calibration cylinder was
recently found to be 6.5 percent low. The reported NO, NO-, and NO data
2 x
have not been corrected, and a correction factor (multiplier) of 1.065 would
be required to account for the above difference.
38
-------
It has been demonstrated that nitric acid, PAN, and ethyl nitrate inter-
fere with N02 and N0x determinations in instruments of the type employed in
this study (ref. 21). The interfering species were not determined in this
study. Therefore, the reported NO- and NO data have not been corrected for
A
interferences.
Nitrogen Dioxide
In addition to the chemiluminescent measurements, the Saltzman method was
used to determine nitrogen dioxide levels in the chambers (ref. 22). Chamber
air was drawn through a glass, fritted Mae West bubbler containing Griess-
Saltzman reagent. Sampling times were normally 15 minutes at flow rates of
600 to 800 ml min . Flow rate was controlled by a calibrated hypodermic
needle protected from overspray by a dessicant cartridge and glass wool
trap. Samples were analyzed with a Bausch and Lomb Spectronic 100
spectrophotometer. The reported data have not been corrected for inter-
ferences from ozone or peroxyacyl nitrates. In the reported data, the
time assigned to a measurement of a chamber is the automated instrument
sampling period for that chamber which is closest to the beginning of
the bubbler sampling period.
Sulfur Dioxide
Sulfur dioxide was monitored with a TECO Model A3 Pulsed Fluorescent SO-
Analyzer. The principle of operation employs the fluorescent decay of excited
SO- molecules which have been energized by pulsed ultraviolet light (190-230 nm)
The instrument operates in the continuous mode with a range of 0 to 5 ppm and
an MDC of 0.002 ppm. Calibration was performed by the use of cylinders con-
taining ppm levels of S0~ in air. Cylinder concentrations were referenced to
an NBS S0? permeation tube calibration system.
Specificity to SO- was demonstrated by the absence of response for unirra-
diated air mixtures of each of the following compounds: methanethiol, methyl
sulfide, methyl disulfide, thiophene, carbonyl sulfide, and dimethyl sulfoxide.
An absence of response was also noted for irradiated smog chamber mixtures of
air, NO, NO-, 0-, and either propylene, furan, or pyrrole.
* 3 ^
Individual Hydrocarbons
The concentrations of individual hydrocarbons in the bag and smog chamber
studies were determined by gas chroraatographic separation with flame ioniza-
tion detection. A modified Perkin-Elmer Model 900 chromatograph was employed.
39
-------
In the bag studies the 125-1 Teflon bag reactors were brought into the
laboratory for direct sampling. Ten-liter Teflon bags were used in the chamber
studies to collect samples for subsequent hydrocarbon analyses. A Metal-
Bellows MB-41 pump was employed to draw the sample from the Teflon bag through
a 1-m long, 3.2-mm OD Teflon tube, into the gas sampling assembly of the GC,
and through 1-ml sampling loop. After 30 seconds of sampling to insure
adequate purging of the line and the sampling loop, the pump was turned off,
and the 1-ml volume of sample was injected directly onto the analytical column
with a gas sampling valve.
For analysis of most of the organic compounds except C* to C, hydro-
carbons, separation was accomplished on a 60-m S.C.O.T. OV-101 column operating
at 90ฐ C. Flow rate of the helium carrier was 25 ml min .
Separation of propylene and other Cป and Cg hydrocarbons was accomplished
on a 1.8-m long, 3.2-mm OD stainless steel column packed with Durapak n-
octane. The column temperature was 23ฐ C, and the helium carrier flow rate
was 12 ml min
A Hewlett-Packard Model HP-3352 data system acquired the output signal,
integrated peak areas, and converted the areas into concentration values which
were printed out by a teletype. Strip chart records of output signals were
maintained to supplement data system records. A nominal MDC from the data
system using a 1-ml direct injection was 0.05 ppm (V/V). Slightly lower
concentrations could be observed from strip chart records. The effective MDC
can be improved significantly to values lower than 0.1 ppb (V/V) by sample
concentration techniques employing liquid oxygen trapping.
Identification and quantification of compounds was based on comparison of
retention times and peak areas with those of calibration mixtures. Cali-
bration was performed at three-week intervals and showed a precision of +5
percent. Propylene and the other C- to C- hydrocarbon calibrations were
performed using mixtures of each compound in air. These calibration mixtures
were commercially supplied (Scott Research Laboratories) and certified to +1
percent accuracy. Commercial calibration mixtures for the remaining compounds
used in this study were not available. In view of this, the needed calibra-
tion mixtures were prepared at RTI by quantitative syringe injection of the
pure compounds into Teflon bags containing 125-1 of clean, dry air from the
air supply.
40
-------
Fo rmald ehyde
In the chamber studies, formaldehyde was determined by the chromotropic
acid method (refs. 23,24). A 1% sodium bisulfite solution was employed as the
collection medium. Chamber air was drawn through two glass midget impingers
in series. Sampling times were normally 30 minutes, and flow rates ranged
from 600 to 700 ml min~ . Flow rate was controlled by a calibrated hypodermic
needle which was protected from overspray by a dessicant cartridge and glass
wool trap. Samples were analyzed with a Bausch and Lomb Spectronic 100
spectrophotometer after treatment with chromotropic and sulfuric acids. The
reported data have not been corrected for interferences from ethylene, propylene,
or other hydrocarbons. In the reported data, the time that has been assigned
to a measurement of a chamber is the automatic instrument sampling period for
that chamber which is closest to the beginning of the bubbler sampling period.
Solar Radiation
Total solar radiation data reported in this study were collected by the
U.S. Environmental Protection Agency Division of Meteorology. The solar
radiometer, an Eppley Precision Spectral Pyranometer was located at a point
approximately 0.5 km from the RTI Smog Chamber Facility. This instrument
employs a thermopile sensing element and determines light intensity at wave-
lengths longer than 295 nm. The hourly average values reported in Appendix D
were reduced from continuous strip chart records.
Environmental Variables
Other environmental variables reported in this study (see Appendix D) are
ambient air temperature at 3-hour intervals, the daily maximum temperature
(T ), and the percent of possible minutes of direct sunshine (% SS). The % SS
max
is determined by a 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 U.S. Weather Service (ref. 18) at the
Raleigh-Durham Airport (RDU). RDU is located at a distance approximately 10 km
from the RTI Campus.
PROCEDURE
The experimental program is summarized in Table 1. In addition to the
static and dilution runs conducted in the smog chambers, six types of experi-
41
-------
merits were conducted in bag reactors. The procedures used in conducting the
bag and chamber studies are described below.
Bag Studies
The six types of bag studies included ozone-forming studies at a high
HC/NO ratio, ozone-forming studies at a low HC/NO ratio, dark stability
x x
tests of selected study compounds in air, light stability tests of selected
study compounds in air, dark phase reactivity studies of selected compounds
with ozone, and dark phase reactivity studies of selected compounds with N0x>
Chemical analyses in these studies involved instrumental determination of
the following species: CL, NO , SO,, and HC. In most of the experiments a 1-m
j X fc
long, 3.2-mm OD Teflon tube was used sequentially to allow direct sampling
by each instrument. Midway through the experimental program in an effort to
maintain continuous irradiation of the bag samples, a 5-m long 4.8-ram ID
Teflon sampling tube was used to connect the instruments in the laboratory
with bags located outdoors. This procedure was abandoned after implementation
in favor of the original procedure of bringing bags into the laboratory for
analysis. This measure was taken due to an apparent modification of NO
A
levels by the longer sampling line.
During the battery of analyses, samples were drawn by each of the con-
tinuous analyzers (0ป, NO , and SO ) for a duration of 3 to 4 minutes to allow
j X X
adequate time for the signal to become stable. The concentrations were
recorded on strip charts and also manually recorded from a DVM display.
Sampling duration for hydrocarbon analysis was 30 seconds. Gas chromato-
graphic data were recorded on strip charts, acquired and integrated by a data
system, and printed out on a teletype.
Ozone-Forming Potential
To evaluate the ozone-forming potential of each of the selected com-
pounds, a reactivity screening test was devised and conducted. Mixtures of
air, NO , and each selected compound were exposed to natural sunlight irradia-
X
tion at ambient temperatures in 125-1 Teflon bag reactors.
The decision to conduct a run was based on forecasts supplied by the
National Weather Service Forecast Office at RDU. After the decision to con-
duct the experiment was made, each bag was filled with 25 liters of air from
the air supply and then exhausted with a vacuum pump. This purging procedure
was repeated. Each bag was then filled with 125 liters of clean, dry air by a
42
-------
timed fill from the air supply. Appropriate amounts of NO and N02 were added
to each bag by timed injections. After storage in the dark for 15 minutes,
nitrogen oxides were measured to allow comparison with the target initial
conditions. Next, the test hydrocarbon compounds were introduced into the
bags by syringe injection of the pure gas or liquid compound. The bags were
then stored in the dark for 30 minutes to allow for volatilization and adequate
mixing prior to initial NO, N02, and hydrocarbon analyses. Target initial
conditions were 10 ppmC of the test compound and either 2.0 or 0.5 ppm NO
X
(20% N0_). Two NO levels were chosen to provide information at nominal
* X
initial HC/NO ratios of 5 and 20.
A
At the conclusion of the initial analyses, typically between 0900 and
1000 EST, the bags were taken more or less simultaneously outside and suspended
from the bag support for exposure to sunlight. The irradiation period typi-
cally continued until 1600, except for the three or four brief interruptions
required by chemical analyses. The duration inside the laboratory for 0_, NO,
N02ป and hydrocarbon analyses was kept to a minimum and ranged from 15 to 20
minutes for each battery of analyses.
Dark Stability
Tests were conducted to evaluate the stability of air mixtures of selected
test compounds in the dark. Results from these tests can be used to assess
thermal decomposition, thermal oxidation, or dark phase surface-mediated
effects contributed by the Teflon reactor walls.
The same 125-1 Teflon bags that were employed in the ozone-formation
screening test were used in this test. The procedure was similar to that used
in the ozone-formation study. The bags were purged twice and then filled with
clean, dry air from the air supply. The compounds of interest were introduced
into the bags by syringe injection such that a concentration of 10 ppmC was
achieved. To allow for volatilization and adequate mixing prior to initial
hydrocarbon analyses, the bags were stored in the dark for 30 minutes. After
the initial GC analyses, the bags were stored in the dark at room temperature
and reanalyzed several times over an 8-hour period. Selected samples, how-
ever, were monitored periodically for longer periods, up to four days.
Light Stability-
Experiments were conducted to evaluate the stability of air mixtures of
selected test compounds during and after exposure to natural irradiation.
43
-------
Aside from the fact that NO was not injected, the procedure was the same
2v
as that employed in the ozone-formation study.
Dark Phase Reactivity with Ozone
Tests were conducted to evaluate the dark phase reactivity of selected
compounds with ozone. The same 125-1 Teflon bags that were employed in the
ozone-formation tests were used with this study. The bags were purged twice,
and each bag was then filled with 125 liters of dry, ozonized, and otherwise
clean air by a timed fill from the air supply. The initial ozone concentra-
tion of approximately 1.0 ppm was achieved by a timed activation of the ozone
generator that had been installed in the line between the air supply and the
bag. After storage in the dark for 30 minutes to allow for adequate mixing,
ozone was measured. Next, selected test compounds were introduced into the
bags by syringe injection to a concentration of 10 ppmC. After 30 minutes to
allow for volatilization and adequate mixing, measurements of ozone and the
test compound were conducted periodically for up to 6 hours.
Dark Phase Reactivity with NO
Experiments were conducted to evaluate the dark phase reactivity of
selected compounds with nitrogen oxides. Aside from the fact that during
these tests the bags were stored in the dark at room temperature, the
procedure was the same as that used for the ozone-formation study conducted
at the lower HC/NO ratio. The target initial conditions were 10 ppmC of
X
the test hydrocarbon and 2.0 ppm of NO (20% NO-).
2k ฃป
Smog Chamber Studies
Based on the results of the screening studies conducted in Teflon bags,
six compounds were selected for three-day smog chamber experiments. These
selected compounds are thiophene, pyrrole, furan, methanethiol, methyl
sulfide, and methyl disulfide. The three-day experiments were conducted
in the four-chamber RTI Smog Chamber Facility. Target initial conditions of
5 ppmC of the compound and 1 ppm of NO (20% NO-) were employed. Three test
X ฃ
compounds were studied simultaneously with one in each of the first three
chambers. Propylene was employed in the fourth chamber as a control. Each
of the selected compounds was subjected to experiments designed to simulate
static and transport (dilution) atmospheric conditions.
44
-------
Static Experiments
A three-day smog chamber run requires four days of chamber activities.
On the day before a run is to start the chambers are operated in the purge
3 -1
mode. Each chamber is flushed with ambient air at a flow rate of 2.0 m min
starting at 0900 and lasting for six to eight hours. At approximately
1400 the purging operation is terminated, each chamber is sealed, and the
cleanup operation is begun. Hydrocarbon and NO contaminants in the captive
2t
air parcel are removed by recirculation through the purification unit for
3 -1
8 to 12 hours at a flow rate of 0.28 m min . The cleanup operation is
terminated two hours prior to sunrise. For these experiments, the humidity
of the captive air parcel was not altered during the cleanup. This was
accomplished by "by-passing" both the humidifier and the desiccant columns
during the cleanup operation.
The next step is pollutant injection. Appropriate amounts of NO and
NO- were introduced sequentially into each chamber using the chamber injec-
tion system described earlier. After the NO injection, propylene was in-
A
jected into the fourth chamber also using the injection system. Each of
three different test compounds was then introduced into one of the three
remaining chambers by syringe injection. The injection procedure was com-
pleted one hour before sunrise. This allowed 30 minutes for adequate mixing
and 30 minutes for initial reactant sampling prior to sunrise.
The contents of the chambers were sampled and monitored for the next
three days. Ozone, NO , and S0? were monitored once per hour for each
X ฃ*
chamber. Wet bubbler samples for oxidant, NO. and CH_0 analyses were typi-
cally collected from each chamber twice per day at 0900 and 1600 EST.
Samples for hydrocarbon analyses were collected in 10-1 Teflon bags at
0500 and 1300 EST on the first day. Generally, by the second day the concen-
tration of the compound of interest had been reduced to nondetectable levels.
Therefore, hydrocarbon samples were not collected on the second and third
days. Generally, each three-day run was terminated at 1700 EST on the after-
noon of the third day.
Dilution Experiments
With one exception, the procedure emloyed in the dilution runs is the
same as that described above for the static runs. The same target initial
45
-------
conditions were employed in both studies. After reactant injection had been
completed, simulated dilution was initiated at 0800 EST on the first
day. The chambers were operated in the dilution mode with a recirculation
3 1
flow rate through the air purification system of 0.058 m min . Dilution was
terminated after 24 hours of operation, and the chambers were operated under
static conditions, similar to those described above, for the remaining two
days of the three-day run. The dilution flow rate is such that after 24
hours of operation, 95 percent of an unreactive material originally present
would be removed. The object of operation in the dilution mode is to simulate
the dilution experienced by an air parcel as it is transported downwind.
46
-------
SECTION 5
RESULTS AND DISCUSSION
CHOICE OF COMPOUNDS FOR STUDY
The 17 compounds chosen for examination in this study are listed in
Table 1. These compounds were selected for several reasons. A primary
objective was to select species which are expected to be released into the
atmosphere by synthetic fuels processing operations. Potential emissions
from such fuel conversion operations as coal gasification and liquefaction,
shale oil production, and petroleum refining were identified from a litera-
ture survey (ref. 1). This report provided a basis for selecting many of
the 17 compounds chosen for testing. Identified compounds with sulfur or
nitrogen in their molecular structure, which had not been subjected to
extensive smog chamber investigation, were given special consideration in
the selection process. Other compounds, although not identified in the
literature survey, were chosen because they were representative of a class
of identified compounds or because of chemical or structural similarity to
identified compounds. Emissions of a variety of saturated and unsaturated
hydrocarbons are also anticipated. Considerable attention has been directed
to elucidating the atmospheric chemistry of these compounds. For this reason,
they are not considered in this study.
The sulfur-containing compounds, carbonyl sulfide, methanethiol,
methyl sulfide, methyl disulfide, thiophene, and a substituted thiophene,
2-methylthiophene, were specifically identified in the literature survey
and were chosen for testing. Other sulfur-containing species such as
sulfur dioxide, hydrogen sulfide, and carbon disulfide were also identified.
Examination of this latter group of compounds, however, is deferred to
future studies.
Many of the nitrogen-containing species, which were identified as
potential emissions, were found to include heterocyclic compounds such as
pyrroles and pyridines. Pyrrole was chosen as the nitrogen-containing
compound for study, leaving such species as ammonia, hydrogen cyanide,
substituted pyrroles, and pyridines to future investigations.
47
-------
Although furan was not identified in the literature review, it was
chosen to complete a study of the five-membered heterocyclic class of
compounds: sulfur-containing thiophene, nitrogen-containing pyrrole, and
oxygen-containing furan. Two substituted furans, 2-methylfuran and 2,5-
dimethylfuran, were chosen to examine the influence of added methyl
groups on the ozone-forming potential.
Cyclopentadiene has been identified in coal gas, although it is not
expected to be a major atmospheric emission. It was chosen because of its
molecular structure. As a five-membered, all-carbon, cyclic molecule, its
behavior can be compared with the five-membered heterocyclic compounds
chosen for study.
The coal matrix is highly aromatic. Therefore, it is not surprising
to find aromatic hydrocarbons identified as potential pollutants from fuel
conversion operations. Toluene, ethylbenzene, and ortho-, meta-, and
para-xylene were chosen for testing.
Although small amounts of propylene may be released from fuel con-
version facilities, this compound is not expected to be a major emission.
Propylene is the hydrocarbon that has been most frequently examined in
smog chambers. For this reason, propylene was chosen as a control test
compound.
BAG STUDIES
Several types of investigations were conducted in bags. A total of 106
bag experiments was performed. The first study was directed at assessing the
ozone-forming potential of 16 compounds. Based on the results, six compounds
were selected for additional bag and smog chamber experiments. The additional
bag studies included dark stability tests of the selected compounds in air,
light stability tests of the compounds in air, dark phase reactivity studies
of the compounds with NO , and dark phase reactivity tests of the compounds
X
with ozone. The raw data from these bag studies are compiled in Appendix B
and are discussed in the following paragraphs. Results of the chamber studies
are discussed in a subsequent subsection.
Ozone-Forming Potential
The reactivity of an organic material is the intrinsic ability of
that compound to participate in atmospheric reactions which result in smog
48
-------
formation. Several attempts to quantify reactivity have been based on
various manifestations of photochemical smog: hydrocarbon conversion, NO
photooxidation rate, maximum CL concentration, 0_ formation rate, 0 dosage,
N02 dosage, formaldehyde yield, PAN yield, eye irritation index and others
(ref. 25). The object of the screening tests presented here is to assess
the reactivity of the test compounds on the basis of the maximum achieved
0 concentration.
Previous studies (ref. 26) have shown the relationship between
precursor concentrations and the resulting maximum ozone level to be highly
nonlinear. This relationship may be represented in two dimensions by equal
concentration lines (isopleths) of ozone maxima as a'function of initial
nitrogen oxides and initial hydrocarbon concentrations. This relationship
may also be represented by a three-dimensional surface projection of ozone
maxima as a function of initial nitrogen oxides and hydrocarbon concentra-
tions. A hypothetical representation is presented in Figure 8. On this
"ozone mountain" lies a ridge which defines the combinations of precursor
concentrations required for maximum ozone production. The slope of this
ridge of maximum ozone production may be represented by a HC/NO ratio.
X
The critical HC/NO ratio which defines the conditions for maximum
ozone production is not the same for every organic molecule. The critical
HC/NO ratio for propylene has been reported to be between 3 and 6 ppmC/ppm
(ref. 27). Alkanes are considered to be less reactive than the olefin,
propylene. For alkane-NO photochemical systems the HC/NO ratio which
X X
results in maximum ozone production ranges from 15 to 60 (refs. 4, 28, 29).
The objective of this study was not to identify the critical HC/NO
X
ratio for each compound. Instead, it was to identify, for subsequent smog
chamber testing, those compounds which can produce significant quantities
of ozone. Toward this end, target initial conditions of 10 ppmC of the
test compound and 2.0 and 0.5 ppm of NO were selected. These test conditions
A
provide for initial HC/NO ratios of 5 and 20, which are expected to encompass
X.
regimes of potential ozone production ranging from that typical of propylene
to that representative of an alkane hydrocarbon. Environmental variables,
measured initial conditions, and selected results of the ozone-forming
studies conducted at both low and high HC/NO ratios are summarized in
X
Tables 7 and 8. If more details are desired, Appendixes A and B should
49
-------
RIDGELINE
(CRITICAL HC/NOX RATIO
OZONE ISOPLETHS
Ln
O
103)
Figure 8. Hypothetical representation of Ozone Maxima as a function
of initial nitrogen oxides and hydrocarbon concentrations.
-------
Table 7. SUMMARY OF SELECTED RESULTS OF OZONE-FORMING STUDIES
CONDUCTED IN BAGS AT LOW INITIAL HC/NO RATIOS
x
Environmental Variables Initial Conditions Results
Compound Date I , 'C ISS* ESR.,b (HC]iC (N0lid [NO.
max 12 2
]id [N01id UC/M X" X ฃ 6xQ8 [0]d^ [SO]^
X X tlw VnJ XO J EDoX ฃ DIcJA
S'
Furan
Pyrrole
Thiophene
Methanethiol
Methyl sulfide
Methyl disulfide
Carbonyl oulfide
Cyclopes tadieoe
2-Hethylfuran
2 , 5-Diae thy If uran
2-Methylthiophene
Toluene
Ethylbenzene
0-Xylene
M-Xylene
P-Xylene
Propylene
6-10-76
6-2-76
6-10-76
6-9-76
6-10-76
6-29-76
7-1-76
6-29-76
7-1-76
6-29-76
7-1-76
7-1-76
7-16-76
6-10-76
6-10-76
6-29-76
6-22-76
6-22-76
7-23-76
7-23-76
7-23-76
8-19-76
33
29
33
33
33
33
29
33
29
33
29
29
35
33
33
33
29
29
34
34
34
27
28
32
28
40
28
66
55
66
55
66
55
55
71
28
28
66
24
24
34
34
34
92
226
150
226
144
226
152
170
152
170
152
170
170
110
226
226
152
116
116
152
152
152
283
10.1
9.62
12.2
11.4
10.1
9.48
8.71
9.36
10.2
9.03
12.1
10. 01
10.7
10.8
15.9
8.91
12.0
11.9
10.3
10.4
10.1
8.55
1.154
1.370
1.186
1.700
1.108
1.570
1.696
1.608
1.684
1.866
1.960
1.712
1.606
1.134
1.114
.570
.648
.832
.786
.920
1.814
1.318
0.264
0.310
0.316
0.282
0.274
0.462
0.492
0.518
0.456
0.522
0.496
0.512
0.720
0.264
0.318
0.473
0.388
0.472
0.494
0.530
0.552
0.320
1.418
1.680
1.502
1.982
1.382
2.032
2.188
2.126
2.140
2.388
2.456
2.224
2.326
1.398
1.432
2.043
2.036
2.304
2.280
2.450
2.366
1.638
7.1
5.7
8.1
5.8
7.3
4.7
4.0
4.4
4.8
3.8
4.9
4.5
4.6
7.7
11.1
4.4
5.9
5.2
4.5
4.2
4.3
5.2
i.ooJ
1.00
1.00
1.00
0.58
0.66
0.85
0.82
0.91
1.00
1.00
0.80
1.00
1.00
1.00
0.27
0.21
0.62
0.62
0.14
0.98
0.88
0.83
0.89
0.84
0.58,
0.92*
0.83*
0.99*
0.99*
0.99*
0.98*
0.88*
0.77*
0.58
0.44
0.97*
0.51*
0.47*
0.49*
0.58*
0.05
0.52
<66
<114
<104
<60
88-175
71-181
>270
<106
<78
<130
<90
>285
<122
<71
<113
<83
>312
>328
81-285
<94
>333
<125
1.066
1.133
0.627
0.305
0.256
0.013
0.0
0.327
0.261
0.180
0.212
0.0
1.596
0.925
0.841
0.333
0.0
0.0
0.385
1.008
0.0
1.470
0.409
0.928
1.56
0.926
1.78
2.13
0.045
0.766
0.31
0.13
0.43
0.20
0.20
0.18
0.005
0.53
Percent possible minutes of direct sunshine measured at RDU Airport (ref. 18).
Summation of solar radiation from beginning the exposure until 1200 EST; expressed in Lang ley a (cal cm" ); measured by EPA; see text.
GUnits - ppmC
Units - ppn
X is the fractional conversion (loss) of hydrocarbons during the experiment; conversion of compound "a" at time t is defined as X
(l '
initial
initial.
X..., is the fractional conversion (loss) of HO during the experiment.
nu x
x
*Iime to NO - NO., crossover, 6 , is expressed in minutes; the Infrequent NO determinations in these bag studies prevent good resolution of
this parameter.
Represents max! BUD observed concentration, not necessarily maximum attained concentration.
* is the yield of SO determined at [SO ] and is a measure of molecules of SO formed per molecule of consumed sulfur.
'Based on estimated final concentration.
Baaed on questionable concentration data.
Initial UC concentration is calculated based on injected volume; no determinations were conducted.
-------
TABLE 8. SUMMARY OF SELECTED RESULTS OF OZONE-FORMING STUDIES
CONDUCTED IN BAGS AT HIGH INITIAL HC/NO RATIOS
x
Ul
N>
Environmental Variables
Coupound
Pur-n
Pyrrole
Tlilophene
Metlidnethlol
Methyl suicide
Hethyl dlaulflde
Carbonyl uulflde
Cyclopeatadlene
2-Hethylfuran
2,5-Ulmetliyl furan
2-Mc t hy 1 thlophene
Toluene
Etbylhcnzene
0-Xylene
M-Xylene
P_-Xylene
Propylene
Initial Conditions
uidx 12 2 jt
6-2-76
6-9-76
6-29-76
7-1-76
6-29-76
6-29-76
7-1-76
7-16-76
6-10-76
6-10-76
6-29-76
6-22-76
6-22-76
7-23-76
7-23-76
7-23-76
8-19-76
29
33
33
29
33
33
29
35
33
33
33
29
29
34
34
34
27
32
40
66
55
66
66
55
71
28
28
66
24
24
34
34
34
92
150
144
152
170
152
152
170
110
226
226
152
116
116
152
152
152
283
10.4
10.4
7.83
11.2
10.7
11.0
10. Ok
11.5
10.8
10.4
12.0
11.2
11.4
9.9
10.1
9.9
9.0
0.370
0.40t)
0.394
0.444
0.392
0.404
0.430
0.502
0.292
0.290
0.506
0.376
0.462
0.438
0.466
0.472
0.318
0.075
0.080
0.110
o.ioa
0.128
0.094
0.128
0.118
0.062
0.062
0.154
0.096
0.172
0.112
0.126
0.124
0.074
0.445
0.488
0.504
0.552
0.520
0.498
0.558
0.620
0.354
0.352
0.660
0.472
0.634
0.550
0.592
0.596
0.392
1 IIC/NO
23.4
21.3
15.5
20.3
20.6
22.1
17.9
18.5
30.5
29.6
18.2
23.7
18.0
18.0
17.1
16.6
23.0
"I/
0.95
1.00
0.79
0.66
0.49
1.00
1.00
0.97
1.00
0.90
0.36
0.51
0.60
0.80
0.48
0.82
X
0.74
0.88
0.97^
0.85^
0.97}
0.97^
0.86]
0.90J
0.46
0.19
0.96^
O.B7J
0.8?]
O.bl]
0.61J
0.53d
0.45
Kebultb
0 *
no
<130
<30
<58
43-162
<118
<151
>338
<135
<76
<117
<94
<89
x 99
<75
<88
<98
<130
lฐ3J!ax IS(V';
0.107
0.385
0.060 0.426
0.005 0.824
0.086 0.520
0.241 2.70
0.0 0.022
0.622
0.088
0.297
0.038 0.591
0.343
0.313
0.521
0.569
0.594
0.289
;* x1
0.29
0.12
0,20
0.25
0.002
0.29
1'crcent poaalblu minutes of direct aunaliiae Measured at K1)U Airport (ref. 18).
of ปolซr rtdlatloa ttoป
~ 2
'units -
~
the expoaure- until 1200 ESTj enprusboJ la Lftngloyg (col era ); meflsureJ by tPA; sec text
er la the fractloiMl couveraloo (loss) ot hyiirocarbons during the experiment; conversion of compound 'V at tlue t la dafiuod aa
/ (' 'initial - I V" llปUl.l
X_ la the frซctloQซl conversion (loaa) of NO^ during the experiment.
'"Tloe co HO - HU. crossover, a , la cxprestiiiil In wlnutea; die Infrequent NO^ determinations In clitac bag studies
prevent goad ruaolutlon of thla parameter.
niepreaenta BaxiBun observed cuncuntratlon, not nc-ceaaarJly uanlmuiii attained concentration.
4X la the yield of SO Jeternlned at ISO.,) and la a measure of uoleculea of SO^ forued per molecule of
consumed aulfur.
Baaed on questionable concentration data.
''initial IIC concentration la calculated buaed on Injected voluoc; no deteriui nations were conducted.
-------
be consulted. Appendix A is a summary of environmental conditions for
each day of bag and chamber experiments. Appendix B provides a chronological
tabulation of all the concentration-time data collected in the bag studies.
Examination of Tables 7 and 8 reveals that the oxidant standard,
0.08 pptn, was exceeded in at least one of the two test conditions for
every test compound except carbonyl sulfide and methanethiol. Although
methanethiol produced only small quantities of ozone, significant quantities
of S00 were produced.
Ratios of maximum ozone levels achieved by the test compound to that
produced by propylene are compared at both HC/NO ratios in Table 9. At
X
the low HC/NO ratio, propylene produced 1.470 ppm of ozone. Only cyclo-
X
pentadiene produced more ozone than propylene. Four hydrocarbonsthe
three furans and m-xyleneproduced more than 50 percent of the amount
generated by propylene. During the 300-minute exposure to natural irradia-
tion only five of the test compounds failed to achieve NO-NO- crossover and
therefore also failed to produce ozone. Nevertheless, this does not
eliminate the possibility of ozone generation for multiple-day exposures.
At the high HC/NO ratio, propylene produced 0.289 ppm ozone. Eight
X
compounds produced more ozone than propylene for this test condition. The
three xylenes and cyclopentadiene produced approximately twice this amount.
Pyrrole, methyl disulfide, 2,5-dimethylfuran, toluene, and ethylbenzene
produced only slightly more ozone than did propylene.
The ratios of the ozone maxima observed at the low HC/NO condition to
X
that at the high value are also presented in Table 9. The value for propy-
lene is 5.09. It may be postulated that compounds with similar values may
have reactivities similar to propylene, while compounds with lower values
have reactivities more typical of alkane hydrocarbons. Certainly additional
experiments at other HC/NO ratios are required to obtain an ozone response
JL
surface for each compound, which would allow this hypothesis to be tested.
Substituted Methyl Groups
The influence of substituted methyl groups on ozone production may be
examined by comparing the behavior of the three furans, the two thiophenes,
the thiol and sulfide, and the aromatics.
53
-------
Table 9. COMPARISON OF MAXIMUM OZONE CONCENTRATIONS ACHIEVED
IN BAGS AT LOW AND HIGH HC/NO RATIOS
X
Compound
Fur an
Pyrrole
Thiophene
Me thane thiol
Methyl sulfide
Methyl disulfide
Carbonyl sulfide
Cyclopentadiene
2-Methylfuran
2 , 5-Dimethylf uran
2-Methylthiophene
Toluene
Ethylbenzene
0-Xylene
M-Xylene
_P-Xylene
Propylene
RLOW&
0.73, 0.77
0.43, 0.21
0.17, 0.009
0.0
0.22, 0.18
0.12, 0.14
0.0
1.09
0.63
0.57
0.23
0.0
0.0
0.26
0.69
0.0
1.00
b
^TTTr1!!
H.-L.O'Il
0.37
1.33
0.21
0.02
0.30
0.83
0.0
2.15
0.30
1.03
0.13
1.19
1.08
1.80
1.97
2.06
1.00
ฐ3,L/03,HC
10. 6d
0.79d
0.22d
0.0
3.80d
0.75d
2.57
10.5
2.83
8.76
0.0
0.0
0.74
1.77
0.0
5.09
Tlatio of [0_] for specified compound to [0_] for propylene
at low HC/NO ratio; see Table 7 .
i X
Ratio of [0 ] for specified compound to [0 ] for propylene
j IH3.X j msx
at high HC/NO ratio; see Table 8 .
cRatio of [0,] at low HC/NO to [0_] at high HC/NO for
j max x j max x
specified compound; see Tables 7 and 8 .
In those cases where two runs were conducted at the low HC/NO
x
condition, the tabulated ratios were calculated using same day
results.
54
-------
At the low HC/NO ratio for the furans, less ozone is produced with the
X
addition of methyl groups. At the higher HC/NO ratio the reverse situation
X
occurs. This suggests that the addition of methyl groups to furan reduces
the critical HC/NO ratio.
Although data for the thiophenes are more scattered, these results also
suggest that the conditions for maximum ozone production occur at a lower
HC/NO ratio for 2-methylthiophene than for the unsubstituted molecule. The
X
data do not allow speculation on the location of the critical HC/NO ratio
X
for methanethiol or methyl sulfide. Comparison of ozone maxima for these
two species also suggests increased ozone generation with substitution.
Five aromatic hydrocarbons were examined: toluene, ethylbenzene, and
o_, m, and _p_-xylene. Toluene and ethylbenzene exhibited similar behavior
and produced the least ozone of the examined aromatics. Both species failed
to produce ozone at the low HC/NO ratio while producing in excess of 0.3
X.
ppm at the higher ratio. This suggests that the critical HC/NO ratio for
X
these compounds is greater than 5 and may be in the range of 10 to 30. The
xylenes exhibit similar behavior at the high HC/NO ratio forming almost
X
twice the ozone produced by either toluene or ethylbenzene at these conditions.
At the low HC/NO ratio, ozone production by each of the xylenes is dramatically
X
different. Meta-xylene produced over 1.0 ppm ozone, para-xylene produced
no ozone, and ortho-xylene produced an intermediate amount. From this be-
havior it may be speculated that the critical HC/NO ratio is low for m-xylene
X
and may be around 5. The analogous value for para-xylene should be in the
range of 10 to 30. The ortho-xylene may have a critical HC/NO value inter-
x
mediate between the values for the meta and para isomers.
The trends of ozone production reported for the aromatic hydrocarbons
in this study are generally consistent with results observed in other smog
chamber studies (refs. 25, 30, 31). Substitution of a methyl group on a ring
carbon of the toluene molecule has a considerable impact on the ozone-
generative capacity of the molecule. Lengthening the side chain has little
effect as is seen by comparing experiments conducted with toluene and
ethylbenzene. Addition of a methyl group to a ring carbon of toluene forms
a xylene and significantly increases the ozone-generative capacity of the
moleculealmost doubling the maximum ozone at the high HC/NO ratio. Among
X
the xylenes at the low HC/NO conditions, the meta isomer produces significantly
X
55
-------
more ozone than the other two isomers. The consumption of m-xylene is
also the highest of the tested aromatic hydrocarbons.
The hydroxyl radical is believed to be the primary reactive species in
photochemical smog reactions. Rate constants for HO attack on toluene,
3 3
ethylbenzene, p_-xylene, o-xylene, and m-xylene are 8.8 x 10 , 11.8 x 10 ,
18.3 x 103, 20.6 x 103, and 34.6 x 103 ppnf1 min"1 (ref. 32). Comparison
of the relative magnitudes of these rate constants for the aromatic
hydrocarbons is generally consistent with ozone production observed at
the low HC/NO ratio in this study. For the xylenes which exhibit
X.
dramatically different behavior at the low HC/NO ratio, the rate constant
X
for the reaction of hydroxyl radicals with m-xylene is approximately 80 percent
larger than the values for _o_- or ฃ-xylene.
Heterocyclics
Three five-membered heterocyclic compounds having cis-diene structures
were examined: furan, pyrrole, and thiophene. At the low HC/NO ratio, furan
2t
formed the most ozone followed by pyrrole and thiophene. The five-member
all-carbon cyclic cis-diene compound, cyclopentadiene, formed more ozone than
any of the heterocyclics. In fact, among all the compounds tested, cyclo-
pentadiene formed the most ozone. The increased ozone-generative capacity may
be attributed to the molecular structure of the diene. Cycloolefins have been
found to be among the most reactive of olefinic hydrocarbons (ref. 33).
During each experiment a fraction of the NO was converted to species
X
nondetectable by the chemiluminescent NO analyzer. At the conclusion of
a run with the heterocycles, up to 90 percent of the NO was unaccounted for.
X
This is almost double the value for propylene. This may also suggest the
generation of increased levels of NO -scavenging radicals for the hetero-
X
cyclics as compared to propylene.
Among the heterocyclics, thiophene was the slowest reacting species.
At the low HC/NO ratio, thiophene required approximately twice as much
X
irradiation time as either furan or pyrrole to achieve NO-NO- crossover.
At each HC/NO ratio, hydrocarbon consumption was near 100 percent for pyrrole
X
and furan, while thiophene consumption ranged from 58 to 79 percent. This
suggests that thiophene may have the potential for ozone production, which
could extend for several days.
56
-------
In addition to the ozone formed by the photooxidation of thiophene,
sulfur dioxide was also observed as a product. Maximum SO,, concentrations
in excess of 0.4 ppm were achieved. The maximum yields of SO- (molecules
of SO- formed per molecule of consumed sulfur at the time of the maximum
[SO-]) were approximately 0.30. These values were observed with concurrent
ozone maxima below 0.1 ppm. For 2-methy1thiophene at the low HC/NO
X
ratio, a maximum SO- yield of 0.53 was observed concurrently with 0.33
ppm ozone. This suggests that for thiophenes, combinations of initial
conditions which give rise to increased ozone generation may also enhance
SO- production.
Sulfur-Containing Compounds
Six sulfur-containing species were examined: methanethiol, methyl
sulfide, methyl disulfide, carbonyl sulfide, thiophene, and 2-methyl-
thiophene. Two of these compounds, methanethiol and carbonyl sulfide,
failed to generate ozone at either HC/NO ratio. In contrast, methyl
JS.
sulfide, methyl disulfide, thiophene, and 2-methylthiophene, were
observed to produce ozone at both HC/NO ratios. Ozone production for
Jv
thiophene in comparison to the sulfides appears to be more sensitive to
initial HC/NO ratio.
x
Although the data do not allow clear resolution^ methyl disulfide may
have the largest ozone-generative capacity of the tested sulfur-containing
compounds. Based on measured hydrocarbon consumption, methyl disulfide and
2-methylthiophene are the most reactive of the tested sulfur species.
Hydrocarbon consumption for both compounds was 100 percent at the low
HC/NO ratio, whereas consumption of the other species ranged from 58
to 91 percent.
Sulfur dioxide was observed as a product of the photooxidation of each
of the sulfur-containing compounds. This is contrary to the finding of Cox
and Sandalls (ref. 34) who failed to detect S02 during photooxidation experi-
ments with methyl sulfide. This discrepancy may be attributed to the reduced
light intensity employed in their study. The k. value (cj>k for N0_) used
-2-1 a z
in their study was 3.1 x 10 min ; this is approximately 10 percent of
-2 -1
the accepted noontime value of 50 x 10 min
57
-------
In most cases, the maximum SO- yields observed for each species
were relatively insensitive to changing HC/NO ratio. Carbonyl sulfide
X
produced the least SCL, 20 to 50 ppb. Methanethiol produced levels of
SO slightly less than 1.0 ppm and had maximum yields of 0.13 and 0.12.
Methyl disulfide produced the largest observed concentration of SC^, 2.7
ppm. Both methyl sulfide and methyl disulfide produced S02 yields of
approximately 0.20. The largest SCL yields were observed for thiophene
and 2-raethylthiophene with values ranging from 0.29 to 0.53.
Selection of Compounds for Subsequent Bag and Chamber Studies
Three families of compounds were examined in screening tests: aromatics,
heterocyclics, and open-chain sulfur species. The results of the screening
tests have shown that in the photooxidation of 14 of the 16 test compounds,
ozone in excess of the NAAQ'o was produced. Although photooxidation of
methanethiol produced no ozone, substantial amounts of S0_ were formed.
Among the test compounds, the aromatic hydrocarbons have received consider-
able smog chamber investigation (refs. 25, 30, 31). This leaves two
families of compounds for additional bag and smog chamber investigations:
the heterocyclics and the sulfides. Three compounds were chosen from
each category. The unsubstituted (parent) heterocyclic molecules,
furan, pyrrole, and thiophene, were selected from the first group. The
sulfur-containing compounds, methanethiol, methyl sulfide, and methyl
disulfide, were chosen from the second category. As in the screening
tests, propylene was chosen as a control test compound for many of the
bag and chamber experiments.
Dark Stability
The stability of each of the six selected compounds was evaluated in
the dark at room temperature. A nominal concentration of 10 ppmC in air
was employed. Results from this study are summarized in Table 10. Rate
constants for assumed first order decays and the corresponding coefficients
2
of determination, r , were calculated. Half-lives were calculated in the
usual manner for first order reactions by dividing In 2 by the rate constant.
Stability tests were conducted over periods ranging from 3 to 6 days
for the heterocyclic species. These compounds are highly stable in the dark
with half-lives in excess of 300 hours and loss rates ranging from 8 to 25
58
-------
Table 10. SUMMARY OF DARK STABILITY RESULTS
Compound
Furan
Thiophene
Pyrrole
CH3SH
CH SCH
(CH3S)2
Date
5-25-76
5-26-76
5-27-76
8-5-76
8-5-76
8-5-76
Initial
Concentration
ppmC
10.8
9.8
11.2
8.16
11.4
12.3
Test
Duration,
hr
71
144
114
6.0
4.7
4.7
Mean
Concentration
(+1SD) ppmC
10.31 + 0.52
9.68 + 0.39
10.00 + 1.09
9.13 + 0.69
11.15 + 0.35
12.05 + 0.35
Number
of
Measurements
8
7
4
5
2
2
k hr
1.64 x 10~3
0.78 x 10~3
2.07 x 10~3
4/
9.60 x 10"3"
-si/
8.89 x 10
&
0.77
0.79
0.92
Half-life, -
hr
420
880
330
4/
72^
,
78-
vo
Rate constant for an assumed first order decay.
21
Coefficient of determination for a least squares fit of ฃn C vs t
in 2/rate constant
^Half-life
4/
The variability of the methanethiol determinations masked any trend in behavior.
These values may be questionable because they are based on only two determinations.
-------
ppb hr . Among the tested heterocycles, pyrrole is the least stable and
thiophene is the most stable.
The stability tests for methanethiol, methyl sulfide, and methyl
disulfide were conducted over periods of 5 to 6 hours. This is slightly
less than the duration of a typical one-day ozone-forming irradiation.
These compounds exhibited moderate stability over the test periods.
No loss rate could be calculated for methanethiol because the variability
of the measured values over the 6-hour test masked any trends. Although
a loss is indicated for the sulfide and disulfide, two determinations are
considered to be too few to yield reliable results.
Methyl disulfide and methanethiol have been reported in the litera-
ture to be relatively stable in the dark. At concentrations of less than
0.5 ppm of the disulfide, a 1-day loss rate in Teflon bags of 0.4 percent
hr has been reported (ref. 35). This value is consistent with the value
in Table 10. Methanethiol at 1,000 ppm was reported to decay by only 10
percent over a 9-day period (ref. 36). This reported stability may not be
indicative of the stability of the compound at the lower concentrations
used in our study.
These results suggest that air mixtures of all six test compounds are
relatively stable in the dark. The methanethiol concentration may have
been influenced by interactions with the Teflon walls of the bag reactor or
other unknown phenomena, which could give rise to the observed erratic
behavior. The other five species exhibited no behavior in these experiments,
which would suggest the occurrence of spontaneous or surface-mediated de-
composition or oxidation processes. Additional experiments may be necessary
to provide better definition of the long-term behavior of methanethiol,
methyl sulfide, and methyl disulfide in the dark.
Light Stability
The stability of five of the six test compounds was evaluated during
single-day irradiations at a nominal initial concentration of 10 ppmC in
air. A leaking bag prevented the completion of the experiment with methane-
thiol. The duration of each experiment was approximately 6 hours. Concen-
tration-time data were fitted to the form of a first order decay. Each rate
2
constant with its coefficient of determination, r , was calculated. The
half-life of each test species was determined in the usual manner under the
assumption of first order reactions.
60
-------
Except for methyl sulfide, the introduction of sunlight enhanced the
decay rates of the tested species in comparison to the rates observed in the
dark. The ratio of the dark to the light half-lives can serve as a parameter
for comparing decay rates. Using this approach and the half-lives in Tables
10 and 11, furan is seen to decay approximately 6 times faster under natural
irradiation than in the dark. For thiophene, pyrrole, and methyl disulfide
the effects of sunlight are even more pronounced: increasing the decay
rates by over 20-fold.
On an absolute basis, only pyrrole and methyl disulfide were observed
to have half-lives of less than 1 day. This suggests that in the atmosphere
in the absence of NO -mediated photooxidation, pyrrole and methyl disulfide
X
are removed relatively quickly. Product information is not available for
the heterocycles; however, sulfur dioxide was measured as a decay product
of the sulfides. The highly stable methyl sulfide has a half-life of 57
hours and produced only 44 ppb of SO-. In contrast, methyl disulfide, with
a half-life of only 3 hours, produced significant quantities of S0ป: a
maximum SO,, concentration of 2.4 ppm was observed. This corresponds to an
SO- yield of 0.28 which is slightly higher than the yields observed in the
ozone-forming studies discussed earlier.
Rayner and Murray (ref. 36) conducted irradiations of methanethiol,
methyl sulfide, and methyl disulfide at concentrations of 1,000 ppm in air.
These studies were conducted with artificial irradiation at 360 nm. Under
the 360 nm light, methyl sulfide was stable, decaying by only 3.5 percent
after 9 days of exposure. In addition, methanethiol was exposed to natural
sunlight. Methanethiol decayed at approximately equal rates under artificial
and natural irradiation, decaying by 68 percent and 65 percent after 9 days.
Methyl disulfide was the least stable of the three compounds and exhibited
a 91 percent loss after 9 days.
The results of the Rayner and Murray study at high concentrations are
qualitatively consistent with the results for methyl sulfide and methyl
disulfide presented in Table 11. If the referenced findings may be extrap-
olated to the low concentration behavior of methanethiol, then a half-life
between 3 and 57 hours (perhaps 10 hours) is anticipated at 10 ppmC (the
conditions shown in Table 11).
The reason for the increased decay rates under exposure to natural
irradiation is not apparent. It may be theorized that the enhanced decay
61
-------
Table 11. SUMMARY OF LIGHT STABILITY RESULTS
Compound
Furan
Thiophene
Pyrrole
CH3SCH3
(CH3S)2
Date
6-2-76
6-8-76
6-9-76
7-1-76
7-1-76
Initial
Concentration ,
ppmC
9.0
10. i
11.1
11.1
12.0
Test
Duration,
hr
5.7
5.7
5.4
5.3
1.9
Number of
Measurements
4
5
5
4
4
I/ 1
k , hr
1.06 x 10~2
1.65 x 10~2
4.62 x 10~2
1.22 x 10~2
21.9 x 10~2
^
0.90
0.92
0.95
0.87
1.00
Half-Life, -
hr
65
42
15
57
3.2
NJ
Rate constant for an assumed first order decay.
21
Coefficient of determination for the least squares fit of ฃn C vs
3/
Half-life = ฃn 2/rate constant.
t.
-------
rates are due to photolysis of the tested species. Published UV absorption
spectra suggest that furan, pyrrole, thiophene, and methyl sulfide do not
absorb at 290 nm (refs. 37, 38). Methyl disulfide was found to absorb
at 290 nm (e - 60), and methanethiol was found to absorb weakly at 280
nm (e = 20) (ref. 38). The symbol c (1 mole" cm ) represents the
decadic form of the molar extinction coefficient. Bond energy considerations
for these two species have shown photodissociation to be theoretically
possible in natural sunlight. Absorption and photolysis data which
could be employed to confirm and perhaps quantify the behavior of these
two species were not found in the literature.
An alternate explanation for the increased decay rates on exposure to
natural sunlight may involve destructive secondary reactions following
photoexcitation. Wood and Heicklen (ref. 39) have suggested that this mechanism
accounts for the photooxidation of CS,, at 313 nm, whereas wavelengths below
230 nm are required for direct photodissociation. This may also occur for
compounds in our study.
A third explanation for the enhanced decay rates may be the so-called
"dirty-chamber" effect. It has been suggested that irradiation chambers
exhibit this effect in the form of a wall source of HO radicals (ref. 40).
If this is the case, then a chain reaction initiated by HO radicals may be
required to explain the data. This hypothesis may be questioned, however,
considering that the rate of methyl sulfide decay was unaffected by irradiation.
Dark Phase Reactivity with Ozone
Experiments were performed to determine the reactivity of ozone in the
dark with each of the six test compounds. Propylene was also tested as a
reference compound. These tests were conducted in the batch mode in 125-1
Teflon bag reactors. The duration of each test was dependent on the reac-
tivity of the test compound and was generally between 2.0 and 8.0 hours.
During each test, both HC and 0, determinations were performed. Target
initial concentrations were chosen to maintain an excess of hydrocarbon
and simplify data treatment.
A summary of the results of these tests is presented in Table 12.
Ozone concentration-time data were fitted to the form of a first-order
decay. The resulting uncorrected rate constants and corresponding coefficients
63
-------
Table 12. SUMMARY OF RESULTS OF DARK REACTIVITY EXPERIMENTS WITH OZONE
Compound
Furan
Thiophene
Pyrrole
CH SH
CH3SCH3
(CH3S)2
Propylene
Date
6-2-76
2-4-77
6-3-76
2-4-77
6-3-76
2-4-77
8-5-76
8-5-76
8-5-76
2-4-77
tฐ3l Initial
ppm
0.77
0.31
0.85
0.71
0.88?/
0.24-
1.10
0.90
1.12
0.23
[RC] Initial
ppmV
0.57
f\ Q r\ * 1
1.23
4.49
2.25
7.71
4.87
6.37
1.60
kl/
hr-1
0.158
0.625
0.0225
0.220
0.548
2.81
0.0465
0.0573
0.0254
1.48
r2-'
0.98
1.00
0.96
0.99
0.98
0.99
1.00
0.99
1.00
1.00
kl/
0.149
0.616
0.0136
0.212
0.539
2.80
0.0376
0.0484
0.0165
1.47
ppmV
0.485
3.72
1.14
4.44
Q.625^
1.97
7.71
4.87
6.37
1.44
ppm'lhr 1
0.307
0.166
0.0119
0.0477
0.862
1.42
0.00488
0.00994
0.00259
1.02
Half-Life^
hr
2.3
4.2
58
15
1.2
0.49
140
70
270
0.68
Pseudo-first order rate constant based on 03 concentration-time data; these values are uncor-
rected for dark phase 03 decay in the Teflon bag reactors.
2/
Coefficient of determination for a least squares fit of ฃn[0ป] vs t.
3/
Pseudo'-first order rate constant corrected for dark Q-, decay measured in the bags (k , , =
8.86x10-3 hr^). 3 03,dark
4/
Mean HC concentration over the duration of the test.
Second order rate constant for reaction between the test compound and ozone.
Half-life is tabulated for either compound, assuming a constant concentration 1 ppmV for the other;
this assumes a stoichiometry of 1:1 and may not be valid for the sulfur-containing compounds (see
text.
Estimated concentrations.
-------
of determination for the first order fits are tabulated. Each uncorrected
pseudo-first order rate constant is then corrected for dark phase decay of
ozone within the bag. This value is divided by the mean concentration of
the test compound for the experiment, yielding the approximate second order
rate constant. A half-life for one reactant (either HC or 0-) is then
calculated based on an assumed constant concentration of 1 ppm for the
second reactant.
The tabulated second order rate constants are based on only one or
two experiments and should therefore be considered as approximate values.
2
The r values for these determinations were generally better than 0.95,
suggesting good agreement between the concentration-time data and the
assumed model. In addition, the agreement between the experimentally
determined rate constant for propylene, 1.02 ppm" hr~ , and the established
value, 0.954 ppm hr (ref. 11), increases confidence in the quality of
the data.
Two rate constant determinations were performed for each of the hetero-
cycles. The initial reactant concentrations differed substantially for the
two determinations. This difference may account for the discrepancies
between the rate constants determined for these two conditions.
Reaction stoichiometries could be determined with confidence for only
furan and propylene. In the two furan experiments 1.1 and 0.8 molecules
of ozone were required to remove 1 molecule of furan, while propylene
required 0.7. These values are in line with the generally accepted value
of 1.0 for propylene (ref. 41). The concentration behavior of the remaining
five compounds during the experiments did not allow an accurate assessment
of their stoichiometries. Qualitative evaluation of this data indicates
that the AO-/AHC ratios for the aliphatic sulfides are greater than 1.0.
This is consistent with the values of 1.8 and 3.9 reported for the reaction
of ozone and methanethiol and ozone and methyl disulfide in aqueous solution
(ref. 42).
The literature is generally lacking in gas phase ozonolysis studies
of the test compounds. Palmer (ref. 37) suggested from solution-phase studies
that ozone electrophilically attacks the 2- and 5-positions of the five-
membered heterocyclic molecule. The anionic oxygen atom of the intermediate
then attacks the 3- or 5-positions. Decomposition of the resulting molecules
may yield glyoxals, keto aldehydes, and other oxygenates.
65
-------
Although product identification was not attempted in our study, gas
phase ozonolysis of alkyl sulfides at high ozone concentrations (>1%) have
been reported to yield both the sulfoxide and the sulfone (ref. 42). Cox
and Sandalls (ref. 34) have reported that methyl sulfide is unreactive with
ozone (at 2.8 ppm) in the dark. It is likely that the heterogeneous com-
ponent contributing to ozone decay in their experimental system was sufficient
to mask any contribution to ozone decay by reaction with methyl sulfide.
This is consistent with the small rate constant presented in Table 12.
The ozonolysis of ethanethiol was studied by Kirchner et al. (ref. 43).
The reaction was found to proceed by carbon-sulfur bond cleavage, and a rate
constant of 0.35 ppm~ hr~ was reported. This is approximately 73-fold
larger than our finding of 0.0049 ppm~ hr~ for the homologue, methanethiol.
The strength of the C-S bond is 2.5 kcal larger for methanethiol than
ethanethiol. This would sv.ggest a reduced rate constant for methanethiol,
although the reduction is difficult to quantify. Initial reactant concen-
trations used by Kirchner were an order of magnitude larger than were
employed in our study. This may also contribute to the above differences
in ozonolysis rate constants.
The results in Table 12 indicate that among the six test compounds,
pyrrole and furan react most rapidly with ozone. The reactivity of pyrrole
is very similar to that of the reactive olefin, propylene. In contrast,
the sulfur-containing species are considerably less reactive. Among
the tested sulfur compounds, the heterocycle, thiophene, is the most reactive
with ozone. Reactivity among the open chain sulfur species decreases from
methyl sulfide to methanethiol to methyl disulfide. These relative reac-
tivities are somewhat speculative due to the approximate nature of tabulated
rate constants. The concentration of each of these compounds remained
essentially unchanged over the 5 to 6 hours required for the ozone reactivity
experiments. This, in addition to the results in Table 12, suggests that
the tested open-chain sulfur species are not highly reactive with ozone.
Dark Phase Reactivity with NO
_, L jr.. _, -y*
Tests were conducted to evaluate the dark phase reactivity of nitrogen
oxides and each of the test compounds. In addition to the six test compounds,
carbonyl sulfide (COS) was also chosen for testing. In the ozone formation
66
-------
tests conducted earlier, irradiated mixtures of COS and NO exhibited
x
peculiar behavior. Although N0-N02 crossover was not achieved, and no
ozone was formed, NO was consumed quickly at both HC/NO ratios. Carbonyl
x x
sulfide was therefore chosen for dark phase reactivity tests with NO to
investigate this phenomenon. Furan, thiophene, and pyrrole were monitored
in the presence of N02. Methanethiol, methyl sulfide, methyl disulfide,
and carbonyl sulfide were tested in the presence of NO (a mixture of 80%
Ji
NO and 20% N0_). In addition, control experiments were conducted with air-N02
mixtures and air-NO mixtures. Results of these experiments are summarized
X
in Table 13.
Mean hydrocarbon concentrations for each experiment are presented in
the second major column of Table 13, and if decay was observed with time,
a first-order decay constant is tabulated. Concurrent NO behavior is
X
displayed in the third column as a first-order decay constant. In the
fourth major column, the concurrent behavior of NO in the presence (and
absence) of hydrocarbons is tabulated as the ratio of the experimentally
determined second order NO oxidation rate constant to the established value
(ref. 11).
The dark phase stability of furan, thiophene, and pyrrole was examined
in the presence of NO-. The thiophene and pyrrole decay rates exceeded
those observed in the dark stability tests conducted in the absence of N0?
(see Table 10). The largest increase, a factor of 10, was observed for
pyrrole; whereas increases of approximately 3 were observed for thiophene.
In these tests, NO,., behavior in the presence of either thiophene or pyrrole
was similar to that observed in the absence of hydrocarbons (control). The
decay rate of N0_ in the presence of furan, however, was increased by over
threefold in comparison to that of the control.
It should be noted that these results are based on single experiments
and may not be totally valid. The results do suggest, however, that in the
dark, furan, thiophene, and pyrrole are relatively unreactive with N0ป
in comparison to their behavior with NO under irradiation.
Dark phase stability tests in the presence of NO were conducted with
A
methanethiol, methyl sulfide, methyl disulfide, and carbonyl sulfide. Among
these compounds, concentration-time data of CH-SH and CH-SCHL displayed no
67
-------
cr>
oo
Table 13. SUMMARY OF RESULTS OF. DARK REACTIVITY EXPERIMENTS WITH NO,
Compound Date
Fur an 6-17-76
Thiophene 6-17-76
Pyrrole 6-17-76
f*l3 CU O ฃ "7 fi
L.n_on o O / O
f*\3 Cr*II Q ฃ ~J t\
on-oL.n_ QO / O
(CH3S)2 8-6-76
COS 8-6-76
Control, N02 6-17-76
NO 8-6-76
NO 6-17-76
[IIC](+1SD), kHC!/ 2l/
ppmC hr"1 r
10.20 + 0.15
8.74 4- 0.05 2.73xlO~3 0.89
8.88 4- 0.46 21.5xlO~3 1.00
7.82 4- 0.41
11.1+0.04
14.63 + 0.83 20.9xlO~3 0.73
iO.O5./
0.0
0.0
0.0
[Nฐxl Initial kNOx- rZ?./
ppm hr"1
1.182 43.8xlO"3 1.00
0.958 9.66xlO~3
1.166 10.6xlO~3 0.81
1.095 10.3xlO~3 0.97
1.159 9.21xlO~3 0.74
1.114 14.0xlO~3 0.71
1.106 8.26xlO"3 1.00
0.986 12.9xlO~3 1.00
1.166 5.34xlO~3
1.122 10.2xlO~3 0.99
ppm1 3 kexpt/ktherm~ r
o.o
0.0
0.004
0.893 1.53 0.99
0.926 1.66 0.95
0.875 1.87 0.95
0.882 1.53 1.00
0.0
0.943 1.22
1.062 1.56 1.00
Rate constant for an assumed first order decay.
21
Coefficient of determination for a least squares fit of in C vs t.
kexpt is the rate constant calculated from the data assuming a second order reaction; kjfherm *s tne
established rate constant for the thermal oxidation of NO at 300ฐK, k ซ 1.77 x 10~* ppm"1 hr"1 (
Coefficient of determination for
ref.ll),
as calculated from a least squares fit of [NO] vs t.
Initial HC concentration is calculated based on Injected volume.
-------
apparent trends, and COS determinations were not performed. Methyl disul-
fide was observed to decay at a rate approximately twice that observed in
the absence of NO . The NO decay rates for the control compared closely
X A
with those for CH-jSH, COS, CH,jSCH3> and (CH3S)2. The ratios of NO oxidation
rates, however, suggest that the presence of (CH.S)- may enhance the NO
oxidation rate slightly in comparison to the control values or those with
CH3SH, COS, or CH3SCH3.
These experiments indicate that CH3SH, COS, CH^SCH.,, and (CH3S)2 are
all relatively unreactive with NO (mixtures of NO and N09). Among these
Xi ฃ
species, methyl disulfide is probably the most reactive with NO , and its
3t
presence may enhance the NO oxidation rate slightly. In view of these
results, the increased NO consumption noted earlier for irradiated mix-
A.
tures of COS and NO are not due to thermal reactions with NO and may be
x x
attributed to light-induced reactions.
Overview of Bag Studies
A summary of half-lives of the six test compounds observed in each of
the various test conditions is presented in Table 14. The half-lives for
each test condition except the photooxidation experiments were calculated
from first-order decay constants which were tabulated previously. The
photooxidation half-lives are highly approximate and were calculated from
data presented in Appendix B. These results may be used to reiterate pre-
viously stated observations. The stability of the heterocycles decreases
from the "dark stability" to "dark phase reactivity with NO ," to "light
X
stability," to "dark phase reactivity with ozone," to the "photooxidation"
experiments. The high reactivities of pyrrole with 0- and furan with fl-
are clearly indicated. The stability of the alkyl sulfides in the presence
of ozone is noteworthy, as is the enhanced decay rate of methyl disulfide
on exposure to sunlight. The most significant observations, however, are
dramatically illustrated by comparing the photooxidation half-lives with
the other tabulated values. These results indicate that each of the test
compounds can participate in atmospheric photooxidation reactions. Although
many chemical reactions may contribute to the removal of these compounds
from the atmosphere, these results suggest that photooxidation is a major
pathway.
69
-------
Table 14. SUMMARY OF TEST COMPOUND HALF-LIVES EXPRESSED IN HOURS
"^^^Experiment
Compound ^^-^^
Furan
Thiophene
Pyrrole
CH3SH
CH3SCH3
(CH3S)2
Dark ,
Stability^
420
880
330
72
78
Light 2/
Stability-'
65
42
15
57
3.2
Dark Phase
Reactivity
with NOxJ/
250
32
33
Dark Phase
Reactivity
with Ozone_t'
2.9
23
0.61
140
70
270
Photooxidation
with NO-JL/
0.20
3.5
0.11
1.8
1.1
0.33
-See Table 10.
-''see Table 11.
3/
Calculated from kH_ values in Table 13.
Assumes a constant 03 concentration of 1 ppm; see Table 12.
Calculated from HC behavior exhibited in the ozone-forming studies assuming a first order
decay; see Appendix B for the tabulated, raw, concentration-time data.
-------
CHAMBER STUDIES
Multiple-day experiments were conducted with furan, thiophene, pyrrole,
methanethiol, methyl sulfide, methyl disulfide, and the control hydrocarbon,
propylene, in the RTI Outdoor Smog Chamber Facility. A total of 20 smog chamber
experiments was performed. The test compounds were chosen based on the results
of ozone-formation screening tests conducted in Teflon bag reactors. Findings
from the bag studies were presented and discussed in the previous subsection.
Target initial conditions for the smog chamber tests were 5.0 ppmC of
the test compound and 1.0 ppm NO (20% N0_). The initial HC/NO ratio of
X t* X
5.0 was chosen to correspond to one of the two test conditions employed in
the earlier bag screening tests and to correspond to the conditions required
for maximum 0 production from a highly reactive organic species such as
propylene (ref. 27). These initial concentrations also correspond to those
employed in outdoor smog chamber studies with a simulated urban mix con-
ducted previously at RTI (ref. 9). Therefore, the chosen initial conditions
allow convenient comparison with results from the urban mix runs.
The duration of each chamber experiment was 3 days. The object of a
3-day experiment is to simulate, roughly, the behavior of a photochemically
reactive mixture of organics and NO which could occur in the atmosphere
A
over several diurnal cycles.
Two types of smog chamber studies were conducted: static and dilution
runs. In the static runs, the initial reactants were injected just prior
to sunrise on the first day, and the photochemical reactions proceeded in the
batch mode. Concentrations of reactant and product species were monitored
for the 3-day run. The only dilution experienced by the reacting volume
was due to sample replacement and chamber "breathing" caused by diurnal
temperature variations and buffeting by winds.
The procedure employed for the dilution runs was similar to that used
for the static runs except that the chamber contents were diluted with
purified air at a fixed rate starting at 0800 EST on the first day. The
dilution rate was chosen so that after 24 hours of operation, 95 percent
of an unreactive tracer initially present would be removed. Dilution was
terminated 24 hours after initiation, and the remaining 2 days of the run
were conducted in the static mode. The object of dilution experiments was
to simulate the dilution experienced by an air parcel in the atmosphere
as it is transported downwind.
71
-------
The data collected in the smog chamber studies are presented in the
Appendixes. Concentration-time data are tabulated in Appendix D and are
also presented in graphical form in Appendix E. Solar radiation profiles
are also presented in Appendix E. Environmental parameters, initial
conditions, and selected results from the 3-day chamber studies are
summarized in Tables 15, 16, and 17. Day-one results are presented in
Table 15, day-two results in Table 16, and day-three results in Table 17.
The variability of solar radiation and other environmental factors can
make the results from outdoor smog chambers difficult to interpret. Three
environmental parameters have been tabulated. Maximum daily temperature
(T ) and percent of possible minutes of direct sunshine (%SS) were measured
max re ^
at the Raleigh-Durham Airport. Daily irradiance (SSR) in Langleys (cal cm )
was calculated from total solar radiation data collected by EPA at a site
0.5 km from the chamber facility. These parameters are similar across most
of the runs. The maximum temperatures ranged from 27 to 37ฐ C (81 to 99" F).
The %SS was generally greater than 60 percent, and the ESR was typically between
500 and 600 Langleys. This indicates that none of the run days was overcast
and that most of the days experienced typical summertime irradiation for
Piedmont North Carolina: sunny mornings with partly cloudy afternoons. This
data provides only a broad assessment of the light conditions on each run
day. The Appendixes D and E should be consulted for intensity-time data
which can be used for comparison and interpretation of light history and
corresponding specific chemical events.
The target initial conditions of 5.0 ppmC HC, 0.8 ppm NO, and 0.2 ppm
N02 may be compared with the measured values listed in Table 15. The agree-
ment is generally good, although three discrepancies should be noted. The
thiophene injection on 8-17-76 in Chamber 2 is high by a factor of two;
this was probably due to operator error. Comparison of target and measured
initial concentrations for pyrrole and methanethiol reveals that in four
out of five initial determinations, these compounds were not detected. This
is somewhat surprising in view of the absence of such problems in the earlier
bag studies. Concentration-time data for various reactants and products in
the chamber runs, however, do confirm the presence of photochemically
reactive species in the chambers after hydrocarbon injections. The observed
difficulties may have arisen during injection, sampling, or analysis and
remain to be resolved.
72
-------
Table 15. SUMMARY OF SELECTED SMOG CHAMBER RESULTSDAY 1
CJ
Hydrocarbon Date Dilution Chamber T ,ฐC ZSSa >:.SRb [HCJ C
Furan 7/l3-l5/7fc Static
lliiophene
Pyrrole
Propylene
Furan 8/17-19/76 Static
Thlophene
Pyrrole
Propylene
Furan 7/20-22/76 951'
Thlophene
Pyrrole
Propylene
Methanethiol 7/28-30/76 Static
Methyl disulfide
Methyl sulfide
Propylene
Methanethiol 8/10-13/76 95P
Methyl disulfide
Methyl sulfide
Propyleae
Urban Mix* 8/12-14/75 Static
Urban mlxr 7/28-30/75 95P
1
2
I
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
3
3
32 93 661 4.72
4.01
2.94
5.16
28 91 607 4.90
11.9
5.23
34 74 613 5.03
5.54
HO"
4.96
33 45 533 ND
ND
5.81
5.22
31 83 406 ND
7.17
5.24
4.14
32 71 545 3.81s
32 87 620 3.95"
INOI/
0.797
0.816
0.864
0.688
0.726
0.741
0.711
0.648
O.B45
O.B44
0.770
0.810
0.798
0.797
0.773
0.820
0.752
0.768
0.783
0.782
0.537
0.545
IN0211<1 Mc/nox 8xoe [Ojl^,, pf t0 * I "'V 1700
0.217
0.213
0.173
0.175
0.235
0.235
0.232
0.215
0.185
0.196
0.186
0.195
0.210
0.239
0.235
0.239
0.246
0.249
0.247
0.199
0.129
0.170
4.7
3.9
2.8
6.0
5.1
12.2
6.1
4.9
5.3
4.9
5.8
4.9
_
7.1
5.1
4.2
5.7
5.5
2.85
5.30
1.68
2.90
2.08
5.25
1.58
1.90
2.43
4.15
1.70
2.50
2.67
1.48
1.42
2.25
2.60
1.20
1.15
2.17
2.90
2.88
0.746
0.044
0.058
1.125
0.507
0.007
0.025
0.969
0.650
0.225
0.058
0.935
0.745
0.661
0.448
1.280
0.713
0.629
0.468
0.951
0.998
0.668
9.13
16.30
8.47
15.63
10.13
15.30
8.47
15.63
9.13
16.30
8.47
10.63
10.13
9.30
8.47
12.63
10.13
9.30
8.47
10.63
15.97
14.97
0.043
0.291
0.218
0.192
0.056
0.431
0.217
0.223
0.027
0.045
0.043
0.061
0.071
0.056
0.038
0.149
0.022
0.027
0.013
0.095
0.080
0.037
a v i
*NฐX
0.958
0.717
0.790
0.778
0.942
0.558
0.834
0.742
0.974
0.957
0.955
0.939
0.930
0.946
0.962
0.859
0.978
0.973
0.987
0.903
0.880
0.948
d I
I SO.)
0.185
0.227
0.125
1.610
1.890
0.490
1.021
1.230
0.357
__
~
cso J *sok
17.30 0.251
_ -_
17.30 0.08ฐ
13.30 0.11
10.13 O.J&*
9.30 0.38ฐ*1
9.47 0.17ฐ
_
10.13 0.2Oฐ*
8.30 0.17ฐ
8.47 0.14ฐ
_ _
-_
Percent possible Minutes of direct sunshine Measured at RDU airport (ref .
Summation of solar radiation for the day (dally irradlance), expressed
in Langleys (cal cm ); Measured by EPA, see text.
cUnlts - ppmC.
Units - ppป-
'Tine fro* first exposure to light (dawn in this case) until NO-NO.
crossover, expressed In hours.
Represents maximum observed concentration, not necessarily maximum
attained concentration.
*TiMe of day of lOJt expressed in hours.
oncentration of NO^ observed at 1700 EST.
Fractional conversion (loss) of NO between dawn and 1700 EST.
"Time of day of (SO^' *Prซ*sed in hours.
18). 11 la the yield of SO. determined at [SO.] and is a Measure of
SO. * * wax
molecules of SO, formed per Molecule of consumed sulfur.
i ^
Calculated based on a thlophene concentration estimated to be
1.0 ppปC at 17.3 hours.
*HU - not detected.
Pyrrole peak could not be clearly resolved.
Calculated baaed on an assumed cero concentration of the sulfur-
containing compound at the time of [SO.]
PUlluatlou initiated at approximately 0800 tST on Day 1.
''initial concentration assumed to be the target concentration of 5.0 ppmC.
rPor original data see ref 9 .
8DeterMiued as NMHC.
-------
Table 16. SUMMARY OF SELECTED SMOG CHAMBER RESULTSDAY 2
Hydrocarbon
Furan
Thlophene
l'yrrolซ!
Propylene
Furan
Thlophene
I'yrrole
Propylene
Furan
Thiophene
Pyrrole
Propylene
Hethanethiol
Methyl disulfide
Methyl sulfide
Propylene
Hethanethiol
Methyl disulfide
Methyl sulfide
Propylene
Urban mix
Urban mix'
^Percent possible
Date
7/13-15/76
8/17-19/76
7/20-22/76
7/28-30/76
8/10-13/76
8/12-14/75
7/28-30/75
Dilution Chamber T ,ฐC ZSb" >1SR (0 ) C |O ) c t. to t>e [SO )
Static
Static
95^
Static
H*
Static
951
I J2
It
I 29
2
1
i*
1 35
2
3
4
1 36
2
3
4
1 32
2
3
4
3 33
3 32
83 576 0.173
0.000
0.000
0.700
91 601 0.122
0.000
0.000
0.6O9
70 589 0.002
0.002
0.000
0.043
70 508 0.068
0.084
0.010
0.430
88 584 0.004
0.003
0.002
0.108
96 601 0.415
85 542 0.014
minutes of direct sunshine measured at RDU airport (ref 18)
SuBBStlon of solar radiation
in Langleys (cal
CUnits - PPM.
dTlปe of day of (I
for the day
cm *); neasured by EPA,
(dally irradiance)
see text.
, expressed
0.194 15.13
0.201 15.30
0.043 15.47
0.708 11.63
0.208 15.13
0.132 16.30
0.100 16.47
0.698 14.63
0.109 17.13
0.135 16.30
0.101 16.47
0.111 15.63
0.297 14.13
0.313 14.30
0.201 11.47
0.538 13.63
0.168 16.13
0.241 16.30
0.169 16.47
0.314 14.63
0.609 14.97
0.214 15.97
0.021
0.201
0.043
0.008
0.086
0.132
0.100
0.089
0.107
0.133
0.101
0.068
0.229
0.229
0.191
0.108
0.164
0.238
0.167
0.206
0.194
0.200
.8Net sulfur dioxide, ASO, -
n 2
(AS02 x lOO)/Day 1
lsฐ2lma
Konappllcable entries are
Jjl , expressed in hours.
^Chambers operated
approximately 0800
0.020
0.017
0.000
0.000
0.000
0.000
o.ooo
0.000
0.000
(so,)
2 max
X*
signified
(SO ] c tr,. ฃ ASO C'K XDay 1 fiSO ''
2 max SO. 2 t
0.090
0.191
G.003
0.056
0.000
0.000
0.027
0.032
0.014
- [so2J
14.30
16.30
__
10.13
14.13
15.30
12.47
in*
0.070
0.174
0.003
0.056
0.000
0.000
0.027
0.032
0.014
38
77
2
3
0
0
3
3
4
__
by blanks.
in static mode after the
EST on
day 2.
termination of
dilution at
H.t ozone. AO, - (O,^ - lOj]^.
Tine of day of [SC^J^,, expressed la hours.
'For original data see ref 9-
-------
Table 17. SUMMARY OF SELECTED SMOG CHAMBER RESULTSDAY 3
Ul
Hydrocarbon Date Dilution Chamber
Furan 7/13-15/76 Static
Thlophene
Pyrrole
Propylene
Furan 8/17-19/76 Static
Thlophene
Pyrrole
Propylene
Furan 7/20-22/76 S51
Thlophene
Pyrrole
Propylene
Hetbaaethlol 7/28-30/76 Static
Methyl diaulflde
Methyl aulflde
Propylene
Methanethiol 8/10-13/76 95J
Methyl dlaulflde
Methyl aulflde
Propylene
Urban mix!' 8/12-14/75 Static
Urban mix 7/26-30/75 95^1
1
2
3
4
1
2
3
4
1
2
3
4
I
2
3
4
1
2
3
4
3
3
a b r
T ,*C ZSS ESR [0 )
37 76 544 0.085
0.013
0.002
27 92 586 0.065
0.000
0.020
0.377
37 69 556 0.044
0.037
0.033
0.068
37 65 587 0.065
0.085
0.023
0.226
33 66 607 0.043
0.059
0.068
0.171
33 79 569 0.246
31 59 437 0.038
|0 ) C 10 d 40 C'e (SO | C (SO ] C tso f fiSO C'8 ZDay 1 480^
0.162
0.178
0.196
0.172
0.173
0.136
0.400
0.152
0.152
0.147
0.144
0.292
0.324
0.280
0.317
0.200
0.225
0.183
0.246
0.474
0.190
14.13
14.30
13.47
14.13
14.30
13.47
13.63
15.13
15.30
15.47
13.63
14.13
15.30
12.47
14.63
15.13
15.30
14.47
14.63
14.97
13.97
0.077
0.163
0.194
0.107
0.173
0.116
0.023
0.108
0.115
0.114
0.076
0.227
0.239
0.257
0.091
0.157
0.166
0.115
0.075
0.228
0.152
1
0.000
__
0.005
__
0.000
0.000
0.000
0.000
0.000
0.000
0.000
__
__
0.020
__
0.035
.
0.000
0.000
0.000
0.000
0.012
0.013
0.007
__
12.30 0.020
__
__
13.30 0.030
0.000
_
0.000
0.000
0.000
15.13 0.012
16.30 0.013
16.47 0.007
_
11
13
0
0
0
0
1
1
2
"Percent possible minutes of direct aunshlne measured at HDD airport (ref 18).*Het sulfur dioxide, ASO2 -
Summation of solar radiation for the day (daily irradiance), expressed
In'Langleya (cal c*~2); treasured by EPA, aee text.
ฐUnita PP".
Tiปe of day of (ฐ3)Baz> expreaaed in hours.
ozone
A03 '
*TlBe of day of
' >IP'""*ed ln
h(AS02 x 100)/Day 1 ISOj,)^.
Hlonapplicable entries are signified by blanks.
^Chambers operated in static node after the termination of dilution at
approximately 0800 EST on day 2.
for original data see ref 9.
-------
The injection temperature required for pyrrole (~131ฐ C) was the
highest of the three tested hydrocarbons. In addition, pyrrole is more
sensitive to air oxidation than either thiophene or furan, and the pure
liquid is known to oxidize readily in air (ref. 44). Rapid volatilization
of liquid pyrrole in the heated injection manifold may have led to
molecular decomposition. Furthermore, the use of stainless steel (tubing
and pump) in the sampling system may have promoted sample modification
or air oxidation of pyrrole. Finally, the GC column was not optimized
for pyrrole, but was selected to allow analysis of many of the test
species. Although a peak was observed on the GC trace at an appropriate
retention time for pyrrole, it was not clearly resolved from surrounding
peaks. The appreciable stability of pyrrole noted earlier in the bag
studies suggests that the difficulties may have arisen either during the
heated injection or during sampling.
Methanethiol was not detected during the runs which began on 7-28-76
and on 8-10-76. It is clear, however, that sulfur-containing species were
injected on these dates, based on the measured maximum SO- concentrations
presented in Table 15. On 7-28-76, neither methanethiol nor methyl
disulfide could be clearly resolved from the GC records of initial analyses
of Chambers 1 and 2. However, on 8-10-76, 7.17 ppmC of methyl disulfide
was determined in Chamber 2, and a peak having a retention time similar to
methyl disulfide was observed in Chamber 1. If the peak in Chamber 1 was
from the disulfide, then the initially injected methanethiol was converted
to and detected as approximately 3.8 ppmC of methyl disulfide. This
apparent thiol-disulfide conversion may have occurred during either
injection or sampling, although the possibility of conversion within the
smog chamber cannot be completely ruled out. Methanethiol was injected
as a pure gas at ambient temperature, and it may have been converted to
the disulfide during injection.
Comparison of the chamber runs with the low HC/NO ratio bag studies
X
presented earlier in Table 7 also supports the hypothesis of thiol to
disulfide conversion. In the bag studies, methanethiol was clearly detected
throughout the 1-day irradiation; the thiol system failed to achieve N0-N02
crossover and consequently produced very little ozone. The disulfide,
however, was consumed quickly, achieved early NO-NO- crossover, and produced
76
-------
approximately 0.2 ppm of ozone in the bag studies. In contrast, the thiol
and disulfide behaved similarly in the chamber studies: requiring short
times to NO-NO- crossover and producing maximum day-one ozone concentra-
tions of approximately 0.7 ppm.
Conclusive evidence defining the initial reactant identity or concen-
tration conditions in the pyrrole and methanethiol smog chamber experiments
is lacking. Results from these runs must be viewed with caution and must
await additional chamber experiments with improved analytical capabilities
before detailed interpretation can be undertaken.
First-Day Behavior
Many chemical transformations occur during the first day of each run.
This is evidenced by the behavior of reactant and product concentration-time
profiles presented in Appendix E. In addition, dilution is also initiated
on the first day of each of the dilution runs. The following paragraphs
will therefore address several characteristics of first-day behavior:
NO-NO, crossover times, ozone formation, NO conversion, sulfur dioxide
** X
formation, and first-day dilution effects.
N0-N02 Crossover Times
An indicator of the rate of the photochemical process is the time
required from the first exposure to light (dawn in this case) until the
concentrations of NO and NO- are equal. This parameter, 9 , is known as
the NO-NO- crossover time and is tabulated for each run in Table 15.
Crossover times should not be influenced appreciably by dilution in
runs involving highly reactive compounds which achieve rapid NO-NO- conversion.
For these systems, crossover occurs near the time that dilution is initiated,
and there is essentially no opportunity for dilution to influence the early
chemical behavior which determines the time to reach crossover. This is
supported by the results in Table 15. Except for thiophene, which was the
slowest to reach crossover of the tested compounds, crossover times for the
tested compounds are similar for both static and dilution runs.
The control hydrocarbon, propylene, required approximately 2.3 hours
past dawn for crossover, while the less reactive urban mix required 2.9
hours. Furan behaved similarly to propylene in each of the three cases.
Thiophene, as noted earlier, was the slowest of the tested compounds in
77
-------
promoting the photooxidation of NO and required over 5 hours to achieve
NO-NO., crossover. Pyrrole was the fastest heterocycle and required only
1.7 hours to reach crossover. Among the alkyl sulfides, methanethiol was
the least reactive. Methyl sulfide and methyl disulfide behaved similarly
and exhibited the shortest crossover times of the tested compounds.
Ozone Formation
The maximum first-day ozone concentration, [0_] , and the time of
j lUcLX
day that it was observed are tabulated for each chamber run in Table 15.
In addition to the chamber experiments, replicate bag studies were conducted
concurrently with the chamber runs on two occasions. Data from the bag
experiments are compiled in Appendix B, and [0_] data are compared for
j m&2c
selected bag and day-one static chamber runs in Table 18. These results show
reasonable agreement in all cases except for pyrrole and methanethiol. Similar
discrepancies for these two compounds, as noted in earlier discussions, were
tentatively attributed to injection anomalies in the chamber runs.
The results in Table 15 indicate that in the chamber runs propylene
produced the highest level of ozone, approximately 1.0 ppm. The static
urban mix run also produced approximately the same amount. Furan produced
the highest level of ozone among the heterocycles with maximum values
ranging from 0.51 to 0.75 ppm. The static thiophene run produced less
ozone than any of the other tested compounds and did not exceed the NAAQS
of 0.08 ppm. Although the results for pyrrole and methanethiol may be
questionable, low levels of ozone were produced in the chamber into which
pyrrole had been injected, and maximum ozone levels of 0.70 to 0.75 ppm
were found in the methanethiol runs. Methyl disulfide produced approxi-
mately 0.65 ppm ozone and methyl sulfide produced slightly less, 0.45 ppm.
Maximum ozone concentrations were achieved in the afternoon between
1300 and 1600 EST for static propylene runs. The urban mix behaved similarly
and achieved [03]max at 1600. The ordering of the times to [0_] for the
remaining test compounds roughly duplicated that for the times to N0-N09
crossover. Thiophene, the slowest compound to crossover, achieved [0ป1
L 3Jmax
after 1500; the other five compounds reached [0-1 by 1000.
3 max
NO Conversion
x
Based on NO concentrations determined prior to dawn at the start of
X
a run and at 1700 EST, fractional NO conversions, X^ , were calculated
x
78
-------
Table 18. COMPARISON OF OZONE FORMATION IN BAG AND CHAMBER STUDIES
Compound
Furan
Thiophene
Pyrrole^-
Propylene
CH3SH^-'
(CH3S)2-7
CI^SCHl'
21
Propylene
Chamber [0_]
L 3 max
0.507
0.007
0.025
0.969
0.745
0.661
0.448
1.280
Bag [03]max
0.952
0.0
0.290
1.113
0.015
0.594
0.580
0.945
Experiments Conducted on 8-17-76.
21
Experiments conducted on 7-28-76.
for day-one results. Conversion is the fraction of the initial NO that
X
cannot be accounted for as either NO or N0_ at 1700 EST. It should be noted
that the chemiluminescent NO readings were not corrected for interferences,
X
and therefore the values represent not only NO and N02, but also other
nitroxy species such as PAN, which may be detected as N02 (ref. 21).
Conversions of 75 to 85 percent were observed for static propylene runs,
and slightly higher values were observed in the urban mix runs. Thiophene,
because of its reduced reactivity in comparison to the other test compounds,
consumed only 60 to 70 percent of the initial NO . In contrast, furan,
raethanethiol, methyl disulfide, and methyl sulfide consumed approximately
95 percent of the initial NO by 1700. Based on the N02 concentration-time
profiles shown in Appendix E, the alkyl sulfides consume NO more quickly
A
than does furan. For the sulfides, within an hour after [03],nax (~HOO EST),
the [NOJ has dropped to low levels, and approximately 90 percent of the
NO has been consumed.
x
Free radical reactions resulting in the formation of PAN and nitric
acid are considered to be the major chemical sinks for NO in classical
79
-------
hydrocarbon-NO photochemical systems (ref. 4) and may be responsible
A
for the loss of NO in the propylene, urban mix, and furan experiments.
X
It is more difficult to speculate on the mechanism for NO removal
Jt
during the pyrrole and thiophene runs. For the alkyl sulfides, the
mechanism for NO removal is also unclear, although it may be postulated
x
to involve reactive free radicals which are generated by photooxidation
processes. The identity of these radicals is unknown at this time. In
view of the molecular structure of the sulfides, however, PAN formation
seems unlikely. Future studies will be required to determine if the
observed NO conversion is due to scavenging by organosulfoxy radicals,
x
incorporation into particles, or some as yet undefined mechanism.
Sulfur Dioxide Formation
Each of the sulfur-containing species tested in the chambers produced
SO,, as a product of photooxidation as indicated by pulsed UV fluorescence
detection. Maximum observed SO- concentration, [S09] ; the corresponding
time that the maximum was observed, tcn ; and the S0_ yield, Xcn , (molecules
oU~ Z oUn
of SO- formed per molecule of consumed sulfur at the time of the [S09] )
are presented in Table 15 for both static and dilution runs. In addition,
concentration- time profiles depicting NO, N0_, 0,, and S09 first-day
behavior for thiophene, methyl disulfide, and methyl sulfide-static runs
are presented in Figures 9, 10, and 11. Figure 12 presents NO, NO-,
and 0. data from a propylene run for comparison. The methane thiol run,
due to previously noted questions, is not considered in this comparison.
However, concentration profiles for methane thiol, found in Appendix E,
display the same general features as are depicted by the disulfide profiles.
Thiophene produced the smallest quantities of SO- of the sulfur-
containing compounds tested in the chambers. On 7-13-76 the [SO,,] for
2 max
thiophene corresponds to an approximate yield of 0.25. The increased [S09]
ฃ, I
on 8-17-76 in comparison to the value on 7-13-76 is due to the three-
fold increase in the initial thiophene concentration. In addition to
the increased [SO,] on 8-17-76, a reduced SO- yield, 0.08, was observed.
ฃ lUaX ฃ
The thiophene determinations shown in Appendix C indicate that a significantly
larger fraction of thiophene was consumed on the first day in the 8-17-76
run than in the 7-13-76 run. In contrast, increased SO- production was
noted on the second and third days of the 8-17-76 run. These observations
80
-------
suggest that the photooxidation of thiophene may produce a rather long-
lived sulfur-containing intermediate which can be further oxidized to
S02 on the second and third days.
Substantial amounts of S02 were produced by the alkyl sulfides on
7-28-76. Methyl disulfide and methanethiol produced 1.9 and 1.6 ppm of
S02 corresponding to approximate yields of 0.4 and 0.3. Although methyl
sulfide produced somewhat lower values, an [S02] of 0.5 ppm and a yield
of 0,2, this may be due to differences in the initial conditions. The
initial concentration of sulfur in this experiment was approximately one
half of the level employed in the thiol and disulfide runs.
The general shape of the S02 profiles may be examined in Figures 9,
10, and 11. Sulfur dioxide was detected as a reaction product simultan-
eously with the onset of NO oxidation. As the NO oxidation rate increases,
so does the production rate of SO,,. The largest increase in SO, concentra-
ฃป 4ป
tion appears to occur between the time of NO-NO- crossover and the time of
the ozone maximum. The concentration profiles indicate that [SO-] and
2 max
[0-] are achieved at approximately the same time. The [SO,.] for the
J max ฃ. max
slow-reacting thiophene occurs late in the day, at 1700 EST. Peak SO-
concentrations for the fast-reacting alkyl sulfides occur around 1000 EST.
These observations suggest that the same radicals which are responsible
for NO oxidation and ozone formation by these sulfur-containing compounds
are by analogy also responsible for the concurrent SO- formation.
After the maxima, SO- and 0- profiles are approximately parallel
for the next few hours. Near dusk, however, a marked difference in 0-
and SO- behavior occurs. Whereas the 0- continues to decay at approximately
the same rate into the night as it did in the afternoon, the S02 decay rate
increases sharply. An inflection point occurs shortly after sundown at
approximately 2000 EST. There are several possible explanations for this
phenomenon.
1. If SO- continues to be produced photo chemically after [S0lป tnen
the slow decay until sundown represents only a small imbalance between
the relative strengths of the source and sink mechanisms. After sun-
down, the photochemical source strength is reduced to zero, and the
sink dominates the behavior.
2. A similar explanation can be postulated to involve a light-mediated
equilibrium between S02 and other as yet undefined species.
81
-------
IM'I'I'I'IM'I'I'I'I'I'I'I'I'I'I'I
07/13/76 #2 THIOPHENE DRY 1 OF 3
1.1
1.2
1.0
0.8
0.6
CO
TJ
9 12 15
TIME OF DRY CEST)
21
0.2
0.0
Figure 9. Concentration profiles for first day (7-13-76) of thiophene-NO, static smog chamber experi-
ment. Initial conditions: 4.01 ppmC thiophene; 0.816 ppm NO; 0.213 ppm N02 In RTI outdoor
smog chamber No. 2.
E
Q.
O.
O
d
l.f
1.2
1.0
0.8
0.6
-' I ' I ' I ' I ' I ' I ' I ' I ' IJ I ' I ' I ' I ' I ' I ' I ' I ' I ' I '
0.2
0.0
07/28/7
H3SSCH3
DRY 1 OF 3
9 12 15
TIME OF DRY CEST)
21
Figure 10. Concentration profiles for first day (7-28-76) of methyl disulfide-NOx static
chamber experiment. Initial conditions: 5.0 ppmC (target) methyl disulfide;
0.797 ppm NO; 0.239 ppm N02 in RTI outdoor smog chamber No. 2.
2.0
1.8
1.6
1.2 P
1.0 |
0.8*
0.6
0.1
0.2
0.0
smog
82
-------
E
Q.
a
I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I ' I I I ' I I I ' I M
DflY 1 OF 3 -
9 12 15
TIME OF DRY CEST)
18
Figure 11.
Concentration profiles for first day (7-28-76) of methyl sulfide-NOx static smog
chaaber experiment. Initial conditions: 5.81 ppmC methyl sulfide; 0.773 ppm
NO; 0.235 ppm N02 in RTI outdoor smog chamber No. 3.
l.f
MI'I'I'MI'I'I'I'I'I'IM'I'I'I'I'I'IH'I'I'IM'
07/28/76 M PROPYLENE DflY 1 OF 3
9 12 15
TIME OF DflY CEST)
18
21
Figure 12. Concentration profiles for first day (7-28-76) of propylซne-NOx static smog
chamber experiment. Initial conditions: 5.22 ppmC propylene; 0.820 ppm
NO; 0.239 ppm N02 in RTI outdoor smog chamber No. A.
83
-------
3. Another hypothetical explanation relies on the increased rate of
ambient cooling that occurs shortly after dark. Cox and Sandalls
(ref. 34) have observed hygroscopic, sulfate aerosol formation during
the photooxidation of methyl sulfide. The natural ambient cooling
of the humid and presumably particle-laden atmosphere could result
in an enhanced rate of SO,., loss.
4. The observed behavior may be due to wall effects. The chamber volume
is stirred continuously. This mixing may facilitate an exchange
between the bulk chamber volume and the chamber walls. If wall
temperature is reduced in comparison to the chamber contents by ambient
cooling, then increased rates of surface condensation and SO- removal
may result .
Additional experiments are needed to resolve these points.
First-Day Dilution Effects
The highly reactive furan, pyrrole, me thane thiol, methyl disulfide,
methyl sulfide, propylene, and urban mix, achieved NO-NO,, crossover
within 3 hours after dawn and exhibited similar crossover times for both
dilution and static runs. This is not surprising, because, for these com-
pounds, crossover was achieved within an hour of the time that dilution
was initiated. The slow-reacting thiophene, however, achieved crossover
1 hour earlier with dilution than without. The reduction of the time to
crossover may be due in part to the role that dilution plays in reducing
the NO concentration in addition to the normally occurring reduction of
[NO] by photooxidation processes. This is in agreement with the findings
of Fox et al. (ref. 45).
In general, the compounds that achieved early [0.] in static runs
j
produced similar, but only slightly reduced, maximum ozone levels with
dilution. Dilution reduced [0^] levels by 17 and 26 percent in propylene
runs and by 33 percent in the urban mix runs. No trends are apparent with
furan or pyrrole. For methanethiol, methyl disulfide, and methyl sulfide
the [0-1 values were constant within + 5 percent for static and dilution
j nici x "***
runs.
Thiophene was the exception and produced in excess of a fivefold
increase in [0.1 with dilution. In the static runs, less than 0.05
J IHcL2C
ppm 03 was formed; whereas, the first-day [03lma was increased significantly
84
-------
to 0.23 ppm for the dilution run. It is recognized that the behavior of
maximum levels of ozone is highly nonlinear with respect to precursor con-
centrations. Nonlinear behavior with dilution has also been noted in this
laboratory: dilution of an (^-producing photochemical system does not
reduce the [O^^^ in direct proportion to the extent of dilution (ref. 9).
The characteristics of the thiophene run are similar to another documented
observation of an increased [t>3] with dilution (ref. 45). Obtaining
this behavior apparently requires a slow-reacting test compound or
initial conditions which promote slow behavior.
The time required to achieve [0,] for propylene was reduced with
dilution. Ozone maxima occurred after 1300 EST in the static runs and
occurred prior to 1100 with dilution. For the other compounds, the times
to [0_] were not sensitive to dilution. It is likely that the compounds
j msx
that achieved early [0,] values were unaffected by dilution because the
j ulcuC
maxima were achieved near the time that dilution was initiated. The
[0_] for thiophene under both static and dilution conditions occurred
o max
late in the solar day. The decrease in light intensity in the afternoon
was probably a major factor in determining the time of [0,] in both of
j nm jC
these runs.
Maximum SCL concentrations and yields were reduced by approximately
33 percent under dilution conditions. For the fast-reacting alkyl sulfides,
the time to achieve [SO.] was relatively insensitive to dilution and was
2Jmax J
reduced by approximately 1 hour with dilution. In the thiophene runs,
although timing of the [0_] was insensitive to dilution, the time of
3 m&x
[S0_] was reduced by 4 hours with dilution. Ozone is formed by a chain
j- HlcL3C
reaction formation mechanism, which can continue to generate 0. in spite
of simultaneous precursor removal. Although S02 formation may also involve
reactions of chain-generated free radicals, S02 production is limited by the
amount of sulfur initially present in the reacting mixture. Dilution should,
therefore, exert a pronounced effect on the timing of [S02]max for the
slow-reacting thiophene.
Second- and Third-Day Effects
Selected second- and third-day results for the chamber runs are presented
in Tables 16 .and 17. A key parameter in these results is the net ozone, AO,,
85
-------
produced during each day. Net ozone is calculated for any one day by sub-
tracting the morning minimum ozone concentration from the maximum ozone
concentration achieved on that day (A0_ = [0_] - [CL] . ). The net ozone
j -1 max 3 rain
and the maximum values are identical on the first day because the morning
minimum is zero. Net ozone concentrations are summarized in Table 19 for
each day of both static and dilution experiments.
Ozone Formation
In the static experiments, propylene generated the largest first-day
AO levels of the tested compounds. Ozone concentration on the second and
third days of the propylene experiments, however, tended to decay from the
elevated first-day levels, and synthesis was indicated by only small values
of AO . Furan behaved similarly to propylene and generally produced second-
and third-day AO values of less than 0.10 ppm. On the third day, furan
produced A0_ values that tended to be slightly larger than second-day values.
Although the pyrrole results may be questionable, as was noted earlier,
trends in the A0_ values are evident. In both the static and dilution runs,
net ozone levels increased from the first, to the second, to the third day.
The NO concentration in the pyrrole experiments displayed a marked increase
after the N0ป peak on 7-13-76 and 8-17-76 (see the concentration profiles
in Appendix E). Although the trends observed in net ozone cannot be ex-
plained, they may be related to the peculiar NO behavior noted above.
The open-chain sulfur species produced not only A0_ values of 0.4
to 0.7 ppm on the first day, but also considerable amounts of ozone on
the subsequent days. Methanethiol and methyl disulfide produced approxi-
mately equal quantities on the second and third days, 0.23 ppm. The net
ozone produced on the third day exceeded the second-day value by only
0.01 ppm in the methyl disulfide runs; whereas, a more substantial
excess of 0-07 ppm was noted for methyl sulfide.
In contrast to the other test compounds, thiophene produced more ozone
in static runs on the second day than on the first day. In two separate
static experiments thiophene produced net ozone levels of 0.20 and 0.13 ppm
on the second days in comparison to the first day values of 0.04 and 0.01.
This is over a fivefold increase from the first to the second days. Figure
ซ
13 depicts 03 profiles for thiophene runs conducted under static and dilution
conditions. The second-day increase in ozone is dramatically illustrated
86
-------
Table 19. NET OZONE PRODUCED IN BOTH STATIC AND DILUTION CHAMBER RUNS
Compound
Furan
Thiophene
Pyrrole
Methane thiol
Methyl Diaulfide
Methyl Sulfide
Propylena
Urban Mix
Operation
frV/
Sr
ST/^
y-
ftSULei
D^
s|-(
&-
s^(
D^"
^
D
-3.4.6/
D=UZ/
S^
D*/
Net Ozone (AO-),^ ppm
Day 1
0.746, 0.507
0.650
0.044, 0.007
0,225
0.058, 0.025
0.058
0.745
0.713
0.661 '
0.629
0.448
0.468
1.125, 0.969, 1.280
0.935, , 0.951
0.998
0.668
Day 2
0.021, 0.086
0.107
0.201. 0.132
0.133
0.043, 0.100
0.101
0.229
0.164
0.229
0.238
0.191
0.167
0.008, 0.089, 0.108
0.068, , 0.206
0.194
0.200
Day 3
0.077, 0.107
0.108
0.163, 0.173
0.115
0.194, 0.116
0.114
0.227
0.157
0.239
0.166
0.257
0.115
10 /
* , 0.023, 0.091
0.076, , 0.075
0.228
0.152
-Results are summarized from Tab-lea 15, 16. and 17.
S - Static run; D - Dilution run.
First entry undar each day from experiment conduct ad on 7/13-15/76.
Second ซntry undar each day from experiment conducted on 8/17-19/76.
First entry undar each day from experiment conducted on 7/20-22/76.
Entry from experiment conducted on 7/28-30/76.
'Entry fwซ experiment conducted on 3/10-13/76.
Entry from experiment conducted on 3/12-14/75.
Entry from experiment conducted on 7/28-30/75.
'ozone decayed aonotonically and therefore a A03 could not be determined.
for the static run. Third-day ozone levels are reduced only slightly from
the second-day levels. It may be postulated that the increased second- and
third-day ozone levels were due to the low reactivity of thiophene. Because
most of the first-day sunlight was required for photooxidation of NO, the
low first-day ozone levels were probably limited by the duration of irradiation.
On the second day, [NO-] exceeded [NO], and the remaining thiophene, along
with any remaining reactive intermediates generated on the first day,
apparently existed in quantities conducive for substantial ozone generation.
One of the causes of the high rural oxidant problem may be the transport
of a partially spent system of ozone precursors from urban areas. In such
systems, low reactivity hydrocarbons and reactive intermediates are likely
to play a significant role in ozone generation within an air parcel on the
second and third days downwind from the source. A possible example is seen
in the AO values from the urban mix experiments presented in Table 19.
The sulfur-containing compounds exhibit A03 behavior similar to the urban
87
-------
mix, suggesting that such compounds can also exert a significant influence
on ozone formation downwind from sources.
A comparison of the times required to achieve [03lmax on each day can
be made from the results of Tables 15, 16, and 17. The time to reach [03
was delayed by up to 6 hours on the second day relative to the first day.
Thiophene, however, exhibited no appreciable differences in the times to
[0_] . In most cases, day-two and day-three [0,] occurred after 1400
j max j max
EST. For the heterocycles in static runs, second-day [0_] occurred later
j uicLX
in the afternoon than the third-day [CL] values. The open chain sulfides,
j
however, exhibited no appreciable timing differences between days two and
three. Dilution had a noticeable effect on the day-two times of ^^max*
delaying their occurrence by an hour in comparison to those on the third
day. In comparison with the static runs, dilution delayed the time of
[0_] on both the second and third days. Explanations for these observa-
3 max
tions are not immediately apparent.
The effects of dilution on net ozone production may be examined using
the results in Table 19. In general, the net ozone levels generated on the
first day exceed those produced on the second and third days. In most cases,
second-day levels are slightly higher than third-day levels. This may suggest
a decrease in ozone production on subsequent days downwind from sources of
these compounds. Although most A0_ levels in dilution runs are reduced in
comparison to static values, they are never reduced in proportion to the
extent of dilution and are generally reduced by less than 40 percent. This
finding demonstrates the nonlinear behavior of ozone formation in air parcels
which are experiencing dilution.
Fuel conversion technology is in the early stages of its development.
Additional research is required to define future emissions rates of the
tested compounds from fuels-conversion facilities. The degree to which our
experiments will mimic areas downwind from such facilities is therefore
also uncertain. Nevertheless, the test compounds, with the exception of
propylene, produced net ozone levels in excess of the NAAQS of 0.08 ppm on
the second and third days in both static and dilution experiments. This
suggests that under the proper conditions, the tested compounds can have
a considerable impact on ozone levels generated downwind from the point
of their emission. The behavior of these compounds should therefore be
considered in detail if significant anthropogenic sources are to be constructed.
88
-------
Sulfur Dioxide Formation
Each of the sulfur-containing compounds produced considerable quantities
of S02 as a reaction product. Among these compounds, only thiophene pro-
duced significant quantities of S02 on the second and third days. Maximum
S02 levels achieved on days two and three are presented in Tables 16 and 17.
The open-chain sulfides apparently react quickly, exhausting the
initially present sulfur compound by the end of the first day. In the static
runs, maximum SCL levels between 0 and 60 ppb were generally observed on the
second day. Peak concentrations on the third day ranged from 0 to 15 ppb.
The net S02, ASCL, produced on the second and third days are generally less
than 3 percent of the day-one values.
Thiophene, as noted previously, reacts more slowly than the tested
open-chain sulfides. Figure 14 presents SCL profiles for thiophene runs
conducted under static and dilution conditions. In the 7/13-15/76 static
experiment, ASCL values on the second and third day correspond to 38 percent
and 11 percent of the first day maximum. These percentages are significantly
larger than the 3 percent noted earlier for the alkyl .sulfides and emphasize
the increased multiple-day SO- production potential of thiophene.
The above observations indicate that the slow-reacting sulfur compound,
thiophene, can produce significant quantities of both CL and SCL in multiple-
day static irradiations. Although particle formation was not investigated
in this study, it is likely that sulfate aerosol is formed in the photo-
oxidation of the sulfur-containing compounds. Emission levels of thiophene
are poorly defined, although they are expected to be low. The results
of this study suggest that if emissions from future fuel conversion
facilities include sulfur-containing organics such as thiophene, then under
stagnant conditions, local areas face the possibility of reduced air
quality in the form of increased levels of CL, SCL, and sulfate aerosols.
Dilution reduced the maximum SCL concentrations achieved by the sulfur-
containing species on the first day by 33 percent in comparison with the
static runs. Net SCL levels on subsequent days were reduced to essentially
zero by dilution. The extreme sensitivity of [S02J behavior to dilution
is clearly evident in Figure 14 and may be contrasted to the ozone profiles
shown in Figure 13 for the same runs. As noted earlier, the different
89
-------
o
Q.
2
O
t l
1
ce
i
UJ
C_J
z
0
^
CD
. C. >J U
.225
.200
.175
.150
.125
.100
.075
.050
.025
0.
TITITITITlTITITITITITITITITITITITITITITITITITITI'I'I'I'I'I'I'I'I'I'I'I'I'I'l'I'I'l'I'l'I'I'I'l'
o
0
o xx
X
0 x
X x
x
0 X
- x oฐ -
X 0
- o -/V
0 0 XQ
o ox
x o
" ^n X
-
X X 0
0 x ฐ0 x
- *xx o o x ฐ03 -
^ 0 X * ฐฐ
o x x Xx
x o ปx x
WblihlikkhM'1'''1'1'''1^
- .225
-1 -200 p
.175 8
- .150
o
12 18 0 6 12 18 0 6
TIME OF DflY (EST)
12 18
.125 |
.100 i
.075 i
.050
.025
0.
Figure 13.
Ozone concentration profiles for three-day thiophene-NQg runs conducted in RTI outdoor smog
chamber No. 2. Static run (x) 7/13-15/76; initial conditions: 4.01 ppmC thiophene and
1.029 ppn NO,. Dilution run (O) 7/20-22/76; initial conditions: 3.54 ppmC thiophene and
1.040 ppm NO^; dilution was started at 0800 EST, 7/20 at a rate auch that 95Z of the original
chamber contents would be replaced by purified air whan dilution was stopped at 0800 EST, 7/21.
. cou
.225
.200
e
S .175
.
ง .ISO
M
i .125
QC
\
2 .100
0
I -075
ฃ -050
V J
.025
n
^ITITITITITITITITITITITITITITITITITITITITITITITITITITITnTriTITITITITIT
_ _
_ _
ปxป
ซ K
X
. _
. x5 X .
H *1
X
X X
K _JsQ4^*t ^
- ซ ' ซ :ซ x \
X ป
- . , ซ ซ
-xxxx
"" x % ""xx* * x "~
iimhib.i.iiiM^^^
. cou
.225
.200 p
/^
.175 o
o
.150 2
1
.125 ง
i
14
.100 i
075-
3
.050
.025
n
0 6 12 18 0 6 12 18 0 6 12 18
TIME OF DflY (EST)
Figure 14. Sulfur dioxide concentration profiles for three-day thiophene-NO* runs conducted in RTI
outdoor smog chamber Ho. 2. Static run (X) 7/13-13/76; initial conditions: 4.01 ppnC
thiophene and 1.029 ppa NO,. Dilution run (X) 7/20-22/76; initial conditions: 5.54
ppoC thiophene and 1.040 ppm HO*; dilution was started at 0800 EST, 7/20 at a rate such
that 9SZ of the original chamber contents would be replaced by purified air when dilution
was stopped at 0800 EST. 7/21.
90
-------
shapes of these curves suggest different mechanisms of SO- and 0- formation.
Although S0_ may be formed by oxidation steps involving reactions with
.free radicals which are generated by photochemical chain reactions, the
maximum SCL levels are limited by the initial amount of the sulfur-
containing reactant. In contrast, photochemical chain reactions can
produce many molecules of ozone for each consumed precursor molecule. The
efficiency of this process changes not only with absolute concentration of
the ozone precursors, hydrocarbons, and NO , but with their ratio as well.
Jt
The results of Figures 13 and 14 are perhaps the first to contrast the
reactant-limited behavior of a secondary pollutant, in this case SO-, with
the simultaneous nonlinear precursor-product behavior of the secondary
pollutant, ozone.
91
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95
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APPENDIX A
Environmental Conditions
for Irradiated Bag
and Chamber Studies
96
-------
APPENDIX A. ENVIRONMENTAL CONDITIONS FOR IRRADIATED
BAG AND CHAMBER STUDIES
Date Type of Study3
6-2-76
6-8-76
6-9-76
6-10-76
6-22-76
6-29-76
7-1-76
7-13-76
7-14-76
7-1 c -7 /
ID to
7-16-76
7 on *?ฃ
-ZU /D
7-21-76
7-23-76
7-28-76
7-29-76
7-30-76
8-10-76
8-11-76
8-12-76
8-17-76
8-18-76
8-19-76
B
B
B
B
B
B
B
C
C
C
B
C
C
C
B
C,B
C
C
C
C,B
C
C,B
C
C,B
Time of Initial ^max
Exposure, EST ฐC
0900
0945
1000
0820
0925
1002
0945
0505e
05056
05056
1035
0515e
0515e
0515e
0920
05256
0525e
0525e
0535e
0535e
0535e
0540e
0540e
05406
29
32
33
33
29
33
29
32
32
37
35
34
35
37
34
33
36
37
31
32
33
28
29
27
%ssb
32
89
40
28
24
66
55
93
83
76
71
74
70
69
34
45
70
65
83
88
66
91
93
92
"*12C
150
165
144
226
116
152
170f
110
152
241
268
265
283
ZSRd
376
646
491
470
404
633
516
661
576
544
581
613
589
556
481
533
508
587
406
584
607
607
601
586
aB = Bag Study; C = Chamber Study
Percent possible minutes of direct sunshine measured at RDU Airport.
Summation of solar radiation from beginning the bag exposure until 1200
EST; expressed in Langleys (cal cm~2); measured at EPA.
dSummation of solar radiation for the day (daily irradiance); expressed in
langleys (cal cm~2); measured at EPA.
eDawn; based on solar radiation data; accurate to +10 minutes.
fNonapplicable entries are denoted by blanks, " ".
97
-------
APPENDIX B
Results of Bag Studies
98
-------
Appendix B. RESULTS OF BAG STUDIES
Test description3
5-25 to 5-28-76
Dark stability
Furan
1300 (5-25), injection
5-26 to 6-1-76
Dark stability
Thiophene
1145 (5-26), injection
5-27 to 6-1-76
Dark stability
Pyrrole
1500 (5-27), injection
6-2-76
Ozone formation
Furan
0900
6-2-76
Ozone formation
Furan
0900
6-2-76
Light stability
Furan
0900
6-2-76
NO oxidation (light)
NO NO
11 V f LlUn
0900 (light)
6-2 to 6-3-76
Dark reactivity with 0-
Furan
1225 (6-2), furan
injection
Time of HC
Analysis,
EST
1415 (5-25)
1700
0950 (5-26)
0930 (5-27)
1100
1115
0930 (5-28)
1315
1300 (5-26)
1000 (5-27)
1130
1300
1000 (5-28)
1330
1330 (6-1)
1600 (5-27)
0900 (5-28)
1300
1000 (6-1)
0745
1120
1340
0815
1140
1345
1455
rtQ Ort
0820
1100
1325
1440
1255 (6-2)
1520
0950 (6-3)
1125
[HC]
ppmC
10.8
10.7
10.8
10.0
10.4
10.6
9.60
9.58
9.80
9.67
10.1
9.88
9.88
9.53
8.88
11.2
10.3
9.92
8.58
9.62
10.4
1.38
0.61
0.48
9rt
U
8.62
8.53
8.38
2.27
1.36
0.37
0.32
Time of [NO] [N02] [NOJ [O.j] [S02J
Analyses, ppm ppm ppm ppm ppm
EST
0837 1.37 0.310 1.680
1054 0.572 0.572 1.067
1232 0.456 0.455 1.133
1410 0.280 0.280 1.075
0844 0.370 0.075 0.445
111^ n 1 /. o nil, a n i ni
LH Tl 1 ฃCT
1IUU l./OU U.J// 1.0 Jฃ
1255 1.246 0.372 1.618
i i /. * i ortrt rt -i/\rt i cf\n
14 4 Z 1 . iUU U.jVU J..J7U -
1050 (6-2) 0.813
1237 0.769
1330 0.639
1500 0.524
99
-------
RESULTS OF BAG STUDIES
Test description
6-2 to 6-3-76
Dark reactivity with 0.
Furan
1225 (6-2), furan
injection
6-3 to 6-4-76
Dark reactivity with 0-
Pyrrole, 0.
0710 (6-4)7 pyrrole
injection
6-3 to 6-4-76
Dark reactivity with 0-
Thiophene, 0.
0705 (6-4), Ehiophene
injection
6-3 to 6-4-76
0., decay (dark)C
ฐ3
6-3 to 6-4-76
0., decay (dark)
ฐ3
6-8-76
Ozone formation
Thiophene
0945
6-8-76
Ozone formation
Thiophene
0945
6-8-76
Light stability
Thiophene
0945
Time of HC
Analysis ,
EST
1320 (6-2)
1510
1000 (6-3)
1130
0900 (6-4)
0915 (6-4)
1005
1135
0900
1100
1220
1355
1530
0930
1114
1245
1435
1655
083 5
W0*J J
1050
1235
1350
i 59";
[HC]
ppmC
1.89
1.10
0.19
0.18
4.93
4.59
4.35
9.42
8.85
7.46
5.65
4.80
10.6
9.06
6.51
4.04
3.73
10 1
J.U * J.
9.90
9.56
9.16
a IA
Time of [NO] [NOj]
Analyses, ppm ppm
EST
1055
1240
1335
1455
1402 (6-3)
0750 (6-4)
0835
0910
1005
1430 (6-3)
1530
1602
0745 (6-4)
1205
1355
1348 (6-3)
1552
0755 (6-4)
1217
1348 (6-3)
1540
0800 (6-4)
1228
1419
0901 1.612 0.454
1056 1.480 0.470
1203 1.110 0.788
1348 0.476 1.094
1510 0.196 1.112
0935 0.440 0.124
1045 0.466 0.004
1225 0.198
1415 0.172
i e /. r\ r\ t\f f.
001 1
1055 0.012
1 Itn j
1355 0.010
[N0x] [031 [S02J
ppm pprc PPm
0.933
0.900
0.751
0.651
1.092
0.880
0.531
0.428
0.344
1.183
1.170
1.165
0.847
0.751
0.742
0.666
0.660
0.573
0.540
1.220
1.210
1.006
0.992
0.988
2.066
1.950
1.898
1 CIA
1.308
0.564
01 -I M
.470
0.198 0.276
0.172 0.173
0.066 0.131
0.012 0.010
d 0,008
0.010 0.010
n AI o n AArt
100
-------
RESULTS OF BAG STUDIES
Teat description3
6-8-76
Ozone formation
Furan
0945
6-8-76
NO oxidation (light)ฐ
NO, N0_
0945
6-8-76
Clean air irradiation0
Clean air
0945
6-9-76
Clean air irradiation
Clean air
1025
6-9-76
NO oxidation (light)
NO, NO.
1025 i
6-9-76
Ozone formation
Furan
0949
6-9-76
Ozone formation
Pvrrole
1002
6-9-76
Ozone formation
Pyrrole
1025
Time of HC [HC] Time of [NO] [N'02]
Analysis, ppmC Analyses, ppm ppra
EST EST
0915
1108
1210
0830
0840
0910
0950
1020
1125
0905
1130
0930
1110
1140
9.51 0914
1105
1210
1415
1530
0925
1105
1230
1347
1520
0939
1050
1155
1405
1520
1019
1045
1240
1355
1501
1010
1045
1230
1328
1524
10.6 0945
10.8 1102
10.3 1229
5.12 1328
0.21 1514
11.4 0954
1102
1216
1350
1501
10.4 1015
1055
1240
1355
1514
1.606
1.626
d
1.602
1.598
d
HBH^H>
-
__
MIIIM^M
__
_
1.732
1.688
1.626
1.596
1.516
1.692
1.700
0.408
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
d.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
436
d
606
384
264
474
d
458
440
d
006
008
016
012
010
012
040
0446
058*
324
350*
492e
512e
440
390
668
812
686
414
282
524e
358e
468
320
080
068
070
076
058
ppnK
2.
0.
0.
0.
2.
2.
2.
0.
0.
0.
0.
0.
0.
0.
0.
0.
2.
2.
2.
2.
1.
2.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
042
d
606
384
264
100
d
060
038
d
006
008
016
012
010
012
040e
044e
G58e
056
038e
nae
108ซ
956
082
668e
812
686
414
982
524
358e
468
320
488
068
070
076
058
(o3l [so,i
ppn ?pr.'
>1
>1
>1
>1
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
0.
0.
0.
0.
0.
0.
0.
0.
..4
..4
..4
..4
006
012
013
014
028
030
034
260
303
215
126
305
272
286
268
310
385
371
371
101
-------
RESULTS OF BAG STUDIES
g
Test description
Time of HC
Analysis,
EST
[HC]
pproC
Time of [NO] [N02]
Analyses, ppm ppm
EST
[NOJ [03J [S
ppn ppp pp
6-9-76
Light stability
Pyrrole
1025
0920
1105
1230
1405
1550
11.
9.
9.
8.
8.
1
90
66
84
04
1005
1033
1204
1349
1524
0.032
0.016
0.020
0.082
0.064
0.032
0.016
0.020
0.082
0.064 -
6-10-76
Ozone formation
Fur an
0820
0720
0935
10.1
2.90
0710
0926
1100
1226
1350
1.154
0.264 1.418
0.804 0.804 0.523
0.372 0.372 0.928
0.272 0.272 1.066
0.170 0.170 1.013
6-10-76
Ozone formation
2-Methylfuran
0820
0725
0940
10.8
0715
0931
1103
1230
1353
1.134
0.264
0.708
0.676
0.680
0.590
1.398
0.708
0.676
0.680
0.590
0.881
0.876
0.924
0.925
6-10-76
Ozone formation
2-Methylfuran
0820
0730
0945
1245
1425
10.8
3.18
0.73
0.28
0720
0936
1110
1238
1359
0.292
0.062
0.240
0.212
0.240*
0.190
0.354
0.240e
0.212
0.240*
0.190
0.046
0.029
0.065
0.088
6-10-76
Ozone formation
2,5-Dimethylfuran
0820
0815
1025
15.9
0755
1013
1137
1306
1423
1.114
0.318
0.928
0.826
0.796
0.802
1.432
0.928
0.826
0.796
0.802
0.673
0.716
0.816
0.841
6-10-76
Ozone formation
2,5-Dimethylfuran
0820
0820
1030
10.4
0.09
0759
1017
1141
1308
1428
0.290
062
2406
248e
246e
0.2866
0.352
0.2406 0.026
0.248 0.129
0.2466 0.240
0.2866 0.297
6-10-76
Ozone formation
Thiophene
0820
6-10-76
Ozone formation
2-Methylthiophene
0820
0735
1005
1250
1430
0740
0955
1255
1440
10.1
9.71
5.88
4.25
10.1
8.92
1.52
1.00
0727
0948
1115
1240
1404
0734
0946
1120
1245
1407
1.108
0.994
0.556
1.184
0.800
0.274
0.366
0.712
0.944
0.576
0.270
0.588
0.824
0.602
382
360
268
944
0.538
0.576
1.454
1.388
0.824
0.602
0.538
0.100
0.256
0.176
0.391
0.347
102
-------
RESULTS OF BAG STUDIES
Test description
6-10-76
Ozone formation
2-Methylthiophene
0820
6-10-76
Ozone formation
Pyrrole
0820
6-17 to 6-18-76
Dark reactivity with NO
Pyrrole, NO,
ฃ
6-17 to 6-18-76
Dark reactivity with NO
Thiophene, NO-
&
6-17 to 6-18-76
Dark reactivity with NO^
Fur an, NO-
* 2
6-17 to 6-18-76
Dark reactivity with N0x
NO. (no added hydrocarbon)
Time of HC
Analysis,
EST
0750
1007
1450
0800
1020
0925 (6-17)
1025
1220
1415
0915 (6-17)
1035
1200
1415
0900
1025
1235
1430
[HC]
ppmC
18.6
11.5
0.44
12.2
9,37
d
3.81
8.45
8.81
8.76
8.71
8.69
10.2
10.3
10.3
9.99
Time of
Analyses ,
EST
0740
0953
1125
1253
1411
0750
1004
1133
1301
1419
0927
(6-17)
1156
1305
1358
1455
0745
(6-18)
0912
(6-17)
1149
1250
1345
0733
(6-18)
0903
(6-17)
1153
1309
1402
1441
0755
.(6-18)
0800
(6-17)
1025
1349
1433
0750
(6-18)
[NO]
ppm
0.316
___
1.186
_
____
0.004
0.004
d
0.004
0.004
0.014
___
^-^
i
[NO,]
ppn"
0.080
0.210
0.128
0.120
0.094
0.316
0.394
0.348
0.224
0.170
1.1668
1.162
d
1.026
1.022
0.892
0.958
A
0.932e
0.924*
0.9126
0.772
d
1.182
1.162
1.144
1.111
0.508
0.980*
0.986
0.948
0.930
0.748
[N'O.J (03I [SO,]
ppz" ??n ppa~
0,396
0.210 0.094
0.128 0.044
0.120 0.021
0.094 0.013
1.502
0.394 0.598
0.348 0.627
0.224 0.614
0.170 0.574
1.1706
1.166
d
1.030
1.026
0.906
0.958
0
0.932
0.924e
0.912*
0.772
d
1.182
1.162
1.144
1.111
0.508
0.980e
0.986
0.948
0.930
0.748
103
-------
RESULTS OF BAG STUDIES
Test description
6-17 to 6-18-76
NO oxidation (dark)
NO
6-22-76
Ozone formation
Toluene
0925
6-22-76
Ozone formation
Toluene
0925
6-22-76
Ozone formation
Ethylbenzene
0925
6-22-76
Ozone formation
Ethylbenzene
0925
6-29-76
Ozonfi f onnfl t i.on
Thiophene
1002
6-29-76
Ozone formation
Thiophene
1002
6-29-76
Ozone formation
2-Methylthiophene
1002
Time of HC [HC]
Analysis, ppmC
EST
0835
1240
1435
0850
1215
1500
0905
1350
1550
0915
1305
1510
0855
1145
1405
1615
0905
1200
1415
1625
0910
1220
1425
12
10
8
11
8
7
11
9
9
11
7
5
9
8
4
3
7
3
2
1
8
3
.0
.9
.77
.2
.83
.16
.9
.45
.39
.4
.99
.56
.48
.39
.83
.27
.83
.76
.14
.66
.91
.11
Time oE [NO]
Analyses, ppm
EST
0810
(6-17)
1144
1300
1354
1450
0741
(6-18)
0847
1049
1217
1329
1437
0854
1054
1224
1338
1442
0915
1059
1233
1342
1453
0920
1104
1243
1346
1459
0858
1113
J. J.X J
1303
1503
0905
1100
1314
1515
0912
1125
1318
1527
d
1.
1.
1.
0.
0.
1.
1.
1.
1.
0.
0.
0.
1.
1.
1.
1.
0.
0.
0.
0.
1.
1
0.
0.
0.
0.
1.
0.
062
028
002
972
670
648,
276*
212*
092*
592*
376,
028*
f
f
f
832
542*
472*
434*
906*
462
222*
014*
f
570,
040
C
100*
006*
394,
012f
r
570,
554*
f
__
[H02J
ppm
d
0.060
0.076
0.091
0.096
0.242
0.388,
0.390*
0.486*
0.560*
0.412*
0.096
0.310f
o.nof
o.oeof
0.062f
0.472,
0.440*
0.440*
0.478*
0.320
0.172,
0.238*
0.334*
0.216*
0.080
0.462,
0 416
v . t JO ,
0.162*
0.162*
0.110,
0.236*
0.046*
0.016
0.473,
0.814*
0.724*
0.064*
ppmx
d
1.122
1.104
1.093
1.068
0.912
2.036
1.666*
1.698*
1.652*
1.004
0.472
0.338f
o.iiof
0.060*
0.062*
2.304
1.982*
1.912*
1.912,
1.226
0.634,
0.460*
0.348*
0.216*
0.080
2.032,
1 476
J. . *+ / D ,
0.262*
0.168
0.504
0.248*
0.046*
0.016*
2.043
1.368*
0.724*
0.061
[o3l
ppm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.051
.343
.338
.259
.006
.060
.268
.313
.013
.060
.060
.056
.333
.246
[so2]
ppm
0.020
0 061
\J ซ \JVJ-
0.224
0.409
0.000
0.178
0.312
0.426
0.016
0.266
0.766
0.575
104
-------
RESULTS OF BAG STUDIES
Test description
6-29-76
Ozone formation
2-Methylthiophene
1002
6-29-76
Ozone formation
CH.SCH
'.002
6-29-76
Ozone formation
CH-SCH
1002
6-29-76
Ozone formation
(CH,S)
iooi 2
6-29-76
Ozone formation
(CH,S),
1002
7-1-76
Ozone formation
CH-SH
0955
7-1-76
Ozone formation
CH SH
0955
7-1-76
Ozone formation
CH.SCH,
0955 3
7-1-76
Light stability
CH, SCH0
095-5 3
Time of HC [HCj
Analysis, ppmC
EST
0920
1150
1435
1625
0925
1210
1440
1635
0930
1225
1455
1645
0950
1240
1505
0940
1250
1530
0855
1035
1245
1450
0905
1045
1300
1440
0915
1100
1310
1520
0910
1115
1320
L500
12.
4.
2.
1.
9.
2.
1.
1.
10.
6.
5.
5.
9.
11.
8.
6.
2.
1.
11.
9.
6.
3.
10.
1.
1.
0.
11.
10.
10.
10.
0
93
36
26
36
35
82
64
7
51
44
44
03
0
71
78
74
28
2
07
81
86
2
42
01
92
1
6
6
3
Time of [NO]
Analyses, ppm
EST
0916
1136
1334
1539
0927
1148
1336
1552
0923
1200
1343
1604
0954
1212
1404
1616
0938
1223
1417
1628
0836
1016
1217
1415
0842
1028
1227
1420
0831
1103
1308
1453
0825
1053
1254
1440
0.506
L
f
e
r
1.608
t
f
f
0.392
L
f
1 " f
f
1.866,
0.012
L
'"" ฃ
r
0.404
r
1.696,
0.318*
0.224.
0.192
0.444
0.072*
0.036
d
1.684
L
ฃ
f
_
f
ppm
0.154,
0.032*
0.030*
0.028
0.518,
0.028*
0.110*
0.028
0.128
0.014*
0.020*
0.014*
0.522,
0.196*
0.076*
0.020
0.094
0.016*
0.016*
0.016
0.492
0.1147.
0.154*
0.172
0.108,
f
0.048f
d
0.456,
0.032*
0.028*
0.028
0.004
0.004*
0. 012
0.012*"
pp=ix
0
0
0
0
2
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
2
0
0
0
0
0
0
2
0
0
0
0
0
0
0
.660,
.032*
J
.028f
.126
.028*
.110*
.028*
.520f
.020*
.014
.388,
.208*
.076*
.020f
.498
.016*
.016,
.016
.188,
.432*
.378*
.364
.552,
f
.084*
d
.140,
.032*
.028*
.028
.004
.004*
.012*
.012*
[o3]
ppni
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
023
033
038
135
327
073
086
057
034
013
101
180
241
195
146
001
005
261
173
136
003
006
001
[so2]
PP=
0.000
0.375
0.497
0.591
0.018
0.90
1.56
0.99
0.000
0.439
0.480
0.520
0.006
0.182
1.78
1.68
0.000
0.272
2.70
2.56
0.014
0.079
0.445
0.928
0.042
0.243
0.824
0.855
0.904
0.926
0.017
0.044
0.043
105
-------
RESULTS OF BAG STUDIES
Test description
7-1-76
Ozone formation
(CH S)
0945
7-1-76
Light stability
(CH S)
0945
7-1-76
Ozone formation
cos
0945
7-1-76
Ozone formation
COS
0945
7-16-76
Ozone formation
Cyclopentadiene
1035
7-16-76
Ozone formation
Cyclopentadiene
1015
-1.U J J
7-23-76
Ozone formation
m-Xylene
0920
7-23-76
Ozone formation
m-Xylene
0920
7-23-76
Ozone formation
ฃ-Xylene
0920
Time of HC [HC]
Analysis , ppm C
EST
0945
1140
0925
1125
1330
1510
12
12
7
4
3
.1
.0
.58
.76
.42
(10. O)8
(10.0)g
0955
1325
1005
1310
0850
1110
1520
0840
1120
1355
1535
0900
1130
1405
1550
10
2
11
10
6
4
10
5
3
2
10
9
8
8
.7
.17
.5
.4
.9
.0
.1
.1
.7
.0
.1
.2
.7
.7
Time of [NO]
Analyses, ppm
EST
0906
1115
1357
1555
0856
1145
1333
1509
0846
1039
1241
1430
0852
1135
1321
1523
0954
1237
1501
1001
1250
1354
1518
X J -LO
0819
1054
1242
1443
0813
1048
1255
1448
0830
1103
1322
1453
1.
1.
0.
0.
0.
0.
0.
0.
0.
1.
0.
1.
0.
0.
1.
1.
1.
1.
96g
f
f
f
i.
f
712
324*
292*
200
430
056*
056,
048r
606
052.
1
f
f
1.
920,
3921
L
466
i
f
d
814f
768*
668*
612f
[N02]
ppm
0.496,
0.244*
0.046!;
0.042
0.008,
0.002*
0.012*
0.0141
0.512,
0.108*
0.102*
0.078
0.128
0.030*
0.032*.
0.032*
0.720
0.628
0.538
0.118
0.118*
0.064*.
Or\f\L
UUH
0.530,
1.770*.
1.032,
1.038*
0.126
0.284*
0.232
d
0.552,
0.552*
0.534*
0.630*
[NO
X
ppm
2.
0.
0.
0.
0.
0.
0.
0.
2.
0.
0.
0.
0.
0.
0.
0.
2.
0.
0.
0.
0.
0.
2.
2.
1.
1.
0.
0.
0.
2.
2.
2.
2.
456
244
046
042
008
002
012
014
224
432
394
278
558
086
088
080
326
628
538
620
118
064
nfii
UOH
450
162
032
038
592
284
232
d
366
] to3]
ppra
\ 0.055
.! 0.212
0.165
f
f
f
f
f
f
J.
f
J.
ฃ
f
1.596
1.499
f
. 0.622
; 0.556
n Sin
\J . .JHU
f
f
, 0.852
1.008
f
* 0.569
0.481
0.441
[so2]
ppm
2,13
2.09
1.87
1.23
1.97
2.39
0.025
0.040
0.045
0.006
0.022
0.021
0.019
320|
202;
242
t
106
-------
RESULTS OF BAG STUDIES
a Time of HC [HC] Time of [NO] [M>2)
Test description Analysis, ppmC Analyses, ppm ppa
EST EST
7-23-76 0910 9.9 0824
Ozone formation 1215 6.8 1058
p-Xylene 1435 4.7 1409
0920 1600 5.1 1517
7-23-76 0825 10.3 0808
Ozone formation 1210 8.1 1041
o-Xylene 1425 4.5 1405
0920 1610 3.9 1508
7-23-76 0835 9.9 0802
Ozone formation 1100 7.1 1035
o-Xylene 1345 4.7 1230
0920 1510 4.0 1437
7-28-76 (5.0)g 0500
Ozone formation 0755
CH SH 0845
0500 0945
1045
1145
1245
1345
1445
1545
7-28-76 (5.0)g 0504
Ozone formation
(CH S)
0501
7-28-76
Ozone formation
CH SCH
05D8
0755
0855
0955
1055
1155
1255
1355
1455
1555
(5.0)g 0508
0755
0855
0955
1055
1155
1255
1355
1455
1555
0.472, 0.124,
0.064 0.466*
*. 0.162*
* 0.278
1.786f 0.494.
1.628 0.602*
* 1.198*
- 1.170
0.438 0.112,
* 0.380*
* 0.232*
0.212
0.917 0.198
0.863 0.240
0.775 0.302
0.605 0.410
0.330 0.580
0.020 0.700
0.905 0.220
0.695 0.385
0.018s 0.125s
d d
0.160e
096*1ฎ
0.912s 0.2086
0.510
Onfปne
0.0426
0.080s
[NO..] [o33 [so,]
pprn''' ppn ?pn"
0.596,
Oeort*
0.162* 0.594
0.278 0.532
2.280,
2.230*
1.198* 0.385
1.170 0.212
0.550-
0.380* 0.281
0.232* 0.521
0.212 0.501
1.115
1.103
0.045
i n-n
0.150
1.015
0.400
0.910
0.720
0.720 0.015
1.125
1.080
0.225 1.40
0.1436 0.545
0.594 1.35
d 0.568
0.532 1.30
0.160s 0.490
0.443 1.27
0.265e 0.410
1.120s
0.510 0.320
0.580 0.53
0.060s 0.563
0.514 0.55
0.042s 0.458
0.405 0.55
d 0.363
0.325 0.54
0.080s 0.295
107
-------
RESULTS OF BAG STUDIES
Test description3
7-28-76
Ozone formation
C H,
0555
8-5-76
Dark reactivity with 0-
CH,SH, 0-
0709
8-5-76
Dark stability
CH^SH
0751
8-5-76
Dark reactivity with CL
CH,SCH.
0657 3
8-5-76
Dark stability
Time of HC
Analysis ,
EST
0920
1100
1220
1350
1540
1000
1120
1250
1435
1600
1050
1230
1400
1545
1005
1445
[HC]
ppmC
(5.0)g
d
6.38
7.12
8.93
8.39
8.16
9.72
9.74
8.71
9.33
9.44
9.93
9.56
9.99
11.4
10.9
Time of [NO] [NOj]
Analyses, ppm ppm
EST
0455 0.920 0.215
AT CA A "7 1 Q f\ 1"7/i
0750 0.738 0.374
0850
0950 0.005 0.950
1050
1150 d 0.590
1250
loert ft f. en
1450
1 C Cfi A Tฃ,T
0923
1102
1225
1353
1537
0928
1052
1231
1400
1542
[NOJ [03] [S02]
ppm ppm ppm
1.135
11 1 *
0.955 0.075
0.509
0.610 0.852
0.945
0.450 0.941
0/1T 1
0.363 0.863
1.101
1.033
0.970
0.901
0.826
0.900
0.804
0.757
0.693
0.620
CH-SCH
0756
8-5-76
p
Ozone decay (dark)
ฐ3
0607
8-5-76
Dark reactivity with 0,,
(CH.S)?
0705
8-5-76
Dark stability
(CH SK
0740
0940
1105
1240
1430
1555
1015
1455
13.5
12.4
12.2
12.8
12.8
12.3
11.8
0803
1115
0937
1112
1235
1402
1546
1.258
1.228
1.119
1.075
1.036
0.999
0.957
108
-------
RESULTS OF BAG STUDIES
Test description
8-6-76
U W / O
Dark reactivity with NO
CH-SH, NO, NO
0720
8-6-76
Dark reactivity with NO
CH-SCH-, NO, NO,
06^7 3 2
8-6-76
Dark reactivity with NO
(CH.S3,, NO, NO, X
0655 L
8-6-76
Dark reactivity with NO
COS, NO, NO, X
2
0727
8-6-76
NO oxidation (dark)0
NO, NO,
0714
8-11-76
Ozone formation
CH-SH
0050
8-11-76
Ozone formation
CH, SCH
0150 J
Time of HC [HC]
Analysis, ppmC
EST
0825
0955
1200
1350
1555
0815
0945
1140
1335
1540
0835
0935
1145
1345
0935
0925
1300
7
/
8.
7.
7.
7.
11.
11.
11.
11.
11.
15.
14.
14.
13.
(10.
(5.
(5.
1.
0.
sg
J7
52
51
80
67
1
2
1
1
1
6
5
8
6
O)8
0)g
O)8
08
72
Time of [NO]
Analyses, ppm
EST
0806
UO Uv-
0942
1146
1347
1543
0743
0925
1136
1330
1537
0755
0925
1140
1341
0810
0952
1152
1354
1549
0746
1156
1456
0040
0845
0950
1140
1340
1440
0140
0758
0855
1050
1150
1350
1450
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
goo
. oyj
.854
.820
.823e
.802e
.926
.903
.839
.832
.820a
.875
.858
791
.763e
.882
.845
.809
.811e
.797e
.943
.869
.848e
.730
.622
.590
.450
.294
.145
.720
[NO, ]
ppa~
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
202
. ฃVฃ
.230
.235
.254e
.2796
.233
.260
.281
.2976
.327s
.239
.267
.270
.277*
.224
.243
263a
.294e
.317e
.223
271e
.317e
.150
.220
.303
.435
.440
.531
.150
.290e
d
.332*
.355e
.245e
.278e
t
?
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
:;o.j [03! [so,}
no 5
no/.
.055
.0776
.0816
.159
1 ฃ-3
.120
.1296
.147e
.114
.125
.061
.040
1 r\t
OB 8
.072
.105ฐ
.114e
1 ฃ.ฃ.
.140
.165e
.880
ooo
.893
one
.734
.676
.870
.290e 0.439
d 0.495
.332 0.380
.355e 0.362
.245e 0.290
.278e 0.260
109
-------
RESULTS OF BAG STUDIES
a
Test description
8-11-76
Ozone formation
(CH S)
0045 -
8-11-76
Ozone formation
C,H,
0150
8-17-76
Ozone formation
C3H6
0530
8-17-76
Ozone formation
Furan
0530
8-17-76
Ozone formation
Thiophene
0530
8-17-76
Ozone formation
Pyrrole
0530
Time of HC [HC] Time of [NO]
Analysis, ppmC Analyses, ppm
EST EST
0940
0915
0500
0905
1040
0530
0910
0520
0900
1040
0510
0855
(5.0)8 0045
0720
0940
1041
1140
1342
1440
(5.0)8 0150
3.4 0758
0855
1050
1 1 "50
J- J. J U
1450
4.38 0455
4.12 0904
1.55 1200
1400
1655
1850
5.70 0520
0.52 0904
1200
1400
1655
1850
7.47 0508
7.18 0855
0.62 1145
1345
1645
1845
4.59 0500
0855,
1145
1345
1645
iflis
0.720
0.298
0.004
0
0
0
0
0
0
0
0
0
0
0
0
0
.730
.420
.022
.608
.198
.671
.698
.670
.595
.538
.464
.444
.653
ppm
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
n
\J
n
u
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
n
140
,487
242
122
d
120
070
170
412
775
6906
6Qfie
\J~ \J
520
185
575
522
482
418
400
198
410
138
120
084
063
223
240
255
272
278
295
162
170
097
070
038
mo
[NO ]
ppm
0.860
0.785
0.246
0.122e
d
0.120
0.070
0.
0.
0.
0.
0.
n
U
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
n
900
832
797
690e
698e
,--
520
793
773
522
482
418
400
869
410
138
120
084
063
921
910
850
810
742
739
815
170
097
070
038
ma
[o3] [so2]
ppm ppm
0.657
0.655
0.590
0.505
0.471
0
i
-L
1
1
1
1
0
0
0
0
0
0
0
0
0
0
n
.922
01 n
ซ/ A *J
.050
.113
.058
.018
.973
.534
.952
.925
.806
.743
.197
.247
.284
.290
O OCt
110
-------
RESULTS OF BAG STUDIES
ซ
Test description
8-19-76
f^T *"*ปTIO f OTTiiii t" 1 fin
wฃUIlC LU L UlClC Jป*J11
C H
S&
8-19-76
Ozone formation
C3H6
0505
8-19-76
Ozone formation
C3H6
0550
8-19-76
Ozone formation
C3H6
0459
8-19-76
Ozone formation
CH SH
0530
8-19-76
Ozone formation
Cซ,SdH_
osL. 3
Time of HC
Analysis,
EST
0545
0755
W / J J
1000
1205
05 A 0
0745
0950
1250
0515
0805
1015
1210
0530
0815
1020
1225
0545
0820
1005
1225
0535
0810
1015
1155
[HC]
PpmC
25.1
18 U
AO *#
2.38
0.76
8.55
7.82
3.63
0.17
9.0
8.5
2.65
1.61
4.50
4.20
2.29
0.19
4.75
4.46
3.97
1.74
5.33
2.35
0.79
0.71
Time of
Analyses,
EST
0511
07 f.n
i// j\j
0950
\JjJ\J
1207
1358
0505
0745
0950
1150
1345
1545
1745
1950
0453
0800
1005
1105
1400
1600
1745
2000
0459
0805
1010
1215
1410
1615
i Qfifi
J.OUU
2015
0530
0815
1010
1215
1410
1615
0518
0805
1010
1150
1345
1550
1745
1950
[NO]
ppm
1.290
___
1.318
0.980
0.318
0.652
0.490
0.692
0.632
0.518
0.320
0.692
_ __
___
[N02]
ppm
0.300
i \if\
J. J / O
1 136
J. J J V
1.274
1.225
0.320
0.594
1.240
1.068
0.940
0.872
0.810
0.780
0.074
0.394
0.228e
0.260
0.240
0.218
0.215
0.215
0.152
0.318
0.672
0.595
0.580
0.540
f) A6Se
U HO J
0.492
0.158
0.210
0.332
0.440
0.555
0.180
0.158
0.346
0.300
0.060
0.090e
0.0686
0.0556
0.062s
[NOJ
ppn
1.590
1 176
J. . J / U
1.336
1.274
1.225
1.638
1.574
1.240
1.068
0.940
0.872
0.810
0.780
0.392
0.394
0.228
0.260
0.240
0.218
0.215
0.215
0.804
0.808
0.672
0.595
0.580
0.540
0 465e
\J H U J
0.492
0.850
0.842
0.850
0.760
0.555
0.180
0.850
0.346
0.300
0.0606
a,
0.090
0.068s
0.0556
0.0626
[o3] [so9l
ppr. ?pa~
0214
\J ฃ At
0.601
0.465
0.630
0.298
1.470
1.315
d
1.130
1.023
0.042
0.289
0.164
0.190
0.178
0.160
0.119
0.254
1.002
0.942
0.870
0 fiTO
V * O J \J
0.772
0.037
0.360
0.332
0.510
0.441
0.335
0.309
0.274
0.255
111
-------
RESULTS OF BAG STUDIES
Test description
8-19-76
Ozone formation
(CH_S)2
2-2 to 2-3-77
0, decay0
ฐ3
2-2 to 2-3-77
0, decay
ฐ3
2-2 to 2-3-77
0, decay0
ฐ3
2-2 to 2-3-77
0, decay
ฐ3
2-4-77
Dark reactivity with 0
C3H6
1043, C,H, injection
j 0
2-4-77
Dark reactivity with 0,
Furan
0717, furan injection
Time o HC
Analysis,
EST
0540
0900
1055
1110
1145
1220
1305
1335
1400
1500
1600
0750
0845
0925
1005
1115
1155
1255
1310
1340
1420
1520
1620
[HC]
PpmC
6.48
ซM*^^
4.79
4.56
4.12
4.00
3.87
3.85
3.83
3.87
3.80
16.91
15.59
15.11
14.83
14.42
14.32
14.20
13.99
14.06
14.06
14.10
13.99
Time of [NO] [N02]
Analyses, ppm ppm
EST
0524 0.664 0.166
0805 0.626
1015 0.384
1509 (2-2)
2201
0810 (2-3)
1522 (2-2)
2213
0824 (2-3)
1530 (2-2)
2223
0839 (2-3)
1548 (2-2)
2245
0904 (2-3)
1028
1055
1104
1111
1215
1226
1258
1307
0703
0834
0850
0921
0929
0950
1005
1113
1120
1153
1202
1235
1255
1302
1313
[NO ] [O.j] [S02]
ppm ppm ppm
0.830
0.626 0.074
0.384 0.844
0.870
0.817
0.740
1.133
1.078
0.990
1.019
0.970
0.879
0.926
0.873
0.787
0.401
0.228
0.193
0.164
0.034
0.024
0.012'
0.009
0.898
0.311
0.245
0.185
0.174
0.134
0.116
0.058
0.057
0.039
0.035
0.025
0.020
0.018
0.016
112
-------
RESULTS OF BAG STUDIES
Test descriptiona
2-4-77
Dark reactivity with 0_
Thiophene
0701, thiophene injection
2-4-77
Dark reactivity with 0ป
Pyrrole
1030, pyrrole injection
Time of HC
Analysis,
EST
0740
0855
0950
1130
1205
1245
1030
1100
1140
1215
1230
1325
1350
1440
1540
1635
[HC]
ppmC
18.03
17.77
18.05
17.68
17.50
17.48
8.98
7.26
6.48
6.80
6.58
6.39
7.07
7.35
6.42
6.58
Tine of [NO]
Analyses , ppro
EST
0643
0713
0747
0847
0856
0945
0954
1115
1131
1157
1208
1231
1245
1012
1039
1102
1108
1134
1142
1212
1222
[N02] [NO..] [03! [SO,]
ppra ppn'" ppn ?p=-
0.798
0.711
0.642
0.477
0.460
0.389
0.385
0.293
0.287
0.253
0.238
0.215
0.202
0.509
0.150
0.055
0.043
0.012
0.008
0.002
0.001
aThe test description follows this format: date, type of experiment, test compound, and
time of initial exposure, EST.
Entries denoted by blanks represent nondetected concentrations.
Q
Bag characterization experiment.
Data discarded.
Data questionable.
Data questionable due to sampling line losses.
8Target initial condition, analysis not available.
113
-------
APPENDIX C
Hydrocarbon Analyses From
Chamber Runs
114
-------
Appendix C. HYDROCARBON ANALYSES FROM CHAMBER RUNS
DAY 1
Hydrocarbon Date
Furan 7/13-15/76ฐ
Thiophene
Pyrrole
Propylene
Furan 8/17-19/76ฐ
Thiophene
Pyrrole
Propylene
Furan 7/20-22/76f
Thiophene
Pyrrole
Propylene
Methanethiol 7/28-30/76ฐ
Methyl disulfide
Methyl sulfide
Propylene
Methanethiol 8/10-13/76f
Methyl disulfide
Methyl sulfide
Propylene
Chamber
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
Time3
0432
0440
0448
0456
0436
0445
0453
0504
0430
0440
0450
0500
0430
0440
0450
0500
0530
0535
0540
0545
[HC]b
4.72
4.01
2.94
5.16
4.90
11.9
NDe
5.23
5.03
5.54
NDe
4.96
ND
ND
5.81
5.22
ND8
7.17
5.24
4.14
Time
1225
1235
1245
1255
0920
0910
0900
0850
1250
1300
1310
1320
1440
1450
1500
1510
[HC]
NDd
1.79
ND
ND
ND
0.77
ND
3.67
ND
0.79
ND
ND
ND
ND
ND
ND
DAY 2
Time [HC]
0430 ND
0440 0.52
0450 ND
0500 ND
Time of sample collection, EST.
Concentration of hydrocarbon, ppmC,
ฐStatic run.
m> = not detected.
Pyrrole peak could not be clearly resolved.
Dilution run.
cr
"Compound detected with a retention time similar
to methyl disulfide at a concentration of
3.81 ppmC.
-------
APPENDIX D
Detailed Data Sheets
116
-------
TIME
(ESI)
UZUNE
(PPM)
NU
(PPM)
H02
(PPM)
HT1 SMUG CHAMBER STUDYJ USEPA CONTRACT NU. 68-03-3258
nux
(PPM)
CHAMBER NO. 1. FUKAN
1AHGET INITIAL HC/NOX!
, OX DILUTION
5.0 PPMC/1.00 PP1
OAป 1, 7-13-76
X POSSIBLE MINUTES SUNSHINE, 93
KDU AIRPORT MAXIMUM TEMPERATURE. J1.67 CENT
S02
(PPM)
NBKl
(PPM)
M02-S
(PPM)
CH20
(PPM)
SR
(LANG
CUM-SH
(LANG)
TEMP
(CENT)
PAGE I
DILUTION
-------
HTI SHUU CIIAWUtH STUDfl USFPA CONTRACT NO. 68-02-22Sซ
CMAMHIR NO, I,
FURAN
, OX DILUIIUN
DAY I, 7-l4-7b
1 PUSSIHLt HINUTES SUMSHINtf 83
HDJ A1RPOR1 MAXIMUM TEMPERATURE, 31,67 CENT
PAGE 2
00
1 1 ''ฃ
(CSI)
ti.li
1.13
2.13
3.13
4.13
5.13
(>.I3
7.13
8.13
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
0/OUE
(PPM)
0.2/6
0.267
0.259
0.2S1
0.243
0.235
0.223
0.206
0.187
0.175
0.174
0.173
0.186
0.190
0.192
0.194
0.190
0.180
0.1/2
0.163
0.155
0.119
0.144
0.137
UU
(PPM)
0.0
0.0
0.0
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
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NU2
(PPM)
0.016
O.OIS
0.015
0.015
O.OIS
0.014
0.015
O.OIS
0.014
0.023
(1.024
0.022
0.022
0.019
0.019
O.OIB
0.010
0.017
0.016
0.016
0.014
0.012
0.012
0.012
mix
(PPM)
0.016
0.015
0.015
0.015
0.015
0.014
o.ois
O.OIS
0.018
0.023
0.024
0.022
0.022
0.019
0.019
0.018
0.018
0.017
0.016
0.016
0,014
0.012
0.012
0.012
S02 NHnI NO2-S CM20 SH
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG
CUM-SK 1EMP
(CENT)
DILUTION
(CFH)
BEGAN
(EST)
ENDED
(ESI)
0.183 0.011 0.039
0.166 0.011 0.017
0.0
0.0
0.0
0.0
0.0
0.04
0.16
0.46
0.82
1.08
1.17
1.09
1.13
0.98
0.99
0.83
0.44
0.28
0.12
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.32
3.68
15.68
46.16
97.44
162.96
232.52
298.24
364. P4
423.72
481.84
526.52
553.64
569.16
575.48
576.00
576.00
576.00
576.00
17.78
17.78
17.22
27.22
29.44
30.56
26.67
22.22
-------
HI I SMUG CHAMHtH STUDY! UStPA CONTRACT NO. 6B-02-Ar 3, 7-15-76
X POSSllILt MINUTES SUNSHINE, 76
KUU AIUPUKT MAXIMUM TEMPEHATUKE, 17.a CENT
IH-.L UZUNC UU NIJ2 MUป 302 NklKl U02-S CM20 SH CUM-SH TEMP D1LUTIUH dEGAN ENDED
(tST) (PPM) (PPH) (PPN) (PPM) (PCM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT) (CFM) (EST) (EST)
/MIS)
U.I3
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
10.13
19.13
20.13
22J 13
23.13
0.132
0.127
0.121
0.114
0.109
0.102
0.095
0.080
0.085
0.095
0.111
0.130
0.145
0.155
0.160
0.162
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
U.012
0.012
ft.Ol 1
O.U12
0. "12
0.011
0.012
0.012
0.013
0.014
0.012
0.012
O.UI2
0.012
0.012
0.012
0.012
0.012
0.012
0.011
0.012
0.012
0.011
0.012
0.012
0.013
0.014
0.012
0.012
0.012
0.012
0.012
0.012
0.012
U.2U3 0.017 0.120
0.239 0.017 0.146
0.234 0.014
0.0
0.0
0.0
0.0
0.0
0.01
0.23
0.42
0.76
0.97
1.12
1.22
1.27
0.90
0.7A
0.7
-------
HTI SMUG CHAMBtH STUDYl USER* CONTRACT HO. 6H-02-2258
CHAMBER NO. 2, TH1UPHENE , OX DILUTION
TARGET INITIAL HC/NUXJ 5.0 PPMC/I.OO PPM
DAY J, 7-15-76
x POSSIBLE MINUTES SUNSHINE, 9J
HDU AIHPOHI MAXIMUM TEMPERATURE, 31.67
PAGE I
IIHE
(tST)
UZUNE
(PPM)
NO
(PPM)
HO 2
(PPM)
NUX
(PPM)
SU2
(PPM)
NBM
(PPM)
N02-S
(PPM)
CH20 SK
(PPM) (LANG
CUM-SH
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
Isi
O
0.50
1.50
2.50
5.50
4.50
5.50
6.30
7.50
8.50
9.50
10.50
11.50
12.50
13.50
14.30
15.30
16.30
17.30
18.30
19.30
20.30
21.30
22.30
23.30
0.005
0.004
0.005
0.002
0.001
0.0
0.0
0.0
0.0
0.0
0.001
0.004
0.010
0.018
0.029
0.040
0.044
0.041
0.02S
0.008
0.0
0.0
0.0
0.0
0.013
0.008
0.005
0.021
0.816
O.ซ04
0.778
0.731
0.705
0.596
0.418
0,305
0.196
0.132
0.090
0.066
0.053
0.041
0.030
0.019
0.011
0.007
0.006
0.005
0.006
0.007
0.007
0.213
0.213
0,219
0.211
0.227
0.251
0.321
0.385
0.424
0.411
0.380
0.342
0.500
0.271
0.250
0.240
0.241
0.246
0.245
0.259
0.234
0.019
0.015
0.012
0.254
1.029
1.025
0.989
0.958
0.956
0.917
0.803
0.729
0.609
0.512
0.432
0.366
0.324
0.291
0.270
0.260
0.257
0.250
0.245
0.259
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.010
0.020
0.040
0.075
0.115
0.150
0.160
0.175
0.180
0.185
0.180
0.1/0
0.155
0.110
O.GBS
0.075
0.009 0.584 0.045
0.0
0.318 0.011
0.0
0.0
0.0
0.0
0.0
0.05
0.22
0.57
0.67
0.92
1.20
1.45
1.40
1.29
1.15
0.98
0.74
0.41
0.15
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0,0
0.0
0.0
0.90
6.96
22.86
50.46
95.16
155.40
231.90
518.00
400.02
474.90
540.84
595.52
633.78
653.70
660.36
661.20
661.20
661.20
661,20
22.22
18.33
20.00
24.44
28.33
30.56
28.35
22.78
3This NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
KT1 SMOG CHAMBeR S1UOU USEPA CONTRACT NU. 6B-02-2i!5e
CHAMBEH NU. 2,
THIUPHENE
, OX DILUTION
PACE 2
DAY 2, 7-H-76
x POSSIBLE MINUTES SUNSHINE* 83
HDU AIRPOKT MAXIMUM TEMPERATURE, 11.67 CENT
TIMt
(tST)
O.JO
1.30
2. JO
3.30
4.30
5. JO
6. JO
7. JO
8. JO
9. JO
10.30
11.30
12.30
13.30
14.30
15.30
16.30
17.30
18.30
19. JO
20.30
21.30
22.30
23.30
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.003
0.013
0.016
0.034
0.063
0.098
0.127
0.150
0.171
0.193
0.201
0.199
o.iao
0.165
0.147
0.129
0.110
0.093
0.078
NO
(PPM)
0.004
0.004
0.003
0.003
0.003
0.006
0.023
0.032
0.034
0.022
0.013
0.00ft
0.006
0.005
0.004
O.OOJ
0.002
0.001
0.001
0.0
0.0
0.0
0.0
0.0
ซU2
(PPM)
0.232
0.226
0.223
0.222
0.2IB
0.214
0.1A4
0.148
0.120
0.107
0.087
0.0/0
0.055
0.042
0.031
0.018
0.017
0.023
0.022
0.02U
0.018
0.016
0.016
0.016
NUX
(PPM)
0.236
0.230
0.226
0.225
0.221
0.220
0.207
0.180
0.154
0.129
0.100
0.078
0.061
0.047
0.035
0.021
0.019
0.024
0.023
0.020
0.018
0.016
0.016
0.016
S02 NBKI N02-S
(PPM) (PPM) (PPM)
0.060
0.050
0.040
O.OJO
0.025
0.020
0.020
0.025
0.040
0.055
0.070 0.019a 0.077
0.080
0.085
0.085
0.090
0.085
0.080 0.015 0.065
0.075
0.070
0.060
0.050
0.035
0.025
0.015
CH20 3H
(PPM) (LANG
0.0
0.0
0.0
0.0
0.0
0.04
0.16
0.46
0.82
1.08
0.016 1.17
1.09
1.13
0.98
0.99
0.83
0.008 0.44
0.28
0.12
0.01
0.0
0.0
0.0
0.0
CUH-SB
(LANG)
0.0
0.0
0.0
0.0
0.0
0.72
5.28
20.28
54.36
108.24
174.66
243.42
309.54
374.64
433.62
490.14
532.92
556.44
570.36
575.58
576.00
576.00
576.00
576.00
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (E3T) (EST)
IT. 78
17.78
17.22
27.22
29.44
30.56
26.67
22.22
aThis NBKI measurement nay be low in comparison to the chemiluminescent oฃone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
SMOG LHAMBE.H STUOYJ USEPA CONTRACT NO. 68-02-2258
CHAMBER NO. i., THIOPHENE , OX DILUTION
DA* 3, 7-15-76
X POSSIBLE MINUTES SUNSHINE, 76
HOU AIRPORT MAXIMUM TEMPERATURE, 37.22 CENT
PAGE 3
e
to
II "It
(ESI)
0. 30
1.30
2.30
3.30
4.30
S.30
6.30
7.30
6.30
9.30
10.30
11.30
12.30
13. 30
11.30
15.30
16.30
17.30
ID. 30
19.30
20.30
ฃ1.30
22.30
23.30
OZONE
(PPM)
0.066
0.054
0.045
0.037
0.029
0.021
0.015
0.026
0.051
o.oea
0.116
0.140
0.159
0.173
0.178
0.176
NO
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.002
0.003
0.0
0.0
0.0
0.0
0.0
0.0
UU2
(PPM)
o.ou
0.016
0.016
0.016
0.017
0.017
0.017
O.OIB
0.018
0.016
O.Olb
0.014
0.014
0.014
0.013
0.013
tiOX
(PPM)
0.017
0.016
0.016
0.016
0.017
0.017
0.017
0.020
0.020
0.021
0.015
0.014
O.OU
0.014
0.013
0.013
S02
(PPM)
0.010
U.005
0.002
0.002
0.0
0.0
0.0
0.003
0.010
0.012
0.015
0.015
0.020
0.015
0.010
0.010
0.010
NBKI N02-S CH20 SR
(PPM) (PPM) (PPM) (PPM) (LUNG
/H[N)
CUM-SR TEMP
(LANG) (CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.166 0,013 0.118
0.176 0.005 0.149
0.197 0.003
0.0
0.0
0.0
0.0
o.o
0.04
0.23
0.42
0.76
0.97
1.12
1.22
1.27
0.90
0.78
0.74
0.50
0.10
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.72
6.54
23.76
55.08
104.46
165.36
234.36
306.46
378.00
429.84
475.92
516.00
538.80
543.18
543.60
543.60
543.60
543.60
543.60
21.11
20.00
22.22
31.11
36.11
36.11
28.89
23. B9
-------
KT1 SMOG CHAMBER SfUOYI USEPA CONTRACT NO. 68-02-2256
CHAMHF.H UO. 3, PYHROLE / OX DILUI10N
TARGET 1MTIAL HC/NOX: 5.0 PPMC/1.00 HPM
DAY 1, 7-JJ-76
X POSSIBLE MINUTES SUNSHINE* 9}
KDU AIRPORT MAXIMUM TEMPERATURE, 31.67 CENT
PAGE 1
({SI)
0ฃUNt
(PPM)
HO
(PPM)
f*U2
(PPM)
NOX
(PPM)
302
(PPM)
MJKI
(PPM)
M02-S
(PPM)
CH20 SR
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.47
1.47
2.47
3.47
4.47
5."7
., <>.47
{3 7.47
LO 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
0.001
0.001
0.001
0.0
0.0
0.0
0.0
0.029
0.058
0.041
0.033
0.029
0.027
0.026
0.024
O.U22
0.020
0.015
0.007
0.003
0.0
0.0
0.0
0.0
0.014
0.007
0.005
0.023
0.864
0.842
0.657
0.066
0.033
0.053
0.067
0.072
0.070
0.066
0.063
0.061
0.058
0.054
0.046
0,041
0.035
0.031
0.028
0.028
0.005
0.006
0.006
0.201
0.173
0.190
0.323
0.740
0.428
O.Jo2
0.314
0.274
0.240
0.214
0.194
0.170
0.170
0.164
O.lbb
0.167
0.166
0.166
0.163
0.162
0.019
0.013
0.011
0.224
1.037
1.032
0.980
o.aob
0.461
0.415
0.3H1
0.346
0.310
0.280
0.257
0.239
0.228
0.218
0.212
0.208
0.201
0.197
0.191
0.190
0.094 0.297 0.003
0.0/4 0.207 0.033
0.0
0.0
0.0
0.0
0.0
o.os
0.22
0.37
0.67
0.92
1.20
1.15
1.40
1.29
1.15
0.98
0.74
0.41
0.15
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.40
9.16
26.56
57.16
104.36
167.40
246.40
332.00
412.92
486.40
550.64
602.72
637.86
655.20
660.56
661.20
661.20
661.20
661.20
22.22
18.33
20.00
24.44
28.33
30.56
28.33
22.78
-------
WTI SMOG CHAMBIR STUUt: USEPA CONTRACT NU.
Tll't
(EST)
OZOiJE
(PPM)
NU
(PPM)
N02
(PPM)
NUX
(PPซ)
CHAMUtR NO. J,
PYRHOLE
OX DILUTION
OAT 2, 7-14-76
X POSSIBLE MINUTES SUNSHINE, 63
KDU A1HPORT MAXIMUM TEMPERATURE, 31.67 CENI
SU2
(PPM)
NBKI
(PPM)
N02-S
(PPM)
CH2U SR
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
PAGE 2
DILUTION
(CFH)
DEGAN
(EST)
ENDED
(EST)
0.47
1.47
2.47
3.47
4.47
5.17
6.47
7.47
8.47
9.17
10.47
11.17
12.47
13.47
14.17
15.47
16.47
17.47
18.47
19.47
20.47
21.17
22.47
23.47
0.0
0.0
0.0
0.0
0.0
0.003
0.008
0.013
0.015
0.020
0.024
0.029
0.029
0.039
0.042
0.043
0.043
0.043
0.039
0.032
0.026
0.020
0.015
0.011
0.026
0.025
0.025
0.025
0.023
0.025
0.035
0.045
0.054
0.051
0.041
0.035
0.027
0.024
0.020
0.015
0.010
0.009
0.004
0.001
0.0
0.0
0.0
0.0
O.lbl
0.155
0.155
0.1S3
0.153
0.146
il.132
0.116
0.103
0.098
0.097
0.093
0.095
0.086
0.082
0.080
0.077
0.075
0.075
d. 075
0.069
0.061
0.060
0.056
0.187
0.180
0.180
0.178
0.176
0.171
0.167
0.161
0.157
0.119
0.138
0.128
0.122
0.110
0.102
0.095
0.087
0.084
0.079
0.076
0.069
0.063
0.060
0.056
0.035 0.090 0.0
0.016 0.095 0.017
0.0
0.0
0.0
0.0
0.0
0.04
0.16
0.46
0.82
1.08
1.17
1.09
1.13
0.98
0.99
0.83
0.44
0.28
0.12
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.12
6.88
24.88
62.56
119.04
186.36
254.32
320.84
384.44
443.52
498.44
537.32
559.24
571.56
575.68
576.00
576.00
576.00
576.00
17.78
17.78
17.22
27.22
29.44
30.56
26.67
22.22
-------
RTI SMUU CHAVBtK STUDYl USEPA CONTRACT N(J. 68-02-^258
CHAMblR NO. 4,
PYRHOLC
, ox DILUTION
DAY 3, 7-15-76
X POSSIBLE H1NUIE3 SUNSHINE, 76
AIRPOKT MAXIMUM TEMPERATURE, 37.22 CENT
PACE 3
Ln
TIMt
(EST)
0.17
1.47
2. 4/
3.47
1.17
5.47
6.17
7.47
8.47
9.47
10.47
11.17
12. t7
13.17
14.17
15.17
16.17
17.17
lfl.17
19.17
an. 47
21.47
22.47
23.47
UIONE
(PPM)
0.010
0.007
0.004
0.003
0.002
0.004
0,011
0.029
0.054
O.OD4
0.110
0.141
0.170
0.190
0.196
0.195
NO
(PPM)
O.U
0.0
0.0
0.0
0.0
0.0
o.ooe
0,008
0.007
0.004
0.001
0.0
0.0
0.0
0.0
N02
(PPM)
0.aS3
0.052
0.051
0.050
0.049
0.047
0.040
0.038
0.034
0.032
0.02b
0.021
0.017
0.014
0.013
NUX
(PPM)
0.053
0.052
0.051
0.050
0.049
0.047
0.048
0.046
0.041
0.036
0.026
0.021
0.017
0.014
0.013
S02 fcBKl N02-S CH20 SR CUM-SR TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT)
DILUTION
(CFM)
BEGAN ENDED
(EST) (EST)
0.190 0.026 0.072
0.174 0.020 0.096
0.167 0.021
0.0
0.0
0.0
0.0
0.0
0.04
0.23
0.42
0.76
0,97
1.12
1.22
1.27
0.90
0.78
0.74
0.50
0.10
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.12
6.8ซ
27.96
62.68
114.16
176.56
246.56
321.16
367.00
437.64
463.32
521.00
539.60
543.28
543.60
543.60
543.60
543.60
543.60
21.11
20.00
22.22
31.11
36.11
36.11
28.89
23.89
-------
HII SMOG CHAMBER STODVI USEPA CONTRACT NO. 68-02-2258
CHAMbEH NO. 4, PkOPYLENE , OX DILUTION
TARGET INITIAL HC/NOX: 5.0 PPMC/1.00 PPM
OAf 1, 7-15-76
X POSSIBLE MINUTES SUNSHINE, 93
RDU AIRPOKT MAXIMUM TEMPERATURE, 11.67 CENT
PAGE 1
to
ii ME
(tST)
0.63
I.M
2.63
3.63
'4.63
5.63
6.63
7.63
8.63
9.63
10. bi
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)
0.003
0.003
0.003
0.002
0.001
0.0
0.0
0,0
0.017
0.825
0.991
0.999
.090
.093
.117
.125
.098
.063
.009
0.961
0,922
0.896
0.875
0.855
NO
(PPH)
0.013
0.007
0.005
0.018
0.349
0.688
0.638
0.515
0,089
0.004
0.004
0.004
0.001
0.001
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
MU2
(PPM)
O.OOb
0.006
0.006
0.171
0.175
0.175
0.222
0.313
0.658
0.510
0.3BO
0.355
0.326
0.245
0.263
0.243
0.218
0.192
0.169
0.147
0.134
0.125
0.118
O.llb
NllX S02
(PPM) (PPM)
0.019
0.013
0.011
0.189
0.524
0.663
0.860
0.828
0.747
Q.514
0.384
0.359
0.327
0.296
0.263
0.243
0.210
0.192
0.169
0.147
4.134
0.125
0.118
0.115
NBKI U02-S CH20 SR
(PPM) (PPM) (PPM) (LANG
0.0
0.0
0.0
0.0
0.0
0.05
0.22
0.37
0.67
0.92
1.321 0.053 0.186 1.20
1.45
1.40
1.29
1.15
0.98
1.201 0.044 0.137 0.74
0.41
0.15
0.02
0.0
0.0
0.0
0.0
CUH-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
1.90
11.36
30.26
63.86
113.56
179.40
260.90
346.00
425.82
497.90
560.44
610.12
641.98
656.70
660.76
661.20
661.20
661.20
661.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
22.22
18.33
20.00
24.44
28.33
30.56
28.33
22.78
-------
SMUG CHAMOEH STUDYI USEPA CUNFRACT NO. 6d-ซ2-<><>5B
CHAMUEK NO. 4, PKOPVLENE
OX DILUTION
DAY 2r 7-14-76
x POSSIBLE MINUTES SUNSHINE, ซi
HDU AlHPOWl MAXIMUM TEMPERATUHE, 31,67 CFNF
PAGE
1 IMt
(ESF)
11. bj
1.63
2.b3
3.t>3
-------
HTI SMOG CHAMBEH STUD1TJ UStPA CONTRACT NO. 6B-02-2258
CHAMbf.H NO.
PROPYLENE
OX DILUTION
DAY 1, 7-15-76
X POSSIBLE MINUTES SUNSHINE, 76
HOU AIRPORT MAXIMUM TEMPERATURE, 17.22 CENT
PAGE
00
TIME
(LSI)
U.bl
l.bl
2.6]
i.6l
4.63
5.63
6.61
7.63
8.63
9.63
tป. 63
11.63
12.63
11.61
14. bl
15.61
16.61
17.61
16.61
19.61
20.61
21.63
22.63
21.61
OZONE
(PPM)
0,515
0.504
0.492
0.4ป1
0.471
0,460
0.450
0.435
0.428
0.417
0.402
0.401
0.399
0.391
0.375
0.355
NO
(PPM)
0.0
0.0
0.0
o.o
0.0
o.o
0.001
0.004
0.006
0.004
0.001
0.002
0.001
0.0
0.0
o.o
^02
(PPM)
0.010
0.029
0.029
0.02B
0.02B
0.027
o,02a
0.033
0.014
0.031
0.011
0.029
0.027
0.025
0.021
0.022
NOX S02
(PPM) (PPM)
0.030
0.029
0.029
0.026
0.026
0.027
0.029
0.017
0.040
0.035
0.014
0.011
0.02B
0.025
0.021
0.022
NBK1 N02-S CH20 SR
(PPM) (PPM) (PPM) (LANG
0.0
0.0
0.0
o.o
0.0
0.04
0.23
0.42
0.76
0.601 0.016 0.162 0.97
1.12
1.22
0.519 0.014 0.126 1.27
0.90
0.78
0.74
0.527 0.017 0.50
0,10
0.01
0.0
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0,0
0.0
1.52
11.14
32.16
70.28
123.86
187.76
256.76
311.66
396.00
445.44
490.72
526.00
540.60
541.16
543.60
543.60
543.60
543.60
543.60
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
21.11
20.00
22.22
31.11
16.11
36,11
28.69
23.69
-------
SHUU CMA'iBfcH STUim U3EPA CONTRACT NO.
CHAMtHR NO. 1, FUHAN
TAKUET INITIAL HC/NUXI
, 95X DILUIION
5.0 PPMC/I.OO PPM
PAGE 1
DAY I, 7-20-76
x POSSIBLE MINUTES SUNSHINE, 71
ซDU AIKPCW MAXIMUM TEMPERATURE, JJ.89 CENT
TIKE U2UME HU M02 UOX S02 NUM N02-S CH20 SK CUM-SR TEMP DILUTION BEGAN ENDED
(LSI) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT) (CFM) (EST) (EST)
/HIM)
ro
".13
1.13
2.13
3.13
1.13
5.13
6.13
7.13
0.13
v.i3
10.13
11.13
12.13
13.13
It. 13
1^.13
16.13
17.13
18. U
19.13
20.13
21.13
22.13
23.13
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.030
0.650
O.bSS
0.450
0.370
0.300
0.250
0.206
0.172
0.141
0.112
0.089
0.070
O.OS5
0.043
0.03S
0.030
0.030
0.030
0.035
O.B4S
O.flOO
0.769
0.722
0.090
0.006
0.003
0.007
o.ooa
0.007
0.008
0.009
0.011
0.012
0.013
0.017
O.OJ9
0.020
0.021
0.023
0.001
0.001
0.001
0.082
0.185
0.200
0.213
0.2o5
0.750
0.230
0.137
0.090
0.062
0.044
0.032
0.024
0.020
0.015
0.012
0.012
0.010
0.010
0.009
0.009
0.031
0.031
0.031
0.117
1.030
1.000
0.902
0,987
0.840
0.236
0.140
0.097
0.070
0.051
0.040
0.033
0.031
0.027
0.025
0.029
0.029
0.030
0.030
0.032
0.569
0.494
0.019
0.011
0.422 0.015 0.340
0.020
0.0
0.0
0.0
0.0
0.0
0.03
0.21
0.46
0.73
.00
.03
.14
.10
.24
.15
0.92
0.6B
0.32
0.18
0.03
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.24
3.48
18.08
47.84
93.80
154.04
216.72
284.80
351.92
425.60
492.76
546.04
583.96
602.04
611.64
613.20
613.20
613.20
613.20
21.11
18.89
21.11
28.33
31.67
30.00
27.78
23.89
1.95
8.00
-------
KTI SMUG tlUMBEN SIUOY: USEPA CONTRACT NU. 68-03-2258
CHAMUER NU. 1,
FUHAN
, 9bX DILUTION
DAt 2, 7-21-76
x POSSIBLE MINUTES SUNSHINE/ 70
HUU AlkPURT MAXIMUM TEMPERATURE, 35.00 CENT
PAGE
TI^E
(E3T)
O.li
l.li
a. 13
3.13
ซ.i3
5.11
6.11
7.13
8.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
17.13
16.13
I1*. 13
20.13
21.13
22.13
23.13
UZUNE
(PPM)
0.026
0.022
0.017
0.011
0.006
0.004
0.002
0.002
0.006
0.018
0.030
0.045
0.061
0.0/5
0.066
0.100
0.106
0.109
0.105
0.099
0.093
0.088
0.064
0.079
NU
(PPM)
0.028
0.026
0.027
0.027
0.025
0.026
0.02S
0.026
0.015
0.025
0.027
0.025
0.021
0.008
0.017
0.017
0.014
0.013
0.010
0.012
0.012
0.016
0.019
0.020
NU2
(PPM)
0.011
0.007
0.008
0.007
0.007
0.007
0.006
0.006
0.007
0.007
0.008
0.009
0.009
0.010
0.010
0.010
0.011
o.oto
0.010
0.010
0.010
0.009
0.009
0.009
MOX SU2
(PPM) (PPM)
0.039
0.033
0.03S
0.034
0.032
0.033
0.031
0.032
0.022
0.032
0.035
0.034
0.030
0.018
0.027
0.027
0.025
0.023
0.020
0.022
0.022
0.025
0.026
0.029
HHKI HU2-S CH2U 3H
(PPM) (PPM) (PPM) (LANG
/M1N)
0.0
0.0
0.004 0.0
0.0
0.0
0.03
0.19
0.42
0.68
0.94
0.024 0.006 0.269 1.04
1.11
1.24
1.11
0.96
0.91
0.65
0.017 0.006 0.36
0.13
0.02
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.24
3.32
16.56
43.84
66.72
143.92
206.88
274.52
347.68
413.28
470.48
S23.00
559.84
580.64
587.56
588.60
586.60
588.60
588.60
TEMP
(CENT)
22.76
21.67
21.67
30,00
32.22
33.33
31.11
25.56
DILUTION BEGAN ENDED
(CFM) (EST) (EST)
1.95 6. 00
-------
TIi:t
(tST)
OZOHE
(PPM)
NO
(PPM)
N02
(PPM)
R1I SMOG CHAMbtH STUDTl USEPA CONTRACT NO. 68-02-2256
HOX
(PPM)
CHAMBER NO. 1,
FURAN
, 95X DILUTION
OAT 3, 7-22-76
X POSSIBLE MINUTES SUNSHINE, 69
KDU AIRPORT MAXIMUM TEMPERATURE, 36. 67 CENT
SO?
(PPM)
NBM
(PPM)
N02-S
(PPM)
CH20 SR
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
PAGE 3
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.13
l.li
2.13
3.13
4.13
5.13
6.13
7.11
0.13
9.13
10.13
11.13
12.13
13.13
14.13
15.13
16.13
I/. 13
18.13
19.13
20.13
21.13
22.13
23.13
0.075
0.073
0.066
0.065
0.060
0.056
O.OSO
0.041
0.045
0.063
0.069
0.107
0.126
0.136
0.144
0.152
0.02b
0.028
0.030
0.033
0.034
0.035
0.032
0.038
0.036
0.033
0.030
0.024
0.016
0.016
0.012
0.010
0.008
0.008
0.006
0.006
0.003
0.004
0.008
0.009
0.010
0.012
0.012
0.011
0.011
0.012
0.011
0.011
0.033
0.036
0.036
0.041
0.042
0.043
0.040
0.047
0.046
0.045
0.042
0.03S
0.029
0.028
0.023
0.021
0.091 0.008 0.056
O.U85 0.002 0.004
0.0
0.0
0.0
0.0
0.0
0.03
0.20
0.40
0.68
0.68
1.16
1.2/4
1.27
0.87
1.16
0.66
0.11
0.25
0.13
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0
0.24
3.40
17.00
43.24
65.64
140.66
210.92
285.56
356.56
413.08
460.28
525.68
533.60
547.64
554.56
555.60
555.60
5S5.60
555.60
23.69
22.78
22.78
31.67
35.00
32.22
29.44
27.22
-------
HT1 SMOG CHAMBEN STUDU USEPA COMIHACT UO. <>B-02-22bB
CHAMBER NO. 2, TMIOPHEUE , 95* DILUTION
TAKGET INITIAL HC/NOX! 5.0 PPMC/1.00 PPM
DAY 1, 7-20-76
X POSSIBLE MINUTES SUNSHINE, 74
HUU A1KPOKF MAXIMUM TEMPERATURE, 33.89 CENT
PAGE 1
10
I 1Mb
US!)
11.30
1.30
2.30
3. JO
4.30
5.30
6.30
7.30
ซ. 30
9.30
10.30
11.30
12.30
13.30
lซ.3l>
15.30
16.30
17.30
18.30
19.30
20.30
21.30
22.30
33.30
OZONE
(PPM)
0.004
0,003
0.002
0.001
0.0
0.0
0.0
0.0
0.0
0.0
0.005
0.026
0.070
0.130
0.185
0.215
0.225
0.199
0.160
0.124
0.096
0.075
0.058
0.044
NO
(PPH)
0.031
0.032
0.030
0.045
O.B44
0.600
0.777
0.745
0.644
0.420
0.215
0.094
0.042
0.022
0.016
0.015
0.016
0.016
0.014
0.020
0.021
0.022
0.027
0.028
N02
(PPM)
0.012
0.012
0.010
0.211
0.196
0.210
0.220
0.240
0.294
0.350
0.366
0.325
0.257
0.175
0.108
0.064
0.040
0.029
0.023
0.020
0.015
0.012
0.012
0.010
riOX
(PPM)
U.043
0.044
0.040
0.256
1.040
1.010
0.997
0.985
0.938
0.770
0.581
0.419
0.299
0.197
0.124
0.079
0.056
0.045
0.037
0.040
0.036
0.034
0.039
0.038
SU2 NBM NU2-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.002
0.005
0.005
0.017
0.045
0,075 0.009a 0.322
0.105
0.125 0.157
0.125
0.120
0.115 0.041
0.105
0.090 0.127 0.245
0.075
0.055
0.040 0.123
0.030
0.020
0.015
CH2U SR
(PPM) (LANG
/HIM)
0.0
0.0
0.0
0.0
0.0
0.03
0.21
0.46
0.73
.00
0.479 .03
.14
.10
.24
.15
0.92
0.68
0.169 0.32
O.IK
0.03
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.54
5.58
22.68
55.14
103.80
164.34
228.12
295.80
364.32
437.10
501.96
552.84
587.16
603.84
611,94
613.20
613.20
613.20
613.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
21,11
18.89
21.11
2.32 6.00
28.33
31.67
30.00
27.78
23.89
aThis NBKI measurement may be low in comparison to the chemiluninescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
HTI SMUG CHAMBER SIUOM USEPA CONTRACT NO. 66*02-2256
CHAMBER NO. i, THIDPHErJE , 95X DILUTION
DAY 2, 7-21-76
X POSSIBLE MINUTES SUNSHINE, 70
KDU AIRPORT MAXIMUM TEMPERATURE, 35.00 CENT
PAGE 2
U>
Tlwt
(LSD
0.30
1.30
2.30
3.30
1.30
5.3U
6.30
7.30
B.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
OZOi.ll
(PPM)
0.033
0.023
0.017
0.010
0.006
0.003
0.002
0.009
0.023
0.045
0.070
0.091
0.107
0.120
0.120
0.129
0.135
0.131
0.125
0.117
0.110
0.103
0.097
0.091
NU
(PPM)
0.026
0.028
0.028
0.028
0.026
0.026
0.027
0.027
0.020
0.027
0.026
0.026
0.021
0.012
0.019
0.016
0.017
0.015
0.013
0.013
0.013
0.019
0.020
0.022
N02
(PPM)
0.010
0.010
0.009
0.009
0.009
0.009
0.009
0.019
0.011
0.011
0.011
0.011
0.011
0.011
0.011
0.010
0.010
0.010
0.010
0.010
0.009
0.007
o.noa
0.007
NUX
(PPM)
0.03H
0.03d
0.037
0.037
0.035
0.035
0.0)6
0.437
0.031
0.036
0.039
0.037
0.032
0.023
0.030
0.028
0.027
0.025
9.023
0.023
0.0
-------
WII SMUG tHAMHLN STUUn UStPA CUNTNACT NU. 68-02-2258
CHAHUtR NO. 2, THIOPHENE
. 95* DILUTION
DAY 3, 7-22-76
X POSSIBLE MINUTES SUNSHINE, 69
RDU AIHPORT MAXIMUM TEMPERATURE, 36.67 CENT
PAGE
to
lift
(tST)
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
16.30
19.30
20.30
21.30
22.30
23.30
UZOUE
(PPM)
0.085
0.079
0.073
0.06b
0.057
0.050
0.041
0.037
0.049
0.073
0.094
0.115
0.133
0.140
0.147
0.152
NO
(PPM)
0.025
0.027
0.029
0.030
0.032
0.033
0.032
0.03R
0.038
0.034
0.031
0.027
0.021
0.019
0.018
0.013
U02
(PPM)
O.OOB
0.007
0.004
0.008
0.005
0.009
0.010
0.012
0.012
0.012
0.012
0.011
0.010
0.010
0.010
0.010
riox
(PPH)
0.033
0.034
0.037
0.038
0.040
0.042
0.042
0.050
0.050
0.046
0.043
0.038
0.031
0.029
0.028
0.023
S02
(PPM
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
S02 NHK1 N02-3 CH20 SR CUM-SH TEMP
(PPH) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(E3T)
0.079 0.008 0.032
0.072 O.OOB 0.087
0.0
0.0
0.0
0.0
0.0
0.03
0.20
0.40
0.68
o.ea
1.16
1.24
1.27
0.87
1.16
0.86
0.11
0.25
0.13
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.54
5.00
21.00
50.04
94.44
152.28
223.32
296.26
367.26
424.68
488.88
526.98
536.10
546.94
554.76
555.60
555.60
555.60
555.60
23.69
22.78
22.78
31.67
35.00
32.22
29.44
27.22
-------
HI I SMUli CHA^HtH SIUOTI USEPA CUNTH4CT NO. 66-02-2258
CHAMbtR NO. 3, PYKHOLE ,
-------
HU SMOG CHAMHEK STUOYt USEPA CONTRACT NO. 68-02-2258
CHAMULR NO. J, PYRROLE , 9SX DILUTION
DAY 2, 7-21-76
X POSSIBLE HINDUS SUNSHINE, 70
HDU A1HPOK1 MAXIMUM TEMPERATURE, 35,00 CENT
PAGE
CO
MMt
(tST)
0.47
1.17
2.47
3.ซ7
a. ซ7
5.47
6.47
7.47
8.17
9.47
10.47
11. a?
I*. 47
13.47
11.17
15.ซ7
16.47
17.47
16.47
19.47
20.47
21.17
22.47
23.47
02 DUE
(PPM)
0.009
0.006
0.003
0.002
0.001
0.0
0.001
0.008
o.oie
0.033
0.047
O.Obl
0.073
0.064
0.090
0.099
0.101
0.100
0.09S
0.090
0.084
0.078
O.U74
0.070
NU
(PPM)
0.028
0.028
0.027
0.027
0.026
0.025
0.027
0.027
0.020
0.026
0.027
0.025
0.022
0.014
0.019
0.01B
0.017
0.015
0.012
0.013
0.013
0.019
0.020
0.022
NU2
I PPM)
0.010
0.009
0.008
0.008
0.008
0.007
0.007
0.008
0.006
0.008
0.009
0.009
0.009
0.009
0.009
0.010
0.009
0.009
0.010
0.009
0.008
0.008
0.008
0.007
NUX
(PPM)
0.038
0.037
0.035
0.035
0.034
0.032
0.034
0.035
0.028
0.034
0.036
0.034
0.031
0.023
0.028
0.028
0.026
0.024
0.022
0.022
0.021
0,027
0.028
0.029
NUX 302 NBKI N02-S CH20 SR CUM-SR TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT)
/MIN)
0.006
0.062 0.009 0.269
0.044 0.007 0.037
0.0
0.0
0.0
0.0
0.0
0.03
0.19
O.D2
0.68
0.94
1.04
1.11
1.24
1.11
0.96
0.91
0.65
0.38
0.13
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.84
7.12
24.96
57.44
105.52
164.72
229.08
299.32
370.08
132.48
488.68
536.00
567.44
583.24
587.96
588.60
588.60
588.60
588.60
22.78
21.67
21.67
30.00
32.22
33.33
31.11
25.56
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
2.05
8.00
-------
HTI SMOG CHAMOEN STUOYJ USEPA CONTRACT NO. 68-02-2256
CHAMbtR NO. i,
PYRROLE
, 95X DILUTION
DAY 3, 7-22-76
* POSSIBLE MINUTES SUNSHINE, 69
HOU AIRPOHT MAXIMUM TEMPERATURE, 36.67 CENT
PAGE 3
riMfc
(EST)
H.tl
1.47
a. 17
3.47
4.17
5.47
6.47
7.47
H.47
9.47
10.47
11.47
12.47
13.47
14.47
15.47
lb.47
17.47
in. 17
11.47
20.47
21.47
22.47
2i.47
QlUUf.
(PPM)
0.065
0.061
0.056
0.052
0.046
0.041
0.035
0.033
0.045
0.072
0.095
0.115
0.131
0.140
0.144
0.147
NO
(PPM)
0.024
0.026
0.029
0.030
0.032
0.031
0.032
0.038
0.038
0.034
0.031
0.020
0.022
0.020
0.018
0.013
N02
(PPM)
0.007
0.006
0.006
0.006
0.007
0.008
0.008
0.010
0.011
0.012
0.012
0.010
0.010
0.010
0.010
0.010
NOX
(PPM)
0.031
0.032
0.035
0.036
0.039
0.039
0.040
0.048
0.049
0.046
0.043
0.036
0.032
0.030
0.028
0.023
S02 NBK1 NCI2-S CH2U SR
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG
CUK-SR TEMP
(LANG) (CENT)
DILUTION
(CM)
BEGAN
(EST)
ENDED
(EST)
0.099 0.009 0.002
0.065 0.013 0.008
0.0
0.0
0.0
0.0
0.0
0.03
0.20
0.40
0.68
0.88
1.16
1.24
1.27
0.87
1.16
0.86
0.11
0.25
0.13
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.84
7.40
25.00
56.64
103.24
163.88
235.72
310.96
375.96
436.28
497.48
528.08
538.60
550.24
554.96
555.60
555.60
555.60
555.60
23.89
22.78
22.78
31.67
35.00
32.22
29.44
-------
HTI SMOG ChAMBfch STUDY: USEPA CONTRACT MO. 68-02-2858
CHAMBER NO. 4, PKOPYLENE , 95X DILUTION
TARGET INITIAL HC/NOXj 5.0 PPMC/UOO PPM
DAY I, 7-20-76
* POSSIBLE MINUTES SUNSHINE, 74
ROU AIRPORT MAXIMUM TEMPERATURE, 33.89 CENT
PAGE i
(ESI)
OZONfc
(PPM)
NO
(PPM)
N02
(PPM)
NOX
(PPM)
S02
(PPM)
NBKI
(PPM)
N02-S
(PPM)
CH20 SH
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
00
0.63
l.oi
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
17.63
18.63
19.63
20.63
21.63
22.63
23. 6i
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.020
0.745
0.935
0.893
0.8-59
0.805
0.746
0.669
0.560
0.468
0.403
0.333
0.278
0.233
0.197
0.167
O.U34
0.031
0.030
0.048
0.268
0.810
0.765
0.570
0.110
0.019
0.013
0.012
0.010
0.008
0.008
0.010
0.010
0.012
0.013
0.016
0.019
0.020
0.021
0.021
0.004
0.003
0.003
0.193
0.188
0.195
0.237
0.407
0.725
0.510
0.335
0.262
0.203
0.157
0.119
0.039
0.066
0.049
0.039
0.029
0.022
0.020
0.017
0.014
0.036
0.034
0.033
0.241
0.456
1.005
1.002
0.977
0.835
0.529
0.346
0.274
0.213
U.165
0.127
0.099
0.076
0.061
0.052
0.045
0.041
0.040
0.038
0.015
1.309 0.059 1.096
0.027
0.020
1.108 0.054 0.740
0.015
0.0
0.0
0.0
0.0
0.0
0.03
0.21
0.46
0.73
.00
.03
.14
.10
.24
.15
0.92
0.68
0.32
0.18
0.03
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.14
9.78
31.88
69.74
123.80
184.94
250.92
317.60
369.12
460.10
520.36
566.44
593.56
607.44
612.54
613.20
613.20
613.20
613.20
21.11
18.89
21.11
28.33
31.67
30.00
27.78
23.89
2.30
8.00
-------
HT1 SMUG CHAMBER STUDY! UStPA CONTRACT NO. 68-02-2258
CHAHBtR NO. 4, PHOPfLENE
, 95X DILUTION
OAป 2, 7-21-76
ป POSSIBLE MINUTES SUNSHINE, 70
ROU AIKPORT MAXIMUM TEMPERATURE, 35.00 CENT
PAGE 2
U)
MME
(ESf)
U.t>3
1.63
2.63
3.65
1.61
5.63
6.63
7.63
6.63
9.63
10.63
11.63
13.63
13.o3
14.63
15.63
16.63
17.63
18.61
19. b3
20.61
21.63
22.63
23.63
UZLWE
(PPM)
0.140
0.119
0.101
0.005
0.071
0.060
0.050
0.043
0.044
0.055
0.070
0.083
0.093
0.103
0.106
0.111
0.111
0.107
0.103
0.098
0.095
0.092
0.089
0.086
NO
(PPM)
0.022
0.022
0.022
0.021
0.021
0.021
0.021
0.021
0.016
0.020
0.020
0.020
0.016
0.010
0.012
0.011
0.011
0.009
0.009
0.009
0.010
0.013
0.016
0.020
N02
(PPM)
0.012
0.011
0.010
0.009
o.ooa
0.008
0.000
0.007
0.007
o.ooa
0.009
0.009
0.009
0.010
0.010
0.009
0.010
0.009
0.009
0.008
0,008
0.007
0.007
0.006
NUX S02
(PPM) (PPM)
0.034
0.033
0.032
0.030
0.029
0.029
0.029
0.028
0.023
0.028
0.029
0.029
0.027
0.020
0.022
0.020
0.021
0.018
0.018
0.017
0.016
0.020
0.023
0.026
NBKI N02-S CH20 SR
(PPM) (PPM) (PPM) (LANG
/MIN)
0.0
0.0
0.003 0.0
0,0
0.0
0.03
0.19
0.42
0.68
0.94
0.108 0.011 0.366 1.04
1.11
1.24
1.11
0.96
0.91
0.65
0.107 0,011 0.334 0.36
0.13
0.02
0.0
0.0
0.0
0.0
CUH-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
1.14
9.02
29.16
64.24
114.92
175.12
240.16
311.72
361.18
442.08
497.76
542. SO
5M.24
584.54
588.16
588.60
568.60
588.60
588.60
TEMP
(CENT)
22.78
21.67
21.67
30.00
32.22
33.33
31.11
25.56
DILUTION BEGAN ENDED
(CFH) (EST) (EST)
2.30 S.OO
-------
UME
USD
UZOUt
(PPM)
NU
(PPM)
N02
(PPM)
HTI SMUG CHAMBEH STUOYl USER* CONTRACT NO. 68-03-2258
NQX
(PPM)
CHAMBER MO. 4, PROPYUENE
, 95X OILUIION
DAY i, 7-22-76
X POSSIBLE MINUTES SUNSHINE, 69
RDU AIRPOKT MAXIMUM TEMPERATURE, 36,67 CENT
302
(PPM)
NBK1
(PHH)
N02-S
(PPM)
CH20 SR
(PPM) (LANG
CUM-SH
(LANG)
TEMP
(CENT)
PACE 5
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
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
Ih.bi
17.63
10.63
19.63
20.63
21.63
22.63
23.63
0.004
0.002
0.060
0.076
0.076
0.074
0.072
0.066
0.069
0.077
0.093
0.100
0.123
0.144
V.135
0.137
0.020
0.022
0.025
0.026
0.028
0.029
0.030
0.032
0.032
0.030
0.026
0.023
0.020
0.017
0.014
0.010
0.007
0.005
0.005
0.004
0.005
0.006
0.007
o.ooa
0.008
0.009
0.010
0.010
0.0)0
0.010
0.010
0.010
0.027
0.027
0.030
0.030
0.033
0.035
0.037
0.040
0.040
0.039
0.038
0.033
0.030
0.027
0.024
0.020
O.IU8 0.006 0.012
0.096 0.006 0.03B
0.0
0.0
0.0
0.0
0.0
0.03
0.20
0.40
0.66
0.88
1.16
1.24
1.27
0.67
1.16
0.66
0.11
0.25
0.13
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.14
9.40
29.00
63.64
112.04
175.46
246.12
323.66
364.66
447.66
506.06
529.16
541.10
551.54
555.16
555.60
555.60
555.60
555.60
23.69
22.76
22.76
31.67
35.00
32.22
29.44
27.22
-------
RII SMOG CHAMBEH STUDY: ustPA CONTRACT NO. 68-02-2258
CHAMBER NO. 1, METHANETHJOL , OX DILUTION
TAKGET INITIAL HC/NOX5 5.0 PPMC/1.00 PPM
DAY 1, 7-26-76
x POSSIBLE MINUTES SUNSHINE, as
HUU AIRPUH1 MAXIMUM TEMPERATURE/ 31.33 CENT
PACE
TIME
(EST)
0.13
1.13
2.13
3.13
4.13
5.13
6.13
7.13
0.13
9.13
10.13
11.13
1Z.13
13.13
14.13
lb.13
16.13
17.13
10.13
19.13
20.13
21.13
22.13
23.13
OZONE
(PPM)
0.0
0.0
0.0
0.0
U.O
0.0
0.0
0.0
0.0
0.410
0.745
0.693
0.643
0.580
0.515
0.470
0.434
0.406
0.382
0.356
0.335
0.304
0.2/3
0.241
NO'
(PPM)
0.006
0.009
0.009
0.009
0.161
0.798
0.763
0.660
0.430
0.026
0.000
0.022
0.011
0.023
0.016
0.022
0.012
0.026
0.026
0.037
0.043
0.055
0.066
0.074
NU2
(PPM)
0.004
0.002
0.002
0.116
0.225
0.210
0.217
0.297
0.464
0.531
0.077
0.046
0.047
0.045
0.052
0.045
0.056
0.045
0.040
0.037
0.035
0.035
0.036
0.036
NOX
(PPM)
0.010
0.011
0.011
0.125
0.366
1 .006
0.960
0.957
0.914
0.557
0.065
0.070
0.05b
0.066
I). 066
0.067
0.070
0.071
0.068
0.074
0.076
0.090
0.104
U.IIO
SU2 NBKI N02-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.004
0.010
0.077
0.400
t.540
1.610 0.<>39b 0.029
1.540
1.456
.358
.260
.220
.150 0.043b 0.035
.090
.040
0.960
0.920
0.770
0.660
0.520
CH2U SR
(PPM) (LANG
/M1N)
0.0
0.0
0.0
0.0
0.0
0.01
0.17
0.39
0.61
0.53
0.889 l.ll
1.19
1.16
0.68
1.01
0.84
0.856 0.55
0.31
0.10
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.08
1.96
13.92
39.08
75.04
111.46
178.72
250.04
316.44
372.28
431.52
479.60
510.68
527.60
532. 88
533.40
533.40
533.40
533.40
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
23.69
22.76
23.89
31.11
32.76
32.22
27.78
23.89
aThe NO and
readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
This NBKI measurement Bay be low in comparison to the chemiluminescent ozone reading due to the negative interference of
sulfur dioxide on the NBKI measurement.
-------
HII SMOG CHAMBER STUOM USER* CONTRACT NO, 68-02-3258
CHAMUtH NO. I, METMANETHIOL , OX DILUTION
DAY 2, 7-29-76
X POSSIBLE MINUTES SUNSHINE, 70
KOU AIRPORT MAXIMUM TEMPERATUKE, 35.56 CENT
PAGt
TIME
(ESI)
OZONE
(PPM)
NUa
(PPM)
MU2
(PPM)
NOX"
(PPM)
S02
(PPM)
NBKI
(PPM)
N02-S
(PPM)
CH20 SR
(PPM) (LANG
CUM-SH
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
Ni
0.13
1.13
2.13
3.13
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
I/. 13
16.15
19.13
20.13
21.13
22.13
23.13
0.207
0.176
0.153
0.126
0.106
0.009
0.073
0.066
0.097
0.159
0.213
0.260
0.276
0.288
0.297
0.285
0.277
0.263
0.250
0.230
0.206
0.160
0.157
0.140
0.076
0.076
0.077
0.073
0.066
0.064
0.062
0.069
0.077
0.09b
0.09fa
0.094
0.074
O.U63
0.057
0.038
0.044
0.035
0.036
0.045
0.038
0.043
0.040
O.OJ3
0.040
0.043
0.044
0.045
0.046
0.047
0.046
0.049
0.052
0.053
0.045
0.043
0.040
0.036
0.037
0.038
0.035
0.032
0.02B
0.029
0.030
0.032
0,031
0.036
0.116
0.119
0.121
0.118
0.112
0.111
0.110
0.116
0.129
0.148
0.141
0.137
0.114
0.099
0.094
0.076
0.079
0.067
0.064
0.074
0.068
0.075
0.074
0.069
0.360
0.210
0.112
0.040
0.0
0.0
0.0
0.0
0.0
0.040
0,056
0.056
0.042
0.042
0.028
0.026
0.026
0.0
0.0
0.0
0.0
0.0
o.o
0.0
0.177ฐ 0.022 0.063
0.153" 0.016 0.321
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.39
0.66
0.90
1.10
0.96
1.28
1.13
0.68
0.60
0.31
0.17
0.07
0,01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.16
2,56
14. S2
40.24
82.60
136.40
203.28
263.44
339.04
403.24
443.40
477.08
49(1.56
503.96
507.68
506.20
506.20
506.20
508.20
23.89
22.76
23,69
30,00
32.22
34,44
31.67
26.11
aThe NO and NOg readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
bThis NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of
sulfur dioxide on the NBKI measurement.
-------
RTI SMUG CHAMBLK SrUUYl USEPA CUNTHACI NO. 6H-02-22S8
IHAMBtR NO. I, HLTHANtTHlOL , OX DILUTION
DAY 3, 7-30-76
X POSSIBLE MINUTES SUNSHINE, 65
KOU AIRPOHJ MAXIMUM TfcMPtHATURE, 37.22 CENT
PAGE 3
CO
TIME
(EST)
0.13
1.11
2.13
3.13
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
17.13
16.13
19.13
20.13
21.13
22.13
23.13
UiOlJt
(PPM)
0.126
0.113
0.101
0.092
0.083
0.074
0.065
0.069
0.103
0.151
0.196
0.236
0.273
0.289
0.292
0.290
0.283
0.271
(ID
(PPM)
0.026
0.024
0.024
0.023
0.023
0.023
0.023
0.027
0.032
0.038
0.045
0.036
0.045
0.059
0.035
0.035
0.023
MU2
(PPM)
0.037
0.041
0.042
0.044
0.046
0.053
0.075
0.076
0.065
0.055
0.045
0.041
0.035
0.033
0.031
0.037
0.029
NOX
(PPM)
0.063
0.065
0.066
0.067
0.069
0.076
0.096
0.103
0.097
0.093
0.090
0.077
0.060
0.092
0.066
0.072
0.052
S02
(HPM)
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
NUKI NU2-3 CH20 SR
(PPM) (PPM) (PPM) (LANG
0.0
0.0
0.0
0.0
0.0
0.02
0.15
0.38
0.69
0.94
0.2U5 0.040 0.041 1.15
1.18
1.32
1.21
1.13
0.348 0.014 0.011 0.69
0.61
0.10
0.02
0.0
0.0
0.0
o.o
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.16
2.40
13.24
36.52
81.92
140.00
209.24
281,16
359.48
431.44
497.32
548.48
581.00
566.36
587.40
587.40
587.40
587.40
587.40
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
25.00
23.33
25.00
31.11
33.33
34.44
25.00
23.33
aThe NO and NOX readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
-------
RTi SMOG CHAMBE.H STUUYJ UStPA CONTRACT NO. 68-02-2258
CHAMBtH NO. 2,METHYL DISULFlOt, OX DILUTION
TARGET INITIAL MC/NOXl 5.0 PPMC/1.00 PPM
DAY I, 7-28-76
X POSSIBLE MINUTES SUNSHINE, 45
RDU AIRPOM MAXIMUM TEMPERATURE, 33.1) CENT
PACE I
TIME
(EST)
0.30
1.30
2.30
3.50
1.30
5.30
6. JO
7.30
8.30
9.30
10.30
1 1.30
12.30
13.30
14.30
15.30
16.30
17.30
16.30
19.30
20.30
21.30
22.30
23.30
(JiUHt
(PPM)
0.011
0.010
0.008
0.006
0.0
0.0
0.0
0.0
0.605
0.661
0.651
0.615
0.596
0.566
0.530
0.506
0.476
0.155
0.435
0.414
0.392
0.355
0.314
0.270
NO"
(PPM)
0.006
0.008
0.008
0.006
0.161
0.797
0.640
0.349
0.010
0.021
0.017
O.U22
0.019
0.023
0.023
0.017
0.017
0.028
0.033
0.03B
O.ObO
0.062
0.068
0.070
N02
(PPM)
0.004
0.004
0.003
0.230
0.223
0.239
0.366
0.589
0.194
0.045
0.032
0.030
0.031
0.029
0.031
0.041
0.032
0.02B
0.024
0.022
0.022
0.025
0.026
0.028
NOX S02
(PPM) (PPM)
0.010 0.0
0.012 0.0
0.011 0.0
0.238 0.0
0.384 0.0
1.036 0.008
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.006 0.210
.938 1.610
.204
.066
.049
.052
.050
.052
.054
.056
.049
.056
.057
.060
.072
.087
.890
.820
.790
.720
.680
.610
.580
.510
.480
.460
.400
.320
.090
.094 O.B50
.098 0.520
NBKI N02-S CH2U 3R
(PPM) (PPM) (PPM) (LANG
/M1N)
0.0
0.0
0.0
0.0
0.0
0.01
0
0
0
b o
0.017 0.015 0.728 1
1
1
0
1
b ซ
0.014 0.016 0.671 0
0
0
0
0
0
0
0
.17
.39
.61
.53
.11
.19
.18
.88
.01
.84
.55
.31
.10
.01
.0
.0
.0
.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.18
3.66
17.82
45.18
80.34
122.58
190.62
261.84
327.24
382.38
439.92
485.10
513.78
528.60
532.98
533.40
533.40
533.40
533.40
TEMP DILUTION BEGAN ENDED
(CENT) (CFH) (EST) (EST)
23.89
22.78
23
31
32
32
27
23
.89
.11
.78
.22
.78
.89
aThe NO and NO readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
bThis NBKI seasurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of
sulfur dioxide on the NBKI measurement.
-------
HII SMUG CHAMBER STUOYl USLPA CONTRACT NU. 66-02-2258
CHAMbtK MO. 2,METHYL D1SULF1DE, OX DILUTION
DAT 2, 7-29-76
X POSSIBLE MINUTES SUNSHINE, fO
RUU AIRPOKT MAXIMUM TEMPERATURE, iS.56 CLNf
PAGE 2
Ol
TIMt
(ESI)
O.JO
1.30
2.30
3.30
4.30
5.30
6.30
7.30
8. JO
9.30
10.30
11. JO
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)
0.227
0.193
0.165
0.140
0.122
0.105
0.088
0.064
0.109
0.155
0.206
0.257
0.282
0.304
0.313
0.301
0.293
0.276
0.264
0.224
0.205
0.187
0.171
0.157
NO*
(PPM)
0.074
0.079
0.077
0.071
0.064
0.061
0.061
0.070
0.081
0.109
0.111
0.106
0.107
0.077
0.071
0.069
0.043
0.053
0.042
0.041
0.046
0.039
0.040
0.040
NU2
(PPM)
0.029
0.029
0.031
0.031
0.033
0.034
0.037
0.039
0.041
0.041
0.039
0.035
0.035
0.031
0.029
0.030
0.027
0.028
0.026
0.026
0.029
0.031
0.033
0.036
NUX3
(PPM)
0.103
0.108
0.108
0.102
0.097
0.095
0.098
0.109
0.122
0.150
0.150
0.141
0.142
0.108
0.100
0.099
0.070
o.oai
0.068
0.067
0.075
0.070
0.073
0.076
SUi! NBK1 N02-S
(PPM) (PPM) (PPM)
0.240
0.080
0.003
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0 0.194 0.018
0.0
0.0
0.0
0.0
0.0
0.0 0.199 0.018
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CH20 3R
(PPM) (LANG
/MINI
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.39
0.68
0.90
0.048 1.10
0.96
1.28
1.13
0.68
0.60
0.034 0.31
0.17
0.07
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.36
4.26
18.42
47.04
91.80
149.40
212.88
276.24
350.34
410.04
449.40
480.18
496.26
504.66
507.78
508.20
508.20
508.20
508.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST)
-------
HTI SMOG CHAMBER STUDY: UStPA CUNTHACT NO. 68-02-2258
CHAMUER NO. 2,METHYL DISULFIOE, OX DILUTION
DAY 3, 7-30-76
X POSSIBLE M1NU1E3 SUNSHINE, 65
KOU AIKPOHT MAXIMUM 1EMPEKATUHE, 37.22 CENT
PAGE
-P-
tr
TIME
(LSD
0.3U
1.30
2.30
3. 3D
4.30
5.30
6.30
7.30
0.30
9.30
10.30
11.30
12.30
13.30
14.30
IS. 30
16.30
17.30
18. 30
19.30
20.30
21.30
22.30
23,30
OZUNE
(PPM)
0.145
0.134
0.123
0.113
0.104
0.094
o.oes
0.091
0.113
0.151
0,203
0.256
0.297
0.31S
0.323
0.324
0.320
N0a
(PPM)
0.030
0.024
0.022
0.022
0.422
0.020
0.021
0.022
0.031
0.030
0.041
0.050
0.041
0.047
0.069
0.043
0.032
K02
(PPM)
0.038
0.039
0.041
0.0<ป7
0.017
0.049
0.056
0.071
0.066
0.059
0.050
0.040
0.032
0.030
0.0*7
0.026
0.025
NUX
(PPM)
0.066
0.063
0.063
0.069
0.069
0.069
0.077
0.093
0.097
0.097
0.091
0.090
0.073
0.077
0.096
0.069
0.057
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
0.0
0.0
0.0
0.0
0.0
NUKI M02-S CH2D 3H
(PPM) (PPM) (PPM) (LANG
/HIM)
0,0
0.0
0.0
0.0
0.0
0.02
0.15
0.30
0.69
0.94
0.207 0.039 0.071 1.15
1.18
1.32
1.21
1.13
0.379 0.014 0.06
-------
Nil SMOG CHAMBER STUDY! UStPA CONTRACT HO. 68-02-2258
CHAMBtH NU. 3, MhTHtU SULMDt , OX DILUTION
TAHGET INITIAL HC/HOX: b.O PPHC/I.OO PPM
DAY If 7-28-76
* POSSIBLE H1UUIES SUNSHINE, OS
HDU AIHPOHT MAXIMUM TEMPLHATURE/ 33.33 CENT
PAGE 1
TIME
(EST)
UZONt
(PPM)
NU"
(PPM)
HU2
(PPK)
NOX
(PPM)
SD2
(PPM)
N13KI
(PPM)
N02-S
(PPM)
CH2U SK
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(E3T)
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
18.47
19.47
20.47
21.47
22.47
23.47
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.295
0.448
0.395
0.336
0.275
0.235
0.207
0.178
0.164
0.143
0.130
0.116
0.105
0.094
0.061
0.066
0.052
0.006
0.007
0.006
0.008
0.154
0.773
0.603
0.006
0.001
0.001
0.0
0.0
0.001
0.002
0.003
0.005
0.004
0.007
0.009
0.015
0.022
0.036
O.b55
0.065
0.004
0.004
0.004
0.241
0.220
0.235
0.372
0.530
0.070
0.035
0.029
0.026
0.030
0.02/
0.033
0.030
0.038
0.031
0.026
0.024
0.022
0.022
0.021
O.d2l
0.010
0.011
0.012
0.249
0.374
1.008
0.975
0.536
0.071
0.036
0.029
0.026
0.031
0.029
0.036
0.035
0.042
0.036
0.035
0.039
0.044
0.060
0.076
0.066
0.0
0.0
0.0
0.0
0.0
0.006
0.020
0.250
0.480
0.490
0.490
0.460
0.430
0.420
0.380
0.350
0.340
0.320
0.260
0.250
0.210
0.130
o.oao
0.040
0.076ฐ 0.005 0.612
0.063ฐ 0.009 0.795
0.0
o.o
0.0
0.0
0.0
0.01
0.17
0.39
0.61
0.53
I. 11
1.19
1.18
0.88
1.01
0.84
0.55
0.31
0.10
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
, 0.26
5.36
21.72
51.28
85.64
133.66
202.52
273.64
336.04
392.48
448.32
490.60
516.86
529.60
533.08
533.40
533.40
533.40
533.40
23.69
22.70
23.89
31.11
32.76
32.22
27.78
23.69
"The HO and NOX readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
ฐThis NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of
sulfur dioxide on the NBKI measurement.
-------
RT1 SMUG CHAMBER STUUY: USEPA CONTRACT NO. 6B-02-2258
NO. 3, MFTHYL SULFIUE , ox DILUTION
DA* 2, 7-29-76
X POSSIBLE MINUTES SUNSHINE, 70
RUU AIRPORT MAXIMUM TEMPERATURE, 35.56
PAGE
oo
TIME
(Ebl)
0.17
l.l/
2.47
3.17
4.17
5.17
6.17
7.17
6.17
9.17
10.47
11.17
12.17
13.47
11.47
15.47
16.47
17.47
18.47
19.47
20.17
21.17
22.47
23.17
UZUNE
(PPM)
0.040
0.031
0.024
0.018
0.014
0.011
0.010
0.032
0.095
0.152
0.185
0.201
0.185
0.194
0.183
0.102
0.158
0.141
0.128
0.105
o.oae
0.075
0.065
0.057
NO
(PPM)
0.073
0.075
0.076
0.068
0.063
0.061
0.063
0.068
0.086
0.107
0,107
0.104
0.101
0.080
0.075
0.073
0.046
0.052
0.046
0.046
0.045
0.040
0.042
0.040
N02
(PPM)
0.020
0.020
0.022
0.023
0.023
0.024
0.026
0.034
0.036
0.032
0.028
0.022
0.022
0.022
0.018
0.010
0.017
0.015
0.016
0.016
0.017
u.017.
J.019
0.021
NUXa
(PPh)
0.093
0.095
0.098
0.091
0.086
0.085
0.089
0.102
0.122
0.139
0.135
0.126
0.123
0.102
0.093
0.091
0.063
0.067
0.062
0.062
0.062
0.057
0.061
0.061
SU2
(PPM)
0.010
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
NBKI N02-S CH20 SR
(PPH) (PPM) (PPM) (LANG
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.39
0.68
0.90
0.047" 0.008 0,010 1.10
0.96
1.28
1.13
0.68
. 0.60
0.036D 0.009 0.075 0.31
0.17
0.07
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.56
5.96
22.32
53.84
100.80
160.40
222.48
289.04
361.64
416.84
455.40
483.28
497.96
505.36
507.88
508.20
508.20
508.20
508.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
23.89
22.76
23.89
30.00
32.22
34.44
31.67
26.11
aThe NO and NOx readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or some unexplained interferent or sampling artifact.
bThi9 NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of
sulfur dioxide on the NBKI measurement.
-------
KT1 SMUG CHAMBER STUDY! USEPA COHIHACI NO. 68-02-2258
CHAMtttH NO. 1, METHYL SULF1DE . OX DILUllO'l
DAY 1, 7-30-76
x POSSIBLE MINUTES SUNSHINE, 65
liUU A1HPOK1 MAXIMUM TEMPERATURE, 11.22 CENT
PAGE
vo
TlMf
(EST)
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
18.47
19.47
20.47
21.47
22.47
23.47
U2UNE
(PPrt)
0.049
0.043
0.038
0.028
0.024
0.023
0.052
0.093
0.146
0.207
0.251
0.277
0.280
0.280
0.274
0.270
0.264
uO
(PPM)
0.030
0.023
0.023
0.022
0.022
0.020
0.020
0.023
0.033
0.037
0.045
0.053
0.046
0.047
0.060
0.044
0.033
H02
(PPK)
0.023
0.0?5
0.029
0.032
3.036
0.040
0.047
0.050
0.044
0.036
0.032
0.027
0.025
0.023
0.021
0.019
o.uiB
NOX
(PPM)
0.053
0.048
0.052
0.054
0.05B
0.060
0.067
0.073
0.077
0.073
0.077
O.OBO
0.071
0.070
0.081
0.063
0.051
SO*
(HPM)
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
NBK1 N02-S CH20 SH
(PPK) (PPM) (PPM) (LANG
/M1N)
0.0
0.0
0.0
0.0
0.0
0.02
0.15
0.38
0.69
0.94
0.060 0.008 0.077 .15
.18
.32
.21
0.314 O.OM 0.040 .13
0.89
0.61
0.10
0.02
0.0
0.0
0.0
0.0
0.0
CUH-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.56
5.40
20.84
52.32
100.72
163.00
232.84
307.56
383.68
454.04
515.12
560.68
583.00
586.76
587.40
587.40
587.40
587.40
587.40
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
25.00
23.33
25,00
31.11
33.33
34.44
25.00
23.33
aThe NO and NOX readings in this run may be artificially high following the afternoon of 28 July 1976 due to either zero drift
in the instrument or scae unexplained interferent.or sampling artifact.
-------
KTI SMUG CHAMBER S1UDYS USER* CONTRACT NO. 66-02-2256
CHAMBER NO. 4, PHOPYLENt , 0* DILUTION
TARGET INITIAL HC/NOXJ 5.0 PPHC/I.OO PPM
DAY I, 7-28-76
Z POSSIBLE MINUTES SUNSHINE, 45
HDU AIHPOKT MAXIMUM TEMPERATURE, 33.33 CENT
PAGE 1
G
c
TIME
(ESI)
0.63
1.63
2.63
3.63
4.6J
5.63
6.63
7.63
6.63
9.63
10.63
Ii.b3
12.63
13.63
14.63
15.63
16.63
17.63
16.63
19.63
20.63
21.63
22.63
23.63
OZUWE
(PPM)
0.003
0.002
0.001
0.0
0.0
0.0
0.0
0.0
0.095
0.925
.100
.212
.200
.266
.200
.150
.131
.082
0.950
0.906
0.661
o.ais
0.762
0.755
NO
(PPM)
o.ooa
0.009
0.006
0.006
0.074
0.620
0.745
0.506
0.054
0.044
0.041
0.026
0.018
0.014
0.013
0.013
0.013
0.015
O.U16
0.022
0.016
0.030
0.036
0.041
NU2
(PPM)
0,004
0.004
0.003
0.233
0.225
0.239
0.305
0.506
0,ซH5
0.576
0.456
0.187
0.322
0.263
0.220
0.161
0.158
0.134
0.114
0.101
0.064
0.0/7
0.068
0.065
nux
(PPM)
0.012
0.013
0.011
0.241
0.299
1.059
1.050
1 .012
0.939
0.620
0.4V7
0.413
0.340
0.277
0.233
0.194
0.171
0.149
0.130
0.123
0.100
0.107
0.106
0.106
SU2 NOM N02-S CH20 SK
(PPM) (PPM) (PPM) (PHM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.17
0.39
0.61
0.53
1.402 0.093 1.399 1.11
1.19
1.16
0.86
1.01
0.64
0.397 0.101 1.020 0.55
0.31
0.10
0.01
0.0
0.0
0.0
0.0
CUM-SK
(LANG)
0.0
0.0
0.0
0.0
0.0
0.38
7.06
25.62
57.36
90.94
144.78
214.42
265.44
344.84
402.58
456.72
496.10
519.96
530.60
533.18
533.40
531.40
533.40
533.40
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
23.89
22.76
23.69
31.11
32.78
32.22
27.78
23.69
-------
KTI SMOU CHAMBER STUOn UStPA CONTHACI MO. 66-02-2358
CHAMbtR NO. 4. PROPYLENE
, OZ DILUTION
DAY 2. 7-29-76
i POSSIBLE MINUTES SUNSHINE, 70
RDU AIRPUkT MAXIMUM TEMPERATURE, 35.56 CENT
PACE 2
TIME
(tST)
0.63
1.63
2.03
3.63
4.63
5.b3
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
U20NE
(PPM)
0.723
0.690
0.665
0.636
0.613
0.586
0.549
o.soo
0.443
0.430
0.456
0.500
0.501
0.538
0.525
0.467
0.460
0.456
0.427
0.4IH
0.402
0.387
0.372
0.357
WU
(PPM)
0.044
0.051
0.048
0.047
0.046
0,04o
0.047
0.056
0.101
0.101
0.095
0.100
0.083
0.076
0.068
0.057
0.042
0.044
0.045
0.044
0.040
0.038
0.041
0.038
MOซJ
(PHM)
0.059
0.056
0.053
0,050
0.049
0.050
0.058
0.074
0.076
0.076
0.075
0.068
0.059
0.05S
0.043
0.042
0.03/
0.034
0.029
0.029
0.024
0.023
0.022
0.021
UOX
(PPM)
0.103
0.107
O.IOI
0.097
0.095
0.096
0.105
0.132
0.179
0.179
0.170
0.168
0.142
0.131
0.111
0.099
0.079
0.076
0,074
0.073
0,064
0.061
0.063
0.059
S02 NBK1 NU2-S CH2U SR CUM-SR TEMP DILUTION BEGAN ENDED
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT) (CFM) (EST) (E3T)
/MIN)
0.554 0.020 0.269
0.490 0.016 0.277
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.39
0.66
0.90
1.10
0.96
1.20
1.13
0.68
0.60
0.31
0.17
0.07
O.Oi
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.76
7.66
26.22
60.64
109.80
171.40
232.08
301.64
172.94
423.64
461.40
466.36
499.66
506.06
507.98
508.20
508.20
506.20
508.20
23.89
22.78
23.89
30.00
32.22
34.44
31.67
26.11
-------
HII SHIG CHAMBER STUDY: USEPA CONTRACT NO. 68-02-2258
CHAHHtR NO. 4, PROPYLENE
, 0% DILUTION
DAY 3, 7-30-76
x POSSIBLE MINUTES SUNSHINE, 65
HUU AIRPORT MAXIMUM TEMPERATURE, 37.22 CENT
PAGE
TIME
(EST)
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
16.63
19.63
20.63
21.63
22.63
23.63
OZONE
(PPM)
0.346
0.334
0.322
0.310
0.297
0.285
0.269
0.249
0.226
0.236
0.260
0.287
0.311
0.316
0.317
0.312
0.306
HU
(PPM)
0.026
0.023
0.024
0.023
0.023
0.020
0.021
0.025
0.033
0.039
U.047
0.047
O.OS4
0.053
0.653
0.042
0.032
N02
(PPIO
0.020
0.019
0.019
0.018
0.020
0.020
0.024
0.030
0.033
0.032
0.031
0.031
0.026
0.029
0.026
0.026
0.027
UOX
(PPM)
0.046
0.042
0.043
0.041
0.043
0.040
0.045
0.055
0.066
0.071
0.078
0.078
0.062
0.082
0.081
0.066
0.059
S02 NBKI NU2-S CH2U SR CUM-SR TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (LANS (LANG) (CENT)
DILUTION
(CM)
BEGAN
(EST)
ENDED
(EST)
0.295 0.016 0.111
0.367 0.015 0.122
0.0
0.0
0.0
0.0
0.0
0.02
0.15
0.36
0.69
0.94
1.15
1.16
1.32
1.21
1.13
O.S9
0.61
0.10
0.02
(1.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.76
6.90
24.64
59.22
110.12
174.50
244.64
320.76
395.76
465.34
524.02
566.76
564.00
586.96
587.40
587.40
587.40
587.40
587.40
25.00
23.33
25.00
31.11
33.33
34.44
25.00
23.33
-------
Nil SMOG CHftMUtH SIUOT1 U3EPA COMPACT NO. 68-02-2258
CHAMbtR MO. 1, METHAHETM1UL , 95X DILUTION
TARGET 1NII1AL HC/NUX: 5.0 PPMC/I.OO PPM
DAY 1* 6-10-76
I POSSIBLE MINUTES SUNSHINE, 84
HDU AIRPGHT MAXIMUM TEMPEHAIURE, 31.11 CENT
PAGE 1
Ui
U)
11 ME
(ฃS()
0.11
I. U
2.13
3.13
4.13
5.13
6.IJ
7.13
8.13
9.13
10.11
11.13
12.13
13.13
14.13
15.11
16.13
17.13
ltt.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
0.0
0.157
0.713
o.boa
0.494
0.411
0.354
0.295
0.251
0.213
o.ieo
0.148
0.111
o.oei
0.059
0.004
NO
(PPH)
0.002
o.oou
0.764
0.752
0.750
0.732
0.677
0.468
0.011
0.001
0.001
0.001
0.001
0.003
0.003
0.003
0.003
0.002
0.002
0.003
0.002
0.0
0.0
H02
(PPM)
0.003
0.005
0.0
0.246
0.236
0.237
0.280
0.417
0.567
O.Ofll
0.036
0.029
0.026
0.023
0.022
0.021
0.019
0.017
0.015
0.014
0.014
0.014
0.014
NOX
(PPM)
0.005
0.009
0.764
0.998
0.986
0.969
0.957
0.885
0.5/8
0.082
0.03/
0.030
0.027
0.026
0.025
0.021
0.022
0.019
0.017
0.017
O.UI6
0.014
0.014
302 NBK1 N02-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.010
0.009
0.011
0.039
0.237
0.904
1.021 0.005 0.154
O.B70
0.736
0.627
0.523
0.438
0.3/0 0.011 0.218
0.320
0.269
0.209
0.132
0.075
0.036
0.015
CH20 SH
(PPM) (LANG
/MINI
0.0
0.0
0.0
0.0
0.0
0.01
0.04
0.11
0.23
0.41
0.492 0.69
1.10
1.03
0.84
0.73
0.59
0.482 0.61
0.28
0.07
0.02
0.0
0.0
0.0
0.0
CUM-5R
(LANG)
0.0
0.0
0.0
0.0
0.0
0.06
0.92
3.86
11.44
26.66
53.52
96.20
163.64
223.92
273.44
316.12
351.68
385.64
400.76
404.56
405.60
405.60
405.60
405.60
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
21.67
20.00
20.00
1.95 6.00
25.56
30.00
30.56
27.22
22.22
aThia NBKI measurement nay be low in comparison to the chemiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
RTI SMOG IHAMUtK STUDY: UStPA CONJKACT NO.
CHAMIHR M). 1, METHANETHIOL , 95X DILUTION
DAY 2, 8-11-76
X POSSIBLE MINUTES SUNSHINE, Bfl
RUU AIRPORT MAXIMUM TEMPERATURE, 32.22 CENT
PปGt
I-1
in
TIMt
(tSI)
O.I 1
1.11
2.13
3.13
4.13
5.13
6.13
7.13
a. 13
9.13
10.13
11.13
12.13
13.13
14,1 J
IS. 13
16.13
17.13
IB. 13
14.13
20.13
21.13
22.13
23.13
OZUHE
(PPM)
0.029
0.024
O.Olb
0.011
0.008
0.003
0.004
0.010
0.026
0.051
o.oeo
0.103
0.123
0.142
0.156
0.163
0.168
0.164
0.157
0.147
0.133
0.116
0.102
0.093
NO
(PPM)
0.009
0.006
0.007
0.008
o.ooe
0.008
0.006
0.010
0.013
0.006
0.019
0.016
0.016
0.016
0.014
0.014
0.011
0.013
0.011
0.010
o.ooe
NU2
(HPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.013
.013
.013
.013
.012
.012
.012
.013
.010
.021
.026
.034
.041
.03U
.026
.023
.020
.018
.018
.017
.017
NOX
(PPM)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.022
.019
.020
.021
.020
.020
.016
.023
.031
.027
.045
.050
.057
.046
.040
.037
.034
.031
.029
.027
.025
SU2
(PPM)
0.011
0.006
0.006
0.0
0.0
0.0
0.0
0.0
0.019
0.019
0.022
0,1)24
0.027
0.024
0.022
0.024
0.022
0.019
0.014
0.007
0.006
0.0
NBKI N02-S CH20 SH
(PPH) (PPM) (PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.36
0.68
0.93
0.042 0.018 0.609 1.12
1.25
1.28
1.24
0.87
. 0.83
0.043 0.026 0.495 0.62
0.32
0.10
0.0
0.0
0.0
0.0
0.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.08
1.56
10.68
34.84
77.64
134.96
203.20
278.44
154.92
426.36
476.24
526.36
561.16
578.60
583.80
583.80
583.60
583.80
583.80
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
18
17
19
27
30
31
25
21
.89
.22
.44
1.95 8.00
.78
.00
.11
.00
.67
aThis NBKI measurement may be low in comparison to the chemiluninescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
RTI SMUG CHAMHEK SIUDYJ USEPA CONTRACT NO. 66-02-2258
CHAMBER NO. 1, MtTHANETHlOt , 95X DILUTION
DAY J, 8-12-76
x POSSIBLE MINUTES SUNSHINE, 66
HOU AIRPORT MAXIMUM TEMPERATURE, 11.33 CENT
PAGE 3
TIME
(LSI)
u.li
l.li
2.13
3.13
1.13
-3.13
6.13
/.IS
6.15
9.13
10.13
11.13
12.13
13.13
11.13
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
UiUUt.
(PPM)
O.U83
0.074
0.066
0.060
0.054
0.018
0.013
0.043
0.060
0.094
0.130
0.156
0.164
0.184
0.199
0.200
0.192
0.186
0.178
0.170
0.163
0.155
0.148
0.139
NO
(PPM)
0.008
0.007
0.007
0.007
0.006
0.006
0.006
O.U10
0.013
0.014
0.014
0.014
0.013
0.013
0.012
0.012
0.012
0.012
0.012
0.013
0.014
0.015
0.017
0.018
NU2
(PPM)
0.016
0.016
0.015
0.016
0.015
0.015
0.016
0.020
0.024
0.024
0.022
0.019
0.018
O.OIR
0.016
0.017
O.OIb
0.016
0.014
0.013
0.012
0.010
0.010
0.010
HOX
(PPM)
0.024
0.023
0.022
0.023
0.021
0.021
0.022
0.030
0.037
0.038
0.036
0.033
0.031
0.031
0.026
0.029
0.028
0.028
0.026
0.026
0.026
0.025
0.027
0.028
SU2 NBKI N02-S
(PPH) (PHM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.007 0.132 0.019
0.007
0.008
0.009
0.010
0.012
o.ooa
0.007 0.224 O.U27
0.007
0.007
0.006
0.005
0.004
0.0
CH20 SR
(PPM) (LANG
/M1N)
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.44
0.72
0.98
0.483 1.11
1.25
1.36
1.23
1.10
0.87
0.54
0.379 0.29
0.03
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.16
2.56
14.92
43.56
88.84
146.68
216.40
292.28
372.84
445.60
509.76
559.32
589.72
605.04
606.68
607.20
607.20
607,20
607.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (E3T) (EST)
20.56
19.44
21.67
30.00
32.22
31.11
27.78
25.00
-------
Hfl SMUG CHAMBER STUDU USEPA CONTRACT NO. 6K-02-2258
CHAMBER NO. 1, MtTHANETHIOL
DILUTION
DAY 4, B-13-76
X POSSIBLE MINUTES SUNSHINE, 66
KOU AIHPURT MAXIMUM TEMPERATURE, 11.13 CENT
PAGE 4
TIMt
(ESI)
0.11
1.11
2.11
3.11
4.11
'j.13
6.13
7.11
ซ. 13
9.11
10.13
11.13
13!l3
11.11
lb.13
16.13
17.13
18. li
19.13
2U.11
21.11
22.13
21.13
OZONE
(PPM)
0.111
0.122
0.111
0.101
0.094
0.086
0.077
MU
(PPM)
0.020
0,019
0.020
0.022
0.022
0.024
0.025
N02
(PPH)
0.010
0.010
0.010
0.011
0.012
0.1)12
0.014
NOX
(PPM)
0.030
0.029
0.030
0.013
0.034
O.Olb
0.039
SU2 NBKI N02-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
CH20 SH CUM-SR TEMP DILUTION BEGAN ENDED
(PPM) (LANG (LANG) (CENT) (CFM) (EST) (EST)
/M1N)
0.0
0.0
0.0
0.0
0.0
0.02
0.16
0.40
0.67
0.91
1.14
0.90
0.95
1.29
1.09
0.37
0.45
0.27
0.08
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.16
2.16
14.00
40.16
82.28
138.72
205.20
259. 6U
119.32
395.12
454.76
477.60
503.16
517.84
522.08
522.60
522.60
522.60
522.60
21.31
22.78
21.13
10.00
31.31
12.22
27.78
25.00
-------
KTI SMUG tHAMHEK STUOVI UStPA COWTKACI NO. 6b-02-
-------
HTI SMOG CHAMBER STUDY; USEPA CONTHACT NO. 68-02-2258
tHAMUtR NO. 2,METHYL DISULFIOE, 95X DILUTION
L)*Y 2, 8-11-76
% POSSIBLE: MINUTES SUNSHINE/ se
HDU AIKPIW MAXIMUM TEMPERATUHE, 32.22 CENT
PAGE
(ESD
UZUNE
(PPM)
NO
(PPM)
1-02
(PPM)
HOX
(PPH)
S02
(PPM)
NBKJ
(PPM)
NU2-S
(PPM)
CH20 SH
(PPM) (LANG
CUM-SH
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
00
0.30
1.30
2.3U
3.30
4.30
5.30
6. ill
7.30
a. 30
9.30
10.30
11.30
12.30
15.30
14.30
15.30
16.30
17.30
16.30
19.30
20.30
21.30
22.30
23.30
0.027
0.019
0.015
o.ooa
0.006
0.003
0.004
0.017
0.045
0.091
0.136
0.175
0.201
0.222
0.234
0.239
0.241
0.235
0.225
0.206
0.177
0.150
0.131
0.117
o.ooa
0.007
0.008
o.ooa
0.007
0.006
0.006
0.012
0.015
0.018
0.009
0.019
0.010
0.024
0.022
0.022
0.023
0.020
0.018
O.OIB
0.014
0.011
0.009
o.ooa
0.016
0.010
0.016
0.015
0.015
0.015
0.015
0.016
0.021
0.019
0.023
0.025
0,050
0.024
0.027
0.029
0.026
0,024
0.022
0.018
o.otu
0.017
O.Olfl
0.017
0.024
0.023
0.024
0.025
0.022
0.021
0.021
0.028
0.034
0.037
0.032
0.044
0.040
0.048
0.049
0.051
0.049
0.044
0.040
0.056
0.032
0.028
0.027
0.025
0.0.09
0.006
0.0
0.0
0.0
0.0
0.0
0.0
0.008
0.017
0.021
0.025
0.026
0.025
0.030
0.032
0.027
0.030
0.027
0.024
0.013
0.007
0.005
0.0
0.100 0.018 0.370
0.091a 0.021 0.304
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.36
0.68
0.93
1.12
1.25
1.28
1.24
0.87
0.83
0.62
0.32
0.10
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.ie
2.76
14.28
41.64
86.94
146.16
215.70
291.24
367.32
435.06
466.54
532.56
564.36
579.60
583.80
583.80
583.80
583.80
583.80
16.89
17.22
19.44
27.78
30,00
31.11
25.00
21.67
2.32
8.00
aThis HBKI Measurement may be low in comparison to the cheroiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
KT1 SMUG CHAMHEH STUDY! USEPA CONTRACT NO. 68-02-2258
CMAMBtH NO. 2,METHYL DISULFIDE, 95X DILUTION
DAY i, 8-12-76
X POSSIBLE MINUTES SUNSHINE, 66
RDU AIRPORT MAXIMUM TEMPERATURE. 33.33 CENT
PAGE 3
1 U-E
USt )
0.30
1.30
a. 30
3.30
4.30
5.30
6.30
7.30
B.30
V.30
10.30
11.30
12.10
13.30
14.30
15.30
16.30
17. 3u
IB. 30
19.30
20.30
21.30
22. iO
23.30
OZONE
(PPM)
0.106
0.096
0.067
0.080
0.073
0.067
0.061
0.059
0.077
0.113
0.152
0.179
0.187
0.209
0.224
0.225
0.218
0.214
0.208
0.199
0.187
0.169
0.155
0.143
HO
(PPH)
u.ooe
0.007
0.006
0.006
0.006
0.006
0.006
0.011
0.01^
0.017
0.017
0.016
0.016
0.016
0.015
0.017
0.016
0.01S
0.016
0.017
0.018
0.019
0.019
0.020
(102
(PPM)
0.017
0.016
0.016
0.016
U.017
0.017
0.018
0.023
0.026
0.024
0.021
0.019
o.oia
0.016
0.015
0.016
0.016
0.015
0.014
0.012
0.010
0.010
0.011
0.012
MIX
(PPM)
0.025
0.023
0.022
0.022
0.023
0.023
0.024
0.034
0.041
0.041
0.038
0.035
0.034
0.032
0.030
0.033
0.032
0.030
0.030
0.029
0.028
0.029
0.030
0.032
SU2 HBKI N02-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0 0.134 0.017
0.0
0.007
0.009
0.009
0.011
0.009
0.013
0.011 0.196 0.020
O.OU
0.009
0.007
0.005
0.002
0.0
CH2U SH
(PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.44
0.72
0.248 0.98
1.11
1.25
1.36
1.23
1,10
0.87
0.54
0.179 0.29
0.03
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.36
4.26
19.32
50.76
98.64
159.78
228.90
305.66
385.14
456.60
518.46
564.72
592.62
605.34
606.78
607.20
607.20
607.20
607.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (E3T) (EST)
20.56
19.44
21.67
30.00
32.22
31.11
27.78
25.00
-------
KT1 SMOG CHAMBEK STUUYl USEPA CUU1HACT NO. fafl-02-2258
tHAHbER NO. I,METHYL DISULFIOt, 951 DILUTION
DAY 4, 8-13-76
x POSSIBLE MINUTES SUNSHINE, bb
hou AIRPORT MAXIMUM TEMPEHAIURE, 33.33 CENT
PAGE a
11 *t
(tSI)
0.10
1.30
?.3u
3.30
4.3o
5.30
b.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14.30
15.30
lb.30
17.3d
16.30
19.30
21/.30
21.30
22.30
23.30
UZUUE
(HPM)
0.132
0.122
0.113
0.104
0.096
0.0d9
0.083
NO
(PPM)
0.021
0.020
0.020
0.022
0.022
0.023
0.024
NU2
(PPM)
0.013
0.014
0.015
0.016
o.oie
0.021
0.024
NUX
(PPK)
0.034
0.034
0.035
0.016
0.040
0.044
0.046
SU2 NBKI
(PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NU2-S CH20 SR
(PPH) (PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.02
0.16
0.40
0.67
0.91
1.14
0.90
0.95
i.a<>
1.09
0.37
0.4S
0.27
o.oe
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.36
4.06
le.oo
46.66
91.38
150.12
214.20
269.10
332.22
406.02
456.46
462.10
505.86
516.64
522.16
522.60
522.60
522.60
522.60
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
23.33
22.76
23.33
30.00
33.33
32.22
27. 7B
25.00
-------
Rfl SMUG CHAMHtK STUDY: UStPA CUNTHACT NU. 6B-02-2258
CHAHbLR NU. 3, METHYL SULFIPE , 9SX DILUTION
TAHGET InltlAL HC/NUXJ 5.0 PHMC/I.OO PPM
DAY lป 6-10-76
x cossibLE MINUTES SUNSHINE, 63
RUU A1KPOR1 MAXIMUM TEMPEKATUHE, 31.it CENT
PAGt I
1 1 .-It
(LST)
0.17
I.i7
2.47
1.17
4.47
5.47
6.47
7.17
B.47
9.47
10.17
11.17
12.17
13.47
J1.4J
IS. 17
lo.47
17.17
lป. 17
19.17
20.17
21.17
22.47
2J.47
UZUUE
(PPM)
0.0
0.0
0.0
0.0
0.0
0,0
0.0
0.161
0,468
0.101
0.316
0.257
0.216
0.191
0.172
0.119
0.133
0.117
0.099
0.0?9
0.05ft
0,010
0.026
0.020
NCJ
(PPMJ
0.001
0.002
0.602
0.763
0.770
0.635
0.003
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
.0.001
0.003
0.003
0.001
0.0
0.009
N02
CHPMJ _
0.003
0.002
0.0
0.247
0.216
0.353
0.698
0.092
0.031
0.021
0.020
0.016
O.Oltt
0.015
0.013
0.013
0.012
0.011
0.010
0.010
0.010
0.011
0.010
NOX
(PPM)
0.001
0.001
0.802
1.030
1.016
0.988
0.701
0.092
0.034
0.024
4.020
0.010
0.016
0.015
0.013
0.013
0.013
0.012
0.013
0.013
0.011
0.011
O.U19
SU2 NDK1 N02-S
(PPM) (PPM) (PPMJ
0.0
0.0
0.0
0.0
0.010
0.009
0.017
0.064
0.357
0.336 0.1193 0.017
0.301
0.260
0.245
0.212
0.176
0.151
0.125 0.099a 0.029
0.101
0.087
0.069
0.043
0.016
0.009
0.001
CH2U SR
(PPM) (LANb
/MIN)
0.0
0.0
0.0
0.0
0,0
0.01
0.04
0.11
0.23
0.669 0.41
0.69
1.10
1.03
0.64
0.73
0.59
0.617 0.61
0.28
0.07
0.02
0.0
0.0
0.0
0.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.26
1.72
6.06
16.04
34.66
67.32
120.20
184.24
240.72
266.04
327.92
363. 68
391.24
402.16
404.96
405.60
105.60
405.60
405.60
TEMP DILUTION OEGAN ENDED
(CENT) (CFM) (EST) (EST)
21.67
20.00
20.00
2.05 6.00
25.56
30.00
30.56
27.22
22.22
aThis NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
HTI SMOG CHAMBER STUDY I USEPA CONTRACT NO. 68-02-2256
CHAMbfcR NU. J, METHYL SULMOE , 95* DILUTION
DAY 2, 6-11-76
x POSSIBLE MINUTES SUNSHINE, ee
KlJU AIKPOKT MAXIMUM TEMPERATURE, 32.22 CENT
PAGE 2
10
liMt
(tST)
0.47
1.17
2.17
3.47
1.17
5.17
b.47
7.17
H.47
9.17
16.17
11.47
12.47
13.47
11.17
15.47
16.47
17.17
18.4?
19.17
20.47
21.17
22.47
23.17
U2UUE
(PPM)
0.014
0.009
0.007
0.005
O.OU3
0.002
0.003
0.016
0.047
0.081
0.109
0.130
0.146
0.157
0.164
0.166
0.169
0.164
0.156
0.149
0.141
0.128
0.117
0.108
NU
(PPM)
0.008
0.008
0.008
0.007
0.006
0.006
0.007
0.012
0.013
0.015
0.016
0.016
0.006
0.018
0.017
0.017
0.015
0.014
0.013
0.013
0.012
0.010
0.009
0.008
NU2
(PPM)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.011
0.015
0.014
0.016
0.023
0.029
0.024
0.028
0.035
0.028
0.024
0.021
0.019
0.016
0.014
0.014
0.014
uux
(PFM)
0.018
0.018
0.018
0.017
0.016
0.016
0.017
0.023
0.028
0.029
0.034
0.039
0.035
0.042
0.045
0.052
0.043
0.038
0.034
O.OT32
0.028
0.024
0.023
0.022
SU2 NliKl N02-S
(PPM) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0 0.071 0.011
0.008
0.013
0.014
0.013
0.011
0.011
0.011 0.071* 0.012
o.ott
0.011
0.006
0.0
0.0
0.0
0.0
CH2U SR
(PPM) (LANG
/1IN)
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.36
0.66
0.474 0.93
1.12
1.25
1.28
1.24
0.67
0.63
0.274 0.62
0.32
0.10
0.0
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
0.28
3.96
17.86
46.44
96.24
157.36
228.20
304.04
379.72
443.76
494.81
538.76
567.56
580.60
583.80
583.60
563.80
583.80
583.80
TEMP
(CENT)
18.69
17.22
14.44
27.78
30,00
31.11
25.00
21.67
DILUTION HEGAN ENDED
(CFM) (EST) (EST)
2.05 8.00
aThis HBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
Hll SMUG CHAMBER SIUUT: USEPA COHTHAC1 HO. 60-02-2258
CHAMUER NO. 3, METHYL SULFlDt , 95X DILUTION
DAY 1, 6-12-76
X POSSIBLE MINUTES SUNSHINE, 66
KUU AIRPORT MAXIMUM TEMPERATURE, 33.33 CENT
PAGE 1
Ill't
(tSf)
U2UIIE
(PPM)
NO
(PPM)
NU2
(PPM)
uux
(PPM)
SU2
(PPM)
NBKI
(PPM)
NU2-S
(PPM)
CH2U SK
(PPM) (LANG
CUM-SH
(LAMG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
U.47
1.47
2.47
3.47
4.47
5.17
6.47
7.4;
8.'* 7
9.47
I o . 'i 7
II. 47
12.47
13.47
14.47
15.47
16.47
17. <17
IH.47
19.47
20.47
21.47
22.47
23.47
0.101
0.094
0.088
0.064
0.079
0.074
0.069
0.068
0.083
0.108
0.136
0. 152
0.159
0.175
O.t83
0.160
0.175
0.169
0.163
I*. 150
0.152
0.147
0.143
0.138
0.007
0.007
0.006
0.006
0.006
0.006
0.006
0.010
0.012
0.013
0.013
0.013
0.012
0.012
0.011
0.012
0.011
0.010
0.011
0.013
0.014
0.016
0.017
0.019
0.011
0.012
0.0)2
0.012
0.012
0.012
0.013
0.018
0.020
0.019
0.017
0.016
0.015
0.015
0.014
0.015
0.014
O.U13
0.012
0.011
0.009
O.OOQ
0.008
0.007
0.020
0.019
0.018
0.018
0.018
0.018
0.019
0.028
0.032
0.032
0.030
0.029
0.027
0.027
0.025
0.027
0.025
0.023
0.023
0.024
0.023
0.024
0.025
0.026
0.0
0.0
O.lf
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.006
0.006
0.004
0.007
0.004
0.005
0.0
0.0
0.0
0.0
0.0
0.112 0.012 0.299
0.156 0.025 0.256
0.0
0.0
0.0
0.0
0.0
0.02
0.17
0.44
0.72
0.98
1.11
1.25
1.36
1.23
1.10
0.87
0.54
0.29
0.03
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.56
5.96
23.72
57.96
108.44
170.68
241.40
319.48
397.44
467.60
527.16
570.12
595.52
605.64
606.68
607.20
607.20
607.20
607.20
20.56
19.44
21,67
30.00
32.22
31.11
27.78
25.00
-------
KTI SMOG CHAMBER STUDY: USEPA CONTRACT NO, 68-02-2258
CHAMbtH HO. 3, METHYL SULF Il)t , 95X DILUTION
DAY ซ, B-13-76
X POSSIBLE MINUTES SUNSHINE, 66
ROU AIRPORT MAXIMUM TEMPERATURE, 33.33 CENT
PAGE
u ME
USD
u.i 7
1.17
2.17
3.17
1.17
5.17
6.17
7.17
8.17
9.17
10.17
II. 17
12.17
Ii.17
I5!l7
16.17
17.17
18.17
19.17
20.17
21.17
22.17
23.17
OZONE
IPPH)
0.131
0.128
0.122
0.116
0.110
0.105
0.099
NO
(PPM)
0.020
0.020
0.020
0.021
0.022
0.023
0.024
NU2
(PPM)
0.007
O.U07
0.007
0.008
0.008
0.008
0.009
NOX
(PPH)
0.027
0.027
0.027
0.029
0.030
0.031
0.033
su,
(ppi
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NBKI NU2-S CH20 SH
(PPri) (PPM) (PPH) (LANG
CUM-SR TEMP
(LANG) (CENT)
DILUTION
(CM)
BEGAN
(EST)
ENDED
(EST)
0.0
0.0
0.0
0.0
0.0
0.02
0.16
0.40
0.67
0.91
1.11
0.90
0.95
1.29
1.09
0.17
0.45
0.27
0.08
0.01
0.0
0.0
0.0
0.0
0.0
u.o
0.0
0.0
0.0
O.S6
5.6B
22.00
S3.S6
100.16
161.52
223.20
278.60
315.12
116.92
162.16
186.60
508.56
519.11
522.28
522.60
522.60
522.60
522.60
23.33
22.78
23.33
30.00
33.33
32.22
27.76
25.00
-------
HII SMOG CHAMBER STUOYj USEPA CONTRACT NO. 68-02-225B
CHAMBER NO. a, PHOPVLENE , 95X DILUTION
TARGET INITIAL HC/NUXJ 5.0 PPMC/1.00 PPM
DAV 1, 8-10-76
X POSSIBLE MIHUTES SUNSHINE, 83
RUU AlKPORI MAXIMUM TEMPERATURE, 31.11 CtNT
PAGE 1
HUE
(tSI)
uzuut
(PPM)
nu
(PPM)
N02
(PPM)
NIJX
(PPM)
SU2
(PPM)
NBK1
(PPM)
N02-S
(PPM)
CH2U SR
(PPM) (LANG
CUM-SR
(LANG)
TEMP
(CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.63
1.63
2.61
3.6S
4.6i
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
0.001
0.001
0.001
0.0
0.0
0.0
0.0
0.0
0.016
0.624
0.951
0.930
0.927
0.922
0.879
0.798
0.723
0.650
0.573
0.500
0.443
0.386
0.347
0.301
0.004
0.005
0.608
0.707
0./82
0.730
0.533
0.111
0.009
O.OOB
0.006
0.003
0.002
0.001
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.008
0.005
O.U06
0.020
0.154
0.199
0.246
0.414
0.726
0.565
0.363
0.301
0.253
0.207
0.167
O.I3B
0.115
0.095
0.076
0.065
0.057
0.048
0.044
0.039
0.009
0.011
0.628
0.861
0.981
0.976
0.947
0.837
O.S74
0.371
0.307
0.256
0.209
0.168
0.138
0.115
0.095
0.076
0.065
0.057
0.048
0.044
0.047
0.042 0.131 0.145
0.0
0.0
0.0
0.0
0.0
0.01
0.04
0.11
0.2)
0.41
0.69
1.10
1.03
0.84
0.73
0.59
0.61
0.28
0.07
0.02
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.38
2.12
7.18
18.34
38.98
74.22
131.20
194.54
249.12
295.34
333.82
369.98
394.04
402.86
405.16
405.60
405.60
405.60
405.60
21.67
20.00
20.00
25.56
30.00
30.56
27.22
22.22
2.30
8.00
-------
HII SMOG CHAHBEH SlUOVl USEPA CONTRACT NU. 68-02-2258
CHAMBER ND. 4,
PHOPYLENE
, 95X DILUTION
PAGE 2
DAY 2, 6-11-76
X POSSIBLE MINUTES SUNSHINE, 88
RUU A1KPOKT MAXIMUM TEMPEHATURE, 32.22 CENT
TI it UZONt NO N02 NOX S02 HBKI NU2-S CH20 SH CUM-SK TEMP DILUTION BEGAN ENDED
(ฃ31) (PPM) (PPM) (PPM) (PPH) (PHM) (PPh) (PPM) (PPM) (LANG (LANG) (CENT) (CFM) (E3T) (ESI)
/MIN)
U.63
1.6i
2.b3
i.oi
f .0}
5.63
6.63
7.63
tt.63
9.63
10.63
11.63
12.63
13.63
11.63
l'j.63
16.63
17.63
18.63
19.63
2U.63
21.63
22.63
23.63
0.263
0.231
0.201
0.176
0.154
0.132
O.llb
0.100
0.127
0.170
0.219
0.261
0.290
0.307
0.314
0.310
0.3U2
0.266
0.274
0.264
0.256
0.218
0.238
0.230
0.007
0.006
0.006
0.006
0.006
0.006
0.006
0.010
0.010
0.012
0.012
0.012
0.012
0.014
0.013
0.013
0.012
0.011
0.010
0.011
o.ou
o.oio
0.008
0.008
0.035
0.033
0.030
0.02f)
0.027
0.026
0.025
0.030
0.033
0.034
0.036
0.042
0.046
0.036
0.042
0.049
0.040
0.034
0.030
0.025
0.022
0.020
0.019
0.01A
0.042
0.039
0.036
0.034
0.033
0.032
0.031
0.040
0.043
0.046
0.050
0.054
0.058
0.052
0.055
0.062
0.052
0.045
0.040
0.036
0.033
0.030
0.027
0.026
0.183 0.020 0.553
0.154 0.017 0.525
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.36
0.68
0.93
1.12
1.25
1.26
1.24
0.87
0.63
0.62
0.32
0.10
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.0
0.0
0.0
0.36
5.16
21.46
55.24
105.54
168.56
240.70
316.84
392.12
452.46
503.14
544.96
570.76
581. 60
583.80
563.60
5B3.BO
563.60
583.80
18.69
17.22
19.44
27.76
30.00
31.11
25.00
21.67
2.30
8.00
-------
Mil SMUG CHAMBER STUDYi USEPA CUNIHACT NU. 68-02-2258
CHAMBER NO. 4, PROPVLENE
, 95X UILUT1UN
DAY 3/ 8-12-76
X POSSIBLE MINUUS SUNSHINE, 66
RUU AIRPORT MAXIMUM TEMPERATURE, 33.ii CEM
PAGE 3
TIME
(ESI)
0.63
1.63
a. 63
3.b3
4.t>3
5.63
6.63
7.63
B.64
9.63
10.63
11.63
12.63
13.63
11.63
15.63
16.63
17.63
18.63
19.63
20.63
21.63
22.63
23.03
UZOME
(PPM)
0.222
0.214
0.207
0.200
0.191
0.186
0.179
0.171
0.171
0.184
0.206
0.217
0.224
0.243
0.246
0.236
0.227
0.219
0.209
0.202
0.196
0.192
0.186
0.183
NU
(PPM)
0.007
0.007
O.OOb
0.006
0.006
0.006
0.006
0.010
0.010
0.011
0.011
0.011
0.010
0.010
0.010
0.010
0.010
0.009
0.010
0.011
0.013
0.01%
0.017
0.018
NU2
(PPM)
0.017
0.016
0.015
0.015
0.014
0.014
0.016
0.020
0.023
0.024
0.023
0.022
0.022
0.022
0.021
0.020
0.020
0.018
0.016
0.014
0.013
0.011
0.010
0.010
HUX
(PPM)
0.024
0.023
0.021
0.021
0.020
0.020
0.022
0.030
0.033
0.035
0.034
0.033
0.032
0.032
0.031
0.030
0.030
0.027
0.026
0.025
0.026
0.026
0.027
0.026
S02 NBK1 N02-S CH20 SH
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG
/MIN)
CUM-SR TEMP
(LANG) (CENT)
DILUTION
(CFM) '
BEGAN
(EST)
ENDED
(EST)
0.194 0.015 0.528
0.267 0.026 0.413
0.0
0.0
0.0
0.0
o.o
0.02
0.17
0.44
0.72
0.96
1.11
1.25
1.36
1.23
1.10
0.87
0.54
0.29
0.03
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.76
7.66
28.12
65.16
118.24
161.98
253.90
333.06
409.74
478.60
535.86
575.52
598.42
605.94
606.98
607.20
607.20
607.20
607.20
20.56
19.44
21.67
30.00
32.22
31.11
27.78
25.00
-------
RTI SMUt CHAMBEK STU0YJ USEPA CONTRACT NO. bfl-02-2258
CHAMblH NU. a, PHUPYLENE
95X DILUTION
DAY 4, 8-13-76
* POSSIBLE MINUTES SUNSHINE. 66
HDU AIRPORT MAXIMUM TEMPERATURE, 33.33 CENT
PAGE
oo
Tint
(EST)
0.63
1.63
2.63
3.63
l.bi
5.63
b.63
7.63
0.63
9.63
10.63
11.63
12.63
13. 6i
1^.03
15. 63
16. 63
17.63
lH.t>3
19.63
Zu.63
21.63
22.63
23.63
UZOMt
(PPM)
0.178
0.174
0.170
0.166
0.163
0.157
0.1S2
NO
(PPM)
0.018
0.018
0.019
0.020
0.022
0.022
0.024
NU2
(PPM)
0.009
0.009
0.008
0.008
0.008
0.008
0.009
MJX SU2
(PPM) (PPM)
0.027
0.027
0.027
0.028
0.030
0.030
0.033
NBKI N02-5 CH20 SK
(PPM) (PPH) (PPM) (LANG
/M1N)
0.0
0.0
0.0
0.0
0.0
0.02
O.lb
0.10
0.67
0.91
1.14
0.90
0.95
1.29
1.09
0.37
0.45
0.27
0.08
0.01
0.0
0.0
0.0
0.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.76
7.2H
26.00
60.26
109.58
172.92
232.20
288.10
358.02
427.82
165.86
191.10
511.26
520.24
S22.3B
522.60
522.60
522.60
522.60
TEMP * DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
23.33
22.78
23.33
30.00
33.33
32.22
27.78
25.00
-------
TUT
(ESI)
IUUNE
(PPM)
NO
(PPM)
tjQ2
(PPM)
KTI SMOG CHAMIltR STUDf! USEPA CONTRACT NO. 68-02-2258
NOX
(PPM)
CHAMI11R MO. 1, FUHAN
TAKGtT INITIAL MC/HOXt
, OX DILUTII1N
S.O PPMC/1,00 PPM
DAT 1, 8-17-76
x POSSIBLE: MINUTES SUNSHINE* 9i
HUU AlHPUKl MAXIMUM TEMPERATURE, 27.78 CENT
SU2
(PPM)
NBM
(PPM)
N02-S
IPPM)
CH20 SR
(PPM) (L*NG
CUM-SK
(LANG)
TEMP
(CENT)
PAGE 1
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.13
J.li
2.1i
3.13
4.13
5.13
6.13
7.13
8.13
9.13
10.13
11.13
12.13
13.13
10. 1U
15. 13
16.13
17.13
18.13
19.13
30.13
21.13
22.13
23.13
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.007
0.506
0.50?
0.476
0.446
0.425
0.392
0.378
0.3t>6
0.330
0.303
0.272
0.252
0.2'
-------
(tSF)
O^Ullt
(PPM)
uO
(PPM)
NU2
(PP.-1)
Hi I SMOG CHAMBEK STUDY: USER* CONTRACT NO. 68-02-2258
UUX
(PPM)
CHAMUtR NO. 1,
FURAN
, OH DILUTION
DAY 2, 6-16-76
x POSSIBLE MINUTES SUNSHINE, 9)
HUU AIRPORT MAXIMUM TEMPERATURE, 29. tn CENT
S02
(PPM)
NBK1 H02-S
(PPM) (PPM)
CH20 SR
(PPM) (LANG
CUM-SH
(LANG)
TEMP
(CENT)
PAGE 2
DILUTION
(CFM)
BEGAN
(E3T)
ENDED
(EST)
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
14.1J
15.13
16.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
0.201
0.192
o.iai
0.172
0.163
0.154
0.146
0.132
0.122
0.123
0.141
0.161
0.182
0.199
0.206
0.2U8
0.204
V.195
O.lfll
0.167
0.151
0.140
0.130
0.122
0.002
0.002
0.002
0.002
0.002
O.OUI
o.oai
0.003
0.006
0.010
0.012
0.013
0.011
0.013
0.014
0.013
0.011
0.010
0.018
0.019
0.018
0.016
0.016
0.014
0.023
0.023
0.022
0.022
0.021
0.020
0.021
0.022
0.029
0.932
0.033
0.032
0.027
0.027
0.026
0.026
0.024
0.023
0.021
0.016
0.015
0.014
0.014
0.014
0.025
0.025
0.024
0.024
0.023
0.021
0.022
0.025
0.035
0.042
0.045
0.045
0.036
0.040
0,0*40
0.039
0.035
0.033
0.039
0.035
0.033
0.030
0.030
0.020
0.179 0.017 0.011
0.256 0.013 0.023
0.0
0.0
0.0
0.0
0.0
0.01
O.IS
0.47
0.72
0.97
1.18
1.32
1.32
1.10
1.02
0.86
0.55
0.28
0.07
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.08
1.80
13.36
43.56
86.76
146.64
220.56
299.76
377.20
442.56
502.48
551.60
562.44
597.56
601.20
601.20
601.20
601.20
601.20
16.67
14.44
17.78
25.56
27.78
28.33
24.44
21.11
-------
Kit SMUG CHAM8EH STUDY! UStPA CONTRACT NU. 66-02-2258
CHAMHIH NO. 1,
FURAN
01 DILUTION
DAY }, 8-19-76
X POSSIBLE MINUfES SUNSHINE* 92
HUU A1HPOKT MAXIMUM TEMPERATURE, 27.23 CENT
PAGE
111 t
(fcST)
0.11
1.13
2.15
3.13
a. 13
5.1)
6.11
7.13
8.13
9.13
10.13
11.13
12.13
13.13
14.13
IS. 13
lb.13
17.13
18.13
19.13
20.13
21.13
22.13
23.13
OZOUE
(PP'l)
0.113
0.105
0.099
0.093
0.086
0.079
0.073
0.065
0.070
0.084
0.107
0.121
0.148
0.166
0.172
0.170
0.157
0.153
0.142
NO
(PPH)
0.011
0.011
0.010
0.010
0.009
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
MO 2
(PPM)
O.OIS
0.014
0.015
0.015
0.015
o.oie
0.010
0.021
0.020
0.035
0.020
0.024
0.020
0.025
0.020
0.023
0.021
0.02"
0.02'J
NUX S02
(PPM) (PPM)
0.029
0.025
0.025
0.025
0.024
0.018
0.018
0.021
0.020
0.025
0.02U
0.024
0.02V
0^025
0.020
0.023
0.021
0.024
0.020
NBKl N02-S CH20 SK
(PPM) (PPM) (PPM) (LKNG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.15
0.45
0.69
1.07
0.133 0.015 0.040 1.15
1.22
1.36
1.41
0.216 0.014 0.037 0.90
0.56
0.46
0.29
0.04
0.01
0.0
0.0
0.0
0.0
CUM-SH
(LANG)
0.0
0.0
0.0
0.0
0.0
o.oe
i.eo
13.20
42.12
86.56
151.40
220.96
295. 2H
377.28
457.60
509.08
541.68
568.12
583.52
585.66
586.20
586.20
586.20
506.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
18.69
15.56
17.22
23.33
26.11
25.00
22.78
20.00
-------
hi I SMUG CHAMHEH STUDY j USEPA CONTRACT NO, 68-02-2256
CHAMBER Ml). 2, TH1UPHENE , OK DILUTION
1AKUE1 INITIAL HC/NOX: 5.0 PPMC/1.00 PPM
DAY li 8-H-76
X POSSIBLE MINUTES SUNSHINE, 91
RUU A1KPOK1 MAXIMUM TEMPERATURE, 27.78 CENT
PACE 1
to
TIME
(ESI)
0.30
1.40
2. JO
3.30
4.30
5.30
6.30
7.30
8.30
9.30
10.30
11.30
12.30
13.30
14.17
IS.iO
16.30
17.30
18.30
19.30
20.30
21.30
22.30
23.30
OZUUt
(PPM)
0.004
0.003
0.003
0.003
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.001
0.002
0.003
0.005
0.007
0.007
0.006
0.001
0.0
0.0
0.0
0.0
0.0
NO
(PPK)
0.003
o.oott
0.009
0.010
0.741
0.717
0,690
0.621
0.55J
0.447
0.366
0.301
0.251
0.2U2
0.177
0,156
0.141
0.134
0.125
0.129
0.130
0.131
0.130
N02
(PPM)
0.008
0.009
O.OOH
0.226
0.235
0.270
0.289
0.324
0.358
0.392
0.367
0.3ป3
0.375
O.i60
0.336
0.317
0.290
0.2B3
0.289
0.299
0.296-
0.2S6
0.280
IlUX
(PPM)
O.U1I
0.017
0.017
0.236
0.976
0.987
0.979
0.94b
0.911
0.839
0.753
0.684
0.626
0.562
0.513
0.473
0.431
0.417
0.414
0.428
0.126
0.419
0.410
S02 NBK 1 N02-S
(HPH) (PPM) (PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.009
0.012
0.025
0.035
0.063 0.021 0.449
0.092
0.122
0.153
0.182
0.202 0.018 0.463
0.223
0.227
0.206
0.156
0.107
0.089
0.072
0.052
CH20 SR
(PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.39
0.57
0.87
0.025 1.18
1,29
1.34
1.26
1.13
0.0 0.91
0.64
0.34
O.Ob
0.0
0.0
0.0
0.0
0.0
CUM-Sซ
(LANG)
0.0
0.0
0.0
0.0
0.0
0.18
2.76
14.82
41.46
61.06
136.84
211.62
289.92
368.88
453.44
505.98
555.72
588.72
604.08
606.60
606.60
606.60
606.60
606.60
TEMP DILUTION BEGAN ENDED
(CE.MT) (CFM) (EST) (EST)
21.11
18.69
19.44
23.89
26,11
27.78
23.89
17.78
-------
TIKE
(EST)
OZONE
(PPM)
NU
(PPH)
M12
(PPM)
KTI SMUG IHAHbtK SIUOY: UStPA CUNIKACT NO. 68-02-2258
NOX
(PPM)
CHAMbES NU. 2, TH1UPMENE
01 DILUTION
DAY 2, 6-18-76
X POSSIBLE MINUTES SUNSHINE, 9}
HOU AIRPORT MAXIMUM TEMPEHATURE, 29,Hit CENT
SU2
(PHM)
NBKI
(PPM)
N02-S
(PPM)
CH2U SR
(PPM) (LANG
CUH-SH
(LANG)
TEMP
(CENT)
PACE 2
DILUTION
(CFM)
BEGAN
(ฃ31 )
ENDED
(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
18.30
19.30
20.30
21.30
22.30
23.30
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.002
0.009
0.016
0.032
0.053
0.079
0.102
0.118
0.130
0.132
0.122
0.101
0.072
0.050
0.033
0.022
0.015
0.132
0.134
0.136
0.137
0.139
0.136
0.139
0.125
0.109
0.086
0.061
0.044
0.031
0.027
0.023
0.020
0.018
0.014
0.022
0.020
0.018
0.017
0.016
0.014
0.272
0.266
0.259
0.255
0.250
0.248
0.240
0.209
0.189
0.176
0.169
0.150
0.129
0.111
0.095
0.0/8
(1.068
0.061
0.054
0.045
0.038
0.035
0.034
0.034
0.404
0.400
0.395
0.392
0.389
0.386
0.379
0.334
0.298
0.262
0.230
0.194
0.160
0.138
0.118
0.098
0.086
0.075
0.076
0.065
0.056
0.052
0.050
0.048
0.04|
0.034
0.028
0.022
0.018
0.017
0.017
0.038
0.071
0.090
0.113
0.141
0.161
0.173
0.181
0.187
0.191
0.179
0.159
0.114
0.084
0.058
0.046
0.031
0.006 0.239 0.052
0.003 0.094 0.034
0.0
0.0
0.0
0.0
0.0
0.01
0.15
0,47
0.72
0.97
1.18
1.32
1.32
1.10
1.02
0.86
0.55
0.28
0.07
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.18
3.30
18.06
50.76
98.46
160.44
233.76
312.96
388.20
452.76
511.08
557.10
585.24
598.26
601.20
601.20
601.20
601.20
601.20
16.67
14.44
17.78
25.56
27.78
28.33
24.44
21.11
aThis NBKI neasurenent may be low in comparison to the cherailuminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
RTI SMOG CHAMBER STUOYJ USER* ClWKACT NO. 68-02-22SB
CHAMBER NO. 2, THIUPHENE
, OX DILUTION
PAGE 3
OAT 3, 8-19-76
X POSSIBLE MINUTES SUNSHINE, 9?
KOU AIRPORT MAXIMUM TEMPERATURE, 32.78 CENT
TIME
(EST)
0.3U
1.30
2.30
3.3U
4. JO
5.30
6.3U
7.30
B.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)
0.010
O.OOb
0.002
0,001
0.0
O.U
0.002
0.020
0.051
0.063
0.097
0.115
0.143
0.164
0.173
O.lbb
0.145
0.153
0.14B
0.139
NO
(PPM)
U.013
0.010
o.otu
0.010
0.010
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
N02
(PPM)
0.033
0.033
0.032
0.032
0.033
0.03b
O.U2H
0.026
U.02J
0.023
0.021
0.02c>
0.021
0.023
0.020
0.022
0.021
0.02-4
0.021
UUX
(PPM)
0.046
0.043
0.042
0.042
0.043
0.036
0.026
0.026
0.023
0.023
0.021
0.022
0.021
0.023
0.020
0.022
0.021
0.024
0.021
SU2
(PPM)
0.024
0.020
0.010
0.009
0.008
0.007
0.005
0.016
0.010
0.021
0.025
0.02B
0.029
0.035
0.034
0.033
0.030
0.026
0.022
0.0 16
NUKl N02-S CH2U SH
(PPM) (PPM) (PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.15
0.45
0.69
a 1'07
0.052a 0.021 0.062 1.15
1.22
1.36
a >"ป
0.170 0.014 0.045 0.90
0.56
0.46
0.29
0.04
0.01
0.0
0.0
0.0
0.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
D.It)
3.30
17.70
49.02
97.26
162.90
233.16
308. 86
391.38
466.80
514.68
546.48
571.02
583.92
585.78
586.20
586.20
586.20
586.20
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
18.89
15.56
17.22
23.33
26.11
25.00
22. 78
20.00
aThis NBKI measurement may be low in comparison to the chemiluminescent ozone reading due to the negative interference of sulfur
dioxide on the NBKI measurement.
-------
RTI SMOG CHAMBER STUUYI UStPA CONTRACT NO. 68-02-2258
CHAMBER NO. 3. PYRROLE / OX DILUTION
TARGET INITIAL HC/NUXj 5.0 PPMC/I.OO PPM
DAY 1, 8-17-76
Z POSSIBLE MINUTES SUNSHINE, 91
RDU AIRPORT MAXIMUM TEMPERATURE, 27.78 CENT
PAGE I
TIME UlUUE NO tiU2 NOX SU2 '4BKI N02-S CH20 3R CUM-SR TEMP DILUTION BEGAN ENDED
(EST) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) (LUNG (LANG) (CENT) (CFM) (EST) (EST)
/HIM)
Ui
0.47
1.17
2.17
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
13.47
14.63
IS. 47
16.47
17.47
18.47
19.47
20.47
21.47
22.47
2J.47
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.025
0.013
0.008
0.006
0.007
0.009
0.010
0.012
0.013
0.011
O.OOi
0.0
0.0
0.0
0.0
0.0
0.004
0.009
0.009
0.010
0.711
0.704
0.626
0.363
0.078
0.111
0.139
0.141
0.139
0.122
0.100
0.065
0.072
0.060
0.046
0,036
0.037
0.036
0.034
0.033
0.006
0.007
0.008
0.233
0.232
0.231
0.286
0.493
0.551
0.413
0.333
0.27B
0.244
0.221
0.199
O.IB2
0.166
0.157
0.150
0.156
O.lfab
0.161
0.160
0.154
0.010
0.016
0.017
0.243
0.943
0.935
0.912
0.856
0.629
0.524
0.472
0.419
0.383
0.343
0.299
0.267
0.23ft
0.217
0.196
0.192
0.202
0.199
0.194
0.167
0.086 0.372 0.056
0.037
0.0
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.39
0.57
0.87
.18
.29
.34
.26
.13
0.91
0.64
0.34
0.06
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.28
3.96
18.72
47.16
89.76
150.64
224,52
303.32
381.46
464.74
515.08
562.12
592.12
604.68
606.60
606.60
606.60
606. 60
606.60
21.11
18.89
19.44
23.89
26.11
27.78
23.89
17.78
-------
KII SMOG CHAMBfcH SIUOT: UStPA CONTRACT NO. 68-02-2258
CHAMBtR HO. 3,
PYRROLE
, OX DILUTION
DAY 2, a-18-76
X PUSS1HLE MlNUTtS SUNSHINE, 9}
ROU A1HPOH1 MAXIMUM TEMPERATURE^ 29.44 CENT
PAGE 2
UIIE
(tST)
0.47
1.17
2,47
3.17
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.17
12.47
13.47
14.47
15.47
16.47
17.47
18.47
19,47
20.47
21.47
22.47
23,47
OZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.003
0.011
0.014
o.oia
0.028
0.042
0.057
0.073
0.086
0.096
0.100
0.097
0.087
0.074
0.065
0.056
0.050
0.045
NO
(PPM)
0.034
0.035
0.035
0.036
0.035
0.034
0.037
0.041
0.047
0.046
0.037
0.030
0.023
0.022
0.020
0,019
0.014
0.013
0.021
0.020
0.018
0.017
0.015
0.014
U02
(PPซ)
0.151
0.149
0.145
0.142
0.139
0.137
0.128
0.104
0.088
0.081
0.076
0.069
0.058
0.053
0.046
0.040
0.035
0.032
o.o
-------
RT1 SMUG CHAMBER SIUOYJ USEPA CONTRACT NO. 60-02-2258
CHAMBER NO. 3,
PYRROLE
, OX DILUTION
DAY J, 8-19-76
X POSSIBLE MINUTES SUNSHINE* 12
Rl>0 AIRPORT MAXIMUM TEMPERATUBE, 27.22 CtNT
PAGE 3
TIME
(tST)
0.07
1.47
2.47
3.47
4.47
5.47
6.47
7.47
8.47
9.47
10.47
11.47
12.47
15.47
14.47
15.47
16.47
17.47
18.47
19.47
20.47
21.47
22.47
25.47
OZONt
(PPM)
0.040
0.05b
0.032
0.028
0.024
0.022
0.020
0.024
0.046
0.060
0.064
0.100
0.121
0.136
0.136
0.130
0.122
0.120
0.11S
O.ltt
NO
(PPM)
0.012
0.009
0.010
0.010
0.009
0.0
0.0
0.0
0.0
o.c
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
N02
(PPM)
O.Oli
0.014
0.013
0.014
0.014
0.020
U.Olb
0.014
0.014
0.01?
0.015
0.016
0.016
0.017
0.015
0.01ซ
U . 0 1 6
0.020
o.oia
MUX
(PPM)
0.027
0.023
0.023
0.024
0.023
0.020
0.016
0.014
0.014
0.017
0.015
0.016
0.016
0.017
O.Olb
0.018
O.OIb
0.020
0.018
S02 NBKI N02-S CH20 SR CUM-SH TEMP DILUTION BEGAN ENDED
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT) (CFM) (EST) (EST)
/MIN)
O.OBO 0.010 0.044
0.151 0.009 0.0
0.0
0.0
0.0
0.0
o.o
0.01
0.15
0.45
0.69
1.07
1.15
1.22
1.36
1.41
0.90
0.56
0.46
0.29
0.04
0.01
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.0
0.0
0.28
4.80
22.20
55.92
107.96
174.40
245.36
522.48
405.48
475.60
520.28
551.08
573.92
584.32
585.88
586.20
586.20
586.20
586.20
18.89
15.56
17.22
23.33
26.11
25.00
22.78
20.00
-------
HT1 SMUG CHAMBlk STUOYS USEPA CONTRACT NO. 68-02-2258
CHAMBER NO. 4, PHOPYLENE , OX OILUTION
TAKGET INITIAL HC/NOXl S.O PPMC/1.00 PPM
OAY lr 8-17-76
X PUSSIBLE MINUTES SUNSHINE, 91
HDU AIRPQH1 MAXIMUM TEMPERATURE, 27.7ft CENT
PAGE
oo
TIME
(EST)
0.63
1.64
3.63
3.63
4.63
5.63
6.63
7.63
8. 63
9.63
10.63
11.63
12.63
13.63
14.80
15.63
16.63
17.63
IB, 63
19.63
20.63
21.63
22.63
23.63
UZONE
(PPM)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.09B
0.737
0.899
0.877
0.901
0.946
0.965
0.969
0.943
0.906
0.866
0.821
0.799
0.775
0.760
0.740
HO
(PPM)
0.004
O.OOB
0.004
0.006
0.282
0.646
O.S99
0.409
0.022
0.010
0.012
0.012
0.011
0.012
0.010
0.010
0.009
0.007
0.003
0.0
0.0
0.0
0.002
0.002
NU2
(PPM)
0.004
o.oos
o.oos
0.1V7
0.203
0.215
0.260
0.432
0.744
0.467
0.370
0.34S
0.32S
0.302
0.276
0.255
0.232
0.216
0.193
0.179
0.17S
0.167
0.163
0.160
NUX SU2
(PPM) (PPM)
0.008
0.013
0.012
0.205
0.485
0.663
0.ซ59
0.641
0.766
0.477
0.382
0.360
0.340
0.314
0.286
0.265
0.241
0.223
0.196
0.179
0.175
0.167
0.165
0.162
NBKI N02-S CH20 SR
(PPM) (PPM) (PPM) (LANG
/MIN)
0.0
0.0
0.0
0.0
0.0
0.01
0.12
0.39
0.57
1.356 0.083 0.963 0.87
1.18
1.29
1.34
1.26
1.13
1.367 0.027 0.339 0.91
0.64
0.34
0.06
0.0
0.0
0.0
0.0
0.0
CUM-SR
(LANG)
0.0
0.0
0.0
0.0
0.0
0.38
5.16
22.62
52.86
98.46
162.44
237.42
316.72
394.08
476.04
524.18
568.52
595.52
605.28
606.60
606.60
606.60
606.60
606.60
TEMP DILUTION BEGAN ENDED
(CENT) (CFM) (EST) (EST)
21.11
18.89
19.44
23.89
26.11
27.78
23.89
17.78
-------
Kit SMUG CHAMBER STUDY! USEPA CONTHACI NO. 68-02-2258
CHAMBER NO. 0, PROPYLENE , OX DILUTION
DAY 2, 8-16-76
X POSSIBLE MINUTES SUNSHINE, 93
RDU AIKPOHT MAXIMUM TEMPERATURE, 29.40 Cf.NT
PAGE 2
TlnE
(ESI)
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
23.63
UZONt
(PPM)
0.722
0.704
0.693
0.680
0.667
0.652
0.641
0.632
0.613
0.609
0.621
0.646
0.675
0.694
0.696
0.669
0.666
0.640
0.617
0.598
0.580
0.563
0.506
0.532
NU
(PPM)
0.002
0.002
0.002
0.002
0.002
0.001
0.001
0.001
0.006
0.008
0.010
0.010
0.006
0.010
0.011
0.011
0.009
0.008
0.016
0.016
0.015
0.010
0.013
0.012
NO 2
(PPM)
0.152
0.148
0.105
0.144
0.141
0.136
0.132
0.135
0.143
0.140
0.132
0.123
0.110
0.103
0.090
0.085
0.076
0.068
0.059
0.053
0.049
0.044
0.042
0.040
NUX
(PPM)
0.154
0.150
0.147
0.146
0.143
0.137
0.133
0*136
0.149
0.146
0.142
0.133
0.118
0.113
0.105
0.096
0.065
0.076
0.075
0.069
0.060
0.056
0.055
0.052
302 NBKI NU2-S CH20 SR CUM-SH TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.671 0.019 0.263
0.91B 0.016 0.097
0.0
0.0
0.0
0.0
0.0
0.01
0.15
0.47
0.72
0.97
1.16
1.32
1,32
1.10
1.02
0.66
0.55
0.28
0.07
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.38
6.30
27.46
65.16
117.66
184.04
260.16
339.36
410.20
473.16
52B.26
566.10
590.84
599.66
601.20
601.20
601.20
601.20
601.20
16.67
14.44
17.78
25.56
27.78
26.33
24.44
21.11
-------
RU S"UG CHAMBER SlUim UStPA CONTRACT NU. 60-02-2258
CHAMBER NO. 4, PROPYLEHE
, OX DILUTION
DAY J, 8-19-76
i POSSIBLE MINUTES SUNSHINE, 92
ROU AIRPOKl MAXIMUM TEMPEHATURE, 27.22 CENT
PAGE
00
o
TIMl
(tSI)
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
23.63
UZO'Jt
(PPM)
0.519
0.503
0.492
0.480
0.470
0.460
0.447
U.432
0.404
0.396
0.377
0.381
0.389
0.400
0.387
0.375
0.353
0.350
0.341
0.338
NO
(PPM)
0.010
0.008
0.008
0.008
0.008
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 2
(PPH)
0.038
0.036
0.035
0.034
0.033
0.036
0.038
O.Oio
0.039
0.040
0.040
0.03ซป
0.040
0.036
0.037
0.035
0.037
0.032
0.032
0.02B
IปOX
(PPM)
0.048
0.044
0.043
0.042
0,041
O.U36
0.036
0.036
0.039
0.040
0.040
0.039
0.040
0.036
0.037
0.035
0.037
0.032
0.032
0.026
502 MBKI N02-S CH2U SR CUM-SH TEMP
(PPM) (PPM) (PPM) (PPM) (PPM) (LANG (LANG) (CENT)
DILUTION
(CFM)
BEGAN
(EST)
ENDED
(EST)
0.511 0.011 0.101
0.4/6 0.013 0.063
0.0
0.0
0.0
0.0
0.0
0.01
0.15
0.45
0,69
1.07
1.15
1.32
1,36
1.41
0.90
0.56
0.46
0.29
0,04
0.01
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.38
6.30
26.70
62.82
118.66
185.90
257.56
336.08
419.58
484.80
525.88
555.68
576.82
584.72
585.98
566.20
586.20
566.20
586.20
18.89
15.56
17.22
23.33
26.11
25.00
22.78
20.00
-------
APPENDIX E
Concentration Profiles
181
-------
Appendix E. CONCENTRATION PROFILES
Symbols:
x Ozone, ppm
D Nitric Oxide, ppm
A Nitrogen Dioxide, ppm
& Sulfur Dioxide, ppm
* Solar Radiation (Langleys per minute)
182
-------
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/7-78-029
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANDSUBTITLE
ATMOSPHERIC CHEMISTRY OF POTENTIAL EMISSIONS
FROM FUEL CONVERSION FACILITIES
A Smog Chamber Study
6. PERFORMING ORGANIZATION CODE
5. REPORT DATE
March 1978
. AUTHOR(S)
J.E. Sickles, II, L.A. Ripperton, W.C. Eaton, 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.
INE625 EA-03 (FY-77)
27709
11. CONTRACT/GRANT NO.
Contract No. 68-02-2258
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, 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
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The atmospheric chemistry of chemical species that may be emitted from fuel
conversion facilities were studied in smog chambers. Of 17 compounds assessed
for ozone-forming potential, 6 compounds were selected along with a control
species, propylene, for testing in the presence of nitrogen oxides in four out-
door smog chambers. Selected compounds were furan, pyrole, thiophene, methanethiol,
methyl sulfide, and methyl disulfide. Multiday exposures were performed, and both
static and transport conditions were simulated. Ozone and sulfur dioxide formation
was examined. The behavior of the test compounds was compared to that of a surrogate
urban mix.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
*Air pollution
*Ozone
*Sulfur dioxide
*Chemical reactions
*Test chambers
Environment simulation
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Held/Group
13B
07B
07D
14 B
3. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
258
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
248
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