STUDY OF THE NATURE OF OZONE, OXIDES OF
NITROGEN, AND NONMETHANE HYDROCARBONS
IN TULSA, OKLAHOMA
VOLUME I
PROJECT DESCRIPTION AND DATA SUMMARIES
by
W. C, Eaton
C. E. Decker
J. B. Tommerdahl
F. E, Dimmock
Research Triangle Institute
Research Triangle Park, N.C. 27709
Contract No, 68-02-2808
EPA Project Officer: Norman C. Possiei, Jr.
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air, Noise, and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, N.C. 27711
April 1979
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This report is issued by the U.S. Environmental Protection Agency
to report technical data of interest to a limited number of readers.
Copies are available free of charge to Federal employees, current
contractors and grantees, and nonprofit organizations - in limited
quantities - from the Library Services Office (MD-35), Research
Triangle Park, NC 27711; or, for a fee, from the National Technical
Information Service, 5285 Port Royal Road, Springfield, VA 22161.
This report was furnished to the Environmental Protection Agency by
Research Triangle Institute, Research Triangle Park, NC 27709 in
fulfillment of Contract No. 68-02-2808. The contents of this report
are reproduced herein as received from Research Triangle Institute.
The opinions, findings and conclusions expressed are those of the author
and not necessarily those of the Environmental Protection Agency.
Mention of company or product names is not to be considered an
endorsement by the Environmental Protection Agency.
Publication No. EPA-450-4-79-008a
i i
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ACKNOWLEDGMENTS
This project was conducted by the Research Triangle Institute (RTI),
Research Triangle Park, North Carolina, under Contract No 68-02-2808 for the
U.S. Environmental Protection Agency. The support of this agency is grate-
fully acknowledged as is the advice and guidance of the Project Officer,
Norman C. Possiel, Jr., and other staff members of the Office of Air Quality
Planning and Standards.
Special acknowledgment is made to personnel of the EPA Environmental
Monitoring and Support Laboratory (EMSL) who assisted in the areas of equip-
ment acquisition, data validation, and instrument performance audits. Also
acknowledged are staff members of EPA Region VI for supplying mobile labora-
tories and conducting quality assurance audits.
Mr. L. Byrum, Oklahoma State Department of Health; and Mr. R. Bishop,
Mr. R. Randolph, and other staff members of the environmental division of
the Tulsa City County Health Department are acknowledged for their unselfish
aid in site selection, site preparation, transportation, and data acquisition.
Work on the data presentation portion of this project was performed by
staff members of the Systems and Measurements Division of RTI under the
general direction of Mr. J. J. B. Worth, Group III Vice President, and Mr.
J. B. Tommerdahl, Division Director. Mr. C. E. Decker, Manager, Environmen-
tal Measurements Department, was Laboratory Supervisor for this program.
Dr. W. C. Eaton served as Project Leader for the ground station program and
was responsible for overall coordination and implementation of the program.
Mr. J. B. Tommerdahl was Project Leader for the airborne sampling program;
Dr. E. D. Pellizzari served as Project Leader for the analysis of organic
species collected on Tenax cartridges.
Other staff members who contributed are: (Field Data) Mr. R. Murdoch,
Mr. F. Dimmock, Ms. D. Zimmerman, Mr. H. White, Mr. M. Lee, Mr, J. Johnson;
(Analytical Chemistry) Mr. R. Denyszvn, Mr. D. Hardison, Mr. J. Harden, Mr.
J. McGaughey, Mr. A. Sykes; (Aircraft Program) Mr. R. Strong, Mr. S. Weikel;
(Data Presentation) Mr. L. McMaster, Mr. F. Farmer, and Ms. D. Franke.
ili
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ABSTRACT
During the summer of 1977, Research Triangle Institute (RTI) conducted
a field measurements program entitled "Study of the Nature of Ozone, Nonme-
thane Hydrocarbons, and Oxides of Nitrogen in Tulsa, Oklahoma." This volume
of the report describes the project and summarizes the data.
The monitoring network described in the report consisted of eight RTI
ground sites and two Tulsa City/County Health Department sites. These
stations were distributed so that one was upwind, four were in, and five
were downwind of Tulsa when winds were southerly. Ozone was monitored at 10
sites; NO/NO^ at eight sites; nonmethane hydrocarbons at four sites; wind
speed and direction at four sites; and solar radiation at one site. An
airborne measurements program employing a Piper Navaho B instrumented for
measurement of ozone, NO/NO^ temperature, dew point, b~scat, and condensa-
tion nuclei, was an integral part of the study and is described in detail.
Morning and afternoon flights were made on 7 selected days that had consis-
tent southerly winds.
Surface data for ozone and oxides of nitrogen are summarized through
tables of mean daily concentrations, cumulative frequency distributions, and
diurnal plots, etc. Wind speed and direction are summarized by tabulation
of frequency of occurrence in 5 mph and 30° increments. Average hydrocarbon
concentrations for the several sites are tabulated, and NMHC/NO^ ratios for
the 6-9 CDT time period are given. Also included in this volume are:
descriptions and results of the quality control and quality assurance aspects
of the field study; an appendix describing the sampling and analytical
methodology for GC/FID identification of hydrocarbons; and an appendix
describing the sampling and analysis by GC/MS of volatile organic compounds
collected on TENAX-GC polymer.
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CONTENTS
Page
Acknowledgments ii
Abstract iii
Figures vii
Tables x
1.0 INTRODUCTION 1
1.1 Background 1
1.2 Research Objectives . 2
2.0 OVERVIEW OF THE STUDY 3
2.1 General Description of Ground Station Monitoring Network ... 3
2.1.1 Monitoring Network 3
2.1.2 Instrumentation for Continuous Monitoring 4
2.1.3 Calibration Techniques 7
2.1.4 Quality Control Program 8
2.2 Sampling and Analysis for Hydrocarbons in Ambient Air 9
2.2.1 Sample Collection: Stainless Steel Containers 9
2.3 Airborne Monitoring Program 10
2.4 Organic Species Identification by TENAX-GC/MS/COMP 10
3.0 FIELD MEASUREMENT PROGRAM 11
3.1 Ground Stations 11
3.1.1 Siting Considerations 11
3.1.2 Descriptions of Monitoring Stations 12
3.2 Data Acquisition and Presentation 22
3.3 Hydrocarbon Species Sampling Program 23
3.4 TENAX GC/MS/COMP Analyses 23
3.4.1 Experimental Methods 24
4.0 AIRBORNE AIR QUALITY MEASUREMENTS 27
4.1 Measurements System 27
4.1.1 Aircraft 27
4.1.2 Air Sampling System 27
4.1.3 Instrumentation 28
4.1.4 Data Acquisition System 34
4.2 Instrument Calibration and Characterization 34
4.2.1 Calibration Methods 34
4.2.2 Pressure Effect Tests 39
4.3 Operational Procedures ^1
4.3.1 Pre-Flight Procedures 41
4.3.2 In-Flight Procedures 41
4.3.3 Post-Flight Procedures • 44
V
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CONTENTS (continued)
Page
4.4 Data Reduction Processing and Validation 44
4.5 Flight Program 46
4.5.1 Flight Protocol 47
4.5.2 Flight Summary 49
4.6 Aircraft Data 49
5.0 QUALITY CONTROL AND QUALITY ASSURANCE PROGRAMS 63
5.1 Introduction 63
5.2 Quality Control and Quality Assurance at Surface Sites 64
5.2.1 Preliminary Testing . 64
5.2.2 Methods of Quality Control in Tulsa 65
5.2.3 Quality Assurance Qualitative Systems Audit 69
5.2.4 Quality Assurance Performance Audits 69
5.2.5 Audit of Continuous Hydrocarbon Monitors . 74
5.3 Quality Control Procedures Associated with Hydrocarbon
Analysis by GC-FID 75
5.3.1 Introduction (Qualitative Systems Audit) 75
5.3.2 Sample Container Evaluation 76
5.3.3 Zero Air Evaluation 76
5.3.4 Hydrocarbon Mixture Quality Control Samples 81
5.3.5 Calibration Procedures 83
6.0 DATA SUMMARIES 94
6.1 Contents of Data Summary Section 94
6.2 Ozone Data Summaries 94
6.2.1 Mean Daily Ozone Concentrations 94
6.2.2 Ozone Cumulative Frequency Distributions 94
6.2.3 Frequency Distribution Plots 108
6.2.4 Mean Hourly Standard Deviation of Ozone
Concentrations 108
6.2.5 Pe rccntage of Hourly Ozone Values >0.08 ppm 108
6.2.6 Diurnal Plots of Mean Ozone Hourly Concentrations . . . 108
6.3 Oxides of Nitrogen and Hydrocarbon Data Summaries 131
6.3.1 Mean 0600-0900 CDT Concentrations of NO and NMHC . . . 131
6.3.2 Mean Hourly Standard Deviations for N02Xaad NMHC .... 131
6.3.3 Mean Daily 0600-0900 CDT NMHC/NO Ratios 131
6.3.4 Diurnal Plots of Mean Hourly THcf CH4, and NMHC
Values 144
6.4 Meteorological Data Summaries 144
6.4.1 Tabulated Frequency of Wind Directions 144
6.4.2 Tabulated Frequency of Wind Speed 144
6.4.3 Precipitation and Maximum Temperatures 144
6.5 Individual Hydrocarbon Species Data Summary 144
6.6 TENAX GC/MS/COMP Results 162
7.0 REFERENCES 164
vi
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CONTENTS (continued)
Page
APPENDIXES
Appendix A, Sampling and Analytical Methodology for GC/FID
Identification of Hydrocarbons ... 165
Appendix B. Sampling and Analysis of Volatile Organic Compounds
in Ambient Air 177
vl'i
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FIGURES
Figure ESSr
2 . 1 Air monitoring network for Tulsa, Oklahoma study j
3.1 Map of Tulsa, Oklahoma, and vicinity lo
3.2 Air monitoring site, near Liberty Mounds, Oklahoma 16
3.3 Air monitoring site, U.S. Post Office Vehicle Maintenance
Facility, Tulsa, Oklahoma 16
3.4 Air monitoring site, Tulsa City/County Health Department .... 18
3.5 Air monitoring site, Sperry, Oklahoma 18
3.6 Air monitoring site, near Skiatook, Oklahoma 20
3.7 Air monitoring site, Wynona, Oklahoma 20
3.8 Air monitoring site, Vera, Oklahoma 21
3.9 Air monitoring site, Ochelata, Oklahoma 21
4.1 Instrumented aircraft 28
4.2 Physical layout of air sampling system 29
4.3 Functional layout of air sampling system 30
4.4 Details of forward section of air sampling system 31
4.5 Layout of aircraft system 32
4.6 Hydrocarbon grab sample system 36
4.7 Block diagram of airborne air quality measurement system .... 37
4.8 Ozone analyzer response (normalized to the analyzer's response
at standard pressure) versus altitude 39
4.9 NO/NO analyzer response (normalized to the analyzers' response
at standard pressure) versus altitude 40
4.10 Format of magnetic tape 45
4.11 Typical transport flight pattern 51
4.12 03 for horizontal tracks-flights T09 and T10 55
4.13 Temperature/Dew point-horizontal traverse for T09 AM flight ... 56
4.14 Temperature/Dew point-horizontal traverse for T10 PM flight ... 57
4.15 b for horizontal tracts-flights T09 and TI0 58
scat.
4.16 AM spiral 1 over Liberty Mounds, flight T09 ..... 59
4.17 AM spiral 2 over downtown Tulsa, flight T09 60
4.18 PM spiral 1 over Ochelata, flight T10 61
5.1 Stainless steel container evaluation (HC's and zero air) .... 77
5.2 Stainless steel container evaluation (HC's, zero air, and
0.01 ppm NO) 78
5.3 Stainless steel container evaluation (HC's, zero air, and
0.01 ppm N02) 79
5.4 Stainless steel container evaluation (HC's, zero air, and
0.1 ppm 03) 80
6.1 Frequency distribution of hourly ozone concentrations, Liberty
Mounds. July 1977 109
viii
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FIGURES (continued)
Page
6.2 Frequency distribution of hourly ozone concentrations, Health
Department. July 1977 109
^•3 Frequency distribution of hourly ozone concentrations, Tulsa
Post Office. July 1977 HO
6.4 Frequency distribution of hourly ozone concentrations, Sperry.
July 1977 110
6-5 Frequency distribution of hourly ozone concentrations, Skiatook
Lake. July 1977 Ill
6.6 Frequency distribution of hourly ozone concentrations, Wynona.
July 1977 . . . . , m
6-7 Frequency distribution of hourly ozone concentrations, Vera.
July 1977 112
6-8 Frequency distribution of hourly ozone concentrations, Ochelata.
J^y 1977 H2
6-9 Frequency distribution of hourly ozone concentrations, Liberty
Mounds. August 1977 113
6.10 Frequency distribution of hourly concentrations, Tulsa City/
County Health Department. August 1977 113
6.11 Frequency distribution of hourly ozone concentrations, Tulsa
Post Office. August 1977 114
6.12 Frequency distribution of hourly ozone concentrations, Sperry.
August 1977 . 114
6.13 Frequency distribution of hourly ozone concentrations, Skiatook
Lake. August 1977 115
6.14 Frequency distribution of hourly ozone concentrations, Wynona.
August 1977 115
6.15 Frequency distribution of hourly ozone concentrations, Vera.
August 1977 ........ 116
6.16 Frequency distribution of hourly ozone concentrations, Ochelata.
August 1977 116
6.17 Frequency distribution of hourly ozone concentrations, Liberty
Mounds. September 1977 117
6.18 Frequency distribution of hourly ozone concentrations, Tulsa
City/County Health Department Post Office. September 1977 . . . 117
6.19 Frequency distribution of hourly ozone concentrations, Tulsa
Post Office. September 1977 118
6.20 Frequency distribution of hourly ozone concentrations, Sperry.
September 1977 118
6.21 Frequency distribution of hourly ozone concentrations, Skiatook
Lake. September 1977 119
6.22 Frequency distribution of hourly ozone concentrations, Wynona.
September 1977 119
6.23 Frequency distribution of hourly ozone concentrations, Vera.
September 1977 120
6.24 Frequency distribution of hourly ozone concentrations, Ochelata.
September 1977 * 120
6.25 Frequency distribution of hourly ozone concentrations, Liberty
Mounds. July, August, and September 1977 ..... 121
ix
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FIGURES (continued)
Figure Pa
6.26 Frequency distribution of hourly ozone concentrations, Tulsa City/
County Health Department. July, August, and September 1977 . . . 121
6.27 Frequency distribution of hourly ozone concentrations, Tulsa
Post Office. July, August, and September 1977 122
6.28 Frequency distribution of hourly ozone concentrations, Sperry.
July, August, and September 1977 122
6.29 Frequency distribution of hourly ozone concentrations, Skiatook
Lake. July, August, and September 1977 123
6.30 Frequency distribution of hourly ozone concentrations, Wynona.
July, August, and September 1977 123
6.31 Frequency distribution of hourly ozone concentrations, Vera.
July, August, and September 1977 124
6.32 Frequency distribution of hourly ozone concentrations, Ochelata.
July, August, and September 1977 124
6.33 Mean diurnal ozone concentrations at Liberty Mounds, Tulsa City/
County Health Department, and Tulsa Post Office July,
August, and September 128
6.34 Mean diurnal ozone concentrations at Sperry, Skiatook Lake, and
Wynona. July, August, and September 1977 129
6.35 Mean diurnal ozone concentrations at Sperry, Vera, and Ochelata.
July, August, and September 1977 130
6.36 Mean diurnal concentrations of total hydrocarbons at Wynona,
Tulsa Post Office, and Tulsa City/County Health Department . . . 145
6.37 Mean diurnal concentrations of methane at Wynona, Tulsa Post
Office, and Tulsa City/County Health Department 146
6.38 Mean diurnal concentrations of nonmethane hydrocarbons at Wynona,
Tulsa Post Office, and Tulsa City/County Health Department . . . 147
6.39 Daily maximum temperature and 24-hour total precipitation, Tulsa
Internationa] Airport, July 1977 157
6.40 Daily maximum temperature and 24-hour total precipitation, Tulsa
International Airport, August 1977 158
6.41 Daily maximum temperature and 24-hour total precipitation, Tulsa
International Airport, September 1977 159
x
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TABLES
Table Page
2.1 Calibration techniques 7
3.1 Linear distances in miles between monitoring stations, Tulsa,
Oklahoma 14
3.2 Tulsa, Oklahoma monitoring sites; S.4R0AD identification. ... 15
3.3 Number and location of hydrocarbon samples collected in
Tulsa, Oklahoma 23
3.4 Ambient air sampling protocol for GC/MS/COMP analysis of
volatile organics 25
4.1 Aircraft instrumentation 33
4.2 Pre-f1ight checklist 42
4.3 In-flight checklist 43
4.4 Format of header records and data records 46
4.5 Tulsa aircraft measurement data flights summary 50
4.6 Aircraft log sheet-hydrocarbon grab samples 52
4.7 Low pass data (ozone) 54
4.8 Sample data printout 62
5.1 Comparison of RTI GPT calibration concentrations to EPA Quality
Assurance Branch 64
5.2 NO in N2 calibration standards used in Tulsa. Results of EPA
Quality Assurance Branch analyses 65
5.3 Comparison of predicted and observed ozone values at the time
of analyzer "precalibration" 67
5.4 Estimates of precision of measurements based on precalibration
span values for ozone analyzers in Tulsa, Oklahoma 68
5.5 Summary of PEDCo environmental audit results 70
5.6 Percent error for ozone 74
5.7 Audit results of methane in air standards, ppm, Tulsa, 1977. . 75
5.8 Results of the analyses of zero air stored in stainless
steel containers 82
5.9 Laboratory decay study of Cs-Cjo hydrocarbons; concentrations
in ppbV 84
5.10 Laboratory decay study of C5-C10 hydrocarbons; concentrations
in ppbV . 85
5.11 Laboratory decay study of Cs-Cio hydrocarbons; concentrations
in ppbV . 86
5.12 Laboratory decay study of C5-C10 hydrocarbons; concentrations
in ppbV. 87
5.13 Percent change in concentration, laboratory mix C$-Cio
hydrocarbons 88
5.14 C2-C5 hydrocarbons in roadside samples, ppbC .... 89
5.15 Olefinic and paraffinic hydrocarbons in roadside
samples, ppbC 90
5.16 Aromatic hydrocarbons in roadside samples, ppbC 91
xi
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TABLES (continued)
Table Page
6.1 Mean daily ozone concentration. July, August, September
1977. liberty Mounds 95
6.2 Mean daily ozone concentration. July, August, September 1977.
Tulsa Post Office 96
6.3 Mean daily ozone concentration. July, August, September 1977.
Tulsa City/County Health Department 97
6.4 Mean daily ozone concentration. July, August, September
1977. Sperry 98
6.5 Mean daily ozone concentration. July, August, September
1977. Skiatook Lake 99
6.6 Mean daily ozone concentration. July, August, September
1977. Vera 100
6.7 Mean daily ozone concentration. July, August, September
1977. Vfynona 101
6.8 Mean daily ozone concentration. July, August, September
1977. Ochelata 102
6.9 Mean daily maximum hourly ozone concentrations 103
6.10 Maximum hourly ozone concentrations, ppm. July 1977 104
6.11 Maximum hourly ozone concentrations, ppm. August 1977 105
6.12 Maximum hourly ozone concentrations, ppm. September 1977 .... 106
6.13 Percentile values, maximum values, and arithmetic mean for
ozone, ppm. July-September 1977 107
6.14 Mean hourly standard deviations and number of values by hour
of ozone for entire sampling period 125
6.15 Summary of hourly ozone concentrations >0.08 ppm. July-
September 1977 127
6.16 Mean 0600 to 0900 CDT NO and NMHC concentrations by month
and entire period 132
6.17 Hourly mean, X, hourly standard deviation, a, and number of
hours for nitrogen dioxide, ppm 133
6.18 Hourly mean, X, hourly standard deviation, o, and number of hours
for nitrogen dioxide, ppmC (Beckmam 6800 data) 135
6.19 Mean daily 0600 to 0900 CDT NMHC/NO ratios with standard
deviations, maximum, minimum, and median values 136
6.20 Daily 0600-0900 CDT average NMHC (Beekman 6800 gas chroma-
tograph) and NO , and ratio of NMHC to NO . Tulsa Post
Office X X 138
6.21 Daily 0600-0900, CDT average NMHC (Beekman 6800 gas chroma-
tograph) and NO , and ratio of NMHC to NO . Tulsa City/County
Health Department X , 139
6.22 Daily 0600-0900 CDT average NMHC (Beekman 6800 gas chroma-
tograph) and NO , and ratio of NMHC to NO . Wynona . . 140
X X
6.23 0600-0900 CDT average NMHC (sum of individual hydrocarbon
species less ethylene) and NO , and ratio of NMHC to NO .
Liberty Mounds X x 141
6.24 0600-0900 CDT average NMHC (sum of individual hydrocarbon species)
and NO , and ratio of NMHC to NO . Tulsa Post Office 142
x' x
Xll
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TABLES (continued)
Table Page
6.25 0600-0900 CDT average NMHC (sum of individual hydrocarbon
species) and NO , and ratio of NMHC to NO . Tulsa
City/County Health Department X ... 143
6.26 Wind direction; tabulation frequency by 10° of direction
increment for entire study period 148
6.27 Hourly frequencies of calms and wind direction by 30°
increments for July-September 1977. Liberty Mounds 149
6.28 Hourly frequencies of calms and wind direction by 30°
increments for Tulsa City/County Public Health Depart-
ment. July-September 1977 150
6.29 Hourly frequencies of calms and wind direction by 30°
increments for Wynona. July-September 1977 . 151
6.30 Hourly frequencies of calms and wind direction by 30°
increments for Qchelata. July-September 1977 152
6.31 Hourly frequencies of wind speed for Liberty Mounds.
July-September 1977 153
6.32 Hourly frequencies of wind speed for Tulsa City/County
Health Department. July-September 1977 154
6.33 Hourly frequencies of wind speed for Wynona. July-
September 1977. . 155
6.34 Hourly frequencies of wind speed for Ochelata. July-
September 1977 156
6.35 Average concentrations, ppbC, alkane hydrocarbon species,
0600 to 0900 CDT, Tulsa, Oklahoma, monitoring sites 160
6.36 Average concentrations, ppbC, alkene, alkyne, and
aromatic hydrocarbon species, 0600 to 0900 CDT, Tulsa,
Oklahoma, monitoring sites 161
6.37 Quantitative comparison of volatile organics in ambient
air from Liberty Mounds, Tulsa, and Vera. C-C/MS analysis .... 163
xiii
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SECTION 1.0
INTRODUCTION
1.1 BACKGROUND
The phenomenon of photochemical smog occurs in most urban areas of the
world. These urban centers represent geographically concentrated sources of
primary pollutants such as nitrogen oxides (NO ) and hydrocarbons (HC).
Hydrocarbons and oxides of nitrogen in the presence of sunlight undergo a
complex sequence of photochemical reactions resulting in the accumulation of
ozone (O3). The relationship between initial concentrations of ozone pre-
cursors (HC and NO^) and the resulting maximum ozone levels is highly non-
linear. This has been illustrated frequently by smog chamber results and by
predictions of computer-based photochemical models. The relationship may be
represented in two dimensions by equal concentration lines (isopleths) of
ozone maxima as a function of initial HC and NO concentrations.
x
The National Ambient Air Quality Standard (NAAQS) for photochemical
oxidants at the time of this study was: a maximum 1-hr concentration of
0.08 ppm is not to be exceeded more frequently than once per year. In 1979
the NAAQS standard was revised to 0.12 ppm. Strategies directed at achieving
this goal are aimed at controlling oxidants by reducing emissions of the
hydrocarbon precursors. Current control strategies are based on Appendix J,
Part 51, Title 40 of the Code of Federal Regulations. Questions have been
raised concerning the applicability of the Appendix J approach, and alterna-
tives based on the oxidant-precursor relationship are being explored.
An alternate known as the isopleth approach is currently under consider-
ation. This approach is based on the previously described relationship
between initial HC and NO^ and the corresponding daily maximum 03 levels
represented as isopleths. It is described fully in a current EPA document,
"Uses, Limitations and Technical Basis of Procedures for Quantifying Relation-
ships between Photochemical Oxidants and Precursors."1 The technique requires
a significant accumulation of ambient air data (HC, NO^, 03) and has not
1
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been extensively validated. The isopleth approach may not be directly
applicable to controlling excessive ozone levels resulting from multi-day,
long-range transport, although transported ozone is considered in the
approach. This study addresses single-day, noritrarisport urban conditions
and short-range transport situations in which the oxidant precursor relation-
ships are similar. The purpose of this field study was to collect data that
can be used to test the isopleth approach and other models.
1.2 RESEARCH OBJECTIVES
The principal objective of the field measurement program was to provide
a high quality pollutant and meteorological data base to EPA for use in
operating various photochemical simulation models. The data base will also
be analyzed to: (1) understand the spatial distribution of ozone, oxides of
nitrogen, and nonmethane hydrocarbon species concentrations (including
hydrocarbons in the vicinity of a medium-sized city); (2) examine the rela-
tionship between ambient nonmethane hydrocarbon/NO^ ratios and maximum
measured ozone concentrations observed downwind; (3) determine or obtain a
measure of the upwind ozone concentrations coming into the city; and (4)
document ozone transport across the study region.
2
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SECTION 2.0
OVERVIEW Of THE STUDY
2.1 GENERAL DESCRIPTION OF GROUND STATION MONITORING NETWORK
The monitoring program designed to meet the specifications and require-
ments of this study consisted of air quality and meteorological measurements
at eight ground stations located upwind of, in, and downwind of Tulsa,
Oklahoma, during the period from July 1 through September 30, 1977. The
following measurements were made at the selected sites: ozone was measured
at one site 36 km upwind, two sites downtown, and five sites downwind to
25-50 km; oxides of nitrogen were measured at each of the sites mentioned
above; total and nonmethane hydrocarbons were sampled at the two downtown
sites; nonmethane hydrocarbon integrated samples were collected from 0600 to
0900 CDT for individual species analysis at the upwind site and the two
downtown sites. Wind speed and wind direction were recorded upwind, downtown,
and at four sites downwind to characterize the airflow across the area.
Solar radiation was recorded at the two sites 25-30 km downwind. Further
details concerning site locations, instrumentation, calibration techniques,
and quality control procedures used in conducting the field measurement
program are described in the following subsections.
2.1.1 Monitoring Network
A brief examination of the historical meteorological records for the
Tulsa, Oklahoma, area indicated that prevailing winds during June, July,
August, and September are from the southerly direction approximately 60
percent of the time with an average wind speed of 4 m/s (9 mph). Based on
this information and the objectives of the measurement program, the station
deployment shown in Figure 2.1 was established for the air monitoring network.
Each circle represents a sampling station; the symbols included inside each
circle indicate the air quality and meteorological parameters that were
measured at each site. The two downtown monitoring stations were employed
3
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to establish the NHHC/NO^ ratios in downtown Tulsa; the five generally
downwind stations were placed on arcs at distances of 15, 25, and 50 km to
provide broad downwind coverage of ozone and oxides of nitrogen concentra-
tions; the one upwind station obtained a measure of the upwind ozone concen-
trations coming into the city.
2.1.2 Instrumentation for Continuous Monitoring
Continuous measurement methods were used to acquire data for ozone,
oxides of nitrogen, nonmethane hydrocarbons, wind speed, wind direction, and
solar radiation at the stations shown in Figure 2.1. Brief descriptions of
the measurement principles for each parameter are presented in the following
paragraphs.
2.1.2.1 Ozone—
Ambient ozone concentrations were measured at all sites using the
Bendix Model 8002 chemiluminescent ozone analyzer. The principle of opera-
tion of this instrument is based on the gas-phase chemiluminescent reaction
between ethylene and ozone. The reliability, stability, specificity, and
precision of ozone measurements by this technique have been adequately
demonstrated and described in the literature.2
2.1.2.2 Oxides of Nitrogen--
Nitric oxide and nitrogen dioxide concentrations were measured at all
eight ground stations using the Bendix Model 8101-B NO-NC^-NO^ analyzer.
The principle of operation of this instrument is based on the gas-phase
chemi1uminescent reaction between NO and 0^. Measurement of the NO2 concen-
tration by this method requires that N02 be reduced to NO, which then reacts
with 03. The sum of the initial NO measurement plus the NO produced by the
reduction of N02 is the nitrogen oxides (NO^) measurement. Electronic
subtraction of the NO measurement from the NO^ measurement gives the N02
concentration.
2.1.2.3 Nonmethane Hydrocarbons--
Nonmethane hydrocarbon (NKHC) concentrations were measured at two
ground stations using the Beckman Model 6800 air quality chromatograph,
which utilizes an automatic gas chromatographic-flame ionization detector
(GC-FID) to measure THC and CH4 in ambient air. The NMHC concentration of
4
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Ozone
WS/WD
NO
Wynona
North
Hydrocarbon Grab Samples
NMHC (Beckrran)
Skiatook Lake
Wind Speed
Wind Direction
WS
WD
WS/WD/SR
Solar Radiation
SR
WS /WD
Vera
Ochelata
50 km
WS/WD/SR
Sperry
Post Office
TULSA
1 WS/WD
Heal Department
Liberty Mounds
W X J WS/WD
Figure 2,1, Air monitoring network for Tulsa, Oklahoma study
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the ambient sample is computed by subtraction of CH4 from the THC measure-
ment .
2.1.2.4 Wind Direction and Speed—
Two different wind sensors were employed in this study. The Climatronics
Wind Direction Transmitter (WD-10B) and Wind Speed Transmitter (WS-10A) were
used at the Skiatook Lake and Vera sites. Wind direction is sensed by a
lightweight counterbalanced vinyl-covered vane. The wind direction is
converted to an electrical signal by a capacitive transducer and the associ-
ated electronics of the transmitter. Wind speed is sensed by a three-cup
anemometer made of plastic. A photochopper rotates with the cup assembly
and its rotation is converted to an electrical signal by a phototransis tor
and light source. The output of the transmitter is a signal whose frequency
is proportional to the wind speed. The threshold for operation of the
sensors is 0.2 m/sec (0.5 raph); the accuracy is ±1 percent.
A Meteorology Research, Inc., Model MSI-I072 mechanical weather station
was employed at the Liberty Mounds, Wynona, and Ochelata sites. With this
sysLern, wind direction is sensed by a ball-bearing-mounted balanced aluminum
blade with nose damping. The wind speed (run) is measured by a cup anemometer
employing three 12 cm (4.5 in.) diameter conical aluminum cups. The starting
threshold for either sensor is 0.3 m/sec (0.75 mph); overall accuracy is ±2
percent of full scale.
Difficulties in operation of the Climatronics wind sensors resulted in
the invalidation or loss of most of the data at the Vera and Skiatook Lake
sites. Other wind data were obtained for the Health Department site (courtesy
of the Tulsa City/County Health Department) and the Tulsa International
Airport (courtesy of National Weather Service).
2.1.2.5 Solar Radiation--
Solar radiation was measured at the Skiatook Lake and Vera sites by
means of a silicon solar cell pyranometer. Much of the data from Vera was
lost due to sensor downtime or moisture condensation problems. The millivolt
output of the pyranometer is converted to a linear voltage versus radiation
by the radiation translator. The sensor responds to both visible and ultra-
violet light and was calibrated by the manufacturer versus a thermopile
sensor, which responds to all solar radiation. Data are reported in units
of Langleys min hourly average.
6
-------
Table 2.1. Calibration techniques
Pollutant
Calibration technique
Ozone
Ultraviolet ozone generator referenced
to NBS-SKM (NO in nitrogen) by Gas Phase
Titration (GPT).
Nitric oxide, nitrogen dioxide Gas Phase Titration technique using
NBS-SRM (NO in nitrogen) standard.
Total hydrocarbon, methane
Compressed gas cylinders containing
methane, referenced to QAB-EMSL
standards for methane.
2.1.3 Calibration Techniques
Dynamic techniques which were used to calibrate each ambient air analyzer
at monthly intervals during the 90-day period of field operations are outlined
in Table 2,1. Similar procedures and standards were used for performing
daily zero and span checks. A brief description of the calibration techniques
is given below.
2.1.3.1 Ozone-Ultraviolet Ozone Generator Referenced to NBS-SRM NO in
Dynamic calibration of the ozone analyzers was accomplished by use of
an ultraviolet ozone generator. The ozone generator consists of a mercury
vapor lamp 20 cm (8 in.) in length that irradiates a 16-mm (5/8-in.) diameter
quartz tube through which clean (compressed) air flows at 5 L/min. Ozone
concentrations over the measurement range are generated by variable shielding
of the mercury vapor lamp. Although the ultraviolet ozone generator has
been shown to be quite stable and reproducible, the gas phase titration
procedure was used as the reference method.3
2.1.3.2 Nitric Oxide/Nitrogen Dioxide: Gas Phase Titration Technique--
The gas phase titration technique was used for dynamic calibration of
the chemiluminescent N0-N02-N0x analyzers.3 The technique is based on the
rapid gas-phase reaction between nitric oxide and ozone to produce a stoichio-
metric quantity of nitrogen dioxide. A certified tank of nitrogen (of an
approximate concentration of 50 ppm by volume) is diluted with zero air to
Nitrogen Standard--
7
-------
provide NO concentrations in the range of 0.015 to 0.8 ppm. Nitrogen dioxide
concentrations are produced by the reaction of NO with ozone. Primary
calibration of the NO in nitrogen concentration was accomplished by reference
to an NBS-SRM. The NO concentration of esch cylinder used was referenced to
the NBS-SRM prior to going t.o the field and at the conclusion of the study.
2.1.3.3 Total Hydrocarbons/Methane/Nonmethane Hydrocarbons--
Calibration of the Beckman 6800 air quality chromatograph was accom-
plished using cylinders containing known concentrations of methane in air
according to procedures in the Federal Register.4 Mixtures of methane in
air were purchased from Airco, Inc., and referenced to appropriate methane
standards maintained at QAB-EMSL.
2.1.4 Quality Control Program
To achieve and maintain a high level of confidence in air quality data,
it is essential to routinely monitor critical instrument parameters and to
maintain appropriate records. In general, quality control for the Tulsa
oxidant study included verification and referencing of calibration standards
to NBS-SRM's; daily, weekly and monthly operational and maintenance checks;
daily zero and span checks; monthly dynamic calibrations; maintenance of
analyzer logs, use of control charts, use of standard stripchart data reduc-
tion procedures; and thorough training of instrument operators.
Calibration data, as well as daily zero and span information, were
examined for excessive zero and span drift. When zero drift exceeded ±2
percent of full scale per 24-hr period, the data of the preceding 24-hr
period were considered to be of questionable validity and were critically
examined and invalidated if necessary. Span drift was determined on a daily
basis and from multipoint calibration data every month. If the span drift
exceeded ±15 percent per 24-hr period, the data were invalidated and an
immediate recalibration of the instrument was performed.
The pollutant and meteorological daLa were reduced from the strip chart
records daily and entered as hourly averages on Storage and Retrieval of
Aerometric Data (SAR0AD) forms. The reduced data were visually compared to
the strip charts and examined for completeness, accuracy, signs of equipment
malfunctions, excessive pollutant levels, and any unusual diurnal patterns.
8
-------
EPA maintained a routine performance audit program for the Tulsa study.
The audit data provided external quality assurance and served as a measure
of the quality of data generated during the study. A more detailed discus-
sion of the quality control program is provided in Section 5.0.
2.2 SAMPLING AND ANALYSIS FOR HYDROCARBONS IN AMBIENT AIR
While many different types of sampling containers have been employed in
collecting hydrocarbons, few have been found to be adequate for the collec-
tion of C2-C10 hydrocarbons. The most widely used sampling containers are
polymeric film sampling bags (Tedlar, Teflon), glass bulbs, stainless steel
containers, and solid absorbents. Each container has advantages and dis-
advantages.5 6
2.2.1 Sample Collection: Stainless Steel Containers
Stainless steel containers are very durable and easily deployed in
field programs. The storage capability of trace organics in passivated
stainless steel containers is excellent.7 For these reasons, stainless
steel containers were chosen for use in this study. These containers were
cleaned in the laboratory by a series of heated, high vacuum evacuations.
Two metal bellows pumps were employed to fill the stainless steel
container. One, a Model MB-41, sampled directly from the station's ambient
air manifold at a rate of several liters per minute to insure that a repre-
sentative sample was obtained. A second pump, Model MB-151, sampled from a
tee on the outlet side of the MB-41 pump. The larger MB-151 pump provided
adequate pressure to insure a constant flow rate through a critical orifice
into the container. A flow rate of 15 cc/min was sufficient to fill the
sampling container to a pressure of 3-5 psig in 3 hr. At the completion of
the sampling period, the sampling container was sealed and shipped back to
RTI for analysis. In order to minimize the time between sampling and analysis,
sample containers were shipped by air freight.
Details of quality control and quality assurance procedures associated
with the hydrocarbon sampling program are given in Section 5.0. Sampling
and analytical methodology are discussed in Appendix A of this volume.
9
-------
2.3 AIRBORNE MONITORING PROGRAM
An airborne measurements program consisting of horizontal traverses and
vertical spirals was included in the study design. Ten days of flights were
conducted to obtain data on the morning atmosphere above and below the
mixing layer; the afternoon atmosphere within the mixing layer; the level of
pollutants upwind, over, and downwind of Tulsa; and any single source or
complex sources that might affect the atmosphere within the Tulsa area.
Both transport and stagnation pattern flights were planned. A thorough
discussion of the airborne measurements program is given in Section 4.0.
2.4 ORGANIC SPECIES IDENTIFICATION BY TENAX-GC/MS/COMP
Another element of the study design was collection of ambient air
samples on Tenax GC for GC/MS/COMP analysis of organic species. The mass
spectra were interpreted to ascertain the qualitative composition of the
organic components in Tulsa's downtown air and air at other sites. The
GC/MS data analyses provide positive identification of the organic constitu-
ents collected and provide confirmation of the qualitative identification of
hydrocarbons that were collected in stainless steel containers and analyzed
by GC/FID.
Complete details on the GC/MS/COMP analysis method are given in Appen-
dix B of this volume.
1C
-------
SECTION 3.0
FIELD MEASUREMENT PROGRAM
This section provides a description of the protocol followed in estab-
lishing and operating the ground station sampling network for the Tulsa
summer study. Site locations, instrumentation, data acquisition, and data
processing and presentation procedures are discussed below.
3.1 GROUND STATIONS
3.1.1 Siting Considerations
Tulsa, Oklahoma, is a medium-sized city (population 350,000) situated
in a region characterized by gently rolling pastureland. Due to the city's
geographic isolation from other urban areas, Tulsa is an ideal location for
a study of pollutant chemistry and transport. Analysis of the Tulsa study
data base is expected to provide a better understanding of the spatial
distribution of ozone, oxides of nitrogen, and hydrocarbon species in and
near a mid-sized city.
Historical meteorological records for the Tulsa, Oklahoma, area indicate
prevailing winds during July through September are southerly at an average
speed of A m/s (9 mph). Since two of the objectives of the program were to
determine the concentrations of ozone, oxides of nitrogen, and hydrocarbons
transported into the city and the impact of local emissions on downwind
ozone and precursor concentrations, an eight-station network was established
along the prevailing wind direction.
One station, Liberty Mounds, was located approximately 37 km (23 mi)
south of downtown Tulsa. This station provided information on the background
concentrations of air masses entering the city during periods of southerly
winds. Two monitoring stations were located within the Tulsa city limits.
The Post Office site, located in the central business district, was within
3.2 km (2 mi) of an oil refinery complex and a major interstate highway
traffic interchange. The other site, Tulsa City/County Health Department,
was in a residential/commercial area of the city.
11
-------
Five stations were located to the north of Tulsa. The closest site was
at Sperry, Oklahoma, approximately 15 km (10 mi) from the Tulsa Post Office
site. Two other sites, Skiatook Lake and Vera, were each approximately
30 km (20 mi) from the central Tulsa area. The northern-most sites were at
Wynona and Ochelata, each about 50 km (30 mi) from the Tulsa Post Office
site.
The location oi each of the monitoring sites is shown in the map in
Figure 3.1. The linear distance between the various sites is presented in
Table 3.1, and the SAROAD number and geographic coordinates for each site
are listed in Table 3.2.
Two other ozone monitoring stations were operated by the Tulsa City/
County Health Department. These sites were located within the city limits
at the corner of Mohawk and Peoria Streets and at the corner of Apache and
Sheridan Streets. The reader should note that the ozone monitors at these
two sites were calibrated by the use of the neutral buffered potassium
iodide (NBKI) procedure, not the gas phase titration (GPT) procedure that
was used at the eight stations in the present study, A laboratory comparison
of these two calibration procedures, conducted at EPA's EMSL-QAB laboratory
during the period of the study, has shown that the ozone concentrations
determined by the analyzers referenced to NBKI are approximately 20 percent
higher than those referenced by gas phase titration.
3.1.2 Descriptions of Monitoring Stations
3.1.2.1 Liberty Mounds--
This site was located in a rural area of Okmulgee County, on property
owned by the rural water works, District No. 6. The area immediately adjacent
to the site is illustrated in Figure 3.2. All ambient air analyzers and
associated equipment were housed in a 2.4-m by 4.8-m air conditioned Avion
trailer. Wind direction (WD) and speed (WS) were measured with an MR I
mechanical weather station, which was mounted on a 4-m (13-ft) tripod. The
tripod was located approximately 9 m (30 ft) west of the trailer. The
station was located approximately 45 m to the north of a hard-surfaced road
and 2 km east of the U.S. Highway 75. The sampling inlet was located on the
south end of the trailer at a height of 4 m above the ground. Surface
elevation was 216 m. Exposure was excellent in all directions.
12
-------
SKIATCOK LAKE
.20-
APACHE ST
KFTSTQS-r /. AXt
j TWJSA INTERNATIONAL
1 AIRPORT
J 676 MSL
72$ MSw m
MOhAWK BLVDjg
£gyi OFRCt]
Oil
,44
STATUTE MILES
20 o
TOO MSL
20
30
liberty mound:
LOCATION OF 3RCUND MONITORING SITE
INTERSTATE HiGHWAY
u S Highway
(^) STATE HiGHWAY
Figure 3.1, Map of Tulsa, Oklahoma and vicinity.
13
-------
Table 3.1. Linear distances in miles between monitoring stations,
Tulsa, Oklahoma, summer, 1977. Distances determined
by measurement between points on U. S. Geological
Survey maps
Liberty
Mounds
Post
Office
Health
Department
Sperry
1
i Skiatook
Lake
Vera
Wynona
Ochelata
Mohawk
Apache
Liberty
Mounds
22.5
20.5
32.5
38.5
45.0
53.0
52.0
24.7
24.0
Post
Of f ice
22.5
4.5
10.0
16.0
21.5
34.0
30.0
3.0
5.4
Health
Department
20.5
4.5
11. 7
19.0
23.0
36.0
31.0
4.8
3.7
Sperry
32.5
10.0
11.7
8.8
12.3
26.0
21.0
7.0
8.8
Skiatook
Lake
38.5
16. 0
19.0
23.0
8.8
12.3
15.4
15.4
14.0
20.0
14.0
17.0
Vera
45.0
21.5
i 26.0
12.0
18.5
19.0
Wynona
53.0
34.0
36.0 26.0
14.0
26.0
20.0
32.0
35.0
Ochelata
52.0
30.0
31.01 21.0
20.0
12.0
20.0
28.5
29.0
Mohawk
24. 7
3.0
4.8
1
7.0
14.0
18.5
32.0
28.5
4.0
Apache
24.0
5.4
3.7
8.8
17.0
19.0
35.0
29.0
4.0
14'
-------
Table 3.2, Tulsa, Oklahoma monitoring sites; SAROAD identification.
Station Name
Liberty Mounds
SAROAD Number
372240999
Coordinates
Longitude W 95 59 56
Latitude N 35 50 34
Post Office
373000998
Longitude W 95 59 49
Latitude N 36 09 il
City/County Public
Health Department
373000997
Longitude W 95 55 26
Latitude N 36 08 26
hperry
373020996
Longitude W 95 59 23
Latitude N 36 17 51
Skiatook Lake
372260995
Longitude W 96 07 35
Latitude N 36 21 23
Vera
373140994
Longitude W 95 52 58
Latitude N 36 26 56
Wynona
372260993
Longitude W 96 19 21
Latitude N 36 32 37
Ochelata
37 3140992
Longitude W 95 58 57
Latitude N 36 35 40
Mohawk Boulevard
373000127
Longitude W 95 58 28
Latitude N 36 07 49
E. Apache Street
373000132
Longitude W 95 54 19
Latitude N 36 11 31
15
-------
TO TULSA 35 Km <22 mi)
4 m TRIPOD
ws.wo
SITE
POWER LINE
GROCERY
N
DISTRICT WATER WORKS
BUILDING
¦V
TO
"HECTORVILLE
>-1.6 Km
( I mile )
TO OKMULGEE 27 Km (17 mi)
Figure 3.2. Air monitoring site, near Liberty Mounds, Oklahoma.
POST OFFICE
MONITORING SITE
POST OFFICE VEHICLE
MAINTENANCE FACIUT
sr. ^U!S'.SAN
°o
llth ST.
15 th ST.
OIL REFINERY
PRODUCTION AND STORAGE
Figure 3,3, Air monitoring site, U. S. Post Office Vehicle Maintenance
Facility, Tulsa.
16
-------
3.1.2.2 Tulsa Post Office—
This monitoring station was located in the northwest corner of property
occupied by the U.S. Postal Service. The facility is located at the southwest
corner of Second and Elwood Streets (see Figure 3.3). Ozone, NC^, and
hydrocarbon analyzers, and associated equipment were housed in a 3-m by
5.5-m air conditioned Coastal trailer. The station was 1.1 km (0.7 mi)
northeast of a major traffic interchange, 1.6 km (1 mi) northeast of the
Arkansas River, and 2.3 km (1.4 mi) northeast of the two petroleum refineries.
The sampling inlet was positioned on the west side of the trailer at a
height of 4.6 m above the pavement. The site elevation was 209 m above mean
sea level. Exposure at this site was relatively good from the south, west,
and north; however, exposure from the east was somewhat obstructed by build-
ings in the adjacent block.
3.1.2.3 Tulsa City/County Health Department--
This station was located in the northeast corner of the Tulsa State
Fairgrounds, approximately 100 m from the corner of 15th Street and Yale
Avenue (see Figure 3.4) The ozone, oxides of nitrogen, and nonmethane
hydrocarbon analyzers and associated equipment were maintained in a 4.8-rn by
13.7-m air conditioned trailer. The trailer was approximately 76 m south-
east of the Tulsa City/County Health Department building. The air sample
inlet was located at the southeastern end of the trailer at a height of
4.9 m above the surface. The area surrounding the fairgrounds was primarily
residential and commercial. Exposure was good in all directions except for
the northwest. Wind speed and direction sensors were maintained at this
site by Health Department personnel. The sensors were mounted on a 10 m
tower atop the three-story Health Department building.
3.1.2.4 Sperry--
This site was located adjacent to the National Guard Armory at Sperry,
Oklahoma (population 1,300), which is 16 km (10 mi) north of the Tulsa Post
Office site. The sLation was anchored in the southwest corner of the Armory
lot as shown in Figure 3.5. The elevation of the station was 190 m above
mean sea level. The ozone and oxides of nitrogen analyzers were housed in
an environmentally controlled room at the south end of a 4.3-m by 10.7-m
trailer. The sampling inlet was 4.8 ni above the ground. Exposure at this
station was good in all directions.
17
-------
15 th. ST.
N
PARKING
TULSA CITY COUNTY
" HEALTH DERARTMENT
STORAGE SHED
OPEN FIELD
STATE FAIRGROUNDS
Figure 3.4. Air monitoring site, Tulsa City/County Health Department.
SPERRY
NATIONAL GUARD
ARMORY
o
SITE
FENCE
TULSA 16 Km (10 mi)
STATE ROAD II
Figure 3.5. Air monitoring site, Sperry, Oklahoma.
18
-------
3.1.2.5 Skiatook Lake--
This site, illustrated in Figure 3.6, was located in a rural, hilly-
area about 26 km northwest of Tulsa and about 11.5 kin west of Skiatook,
Oklahoma. At this station, the ozone and oxides of nitrogen analyzers and
associated equipment were maintained in an air conditioned 3~m by 4,3-m
Teton trailer. Exposure at this rural site was excellent. The site eleva-
tion was 201 m above mean sea level and the sample inlet, located at the
northwestern corner of the trailer, was positioned 4 m above the surface.
The meteorological system (Climatronics Corporation), consisting of an
anemometer, wind vane, and a solar radiometer, was sited on a 10-m (32-ft)
tower approximately 27 m (90 ft) north of the trailer.
3.1.2.6 Wynona—
The northwestern-most monitoring station was located on the grounds of
the Wynona Trailer Court in Wynona, Oklahoma (pop. 1,000), approximately
54.7 km (34 mi) northwest of Tulsa. The area surrounding the site is rural
arid the terrain is fairly flat. Exposure at this station was excellent in
all directions. The ozone, oxides of nitrogen, and hydrocarbon analyzers
were maintained in an air conditioned 2.4-m by 4.3-m Atlantic trailer as
shown in Figure 3.7. The sample inlet was placed on the south side of the
trailer 5.2 m above the ground. The site altitude was 271 m above the mean
sea level. A 4.5-m tripod supported an MRI WS/WD measurement system and was
located approximately 6 m to the east of the trailer.
3.1.2.7 Vera--
This monitoring station was located in Vera, Oklahoma (population 350),
34.6 km northeast of Tulsa. The ozone and oxides of nitrogen analyzers were
sited in a 2.4-m by 4.9-m air conditioned Avion trailer located 36.5 m
southwest of the Vera Post Office building. Figure 3.8 illustrates the
area. The sample inlet was located on the southwestern corner of the trailer
at a height of 4.3 m above the surface. Altitude of the site was approxi-
mately 199 m above mean sea level. A 10-m tower located 9.1 m east of the
trailer supported Climatronics WS/WD and solar radiation sensors. Exposure
at this site may have been somewhat limited from the southeast due to an oak
tree, 15 m tall, located 45 m from the meteorological tower.
19
-------
SITE
TO HOMINY
23 Km (14 mi.)
FARMLAND
TULSA
25.7 Km (16 mi,5
TO SKIATOOK
13 Km (8 mi.)
Figure 3,6. Air monitoring site, near Skiatook, Oklahoma
TOWN OF WYNONA
HOUSE TRAILERS
SITE
TULSA
55Km (34mij
4m TRIPOD; WS,WD
OPEN FIELD
TO HOMINY
16 Km (lOmi.)
Figure 3,7. Air monitoring site, Wynona, Oklahoma.
20
-------
o
r-
<3
P
to
1
I
3!
TOWN HAUL VERA POST OFF
SITE
~
10 m TOWER
WS, WD,SR
HOUSE
\
CE
N
TULSA
34 Km (21 mi)
Figure 3.8. Air monitoring site, Vera, Oklahoma.
TOWN OF OCHELATA
<3
HOUSE TRAILERS
4 m TRIPOD
WS, WD
HOUSE1
SITE
TULSA
48 Km (30mi)
Figure 3.9. Air monitoring site, Ochelata, Oklahoma,
21
-------
3.1.2.8 Ochelata--
The northeastern-most sampling station was located at the Country Aire
Mobile Home Park in Ochelata, Oklahoma. The town of Ochclata (population
500) is located 48 km (30 mi) northeast of Tulsa. The trailer was identical
to the one at the Skiatook Lake site and contained ozone and oxides of
nitrogen analyzers. Figure 3.9 diagrams the features of this site. An MRI
WS/WD measurement system was located 9.1 m (30 ft) southwest of the trailer
on a 4-m tripod. The sample inlet was located on the south side of the
trailer at a height of 3.7 m. The altitude of the site was approximately
230 m above mean sea level. The exposure at this site was excellent in all
directions.
3.2 DATA ACQUISITION AND PRESENTATION
Each of the sites was visited daily. Checks were made of analyzers and
recorders. Items checked were: supply gas pressure and flow rates; vacuum
pressure of sampling pumps; proper operation of valves, fans, and ozone
generator of NO^ analyzer; zero and span response of O3, NO, and NO2 channels;
operation of catalytic ethylene oxidizer. All readings and comments were
entered on a daily checksheet and in the station logbook.
All continuous measurements at the eight field stations were recorded
on strip chart recorders. A least squares linear regression equation relat-
ing concentration of pollutant (ppm) to percent of chart was established for
each multipoint calibration. The regression equation was applied to deter-
mine average hourly concentrations of pollutants from the strip chart readings.
All data were entered on SAROAD daily data forms in Tulsa. The data
forms were mailed to RT1, checked, and then delivered, with strip charts, to
EPA-EMSL for validation, keypunching, and printout in standard SAROAD format.
All continuous data were handled in this way with the following exceptions:
Beckman 6800 data (entered on SAROAD, validated by RTI, keypunched and
printed by RTI); Tulsa Health Department WS/WD data (data obtained from
Tulsa Health Department, printed by RTI); Tulsa ozone measurements at Mohawk
and Apache locations (data received on magnetic tape from National Aerometric
Data Bank). All of the continuous data are presented in Volume II of this
report.
22
-------
Table 3.3. Number arid location of hydrocarbon samples
collected in Tulsa, Oklahoma
Morning
Midmorning
Afternoon
13 to 16 CST
Site or location
05 to 08 CST
08 to 11 CST
Liberty Mounds
Health Department
Post Office
Sperry
Skiatook Lake
Vera
Wynona
Ochelata
Aircraft, upwind
Aircraft, over city
Aircraft, low pass
Aircraft, downwind
70
77
78
10
0
0
0
0
24
10
11
0
7
7
7
7
0
0
0
0
0
0
0
0
0
1
1
5
6
6
5
5
0
0
0
12
3.3 HYDROCARBON SPECIES SAMPLING PROGRAM
Approximately 235 integrated samples were taken during the 0600 to 0900
CDT period at three stations: Liberty Mounds, Tulsa Health Department, and
Tulsa Post Office. An additional 114 samples were taken at other stations
and aloft in different time frames during the period of airborne air quality
measurements. Table 3.3 summarizes the number and location of hydrocarbon
samples.
All samples were collected in 2-L stainless steel containers and shipped
back to the Research Triangle Park for analysis by RTI. Details of the
analysis procedure are given in Appendix A of this volume. Concentrations
of individual species in each sample are compiled in Volume II of this
report. Qualifying statements concerning the hydrocarbons data base are
also given in Volume II.
3.4 TENAX GC/MS/C0MP ANALYSES
Early in the program (July 10 and 11), field personnel collected two
24-hr samples on Tenax cartridges, one at Liberty Mounds and one at the
Tulsa Post Office site. Later, on September 21, 3-hr samples were collected
at the Liberty Mounds, Post Office, and Vera sites. All data and spectra
associated with the GC/MS analyses are given in Volume II of this report.
23
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3.4.1 Experimental Methods
The methods and procedures for the collection and analysis of volatile
organics in ambient air are described in Appendix B of this volume. Briefly,
organic vapors were collected using a solid sorbent, Tenax GC, in a cartridge
by passing ambient air through the cartridge to trap the organic vapors.
Subsequent analysis of the cartridges was performed by high resolution gas
chromatography/mass spectrometry/computer for the separation and charac-
terization of the organic species recovered from the Tenax GC cartridges.
Table 3.4 presents the ambient air GC/MS sampling protocol for volatile
organics in Tulsa and vicinity. Essentially, five different samples were
collected in duplicate on three different dates during the past summer. The
first two samples were collected in July and represented sampling over a
24-hr period on two consecutive days at Liberty Mounds and the Post Office
site in downtown Tulsa. The second set of samples was from Liberty Mounds,
the Post Office site in downtown Tulsa, and Vera and represented volatile
organics collected over a 3-hr period. In the latter set of samples, the
objective was to compare the relative concentrations of volatile organics
present in ambient air at the three sites.
The quantitation of chemical classes as well as individual species was
performed on the GC/MS/COMP system utilizing the mass fragmentographic
technique. The basic program calculates ''area ratio," which is the area
ratio of a selected ion to one specified ion (or the sum of specified ions)
over a selected range of mass spectra. The program uses a subroutine for
searching spectra that are stored on the fixed disk. The program prints out
the "sum of ions" area, which is a specified ion or ions, and "selected ion
area" as well as the area ratio and indicates saturated ion if an intensity
is >32,736. This program was used to sum ion intensities representing
chemical classes of compounds over a selected region of the chromatogram of
the individual samples. The m/e 186 ion was the selected ion and is the sum
of the intensities of the external standards perfluorobenzene and perfluoro-
toluene. The area measurements were of prime interest in this case, not the
area ratios. Using this approach, it was possible to calculate the relative
quantities of various chemical classes as well as individual species for the
samples taken from Liberty Mounds, the Post Office in Tulsa, and Vera.
24
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Table 3.4, Ambient Air Sampling Protocol for GC/MS/COMP Analysis of Volatile Organics
Sampling Site
Location
Code
Date
Period, CDT
Volume
Sampled (L)
Liberty Mounds
District Water Works
Downtown Tulsa, OK Post Office Garage Lot
(2nd & Elwood)
Liberty Mounds
District Water Works
Downtown Tulsa, OK Post Office Garage Lot
(2nd & Elwood)
LM1 7/10-11/77 0355-0355 hrs
DTI 7/11-12/7/ 0600-0600 hrs
LM2 9/21/77
DT2 9/21/77
0600-0900 hrs
0600-0900 hrs
160.8
142.5
351
390
Vera
Vera Post Office
VI
9/21/77
1400-1700 hrs
390
-------
Comparison among the three sites was made on a relative basis. The break-
through volumes and sampling volumes were used to normalize the samples in
arbitrary units per cubic meter of ambient air. The results obtained at
these three sites are discussed in Chapter 6 of this volume and in Volume 111,
"Data Analysis and Interpretation."
26
-------
SECTION 4.0
AIRBORNE AIR QUALITY MEASUKiiMiSJNTS
4.1 MEASUREMENTS SYSTEM
A brief description of the airborne air quality measurements system
is given in the following sections. A more detailed description of the
system design was presented in a previous publication.8
4.1.1 Aircraft
The aircraft used in the program was a Piper Navajo B, shown in the
photograph, Figure 4.1. The aircraft operates at a typical cruise speed
of 280 km/hr (180 mph) which, with a normal crew complement (pilot and in-
strument operator) and instrumentation package, will allow an operational
time of 3.5 hrs with 45 min of fuel reserve. The maximum operational al-
titude is 7,600 m (25,000 ft) with an initial climb rate capability exceed-
ing 305 m/min (1000 ft/min). It is equipped with instrumentation for day
and night VFR and IFR operations. Communications and navigation equipment
include Dual VOR and VHF Communication, DME, ADV, Transponder, and an Al-
titude Reporting Altimeter.
4.1.2 Air Sampling System
A physical layout of the air sampling system is shown in Figure 4.2
and a functional layout of the system is shown in Figure 4.3. The air
intake system consists of two 2.54-cm Teflon tubes inserted in steel
tubes mounted to the nose cone of the aircraft and extending approximately
61 cm in front of the nose of the aircraft (see Figure 4.2). One of the
Teflon probes terminates in an expansion manifold located in the nose com-
partment of the aircraft, supplying a clean air sample to an integrating
nephelometer mounted in the nose compartment.
The second Teflon probe extends to the cabin area of the aircraft
and attaches to a 12.7-cm diameter sample manifold, constructed of alumi-
num and coated internally with heat-cured Teflon. The manifold is de-
signed with an inlet diverging diffuser section to allow deceleration of
27
-------
Figure 4.1, Instrumented aircraft.
flow to a more controllable velocity, typically in the range of 3 m/sec.
Analyzer sample lines, temperature, and dew point probes, etc. are
situated along the main body of the manifold, an adequate distance from
the diffuser, to allow unobstructed, isentropic flow of air sample. Mani-
fold flow velocity, monitored with a hot wire anemometer, can be adjusted
with an exit damper for variations in cabin pressure, altitude, and air-
craft speed. A minimum flow velocity of 2-3 m/sec is maintained to insure
relatively rapid air sample exchange. The manifold exhaust design in-
cludes a diverging diffuser section, minimizing the possibility of contam-
ination from the aircraft cabin.
4.1.3 Instrumentation
Functional and equipment layouts for the aircraft instrumentation
system used in this program are illustrated in Figures 4.4 and 4.5,
respectively. The measured parameters are listed in Table 4.1, along with
corresponding instrumentation, analysis technique, range of operation, and
response time.
28
-------
SAMPLE U
^ROBE 12 (L
MANIFOLD
\ -
SAMriE jV T
probe *1 i ^
tr
(TOP VIEW)
to
\a
Figure 4,2.
SAIIPLE PROBE ^SIDE VIEW'
NEPHELCMETER
BOTTL
RACK
MANIFOLD
SAMPLE OROBE
0.6m
lJLm
2,7m —
~ 4. 4m
Physical layout of air sampling systern,
-------
Exhaust
Pump)
Neplielometer
Expansion
Man!fold -
¦*- Exhaust
2.54 cm Teflon
Steel. Support
Sample Manifold
Crmt rol .1 ed
Exhaust
w
o
Han i f ol d
Temperature
Dew Point
NO.
c;n
!C Canister
Figure 4.3. Functional layout of air sampling system,
-------
Man!fold
Mounting
Bracket
Nephelometer
Steel Tube
3.18 cm diameter
Teflon Tube
2.54 cm diameter
¦+- Exhaus t
0.61 ra
Probe II2
Probe fi 1
To Sample
Manifold,
Main
Cabin
Area
TOTAL TEMPERATURE PROBE
i A/C ^
jBattery
(Profile)
Nephelomcter
Probe
Probe //I
(Cross-Sect ion)
Aircraft
Battery
Figure 4.4. Details of forward section of air sampling system.
-------
127 cm —
COCKPIT AREA
-»"j
BULK HEAD
266 cm
STATION
STATION
iMAIN CABIN
AREA
STATION
OPERATOR
STATION
STATION
2
BATTERY
BACKUP
SYSTEM
o
BAGGAGE AREA
STATION #1
Data System
Ozone Analyzer
STATION #2
NQ/N02 Analyzer
CN Counter
STATION #3
Tape Deck
Strip Chart Recorders
Dew Point/Temperature
Patch Panel
Sample Manifold
STATION #4
Inverters
Power Distribution Panel
SUPPORT
GAS CYLINDERS
FLOOR PI AN, NAVAJO B
figure 4.5. Layout of aircraft system.
32
-------
Table 4.1 Aircraft instrumentation
Parameter
Instrument
Manufacturer
and Model
Analysis/Collecting Measurement Continu- Time
Technique Range ous Response
Nitric Oxide and
Nitrogen Dioxide
Ozone
Hydrocarbons
Condensation Nuclei
Light Scattering
Coefficient (b .)
scat
Monitor Labs
8440
Bendix 8002
RTI
Environment
One Rich 100
MRI 1550B
Che:ui luminescence
0-0.2 ppm
Chemiluminescence 0-0.2 ppm
Grab Samples - SS containers
Light Scattering
Integrating
Nephelometer
1,3,10,30,100,
300, 10Kxl03
CN/CC*
10,40,lOOx
10-4m-l*
20 sec
5 sec
2 min
5 sec
1. sec
Air Temperature
Dew Point
Altitude
True Airspeed
Location
Time of Day/Date
RTI
EG&G 880
Sensotec
Sensotec
King KX170B
(206)
Monitor Labs DAS
Bead Thermistor
Cooled Mirror
Abs. Pressure
Transducer
Diff. Pressure
Transducer
Aircraft VOR/DME
-5 to +45°C x
O
-50° to +50°C x
0 - 10,000 ft x
50 - 150 mph x
0-100 mi from sta. x
5 sec
0.5 sec/°C
1 sec
1 sec
1 sec
1 scan/
15 sec
*
Available operating ranges
-------
4.1.4 Data Acquisition System
The data acquisition system, shown in the overall system diagram,
Figure 4.7, consisted of a Monitor Labs Data Logger, System 9400, a Cipher,
Model 85H magnetic tape recorder, a signal coupler, and three Hewlett-
Packard Model 680 strip chart recorders. Analog signals from the instru-
ments vere coupled to the data system through the signal coupler (junction
box) that also housed all the necessary bridge circuits, scaling networks
and voltage reference source. The analog signals were also available at
a patch panel on the front of the signal coupler for purposes of mainte-
nance and strip chart record selection. The panel included a simultaneous
event marker and zero/span voltages for the three recorders and provided
convenient access when checking instrument status with an external digital
voltmeter.
The Monitor Labs data system included internal clock/control, a digi-
tal 18-column printer, a 20-digit manual data entry, and a 30-channel ana-
log signal input capability.
Manual input data entries were used to indicate the operational status
of the analyzers and instruments.
The Cipher tape transport system produced a computer-compatible, 1/2
in, 7-track magnetic tape with data storage density of 556 B.P.I.
4.2 INSTRUMENT CALIBRATION AND CHARACTERIZATION
4.2.1 Calibration Methods
Dynamic calibration techniques were used to calibrate and characterize
analyzers and instrumentation, both in the laboratory prior to installation
and in the field during the actual measurement program. Multipoint cali-
brations were conducted for the ozone and oxides of nitrogen analyzers
prior to each flight day.
In addition, the ozone and oxides of nitrogen analyzers were audited
by the Pedco, Corp. September 9, 1977. The results of this audit are re-
ported in Section 5.3.2 of this report. Subsystems (pressure, temperature,
etc.) were carefully calibrated at the beginning of the field measurement
program and spot checked periodically throughout the measurement period.
34
-------
Data were recorded on a digital magnetic tape data acquisition sys-
tem. Information, such as position, events, and grab samples, was re-
corded via digit switches on the data system and/or log sheets. A digital
printer was used for backup storages as well as observation of data in
^time and post —flight checks. In addition, three strip chart recorders
were available for recording selected parameters in analog form.
The power system is so configured that equipment and/or subsystems
requiring continuous power may be switched to battery power during periods
when ground power is not immediately available. A battery supply, sepa-
rate from the aircraft system, is provided for this purpose.
Ozone was measured with a Bendix Model 8002 gas phase chemilumines-
cent ozone analyzer, operated continuously on the 0-0.2 ppn range. C. P.
grade ethylene support gas for the analyzer was supplied from a size 3A
gas cylinder. The instrument exhaust was routed through plastic tubing
and dumped overboard through a bulkhead panel, to the rear and underneath
the aircraft.
Oxides of nitrogen were measured with a Monitor Labs gas phase chemi-
lumincsccnt N0-N02~N0^ analyzer, Model 8440. The instrument was operated
continuously on the 0-0.2 ppm range for both NO and NO^ simultaneously.
Condensation nuclei were measured with an Environment One, Model Rich
100, C.N. Counter. According to manufacturer specifications, the unit is
capable of counting particles 0.0016 micron and larger in diameter, with
a maximum concentration of 300 x 10^ particles/cc and with a repeatability
of +3 percent of full scale on all linear ranges.
Visibility (b ) was continuously measured with an integrating
scat
nephelometer, MRI, model 1550B.
Environmental considerations of the air being sampled included tem-
perature and dew point measurements inside the sample manifold and mea-
surements of the adiabatic stagnation temperature of the air relative to
the moving aircraft. Sample air temperature was measured with a YSI bead
thermistor, Type 44202, mounted inside the sample manifold, downstream
from the analyzer's sample lines. The sample dew point was continuously
35
-------
monitored with an EC&C, Model 880, dew point sensor, A YSI, Model 19,
hygrometer was used to monitor the aircraft cabin air temperature and dew
point. Ambient temperature measurements were made with a YSI bead ther-
mister, Type 44202, mounted in a total temperature probe, positioned in
front of the aircraft, mounted to the sample probe.
A Pitot tube, mounted underneath the aircraft wing, provided con-
tinuous measurement of the ambient static pressure, altitude, indicated
airspeed and Mach number. The Pitot tube extended a sufficient distance
below the wing's surface, minimizing measurement error caused by aerody-
namic distortion from the aircraft.
Grab samples for subsequent hydrocarbon analysis were collected with
the apparatus shown in Figure 4.6. Sample air was pumped from the mani-
fold, through 0.64 cm o.d. stainless steel tubing with a single state
stainless steel metal bellows pump. Samples were collected in an evacu-
ated stainless steel canister, sealed with a bellows valve. The inlet to
the canister was carefully purged for several minutes prior to opening the
bellows valve and collecting the sample.
Metal Bellows Pump
Mod. MB-21
Sample Manifold
Stainless Ste
0.64 cm O.D.
Stainless Steel Canister
Vol. 2 liter
Figure 4.6. Hydrocarbon grab sample system.
36
-------
MEPHKI0HET1 R
H ETTRONICS
OUT-BOARU AIRCRAFT
CONDENSATION Nl.Cl.Cl
COUNTER
OK-BOARD AIRCRAFT
GRAB SAMPLES
HYDROCARBON
INTEGRATING Nl I'Hf. OMETER
rtOW METER
SAMPLE HAN i I 01.1:
EXHAUST
RHP. SENSOR
HK)1 STATIC PROBEtf
DEWI'l . SENSOR
TOTAL/01 EE. f, MANIEOU)
PRESSOR! IRAflSlMlf.f KS
[ToiAL i i Mi'. PRC-Ilk
(I/ONE ANALYZE !•
OXIDES OF MTfiOGEf.-
115 Vac
Statiuii ftjwvr
2« Vdt:
Ahudfl"
24 Vdt _
Battery E7:ku|
POWER INVERTERS
— TEST
[LIGHT
I EVEN-
OA TA SYSTEM
(time code;
(MANUAL DATA ENTRY)
STRIP
CHART
RECORDER
STRIP
CHART
RECORDER
INCREMENTAL
MAGNETIC TAPE
RECORDER
Figure 4,7. Block diagram of airborne air quality measurement system.
-------
Ozone Analyzer: Ultraviolet ozone generator verified by the gas
phase titration of NO as described in the Federal Register, Vol. 38,
No. 10.
Nitric Oxides Analyzer: Gas phase dilution of NO with clean air
source. The same reference cylinder of NO was used for both the ozone
and oxides of nitrogen calibrations. This cylinder was referenced to an
NBS cylinder of NO (NBS FF3193) before and after the measurement program.
Condensation Nuclei Counter: Factory calibrated by comparing in-
strument response to that of a Pollak Counter simultaneously sampling
the same air source. The Pollak Counter was considered to be a suitable
standard, and the Environment One instrument was adjusted to give compa-
rable readout.
Temperature Sensors: The thermistors used to measure ambient and
manifold temperature were calibrated at the beginning and throughout the
program by submersing the sensors in a water bath maintained over a range
of temperatures and referenced to a laboratory-type mercury thermometer.
The reference thermometer was calibrated in the laboratory against a Hew-
lett-Packard quartz thermometer, Model 2801A.
Dew Point: Periodically compared to sling psychrometer readings.
The respective thermometers were calibrated using the water bath as des-
cribed above under temperature sensors.
Pressure System: Pressure transducer response was calibrated against
a mercury manometer at the beginning of the program ar.d spot-checked peri-
odically throughout the measurement period. Also, in the beginning, re-
peated low passes were conducted over a runway of known length during a
time when the meteorological conditions were reasonably stable. Several
low passes were made from different directions, varying the aircraft speed
over a maximum safe range. Each pass was timed with a stopwatch. Using
airport temperature and barometric pressure readings, and time and distance
measurements, the differential and total pressure sensor outputs were
scaled to indicate ambient static pressure and true airspeed.
38
-------
4.2.2 Pressure Effect Tests
In addition to routine characterization tests performed on the gas
analyzers, the effects of changing altitude on instrument response were
investigated. The experimental procedures for these tests are described
in detail for earlier investigations of this type and are reported in
Ref. 8.
The ozone and oxides of nitrogen analyzers used in the present pro-
gram were characterized for pressure effect in May, 1977. The environ-
mental test chamber facility at NERC, Las Vegas was used for the tests.
The results of these tests produced a predictable decline in instrument
response to a given concentration with increasing altitude (decreasing
pressure) and are shown graphically in Figures 4.8 and 4.9 for ozone and
NO^ analyzers, respectively.
1.0
w
tn
O
Pj
cn
a
.6
ro
o
n
w
tsl
(4
O
5S
.4
.2
Bendix Model 8002
Ozone Analyzer
X0 J-D
(1524 m) (3048 rn) (4572 m) (6096 m) (7620 m)
ALTITUDE (1000')
Figure 4.8 Ozone analyzer response (normalized to the analyzer s
response at standard pressure) versus altitude.
39
-------
Monitor Labs Model 8840
Oxides of Nitrogen Analyzer
0.8
t
1 I I 1 _J
5 10 15 20 25
(1524 in) (3048 in) (4572 m) (6096 m) (7620 m)
ALTITUDE (1000 ')
Figure 4.9. NO/NO^ analyzer response (normalized to the
analyzers' response at standard pressure)
versus altitude.
40
-------
4.3 OPERATIONAL PROCEDURES
Tn order to insure uniform instrument operation and provide confi-
dence in collected data beyond that established by the analyzer calibra-
tions already described, specific operational and data validation proce-
dures were routinely performed for each data flight.
The following preparations, procedures, and checklist requirements
were performed immediately prior to each mission (pre-flight), during the
mission (in-flight), and after completing the mission with the aircraft
(post-flight). Actual readings were recorded on each checklist and in
the general flight log for subsequent use, and instrument/analyzer test
values or settings different from the normal were noted.
4.3.1 Pre-Flight Procedures
(1) Log observed weather, weather service report, and sling psy-
chrometer readings on appropriate forms.
(2) Observe and inspect general condition of aircraft instrumenta-
tion and equipment, i.e., plumbing, air intake tubes, pitot—
static probes, temperature probe, etc.
(3) Label hydrocarbon canisters for use during flight.
(4) Install clean Magnetic Tape Reel, replace strip chart record-
er paper, ard digital printer paper as required.
(5) Initiate DAS for several scans and observe active channels for
any irregular readings. Observe strip chart records of over-
night analyzer operation.
(6) Complete Pre-Flight Checklist (see Table 4.2).
(7) Review flight pattern with pilot prior to takeoff.
4.3.2 In-Flight Procedures
Initiate the following procedures and checklist after airc.rart start-
up (while on ramp) and immediately after lift-off.
(1) Switch inverters to A/C 28 Vdc.
(2) Reset DAS time, load magnetic tape, and time-mark strip chart
recorders.
41
-------
Table 4.2 Pre-flight checklist
Date
Time
Location
Operator
F1ight No.
03 ANALYZER
Range (0.2ppm)
T.C. (10 sec.)
Span Set
Zero Set
Total Flow (24) _
C2H4 Press.(20)
Internal Zero
Internal Span
N0y ANALYZER
Vacuum (25)
Total Flow (Rot.)
NO Flow (Rot.)
N0X Flow (Rot.)
O3 Flow (Rot.)
Range (N0/N0x)
T.C. (N0/N0x)
Span Set (N0/N0x)
Elect. Test (N0/N0x)
Optic Test (N0/N0x)
Oper. Mode
Data Lamp
Dessicant
SUPPORT GASES
C2H4 Press.
H2 Press.
CN COUNTER
Water Reservoir
Sample Flow
Test Pos.
Span (Low Range)
Oper. Range
NEPHELOMETER
Flash Rate (8/sec)
T. C. (2 sec.)
Oper. Mode _____
Scale
Flash Lamp
DEW POINT
Test and Balance
Oper. Mode
STRIP CHART RECORDER
Select Parameter
Zero Set
Soan Set
Time Mark and Label
D.A.S.
Manual Data Entry
Oper. Mode
42
-------
NOTE: Leave tape deck and DAS in standby mode until actual
data measurements are to be made.
(3) Initiate several scans (DAS printout only) and review all chan-
nels for nominal values. Particularly review systems operating
on 28 Vdc only, i.e., pressure transducer, turbulence, etc.
(4) Observe and complete In-Flight Checklist (see Table 4.3). The
In-Flight Checklist is used immediately after lift-off and
near the end of the flight.
(5) Throughout the flight, a general flight log was maintained by
the operator, which included time, course, airspeed, altitude,
climb/descent rate, position information, and local weather
observations.
Table 4.3 In-flight checklist
Time
Altitude
POWER SYSTEM
A/C 28 Vde _
Inverter Output #1
#2
#3
#4
#5
#6
03 ANALYZER
Total Flow
C2H4 Flow (20)
Oper. Mode
NOy ANALYZER
Vacuum (25)
Total Flow (Rot.)
NO Flow (Rot.)
N0X Flow (Rot.) _
O3 Flow (Rot.)
CN COUNTER
Range
TURBULENCE
Low Test
High Test __
Oper. Mode
43
-------
4.3.3 Post-Flight Procedures
With the conclusion of each flight and after aircraft refueling and
maintenance, the entire instrumentation system (with the exception of grab
sample pumps) was switched from backup battery power to a 115 Vac ground
power source. The instruments aboard the aircraft were then repaired or
adjusted as indicated by operational checks.
The data for the preceding flight were spot-checked and documented,
and flight patterns were mapped with the appropriate time/position infor-
mation. The data spot-checked consisted of reducing several representative
data scans to engineering units and comparing these for realistic values.
4.4 DATA REDUCTION PROCESSING AND VALIDATION
The data from the RTI aircraft consists of a printer tape containing
digitized voltage values from the sensors and gas analyzers located on
board the aircraft. Before these data are analyzed, they must be pro-
cessed to convert the voltage values to engineering units and apply cor-
rections determined from known instrument altitude characteristics. In
addition, some editing of the data must be done, such as the removal of
data recorded during periods of instrument malfunction.
Due to the large volume of data and the repetitious nature of the
calculations, the data were reduced on a computer, specifically the IBM
370 computer. Data from the data logger magnetic tape were dumped for a
quick check on the data. Next, calibration equations were determined from
the field analyzer calibration which was conducted nearest in time prior
to each data flight. These equations for the gas analysers were then com-
pensated based on a known curve of instrument sensitivity change with al-
titude to determine the calibration equation for the analyzer when located
at sea level.
The calibration equations and the raw voltage data were then input
to the main computer processing program which accomplished the following
functions:
•Computed temperature, altitude, from thermistor and pressure
transducer voltage outputs.
44
-------
" equationsf3S CO"ce"t™»™s voltage values and calibration
•Compensated computed gas concentrations fox known changes in
gas analyzer sensitivity with altitude,
"Removed or modified selected portions of data to corrpn- fnr •
strument malfunctions. correct for m-
•Output data in a tabular format which facilitated comparison of
data from different analyzers and allowed scanning of values
from each analyzer or sensor.
The data from this program was inspected to determine which portions,
if any, needed to be edited. Several means were available for establishing
the reasonableness of the data including the following:
• Comparison of values between different parameters whose relative
levels tend to be related.
• Comparison of successive values in one parameter for detection
of outliers.
•Comparison of values from aircraft with those from ground station
during periods when ground levels are likely to be near those at
lower altitudes.
I he computer—processing data validation-correction process is iterated
until the data is correct. Then, a magnetic tape of data in engineering
units is produced. This tape may be used for regenerating reports, further
computer analysis or dissemination of the data. The format of this 9-
track tape is shown in Figure 4.10 and the format of each record is shown
in Table 4.4.
Start
of Tape
TAPE MARK (BOT)
k f -EOF
EOF
'DATA RECORD FOR
LAST FLIGHT
. DATA RECORD
FOR NEXT FLIGH'
HEADER RECORD
. DATA RECORD
FOR NEXT FLIGH'1
HEADER RECORD
EOF MARK
Figure 4.10. Format of magnetic tape.
45
-------
Table 4.4. Format of header records and data records
FIELD
NO.
FORTRAN
FORMAT
HEADER RECORD
DATA RECORD
1st
F6.1
FLAG=8888, 8
FLAG=9999.9
2nd
F6.1
FLIGHT NUMBER
LEG IDENTIFICATION NUMBER
3rd
P6.1
JULIAN DATE
HOUR
4th
F6.1
MONTH
MIN
OF DATA POINT
5th
F6.1
DAY
SEC
6 th
F6.3
YEAR
OZONE
(ppm)
7th
F6.3
TIMECODE 0=MGRNING
NO (ppn)
1=AFTERN0DN
8th
F6.3
0.0
NOx(ppm)
9th
F6.1
0.0
b
scat
(10 /ui)
10th
F6.1
0.0
CN (1000/cc)
11th
F6.1
0.0
Dew Foint (°C)
12 th
F6.1
0.0
Temp.
(°c)
13th
F6.0
0.0
Altitude (feet)
On the tape, each record is 78 characters long and is composed of
13 fields each 6 characters in length. Each flight is separated by an
end-of-file (EOF) mark, and the last flight's data is followed by two
EOF marks to signal end of volume. The tape is generated on a 9-traek
machine using IBM's standard EBCDIC code. The data is unblocked on a
non-labeled tape. Other important information about the tape includes:
the logical record length is 78, the block size is 78, the density is
800 bpl, and record lormat is fixed.
4.5 FLIGHT PROGRAM
The objective of the flight program was to measure selected pollutant
and meteorological parameters aloft from an airborne platform in support
of the 1977 EPA ozone study in the vicinity of Tulsa, Oklahoma.
46
-------
4.5.1. Flight Protocol
Flight patterns and their relative priority were established in
coordination with the EPA Project Officer prior to the field program. The
decision was made to fly four days of transport patterns (preferably with
two consecutive days in a set) as number one priority, and to fly the stag-
nation pattern with one flight day as second order of priority. A mid-day
vertical spiral south of the city and an open box flight pattern around a
power plant were set as possible alternatives if weather conditions, time,
etc. permitted. The types of flight patterns to be flown on a particular
day were determined on a day-by-day basis by the Project Officer who had
access to real-time ground station oxidant data and meteorological forecasts
for the area. Final flight determinations were made by the aircraft crew
based on immediate meteorological conditions and equipment status.
The transport and stagnation patterns are described as follows:
Transport Pattern (To be flown when predicted wind speeds are 6-10 knots
out of the south, and maximum daily 0^ concentration is expected to be 0.1
ppm or higher.)
AM Flight Plan
Purpose: Determine concentrations of ozone and other pollutants
coming into the Tulsa area from the south.
Procedure:
~ Make low pass over MOUNDS site at 0630 LDT
hour before sunrise) . Take HC grab
sample on low pass.
. Spiral up over MOUNDS site to 10,000 ft (3048 m).
Take HC grab samples at 2500 ft (762 m), 5000 ft
(1524 m), and 7500 ft (2286m).
. Descend to an altitude of 2500-3000 ft MSL 36 km
(22.5 miles) W of MOUNDS and make W-E flight
over MOUNDS site, total flight path 7 2 km (45
miles).
• Continue open box or square wave pattern toward
Tulsa (as shown on map-designated to allow or
completion of sprial and arrival at Tulsa
International Airport at 0900 LDT).
47
-------
• Begin spiral just N of Centra], Business District
and ascent! to 10,000 ft MSL. 11C Grab Sample at
2500 ft and 7500 ft MSL.
• Make low pass at 0900 LDT at Tulsa International
(TUL) Airport. HC Grab Sample on low pass.
• Make low pass at Downtown Airport. HC Grab Sam-
ple on low pass.
PM Flight Plan
Purpose: Determine the distributions and maximum concentrations
of ozone, etc. downwind of the city as measured aloft.
Procedure:
Begin 145 km (90-mile) W-E flight at 2500-3000 ft
(MSL) 72 km (45 miles) due E of SPERRY site, at
approximately 1230 LDT. Purpose of first leg is
to identify edges of plume via bscat, CN and/or
O3 with strip chart recordings.
Open box or square wave pattern continued to the
North with E-W legs shortened to allow greater
northern progression in pattern for a given period
of time. Adjust open box to allow for start of
spiral in 0^ max area at approximately 1500 LDT.
Purpose of this set is to identify the approximate
location of the O3 maximum in the Tulsa plume.
Spiral to 12,000 ft in the area estimated to con-
tain the maximum O3 concentration. HC Grab Sample
at 2500 ft and 7500 ft MSL.
Stagnation Pattern (To be flown when wind speed is predicted to be less than
5 knots,
higher.)
AM Flight Plan
5 knots, and maximum daily 0^ concentration is expected tc be 0.1 ppm or
Purpose: Determine O3 and O3 precursor distributions over
and near the city 011 a day with light and variable
winds.
Procedure:
Fly a box pattern approximately 39 km (24 miles) on
a side, at 2500 ft MSL. Start pattern at approxi-
mately 0630 LDT. (Set pattern uniformly on city.)
Fly outer box pattern approximately 77 km (48 miles)
on a side at 2500 ft MSL.
Low passes at Riverside and Downtown Airport. Take
HC Grab Sample at each site.
48
-------
PM Flight Plan
Purpose: Determine O3 and O3 precursor distributions over and
near the city at the expected time of maximum ozone
concentration.
Procedure:
Fly inner box pattern starting at approximately 1300
LDT. (Let drift with winds, keeping city inside
inner box.)
• Fly outer box pattern.
• 2 spirals to 12,000 ft MSL inside inner box at
approximate upwind and downwind locations. I1C
Grab Sample at 2500 ft, 5000 ft and 7500 ft MSL
°n each spiral.
4.5.2 Flight Summary
Data flights were conducted in the Tulsa area during the period
August 25, 197? through September 17, 1977. A summary of the flights
conducted, data acquisition start and finish times, and the type of flight
patterns are given in Table 4.5.
Flight T09 (morning) and Flight T10 (afternoon) shown in Figure 4.11
illustrate a typical transport flight pattern.
4.6 AIRCRAFT DATA
All aircraft data have been processed, validated, and entered in com-
puter-compatible format on magnetic tape. A complete set of computer print-
outs of all of the data is included in Volume II of this report. A log of
hydrocarbon grab samples taken which have been analyzed and validated is
given in Table 4,6. A tabulation of low pass flights is given in Table 4.7,
which presents the flight number, date, time, location, and ozone level
recorded.
An example of the airborne data during the September 2, 1977 AM and PM
transport flights shown in Figure 4.11 includes the following: ozone data
plot for horizontal traverses (oxides of nitrogen are not included since
concentrations were consistantly at or below the minimum detectable limit of
the analyzer), Figure 4,12; temperature/dew point data plot for horizontal
traverses, Figs. 4.13-4.14; bscat data plot for horizontal traverses, Fig.
4.15; data plots of ozone, oxides of nitrogen, temperature, dew point, b3cat
and condensation nuclei for two AM spirals and one PM spiral, Figures 4.16,
4.1/, ana 4.18, respectively. I11 addition, an example computer printout data
sheet for the September 2, 1977 flights is given in Table 4.8.
49
-------
Table 4.5
Tulsa Aircraft Measurement
Data Flights Summary
Flight
Number
Date
(1977)
Flight
Start
Time^ (CST)
Finish
Type of Flight
T-03
T-Q4
25 Aug.
0813
1324
0922
1417
AM
FM
2/
Transport-
Transport—'
T-05
T-06
26 Aug.
0522
1153
07 46
1415
AM
PM
Transport
Transport
T-09
T-10
2 Sept.
2 Sept.
0530
1224
0801
14 36
AM
PM
Transport
Transport
T-ll
T-12
3 Sept.
3 Sept.
0527
1232
0747
1440
AK
PM
Transport
Transport
T-14
8 Sept.
1152
1223
AM
3/
Stagnation-
T-15
9 Sept.
1402
1553
PM
Transport
T-16
11 Sept.
0524
0730
AM
Transport
T-17
T-18
16 Sept.
16 Sept.
0526
1237
0709
1424
AM
PM
Transport
Transport
T-19
T-20
17 Sept.
17 Sept.
0539
12 37
0742
1427
AM
PM
Transport
Transport
1/
2/
3/
Spirals and horizontal flight times, inclusive; does not
include low passes.
No spirals or HC samples.
Inner box only.
50
-------
133830
Leg 7
135230
500'
O
2500
Wvnor.o
j:,,f)On,/]43S]5
], 50071*0143
36 30
2500
\Vera
131MS 95°3C'
Skiatook
Cleveland
Sperrv
12 2'-00
Pryor
2500
Keystone'
Resevoir
Julsa International
Airport
Spiral 7
10,000'/0800^5
2,6007073300
TULSA
Leg 5
C7050C
Low Pass
5C' ACL/120235
2500'
06310C
Leg 3
064?
Spiral 1
10,000' /'J6L13U
1,100'/052930
061100
Barelesville
Lov- Pass ^
Lt;g 7 3CrAGL/OS!250
061100
Q Bristov
¦a Hounds
I
]
qp stat jtt r^ileb ,
Lov Pass
5CTAGL/052400
Okmulg*^
Fig. 4.11. Typical transport flight pattern.
51
-------
Table 4.6. Aircraft log sheet - hydrocarbons grab samples
Flight
Number
Date
(1977)
Flight Pattern
HYDROCARBON SAMPLE
ID ,7
Altitude
Spiral/Low Pass
Location
T-05
8/26
AM Transport
9001
1200
AM Spiral 1
Mounds Monitoring Site
9002
2500
9003
5000
9004
7550
9003
2500
Spiral 2
Tulsa Central Bus. District
9006
725
Low Pass 1
Tulsa Int. Airport
9007
775
Low Pass 2
Tulsa Downtown Airport
T-06
8/26
PM Transport
9008
2 500
PM Spiral 1
Sperry Monitoring Site
9009
7500
T-09
9/2
AM Transport
9010
1100
AM Spiral 1
Mounds Monitoring Site
9011
2600
9012
5000
9013
7600
9014
2600
AM Spiral 2
Tulsa Central Bus, District
9015
7500
9016
725
Low Pass 1
Tulsa Int. Airport
9017
7/5
Low Pass 2
Tulsa Downtown Airport
T-10
9/2
PM Transport
9018
2500
PM Spiral 1
Ramona, Oklahoma
9019
7500
T-ll
9/3
AM Transport
9020
1250
AM Spiral 1
Mounds Monitoring Site
9021
2500
9022
5000
9023
7700
9024
2500
Spiral 2
Tulsa Central Bus. District
9025
7500
9026
775
Low Pass 1
Tulsa Downtown Airport
9027
725
Low Pass 2
Tulsa Int. Airport
T-12
9/3
PM Transport
9028
2500
PM Spiral 1
5 mi E of Ramona, Okla.
9029
7500
-------
Table 4,6. Aircraft log sheet - hydrocarbon grab samples (continued)
Flight
Number
Date
(1977)
Flight Pattern
HYDROCARBON SAMPLE
11) ii
Altitude
Spiral/Low Pass
Location
T-15
9/8
PH Transport
9030
2600
PM Spiral 1
Ramona, Oklahoma
9031
7550
T-16
9/11
AM Transport
9032
1500
AM Spiral 1
Mounds Monitoring Site
9033
2500
9034
5000
9035
7500
9036
2500
AM Spiral 2
Tulsa Central Bus. District
9037
7800
9038
725
Low Pass 1
Tulsa Int. Airport
T-17
9/16
AM Transport
9039
1500
AM Spiral 1
Mounds Monitoring Site
9040
2700
9041
5000
9042
7500
9043
2500
Spiral 2
Tulsa Central Bus. District
9044
775
Low Pass 1
Tulsa Downtown Airport
9045
725
Low Pass 2
T-18
9/16
PM Transport
9046
2500
PM Spiral 1
Talala, Oklahoma
9047
7500
T-19
9/17
AM Transport
9048
1500
AM Spiral 1
Mounds Monitoring Site
9049
2500
9050
5000
9051
7500
9052
2500
Spiral 2
Tulsa Central Bus. District
9053
7500
9054
7 75
Low Pass 1
Tulsa Downtown Airport
9055
725
Low Pass 2
Tulsa Int. Airport
T-20
9/17
PM Transport
9056
2500
PM Spiral 1
Nowata, Oklahoma
9057
7600
-------
Table 4.7. Low pass data (ozone)
Flight Date Tine . ^, Ozone
Number (1977) Nation (ppo)
T-05
8/26
0801
0835
International Airport
Downtown Airport
0.057
0.049
T-09
9/2
0524
0813
0817
Okmulgee
International Airport
Downtown Airport
0.037
0.020
0.038
i
M
O
9/2
1203
Okmulgee
0.068
T-ll
9/3
0523
0758
0802
Okmulgee
International Airport
Downtown Airport
0.019
0.030
0.037
T-12
9/3
1210
Okmulgee
0.090
T-14
9/8
1137
Okmulgee
0.073
T-15
9/8
1439
Okmulgee
0.063
T—1 6
9/11
0518
0739
Okmulgee
International Airport
0.029
0.028
T-17
9/16
0521
0715
0719
Okmulgee
Downtown Airport
International Airport
0.039
0.014
0.008
T-19
9/17
0535
0754
0758
Okmulgee
Downtown Airport
International Airport
0.045
0.039
0.039
T-20
9/17
1215
Okmulgee
0.056
54
-------
£
Q*
-------
35
30
25
20
15
10
5
0
-5
35
30
25
20
15
10
5
0
--5
35
30
25
20
15
10
5
0
-5
35
30
25
20
1.5
10
5
0
-5
Temperature
„ LeS 7
\ N--
Dew Point
Temperature
Dew Point
Temperature
Dew Point
Temperature
Dew Point
2C
Statute Miles
0 10 20
i i i
Leg >
Leg 3
Leg 1
Fig. 4.13. Temperature/Dew point- horizontal traverse
for T09 AM flight.
56
-------
35
30
25
20
15
10
5
0
-5
35,
30
25
20
15
10
5
0
-5
35
30
25
20
15
10
5
0
-5
35
30
25
20
15
10
5
0
-5
Temperature
Leg 7
Dew Point
Temperature
Leg 5
Dew Point"""
Temperature
Dew Point
Leg 3
Temperature
Dew Point Leg 1
0 10 2,0
< 1 1
Statute Miles
'ig. 4.14. Temperature/Dew point - horizontal traverse
for T10 PM flight.
57
-------
3.2r
2.4
] .6
0.8
0.0
Northern Leg 7
PM
- AM
Southern Leg, 7
3.2
2.4
1.6
0.8
0.0
Northern ..eg 5
PM
^ Southern T.ea 5
3.2
2.4
1.6
0.8
0.0
Northern Left 3
/ _ PM
Southern Let; 3
3.2
2.4
1.6
0. 8
0.0
10 20
i , )
Statute Miles
Northern Leg 1
MI
Southern Leg 1
Fig. 6.15. t>scac for horizontal trackn - flights T09 and T10.
58
-------
VJ!
vC
0)
E
12.0
11.0
10.0
9.0
8.0
7.0
6.0
§ 5.0
w 4.0
a
3
H
h 3.0
f—J
2.0
1.0
0.7
_L
"i r
j
(Surface)
-L
_L
I
I
scat
NO/NO Dew Pt
x
0.00 0.03 0.06 0.09 0.12 -15
Ozone Concentration (ppn)
-10 -5 0 5 10
Temperature & Dew Point (°C)
I I 1
15
20
0.00 0.03 0.06
_NO,....W0X Concentration (ppm)
25
0 20 40 60 80 100
Condensation Nuclei (1C'3 counts/cc
J 1 I
0
bscat
0.8 1.6
(10-4)/m
Fig. 4.16. AM spiral 1 over Liberty Mounds, flight T09.
3.66
3.35
3.05
2. 74
2.13
1.83 |
o
1.52 §
1.22 g
- 0.91 J
^ <
0.61
0.31
30
-------
12. Or
11 . C
10. 0
9.0
8.0
7.0
f 6.0
5.0
c 0
R
H 3.0
<
2.0
1.0
0.7
(I NO/NOV
Dew Point
) scat
(Surlace)
_L
0.00 0
Ozone
03 0.06 0,09 0.12 -15
Concentration (ppm)
_L
JL
0.00 0.03 0.06
-10 -5 0 5 10 15 20
Temperature & Dew Point (°C)
1 I I [ L_
25
NO,
».N0X Concentration (ppm)
0 20 40 60 80 100
Condensation Nuclei (10^ counts/cc)
0 0.8 " 1.6
3.66
3.35
3.0b
7.7/4
2.44
2.13
1 .83
1.52
i 1 .22
0.91
0.61
0.31
30
c
o
o
a
p
M
-------
12.0
11.0-
10. 0
9.0
8.0
7.0
6.0
5.0
4.0
2.0
1.
0.
NO/NO
Dew Pt
_L
_L
(Surface)
_L
_L
0.00 0.03 0.06 0.09
Ozone Concentration (pptn)
0.12 --15
I J
0.00 0.03 0.06
-10 -5 0 5 10
Temperature & Dew Point (°C) [
15
20
25
_NG,NO Concentration (ppm)
X
0 20 40 60 80 100
Condensation Nuclei (10^ ccunts/ccy
0 0.8 1.6
3.66
3.35
3.05
2.7/i
2.44
2.13
1.83 |
1.52 §
o
].22 g
n
0.91 5
0.61
0.31
30
bscat (10-')/ra
Fig, 4.18. PM spiral 1 owr Ochelata, flight T10.
-------
Table 4.8. Sample data printout
TULSA FLIGHT NUMBER 10
DATES 9- 2- 1977
LEG
HR
MIN
S6.L
(J ZONE
NU
NUX
B-SCAT
CN
DEW PT
TEMP
ALT
PPM
PPM
PPM
,0001/M
iooo/cc
'C
'C
FEET
12
2a
0
o. 06a
0 . 0
0,002
0,8
0,7
13.9
25,7
2580.
12
2a
15
0 .067
0 , 0
0.0
0,8
0,3
13,7
25.9
2570.
12
2a
3U
0,066
0,0
0,0
0,7
3.2
13,7
25.8
2560,
12
2a
ab
0.070
0.0
0,003
0,8
0.5
13.9
25.8
2580,
12
25
0
0.067
0,0
0.0
0,8
1,7
13,7
25.7
2590,
12
25
15
0,063
0 , 0
0 , 0
0,9
0,9
13.5
25.9
2580,
12
25
30
0,061
0 , 0
o.o
0,7
0,8
13.a
25.9
2680,
12
25
ab
0 ,067
0,0
0,007
0,8
0.9
13.5
25.9
2580,
12
26
0
0 .066
0.0
0.0
0,9
o.a
13,5
2b. 8
2600.
12
26
15
0,071
0.0
o.ooa
1.0
2.3
13,6
25.9
2560 e
12
26
30
0,069
0,0
0,002
0,9
1,8
13,7
25,8
2580,
12
26
a5
0,063
0.0
0,002
1,0
1,6
13,7
25,8
2580,
12
27
0
0,079
0.0
0,007
0.9
1.7
13.7
25,8
2580 s
12
27
lb
0.072
o ,ooa
o, ooa
0 e 7
1 .«
13,7
25,9
2570,
12
27
30
0.072
0 . 0
0.0
0,9
2.a
13.6
25,7
2580 .
12
27
as
0,070
0,0
0,0
0,8
1.0
13,7
25.9
2580 o
12
28
0
0 .068
0.0
0.0
0,8
1.5
13.7
25 ® b
2600a
12
28
15
0.069
0.0
0.0
0.7
1.1
i3»a
25.6
2590 e
12
28
30
0.065
0,0
0,006
0,7
0.6
13,2
25,8
2600 «
12
26
ab
0 ,066
0,0
0,0
0,9
0,6
13.3
25,6
2560,
12
29
0
0.068
0,0
0.006
0.8
1 . i
13.5
25.7
2600.
12
29
lb
0.065
0.0
0,008
0,8
0,7
13.«
25.7
2580 B
12
29 s
30
0.068
0.0
0.013
0,8
0,9
13.a
25 6 5
2500,
12
29
ab
0 ,075
0.0
0.011
0,7
1.0
13.6
25 e 7
2550 „
12
30
0
0,072
0.002
0,007
0.8
0.7
13,7
25,6
2560 e
12
30
15
0.07a
0.0
0,0
0,7
0.5
13,8
25 e 5
2hSQe
12
30
30
0,072
0.0
0,0
0,8
1.2
13,7
25 B 7
2 kj v
12
30
ab
0.072
0,0
0,0
0,8
0.5
13.6
25,6
2 j6 0 e
-------
SECTION 5.0
QUALITY CONTROL AND QUALITY ASSURANCE PROGRAMS
5.1 INTRODUCTION
The RTI quality control program for the Tulsa study began with prelimi-
nary tests of analyzer performance and a training program for field personnel
prior to field monitoring. Also, the traceability of calibration gases to
NBS Standard Reference Material was established. Once in Tulsa, a program
consisting of monthly (or more frequent) multipoint dynamic calibrations of
each continuous analyzer, daily zero and span response checks, and standard
stripchart data reduction procedures was established.
EPA was responsible for maintaining a quality assurance program for the
eight-station RTI monitoring network as well as for the two ozone monitoring
stations maintained by the Tulsa City/County Health Department. PEDCo
Environmental (under contract to EPA, Environmental Monitoring Support
Laboratory), and the EPA Region VI Quality Assurance Office (Dallas, Texas)
each conducted a series of quantitative onsite performance audits to collect
information on the accuracy of the continuous pollutant measurements for
ozone, nitric oxide, and nitrogen dioxide. Other quality assurance measures
included "blind" audits of the Beckman 6800 air quality chromatographs using
EPA-verified methane in air mixtures and quality control activities associated
with the sampling and analysis of individual hydrocarbon species. Much of
the data derived from quality control/qua]ity assurance efforts have been
tabulated and statistically examined.
Quality control and quality assurance aspects of the airborne air
quality measurements portion of this project are included in Section 4.0 of
this volume. Quality control aspects of the Tenax GC/MS/COMP studies are
discussed in Appendix B of this volume.
63
-------
5.2 QUALITY CONTROL AND QUALITY ASSURANCE AT SURFACE SITES
5.2.1 Preliminary Testing
Prior to leaving Research Triangle Park for Tulsa, RTI opera led and
calibrated each government-furnished ambient air analyzer. Also prior to
departure, three RTI project members were verified at the EPA Quality Assur-
ance Branch Laboratory in the conduct of the gas phase titration method3 of
NO by 03 as a means for calibrating ozone and oxides of nitrogen analyzers.
One of these three persons was assigned the responsibility for monthly
multipoint calibrations of all ambient analyzers. The results of these
calibration verifications are given in Table 5.1. Proper operation of two
different calibration systems was also verified at the EMSL QAB Laboratory.
The concentrations of ten different NO in nitrogen calibration standards (in
aluminum cylinders) were also verified at EPA's QAB Laboratory by comparison
to NBS standard reference material prior to (and following) the field study.
The results of the calibration standards verification and referencing are
shown in Table 5.2.
Table 5.1. Comparison of RTI GPT Calibration Concentrations
to EPA Quality Assurance Branch
Concentration, ppm
Gas
QAB
RTIa
QAB
b
RTI
QAB
RTIC
NO
0.001
0.000
0
.000
0.000
0.000
0.000
0.102
0.110
0
.394
0.397
0.402
0.405
0.192
0.205
0.298
0.304
0.277
0.288
0.198
0.203
0.373
0.385
N02
-0.002
0.000
0
007
0.000
0.000
0.000
0.082
0.082
0
097
0.094
0.345
0.345
0.164
0.163
0
187
0.186
0.173
0.170
0.252
0.252
0
217
0.214
0
278
0.279
03
0.000
0.000
0
000
0.000
0.000
0.000
0.084
0.082
0
092
0.095
0.341
0.346
0.166
0.163
0
184
0.188
0.176
0.166
0.255
0.252
0
217
0.216
0
.282
0.281
30perator #1; ^Operator #2; COpe rator #3.
64
-------
Table 5.2. NO in N2 Calibration Standards Used in Tulsa.
Results of EPA Quality Assurance Branch Analyses
Cylinder [NO], ppro [NO], ppm
Number Location June 1977a December 1977
LL
3393
Skiatook Lake
51.5
49.9
LL
3398
Sperry (until 9/20/77)
51.5
49.9
LL
3401
Sperry (after 9/20/77)
51.6
50.1
LL
3402
Spare
51.6
50.1
LL
3416
Post Office
51.3
49.8
LL
3418
Public Health Department
51.3
50.1
LL
3422
Ochelata
51.3
49.9
LL
3423
Vera
51.3
49.9
LL
3425
Wynona
51.5
50.0
LL
3429
Liberty Mounds
51.2
50.0
3These were the values used to generate calibration standards in the field.
Field personnel were familiarized with EPA procedures for visually
reducing strip chart data and reporting hourly data in SAROAD format.
Supervised training in instrument operation, monitoring techniques, and data
reduction qualified the field personnel for the study.
5.2.2 Methods of Quality Control in Tulsa
To maintain a high level of confidence in the air quality data, RTI
routinely monitored critical instrument parameters. Daily checksheet entries
indicated consistency or variability of instrument parameters such as flow
rate, pressure, and temperature. Daily zeros and spans were performed on
the ozone and N0/N02 analyzers. Zero and span gases for the ozone analyzer
were provided from the instrument's internal scrubber and ultraviolet lamp.
Zero and span gases for the N0/N02 analyzers were provided from an external
calibrator by dilution of certified NO in N2 mixtures and by gas phase
titration of NO by ozone. Zero and span results served as indicators of
65
-------
instrument drift. When zero drift exceeded 0.01 ppm (±2 percent of 0.5 ppm
full scale) during a 24-hr period, the data of the preceding 24-hr period
were critically examined and questionable hours were invalidated. If a span
drift of ±15 percent of full scale (0.5 ppm) occurred, the instrument was
immediately recalibrated or replaced and the data recorded during the period
of span drift were invalidated.
Monthly multipoint dynamic calibrations by gas phase titration were
carried out for each ozone and oxide of nitrogen analyzer in the monitoring
network.3 The same person performed every calibration using a single EPA-
verified calibration apparatus and verified NO in N2 calibration cylinders
that were kept at each station.
Estimates of measurement precision of the continuous ozone analyzers
were derived from a comparison of precalibration span concentration (as
calculated from the calibration curve of the preceding calibration) with the
predicted span concentration based on gas phase titration. To determine
these estimates, the means, standard deviations, and coefficients of varia-
tion were derived for each of the series of precalibration span points. The
coefficients of variation were used to establish confidence intervals within
90 percent probability limits. The 90 percent probability limits were
calculated using the following equations:9
Upper 90 percent probability limit = A. + 1.64 (S .)
J-i J) 1
Lower 90 percent probability limit = A^ - 1.64 (S
where:
A^ = the mean of the percent differences between observed and expected
span values.
S . = the standard deviation about the mean of the percent differences
P1 between observed and expected values.
The interpretation of this estimate of precision is that one would expect 90
percent of the individual span measurements to fall within the calculated
confidence intervals for the period of measurement encompassed by the cali-
bration and precalibration dates. Comparison of predicted and observed
ozone span concentrations at the time of precalibration is given in Table
5.3. Precision estimates for each of the continuous ozone analyzers are
given in Table 5.4.
66
-------
Table 5.3, Comparison of predicted and observed ozone values at the
time of analyser "precalibjatlon." Tulsa, Oklahoma
monitoring stations, simmer, 1977
Date
Concentration, ppm
Station
Calibration
Pre-
Calibration
Observed
Predicted
% Difference
Liberty Mounds
6/28
7/02
7/30
9/01
7/02
7/30
9/01
9/28
0.214
0.295
0.132
0.134
0.210
0.297
0.158
0.135
+ 1.9
- 0.7
-16.5
- 0.7
Tulsa Post
Office
7/16
8/05
8/28
8/05
8/28
9/26
0.136
0.135
0.132-
0.135
0.121
0.130
+ 0.7
+11.6
+ 1,5
Tulsa City/
County Health
Department
7/07
8/06
8/22
8/27
8/06
8/22
8/27
9/25
0.141
0.192
0.136
0.210
0.124
0.168
0.132
0.212
+13.7
+14.3
+ 3.0
- 0.9
Sperry
8/02
8/25
9/14
9/18
8/25
9/14
9/18
9/26
0.192
0.293
0.145
0.179
0.196
0.242
0.145
0.181
- 2.0
+21.1
0
- 1.1
Skiatook Lake
8/09
8/29
8/29
9/29
0.132
0.130
0.120
0.129
+10.0
+ 0,8
Wynona
7/20
8/04
8/28
8/04
8/28
9/26
0.143
0.133
0.131
0.164
0.140
0.135
-13.0
- 5.0
- 2.9
Vera
6/30
7/05
7/29
9/09
7/05
7/29
9/09
9/26
0.105
0.124
0.132
0.134
0.096
0.113
0.121
0.133
+ 9.4
+ 9.7
+ 9.7
+ 0.8
Oehelata
6/29
8/07
8/30
8/07
8/30
9/26
0.137
0.135
0.135
0.136
0.130
0.132
+ 0.7
+ 3.8
+ 2.2
67
-------
Table 5.4. Estimates of precision of measurements based on precalibration
span values for ozone analyzers in Tulsa, Oklahoma
Upper
Lower
Mean
Range
Range
Station
Difference (%)
Limit (%)
Limit (%)
Liberty Mounds
-4.0
+9.8
-17.8
Tulsa Post Office
+4.6
+ 11.5
-8.5
Health Department
+7.5
+ 14.4
-10.6
Sperry
+4.5
+19.3
-17.1
Skiatook Lake
+5.4
+ 13.4
-7.9
Wynona
-7.0
+6.4
-11.0
Vera
+7.4
+3.4
-7.2
Ochelata
+0.8
+5.2
-4.6
It should be emphasized that the estimates of precision given in Table
5.4 are based on some precalibration spans performed a day or two after a
zero or span drift was noted. The instrument was calibrated to correct the
problem and the data from the point of the zero or span drift was invalidated
or corrected based on the new ca lib ration. Thus the reader should not infer
that data from the entire period of analyzer performance prior to the precali-
bration check was out of agreement by the percentage stated. The percentages
given in Table 5.4 thus represent the "worst case" based on available data
and should be compared to the results of the performance audits given in
Section 5.2.4.
Another quality control measure was extensive data validation. All
hourly data were checked against analyzer performance prior to reporting the -
data. Occurrences of unusual measurement trends, power failures, and strip
chart problems were noted for use in future data validation. The data were
initially checked by RTI. Next the SAROAD hourly data forms and the com-
puter printout derived from them were validated at EPA using specifications
established by the EPA Environmental Monitoring Support laboratory.
68
-------
5-2.3 Quality Assurance Qualitative Systems Audit
The objective of the onsite qualitative systems audit (performed by a
representative of the EPA Office of Air Quality Planning and Standards) was
to assess the potential of the operator and calibration systems to generate
data of acceptable quality for the duration of the summer study. In con-
currence with the first quantitative audit, an onsite qualitative systems
audit was performed. This audit included a verification of the procedures
used in calibration through a review of written procedures and observation
of a calibration, and an inspection of the station, including sampling
probe, manifold, and instrumentation. Results of this qualitative audit
were favorable.
5.2.4 Quality Assurance Performance Audits
The objective of the onsite performance audits was to collect informa-
tion on the accuracy of the summer study ozone, oxides of nitrogen, and
meteorological measurements. During the summer study, audit teams from
PEDCo Environmental and EPA Region VI visited each Tulsa monitoring station
on three occasions for a total of six audits.
The procedure used by PEDCo to audit the continuous analyzers at each
station consisted of challenging the respective analyzers with known concen-
trations of pollutants at three points. Test concentrations of nitric oxide
were generated by diluting (with zero air) a 43.7 ppm NBS-SRM NO standard
cylinder. Nitrogen dioxide concentrations were generated by gas phase
titration of the NO standard with ozone to produce N02. Test concentrations
of ozone were generated using an ultraviolet ozone generator calibrated by
gas phase titration of NO.
The generated concentrations were introduced to the analyzers through a
glass manifold to which the instrument's sample inlet was attached. Analyzer
response was determined by reduction of the signal from the strip chart
record and application of the appropriate transfer equation, which converted
percent of chart to ppm and had been calculated at the time of the preceding
multipoint calibration. Results of the PEDCo quantitative audits for ozone
and oxides of nitrogen analyzers are given in Table 5.5.
69
-------
Table 5.5. Summary of PEDCo Environmental Audit Results
NO N02 03
Audit Date Audit Analyzer X Difference Audit Analyzer % Difference Audit Analyzer % Difference
Liberty Mounds
July 13
0.0
-0.01
—
0.0
0.0
—
0
0
0.0
--
0.172
0.185
+7.6
0.178
0.180
+1.1
0
178
0.158
-11.2
0.343
0.379
+ 10.5
0.386
0.390
+ 1.0
0
386
0.337
-12.7
August 8
0.0
0.0
—
0.0
0.0
--
0
0
0.0
—
0.150
0.168
+ 12.0
0.203
0.208
+2.5
0
203
0.210
+3.4
0.320
0.361
+ 12.8
0.399
0.407
+2.0
0
399
0.404
+1.3
September 7
0.0
0.0
__
0.0
0.012
--
0
0
0.0
--
0.179
0.186
+4.0
0.163
0.167
+2.5
0
163
0.156
-4.3
0.321
0.335
+4.4
0.375
0.367
-2.1
0
375
0.358
-4.5
Health Department
July 11
0.0
0.0
__
0.0
0.0
__
0
0
0.0
--
0.073
0.076
+4.1
0.110
0. 112
+1.8
0
110
0.097
-11.8
0.184
0.183
-0.5
0.210
0.211
+0.5
0
210
0.195
-7.1
0.389
0.399
+2.6
0.365
0.362
-0.8
0
365
0.357
-2.2
August 12
0.0
0.0
--
0.0
0.0
--
0
0
0.0
__
0.158
0.159
+0.6
0.199
0.200
+0.5
0
199
0.206
+3.5
0.335
0.348
+3.9
0.388
0.374
-3.6
0
388
0.405
+4.4
September 10
0.0
0.002
__
0.0
0.0
__
0
0
0.0
__
0.136
0.145
+6.6
0.195
0.195
0.0
0
195
0.189
-3.1
0.314
0.337
+7.3
0.401
0.395
-1.5
0
401
0.392
-2.0
(continued)
-------
Table 5.5. (continued)
NO N02 03
Audit Date Audit Analyzer % Difference Audit Analyzer % Difference Audit Analyzer % Difference
Post Office
July 12
0
0
0
0
—
0
0
0
0
- -
0
.0
0.0
—
0
147
0
139
-5
4
0
148
0
148
0
.0
0
148
0.155
+4,7
0
367
0
361
-1
6
0
394
0
402
+2
.0
0
.394
0.412
+4.6
August 10
0
0
0
0
__
0
0
0
0
0
0
0.0
__
0
175
0
171
-2
3
0
178
0
172
-3
4
0
178
0.186
+6.2
0
384
0
364
-5
2
0
373
0
364
-2
4
0
373
0.396
+4.5
September 11
0
0
0
0
—
0
0
0
0
__
0
0
0.0
__
0
129
0
125
-3
1
0
181
0
184
+ 1
6
0
181
0.180
-0.6
0
323
0
325
+0
6
0
371
0
372
+0
5
0
371
0.370
-0.3
Sperry
July 13
0
0
0
006
__
0
0
-0
001
—
0
0
0.006
__
0
132
0
134
+ 1.
5
0
189
0
185
-2
1
0
189
0.201
+6.3
0
395
0
394
-0.
3
0
375
0
370
-1
3
0
375
0.386
+2.9
August 11
0
0
0
0
--
0
0
0
0
__
0.
0
0.0
—
0
174
0
178
+2
3
0
207
0
209
+ 1.
0
0.
207
0.216
+4.4
0
363
0
365
+0.
6
0
376
0
383
+ 1.
9
0.
376
0.394
+4.8
September 9
0
0
0
0
--
0
0
0
0
--
0.
0
0.0
0
416
0
385
-7.
5
0
152
0
154
+ 1.
3
0.
152
0.154
+0.3
0
.148
0
135
-8
9
0
313
0
318
+ 1.
7
0.
313
0.314
+1.5
-------
Table 5.5. (continued)
NO N02 O3
Audit Date Audit Analyzer % Difference Audit Analyzer % Difference Audit Analyzer % Difference
Vera
July 14
0
.0
0
0
--
0
0
0
0
__
0,
0
-0.
009
--
0
166
0
178
+7
.2
0
205
0
219
+6
8
0
205
0
207
+ 1.
0
0
.339
0
.371
+9
4
0
407
0
435
+6
9
0
407
0
416
+2.
2
August 10
0
.0
0
0
__
0
0
0
0
0
0
0
0
__
0
176
0
172
-2
1
0
181
0
178
-1
7
0
181
0
185
+2
2
0
364
0
375
+3
i
0
351
0
348
-0
9
0
351
0
360
+2
6
September 8
0
0
0
007
__
0
0
0
0
0
0
0
001
__
0
195
0
188
-3
6
0
179
0
176
-1
8
0
179
0
169
-5
6
0
346
0
352
+1
7
0
362
0
359
-0
8
0
362
0
341
-5
8
Skiatook
Lake
July 14
0
0
0.
0
__
0
0
0
0
__
0
0
-0
007
__
0
168
0
163
-3
0
0
166
0
163
-1
8
0
166
0
161
-3
0
0
388
0.
367
-5
4
0
337
0
340
+0
9
0
337
0
343
+ 1
8
August 11
0.
0
0.
0
__
0
0
0
0
__
0
0
0
0
__
0.
155
0.
153
-1
3
0
190
0
190
0
0
0
190
0
181
-3
5
0.
351
0,
355
+1
1
0
368
0
371
+0
8
0
368
0
355
-4
.7
September 8
0.
0
0.
0
__
0
0
-0
005
__
0
0
0
0
--
0,
198
0.
194
-2
0
0
175
0
174
-0
6
0
175
0
186
+6
.3
0.
392
0.
361
-7
9
0
347
0
361
+4
0
0
347
0
370
+6
6
-------
Table 5.5. (continued)
Audit Date
NO
no2
Audit
o3
Audit
Analyzer
% Difference
Audi t
Analyzer
% Difference
Analyzer
% Difference
Wynona
July 15
0.0
0.0
--
0.0
0.0
__
0.0
-0.008
--
0. 155
0.175
+ 12.9
0.195
0.210
+7.8
0.195
0.184
-5.6
0.326
0.367
+ 12.6
0.358
0.390
+8.9
0.358
0.346
-3.4
August 10
0.0
0.0
—
0.0
0.0
—
0.0
0.0
__
0. 148
0.170
+ 15.1
0.145
0.184
+27.3
0. 145
0.161
+ 11.3
0.328
0.376
+ 14.6
0.322
0.361
+ 12.3
0.322
0.321
-0.2
September 8
0.0
0.0
__
0.0
0.0
__
0.0
0.0
0.146
0.162
+ 11.0
0.194
0.211
+8.9
0.194
0.189
-2.6
0.331
0.367
+10.9
0.342
0.368
+7.7
0.342
0.333
-2.6
Ochelata
July 15
0.0
0.004
__
0.0
0.0
—
0.0
0.0
—
0.178
0.192
+7.9
0.197
0.201
+2.0
0.197
0.185
-6.1
0.323
0.347
+7.4
0.383
0.396
+3.4
0.383
0.368
-3.9
August 9
0.0
0.0
__
0.0
0.0
__
0.0
0.0
__
0.153
0.169
+10.4
0.185
0.181
-2.2
0.185
0.170
-8.1
0.329
0,362
+ 10.2
0.379
0.380
+0.3
0.379
0.351
-7.4
September 10
0.0
0.0
--
0.0
0.0
__
0.0
0.0
__
0.176
0.163
-7.4
0.180
0.184
+2.3
0.180
0.202
+ 12.0
0.356
0.341
-4.2
0.365
0.378
+3.5
0.365
0,411
+12.7
-------
Table 5.6. Percent error for ozone
Percent error
k at 90% ^
Location xa confidence level '
Liberty Mounds
-4.
.7
±6.
.45
-15.3
<
%E
<
5.9
Tulsa Health Department
-2.
.9
±5.
.50
-11.9
<
%E
<
6.1
Post Office
+3.
.2
±2.
.88
-1.5
<
%E
<
7.9
Sperry
+3.
.4
±2.
.23
-0.2
<
XE
<
7.1
Vera
-0,
,57
±4.
.01
-7.2
<
%E
<
6.0
Skiatook Lake
+0.
.58
±5,
.06
-7.7
<
%£
<
8.9
Wynona
-0.
.52
±6.
.04
-10.5
<
%E
<
9.4
Ochelata
-0.
.13
±9.
.78
-16.2
<
IE
<
16.0
ax is average of the x's for the three separate PEDCo audits.
= standard deviation about the mean of the percent differences between
observed and expected values.
CUpper limit = x + 1.64 (S ,). Lower limit = x - 1.64 (S ,).
u d
Confidence intervals or "error bands" were derived from the ozone audit
results. Table 5-6 lists the percent error for the 3-month period for each
monitoring station. This is representative of that ozone analyzer's accuracy
for the period. The overall ozone network "error band" (i.e., for the
eight-station network) is:
-7.3 < %E < +5.7.
5-2.5 Audit of Continuous Hydrocarbon Monitors
Ambient air chromatography were operated at three sites in Tulsa during
the summer of 1977. "Blind" samples of methane in air mixtures were supplied
to the contractor by EPA's Quality Assurance Branch Laboratory. The results
of the use of these audit mixtures are given in Table 5.7. The agreement
is excellent.
74
-------
Table 5.7. Audit results of methane in air standards,
ppm, Tulsa, 1977
Location/date
Audit
concentration
Analyzer
response
Percent
difference
Tulsa Health Department
8/6/77
2.06
2.96
4.40
2.05
2.98
4.49
-0.5
+0.7
+2.0
Post Office
8/9/77
2.06
2.96
4.40
2.03
2.96
4.43
-1.5
0.0
+0.7
Wynona
9/11/77
2.06
2.96
4.40
2.04
2.96
4.35
-1.0
0.0
-1.1
5.3 QUALITY CONTROL PROCEDURES ASSOCIATED WITH HYDROCARBON ANALYSES BY
GC-FID
5.3.1 Introduction
An extensive quality control program for sampling and analysis of
individual hydrocarbons was followed during this study. Before any ambient
air field samples were taken, the stainless steel sampling containers were
evaluated for cleanliness, storage characteristics, and the best methods for
collection and withdrawal of sample. During the field study, monthly quanti-
tative calibrations of the chromatographic columns were performed. The
program of the computerized data acquisition system was updated based on the
retention times, which were checked twice weekly. For details of sampling
and analytical methodology, refer to Appendix A of this volume.
A further quality control measure was the visual examination of every
chromatogram and the assignment of peak identifications using relative
retention times and pattern recognition techniques. This step was necessary
since limitations of the data acquisition system prevented its correctly
identifying all peaks or assigning an area count to peaks having poor slope
characteristics.
Finally, experiments were conducted to examine the extent of "decay" of
hydrocarbon compounds held in stainless steel containers for up to 30 days.
Both laboratory-prepared mixtures and ambient air samples were tested.
75
-------
5.3.2 Sample Container Evaluation
Evaluations of hydrocarbon sample containers by RTI in past studies
have pointed to the stainless steel container as a good choice for the
purpose of collecting ambient air samples. Such containers were used exclu-
sively in both the ground and aircraft monitoring programs in Tulsa.
Controlled experiments were conducted to evaluate the stainless steel
container and the stability of the various hydrocarbons at concentrations
similar to those found in ambient air. The effects of NO, NO2, and O3 on
the components of each mixture were also sought.
One of the hydrocarbon mixtures employed in the test was composed of
ethane, ethylene, acetylene, propane, propylene, and n-pentane. Each test
was conducted over an 18-day period with more intensive analyses during the
earlier part of the test. Samples were withdrawn from the containers on
days 0, 1, 2, 3, 4, 8, 13, and 18. From day 1 to day 4, samples were analy-
zed on a random basis to minimize any systematic error in the analyses.
Figures 5.1 through 5.4 show the results of the evaluation of C2-C5
compounds by plotting the ppb (V/V) concentration of the individual hydro-
carbon compounds versus the day of analysis. It should be noted that the
pumping system employed to pressurize the container during field collection
in Tulsa has been shown to destroy ozone at concentrations of 0.3 ppm.
In these experiments, the stainless steel containers were not heated
during the time of sample withdrawal. It was found that heating the con-
tainer to a temperature of 70° C gave a more quantitative transfer of hydro-
carbons and did not alter the sample. For this reason, the sampling cylin-
ders were heated in all analyses for the Tulsa field study.
5.3.3 Zero Air Evaluation
The zero air experiment provided data on the potential for contamina-
tion ot the sample while stored or shipped in the container. The zero air
had been previously analyzed for trace hydrocarbons and was found to contain
only trace quantities (~20 ppb [V/V]) of ethylene. It was later discovered
that the ethylene was eluting from a small piece of Teflon tubing (FEP)
between the sampling containers and the zero air source. This problem was
solved by replacing the Teflon tubing with flexible stainless steel tubing.
The zero air was introduced to the inside of the containers after it had
76
-------
280
260
240
4
220
200
180
9
8
i
7
6<
5
4
3
2
1
(
LgU
-V jf
J L
2 4
810
I I I L
J L
J
10 12 14 16 13
DAYS
%
~ Ethane-ENE
o Acetylene
~ Propane
A Propylene
• Pentane
5il. Stainless steel container evaluation (HC's and zero air).
-------
~vj
CO
50-
40-
I
30r
20
5r
4-
3-
2-
A Ethane-ENE
° Acetylene
~ Propane
A Propylene
• Pentane
B100
JL
7
Days
JL
10 11 12 13
50
40
30
20
9
8
7
6
5
4
3
2
1
B200
•
2 3
Days
Figure' 5.2. Stainless steel container evaluation (HC's, zero air,
and 0.01 ppm NO).
-------
A Ethane-ENE
O Acetylene
~ Propane
A Propylene
• Pentane
81K
~
A O p
-~
W
A
V
.1 I I 1
12 3 4
DAfS
60
40
20
18'
17
16
15
14
13
12
11
10
9
Figure 5.3.
Container 82K
J 1 1 1 1 L. 1 I 1 L 1 1 1 I i I I I
i 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
DAVS
Stainless steel container evaluation (HC's, zero air, and
0.01 ppm NC>2 ) •
-------
A Fthane-ENE
o Acetylene
~ Propane
A Propylene
• Pentane
B10K
I „ I I I I I f L_
10
40
30
20
17
16
15
14
13
12
11
10
r
o'
13 14 15 16 17 18
B20K
A
,o
n
-cr —A
A-
*
,o
DAYS
DAYS
Figure 5.h . Stainless steel container evaluation (HC's, zero air, and
0.1 ppa O3).
-------
passed through a double dilution system that was later employed to generate
low concentrations of hydrocarbons and other pollutants.
The zero air test samples in the containers were analyzed for both
C2-C5 and C5-C10 hydrocarbons over a period of days. The stainless steel
container showed a slight decrease in the ethylene concentration from 20 ppb
to 12 ppb (18th day). After 18 days, no other components were detected in
the analyses. It should be pointed out that the stainless steel containers
had been pressurized to 40 psig with the use of an MB 151 metal bellows
pump. The absence of contamination over such an extended period is important.
Since in many cases, sampling containers are transported in contaminated
atmospheres, it is imperative that the samples retain their integrity even
though the containers are exposed to pollutant levels several orders of
magnitude higher than those of the collected sample.
In another test, containers were filled with zero air, shipped by air
freight to the study area and sent back to RTI for analysis. QC samples 3
and 4 were shipped on July 19, 1977, and returned on July 28, 1977. QC
samples 5 and 6 were shipped on August 3, 1977, and returned to RTI on
August 12, 1977. Results of these analyses are given in Table 5.8. From
these samples it was concluded that the sample integrity had not been altered
during the transit period, and no material outgassed from the inside surface
of the container.
5.3.4 Hydrocarbon Mixture Quality Control Samples
From the beginning of RTI's experience with captive air samples, con-
cern has been focused on the stability of these samples in various contain
ers. Detailed discussions of the RTI efforts in the field of container
evaluation can be found elsewhere.5 10 As a result of several studies, the
stainless steel bottle, closed with a stainless steel bellows valve, has
proved to be the most practical container for general ambient hydrocarbon
sampling.
Two major factors affecting sample stability are (1) adsorption of the
hydrocarbon species onto the walls of the container, and (2) chemical break-
down of hydrocarbons from reactions with oxygen, ozone, N0x, etc., in the
ambient sample. These factors were evaluated in an in-house program that
has become known as the "Wade Avenue Study."
81
-------
Table 5,8. Results of the/Analyses of Zero Air Stored In
Stainless Steel•Containers
Samp 1 e //
Analysis Date
Methane ppbG_
Ethane
Ethylene
Propane
Acetylene
Isobutane
n-Butane
Propylene
Isopentane
n-Pentane
Cyclopentarie
Isoprene
2-2 Dimethylbutane
2-Methyl pentane
3-Methyl pentane
1-Hexene
2-Methyl pentene-1
n-Hexane
2-4 DimethyIpantane
Cyclohexane
3-Methylhexane
2,2,4 Trimethylpentane
n-Heptane
Methyl cyclohexane
2,3,4 Trimethylpentane
3-Methylheptane -f Isooctane
n-Octane
n-Nonane
n-Decanc
n-Undecane
n-Dodecane
Benzene
Toluene
Ethyl benzene
p-xylene
m-xylene
o-xylene
n-Propyl benzene
1,3,5-Trimethylbenzene
m-Ethyl toluene
t-Butyl benzene
o-Ethyl toluene
a pinene + 8 pinene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
n-Butvl benzene
cj_
7/28/77
QC 4
7/28/77
J?Pbc_
_ppbC_
2.0
1.7
2.7
4.0
2,3
1.1
J2LJL
3.0
QC 6
8/12/77
jppbC
1.3
0.4
0.5
0.5
0.2
0.1
0.1
0.5
2.0
0.6
82
-------
A complex mixture of C5-C10 aliphatic hydrocarbons was diluted to a
concentration of ~20 ppb V/V per component in dry, hydrocarbon-free air.
Four stainless steel containers were filled with this mixture and analyzed
over a 30-day period. The results of these analyses can be found in Tables
5.9-5.13.
The greatest concentration variability is shown in three compounds:
isoprene, cyclohexane, and 2-methyl-l-pentene. The cyclohexane numbers are
somewhat in question, however. If any water is present in a sample, it
forms a false peak on the OV-101 column which, in this analysis program,
corresponds to the cyclohexane elution time. This peak is not very repro-
ducible. Therefore, the cyclohexane concentration fluctuations may be due
to traces of water vapor that passed through the column.
Isoprene (2-methyl-1,3-butadiene) and 2-methyl-l-pentene share a common
trait, a methyl-substituted double bond. Because of their structure, these
compounds might be expected to he more reactive than are the straight-chain
single or double bonds, or the methyl-substituted single bonds.
The heaviest straight-chain hydrocarbon, decane, showed a gradual decay
trend. This could probably be attributed to adsorption on the container
wall since this compound would not be expected to be very reactive.
To evaluate the effects of oxidants, moisture, and other components of
typical urban ambient air, three samples were taken by split sampling tech-
nique on the roadside of Wade Avenue, Raleigh, N.C., at the early morning
rush hour. The samples were analyzed for C2-C5 light hydrocarbons, C5-C10
aliphatics, and C6-C10 aromatics. The samples were analyzed over a 19-day
period and the results are shown in Tables 5.14-5.16. On the whole, these
analyses showed more variability than did the laboratory mixes. The compounds
with unsaturated bonds and those with methyl substitutents showed the greatest
changes in concentration. Also, the heaviest aliphatic and aromatic com-
pounds showed a decreasing concentration trend. On the whole, however, the
concentrations of most components remained quite stable over the 19-day
period.
5.3.5 Calibration Procedures
Periodic calibration was carried out to insure accuracy in both the
quantitative and qualitative aspects of the analyses. The aliphatic and
aromatic standard mixtures were prepared at RTI by injecting appropriate
83
-------
. T«bl e 5<.9*. Laboratory Decay Study of cg-c10 Hydrocarbons; Concentrations in ppbV
Sample Number A-6
Day of Analysi
S
Mean
Standard
1
5 6
9 12 16
19
23
26
30
Deviation
Isoprene
37.9
40.2
37.0
37.8
31
8
34.9
32.4
36
0
3.1
2,2-Dimethylbutane
23.4
25.6
25.4
25.0
22
0
22.9
24.0
24
0
1.4
2-Methylpentane
30.4
29.6
30.5
30.7
28
9
30.6
29.4
30
0
0.7
3-Methylpentane
40.0
40.9
43.3
41.1
39
2
41.0
42.7
41
2
1.4
1-Hexene
47.7
47.0
48.3
48.1
46
7
48.6
47.3
47
7
0.7
2-Methylpentene
84.8
84.8
88.2
85.1
84
1
86.7
85.0
85
5
1.4
2,4-Dimethyl pentane
26.7
24.3
24.5
25.7
26
7
27.7
27.8
26
2
1.4
Cyclohexane
65.2
73.5
65.7
60.4
68
9
71.7
70.3
68
0
4.5
3-Methylhexane
41.9
40.2
39.5
42.2
42
6
44.4
44.4
42
2
1.9
2,2,4-Trimethylpentane
54.6
53.5
54.4
56.4
56
9
58.4
58.8
56
1
2.1
n-Heptane
36.0
35.3
35,5
36.9
36
7
37.2
37.9
36
5
0.9
Methylcyclohexane
28.8
28.7
28.8
29.6
29
1
29.6
30.0
29
2
0.5
2,3,4-Trimethylpentane
26.5
26.8
26.9
26.7
25
9
26.1
26.3
26
5
0.4
3-Methylheptane
25.0
27.0
27.1
26.5
25
1
24.9
25.6
25
9
1.0
n-Octane
26.2
26.7
26.9
26.3
25
7
25.4
26.0
26
2
0.5
n-Nonane
20.7
25.3
25.6
24.2
23
3
22.8
23.5
23
6
1.6
n-Decane
.. , ,
18.1
17.1
15.1
14.9
14
9
15.5
14.5
15
,
7
1.3
-------
Table 5.10. Laboratory Decay Study of Cq-C-jq Hydrocarbons; Concentrations in ppbV
Sample Number A-30
Day of Analysis
Ma a n
Standard
1
5
6
9
12
16
19
23
26
30
Wean
Deviation
Isoprene
33.4
45.3
43.8
37.6
39.2
42
8
38
.0
32
7
30.7
27.9
37.1
5.9
2,2-Dimethylbutane
24.4
27.5
27.6
28.0
27.8
27
4
29
2
25
9
24.8
25.7
26.8
1.5
2-Methylpentane
30.1
32.5
34.0
31.6
33.1
33
6
33
9
33
1
34.0
32.4
32.8
1.2
3-Methylpentane
37.3
40.9
41.3
42.5
42.8
42
1
42
3
40
8
40.8
42.7
41.3
1.6
1-Hexene
45.0
47.0
49.3
47.5
48.0
48
1
49
4
52
3
48.7
46.4
48.2
1.9
2-Methylpentene
104.1
106.5
105.9
109.1
111.9
106
1
107
8
103
3
99.3
97.4
105.1
4.3
2,4-Dirnethyl pentane
30.1
30.6
31.1
31.0
30.9
30
6
31
2
31
0
30.0
30.2
30.7
0.4
Cyclohexane
61.6
64.0
59.1
59.5
52.0
62
5
58.
9
46
8
49.8
47.9
56.2
6.4
3-Methylhexane
39.6
39.7
37.8
37.9
36.5
36
9
37.
8
36
4
36.9
37. 5
37.7
1.2
2,2,4-Trimethylpentane
63.3
63.8
62.6
63.3
63.6
62
3
64.
4
65
1
62.5
63.8
63.5
0.9
n-Heptane
37.3
36.5
35.1
35.5
35.5
34
5
36.
2
35
0
34.5
34.5
35.5
0.9
Methylcyclohexane
35.4
34.2
33.7
33.8
34.3
33
2
34.
7
33
6
33.3
33.6
34.0
0.7
2,3,4-Trimethyl pentane
28.1
29.6
30.1
30.2
30.0
29
7
30.
1
28
8
29.2
29.0
29.5
0.7
3-Methylheptane
26.4
27.9
28.5
26.0
28.8
28
6
28.
7
27
0
27.2
27.3
27.6
1.0
n-Octane
27.0
28.6
29.7
30.2
29.8
29
2
29.
8
28.
2
29.1
29.7
29.2
1.0
n-Nonane
22.8
25.3
27.4
26.8
27.6
28
5
26.
6
25.
2
25.5
25.6
26.1
1.6
n-Decane
18.0
17.1
17.6
16.9
16.5
17
3
16.
0
15.
8
15.5
14.6
16.5
1.1
-------
Table 5,11. Laboratory Decay Study of C^-C^q Hydrocarbons; Concentrations in ppbV
Sample Number A-62
Day of Analysis
Standard
1
5
6
9
12
16 19
23
26
30
Dev iation
Isoprene
40
6
43
6
45
0
42
7
44
4
43
4
37
3
36.7
36.2
41
1
3
5
2,2-Dimethylbutane
25
4
28
7
29
5
29
4
28
4
27
8
24
9
26.7
26.9
27
5
1
7
2-Methylpentane
33
9
34
3
35
3
33
3
35
1
34
3
32
5
35.5
33.2
34
1
1
0
3-Methylpentane
45
0
47
6
48
1
49
3
48
9
47
6
44
1
46.8
48.5
47
3
1
8
1-Hexene
53.
9
55
0
56
4
54
6
54
9
54
2
55
5
55.2
53.1
54
8
1
0
2-Methylpentene
97.
6
98
9
100
3
99
4
100
9
97
5
93
6
95.8
96.0
97
8
2
4
2,4-Dimethylpentane
31
4
32
3
32
2
32
7
32
3
31
6
31
1
32.1
32.1
32
0
0
5
Cyclohexane
74.
0
74
2
74.
7
72
6
71
6
71
1
57
5
48.6
53.6
66
4
10
2
3-Methylhexane
52.
6
61
6
48
4
50
6
50
6
50
0
50
1
53.3
51 .9
51
0
1
5
2,2,4-Trimethylpentane
68.
4
67
0
63.
4
68
2
69
1
67
2
68
4
71.8
70.1
68
2
2
3
n-Heptane
43.
7
43
2
40.
0
43
4
43
2
42
7
41
8
43.1
42.6
42
6
1
1
Methylcyclohexane
33.
9
34
0
32.
2
35
5
34
7
34
1
33
9
34.7
33.8
34
1
0
9
2,3,4-1rimethylpentane
29.
9
30
4
31
1
30
7
30
6
30
1
29
5
29.7
29.8
30
2
0
5
3-Methylheptane
28.
6
30
1
31
2
31
5
31
6
30
2
28
3
29.2
29.1
30
0
1
3
n-Octane
28.
7
29
5
30.
6
30
8
30
6
30
8
28
7
29,4
30.3
29
9
0
9
n-Nonane
24.
5
26
2
28.
2
27
5
28
0
27
6
25
4
26.8
26.3
26
7
1
2
n-Decane
18.
7
18
0
18.
2
17
3
17
6
16.
5
16.
6
16.6
14.9
17
2
1
1
-------
Table 5.12. Laboratory Decay Study of C5-C10 Hydrocarbons; Concentrations in ppbV
Sample Number A-127
Day of Analysis
i Deviation
1
5
6
9
1?
16
19
23
26
30
Mean
Isoprene
35.6
43
7
43
5
39
0
38
4
38
0
37.0
28
.8
29.2
27.9
36.1
; 5.8
2,2-Dimethylbutane
23.8
26
4
26
2
27
3
26
2
26
2
26.3
23
7
23.6
25.6
25.5
1.3
2-Methylpentane
30.5
32
5
32
1
30
2
31
4
31
5
32.2
30
4
32.3
30.0
31.3
1.0
3-Methylpentane
37.0
40
0
38
9
40
8
39
6
39
5
40.1
37
0
37.9
38.4
38.9
1.3
1-Hexene
44.8
47
2
46
4
45
4
44
8
44
9
45.8
46
9
46.6
44.8
45.8
0.9
2-Methylpentene
104.8
103
9
101
0
112
1
108
9
104
5
103.7
96
3
94.6
95.0
102.5
5.8
2,4-Dimethylpentane
28.6
29
8
29
3
30
3
29
5
29
4
29.6
28
5
28.8
28.4
29.2
0.6
Cyclohexane
61.9
65
4
58
9
56
5
54
5
54
7
53.0
45
9
42.0
42.5
53.5
7.9
3-Methylhexane
38.3
36
7
35
9
35
6
34
7
34
2
34.7
35
8
35.2
35.4
35.6
1.2
2,2,4-Trimethylpentane
61.3
60
1
59
3
60
4
60
0
59
0
59.7
60
6
59.5
59.5
59.9
0.7
n-Heptane
35.8
34
2
33
0
33
8
33
6
33
1
33.4
33
0
32.5
32.7
33.5
0.9
Methylcyclohexane
32.7
32
8
31
6
32
3
32
2
31
9
31.9
32
0
31.6
31.3
32.0
0.5
2,3,4-Trimethylpentane
28.0
28
8
28
6
28
8
28
6
28
3
28.5
27
4
27.5
26.9
28.1
0.7
3-Methylheptane
26.1
26
8
26
8
28
3
27
4
27
1
27.1
25
2
25.4
25.0
26.5
1.1
n-Octane
28.8
27
8
28
6
28
7
28
5
27
9
28.4
26.
4
27.4
26.7
27.9
0.8
n-Nonane
24.2
33
2
26
0
25
7
26
2
25
4
25.3
22.
3
23.1
24.1
25.6
3.0
n-Decane
18.3
16
8
16
9
16
5
15
7
15
4
14.6
16.
0
12.8
14.5
15.7
1.5
-------
Table 5.13. Percent Change in Concentration, Laboratory Mix Cg-Cis Hydrocarbons
(Day 30 - Day 1/Day 1) x 100
(Day 30 - Mean/Mean) x 100
A-6
A-30
A-62
A-127
A-6
A-30
A-62
A-127
Isoprerie
-14.5
-16.5
-10.8
-21.6
-10.0
-24.8
-11 .9
-22.7
2,2-Dimethylbutane
2.6
5.3
5.9
7.6
0.0
- 4.1
- 2.2
0.4
2-Methylpentane
- 3.3
7.6
- 2.1
- 1.6
- 2.0
- 1.2
- 2.6
- 4.1
3-Methylpentane
6.8
14.3
7.8
3.8
3.6
3.4
2.5
- 1.3
1-Hexene
- 0.8
3.1
- 1.5
0.0
- 0.8
3.9
3.1
- 2.1
2-Methylpentene
0.2
- 6.4
- 1 .6
- 9.3
- 0.6
- 7.3
- 1.8
- 7.3
2,4-Dimethylpentane
4.1
0.3
2.2
- 0.7
6.1
- 1.6
0.3
- 2.7
Cyclohexane
7.8
-22.2
-27.6
-31 .3
3.4
-14.8
-19.3
-20.6
3-Methylhexane
5.9
- 5.3
- 1.3
- 7.6
5.2
- 0.5
1 .8
- 0.6
2,2,4-Trimethylpentane
7.7
0.8
2.5
- 2.9
4.8
0.5
2.8
- 0.7
n-Heptane
5.3
- 7.5
- 2.5
- 8.7
3.8
- 2.8
0.0
- 2.4
Methylcyclohexano
4.2
- 5.1
- 0.3
- 4.3
2.7
- 1.2
- 0.9
- 2.2
2,3,4-Trimethylpentane
- 0.7
3.2
- 0.3
- 3.9
- 0.7
- 1.7
6.6
- 4.3
3-Methylheptane
2.4
3.4
1.7
- 4.2
-1.1
- 1.1
- 3.0
- 5.7
n-Octane
- 0.8
10.0
5.6
- 7.3
- 0.8
1.7
1.3
- a.3
n-Nonane
13.5
12.3
7.3
- 0.4
- 0.4
1.9
-1.5
- 5.9
n-Decane
-19.9
-18.9
-20.3
-20.8
- 7.6
-11.5
-13,4
- 7.6
MEAN
1.2
- 1.3
- 2.2
- 6.7
0.3
i j
CO j
"-J j
1
- 2.2
- 5.5
-------
Table 5.14, C^-C^ Hydrocarbons in Roadside Samples, ppbC
SAMPLE NUMBER
A-84
A-176
A-
190
Standard
Deviation
DATE OF COLLECTION
7/6/78 (0730-0910 EDT)
7/6/78
7/6/78
Mean
DATE OF ANALYSIS
7/7
7/7
7/18
7/25
7/6
7/7
7/18
7/25
7/6
7/6
//18
7/25
Ethane
12.8
13.2
13
6
13.0
13.3
12.4
12.4
11
9
12.7
13
.8
12
.7
12.5
i 17
.9
0.5
Ethylene
104.8
103.5
98
2
100.5
102.b
99,0
94,6
97
9
108.9
106
.6
100
4
103.1
101
7
4.0
Propane
6.2
6.6
7
1
6.6
6.0
5.8
5.0
6
3
6.0
6
6
6
4
6.0
6
2
0.5
Acetylene
138.1
136.9
126
6
119.4
149.0
130.2
124.5
120
3
149.5
142
2
131
2
12/.8
133
0
10.2
Isobutane
7.0
9.1
6
3
7.6
7.8
6.2
7.4
8
7
10.4
6
4
7
5
7.6
7
7
1.2
n-Butane
38.6
38.8
34
6
37.2
38.7
35.8
35.1
.36
0
40.4
38
0
38
8
36.9
37
4
1.8
Propylene
34.3
31.3
28
6
28.6
32.3
29.5
27,0
27
7
35.8
34
I
31
3
31.2
31
0
2.8
Isopentane
65.1
59.3
58
5
56.3
62.3
60.0
55.4
55
8
61.0
61
2
55
1
59.5
59
1
3.1
Pentane
44.3
42.2
40
5
37.fi
38.5
38.1
38.3
45
1
42.4
32
7
39
0
38.4
39.
8
3.4
SUM
451.2
440.9
414
1
406.8
450.5
417.0
399.7
409
7
467.1
441
6
422.
4
423.0
428.
7
21.0
MEAN
428.
2
419
2
43t
.5
428.
6
9.7
STANDARD DEVIATION
21.
2
22
0
21
.0
-------
Table 5.15. Olefinic and Paraffinic Hydrocarbons in Roadside Samples, ppbC
o
o
SAMPLE NUMBER
A
84
A-176
A-1S
DATE OF COLLEtI ION
7/6/78
7/6/78
7/6/?
DATE OF ANALYSIS
7/7
7/7
7/19
7/25
7/6
7/7
7/18
7/25
7/6
7/5
2-Pentene + Isoprene
------ -
6._5
9.8
(a)
(a)
(a)
9.9
9.1
9.8
10.3
2,2-Dimethylbutane
7.8
6, U
5,9
3.8
6.2
5.9
6.4
5.0
6.7
6.6
2-Methy! pentane
25.6
22.5
26,0
22.1
20.6
21.4
19.1
2' .7
2C, ?
21.2
3-Methylpentane
15.6
16.3
19.8
16.1
17.0
19.9
11.8
14.6
18.5
13,1
1-Hexene
— (b)
—
—
—
--
—
—
—
n-Nexane
13.3
13.7
11.8
12.7
18.0
13.0
11.6
12.4
19.0
12.4
2,4-DimethyIpentane
1.9
1.3
3.4
3.4
2.5
2.9
1.7
1.7
2.3
1.9
Cyclohexane
—
—
—
—
—
—
2-Methy1hexane
18.2
19.2
21.6
28.9
19.6
23.5
21 ,5
19,7
24. 1
29.6
3-Methylhexane
9.5
10.3
10.4
14.9
10.6
8.7
7.1
/ .4
8.5
10.6
2,2,4-Trimethylpentane
16.6
10.7
12.0
9.9
11.7
12.0
11.3
10.1
11.7
13.1
n-Heptane
9. 1
8.2
9.6
6.8
9.2
8.9
7.9
9.6
8.9
9.2
2,5-Dimethylhexane
6.4
5.7
7.1
5.6
0.8
6.1
5.2
4.3
6.5
5.9
2,3,4 Trimethylpentane
5.4
2.2
5.4
2.2
4.5
1 .9
2.8
1.6
5.3
4.8
2-Metliyl heptane
59.4
58.8
59.7
58.5
57.9
57.9
54.2
55.0
57.8
57.4
3-Methylheptane
8.5
9.0
12.4
9.0
10.9
10.6
9.8
10.3
9.7
8.9
n-0ctane
7.6
7.4
8.5
4.8
6.8
6.1
5.3
5.6
6.4
5.9
n-Monane
12.5
11.7
12.1
11.6
11.4
11.4
10.3
10.0
12.6
11.4
n-flfttane
14.2
13.0
7.2
7,3
7.1
7.5
8.2
5.0
8.3
8.8
SUM
242,9
213.5
242.7
217.6
220.8
217,7
204.6
203.6
236.3
231.1
MEAN
229.2
211
7
233
STANDARD DEVIATION
1
5.8
8
8
8
7/19
7.9
5.8
21.6
22.5
13.2
2.0
25.1
11.9
29.3
12.2
6.9
4.4
58.0
9.4
5.2
12.5
8.9
243.J
(«)
(b)
7/25
8.9
5.6
21.4
16,9
12.1
'0,7
29.4
12.7
9.8
7.8
5.6
3.2
57.3
8.5
6.8
10.1
6.6
223,4
Mpan
9.3
6.0
21.9
16.8
13.6
2.1
23.4
10.2
12,1
8.9
6.0
3.6
37.7
9.7
6.4
11.5
224.8
224.8
Standard
Deviation
1.4
1.0
2.0
3.0
2.4
0.8
4.1
2.2
2.1
1.3
0.7
1.5
1.6
1.1
1.1
0.9
2.6
14.3
11.5
Peak obscured by water spike
Not detected
-------
Table 5.16. Aromatic Hydrocarbons in Roadside Samples, ppbC
SAMPLE NUMBER
DATE OF COLLECTION
DATE OF ANALYSIS
A-8'-
7/6/70
7/7 7/7 7/19
7/25
7/6
A-17 6
7/6/78
7/7 7/19
7/25
A- 90
7/6/78
Mean
Renzenp
Toluene
Ethyl benzene
p-Xylene t a. Finene
m-Xylene
o-Xylene
M-Propylbenzene
1,3,5-Trimethylbenzene
m-Ethyltolucnc
t-Butylbenzene
o-Ethyltoluene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
n-Butylbenzene
SUM
MEAN
STANDARD DEVIATION
41.2
49.0
12.0
10.4
19.2
12.0
1.8
4.5
10.8
0.9
10.8
<0.9
37.0
47.6
10.4
11.2
19.2
12.0
1.8
2.7
9.9
1.8
10.8
<0.9
43.3
53.2
12.0
12.0
20.0
11 .2
1.8
1.8
10.8
0.9
9.0
<0.9
<1.0
43.9
48.7
10.6
10.6
18.6
10.6
0.9
2.2
10.0
0.9
7.8
<0.9
36.3
49.0
9.6
11.2
19.2
12.8
0.9
0.9
10.8
<0.9
9.9
<0.9
36.8
48.3
10.4
12.0
19.2
11.2
0.9
3.6
10.8
0.9
10.8
<0.9
<1.0
35.9
49.7
10.4
9.6
18.4
11.2
1.8
1 .4
9.9
0.9
7.2
<0.9
<1.0
39.4
46.0
8.1
6.1
15.3
9.0
<0.9
2.2
6.8
<0.9
5.2
<0.9
36.9
51.1
10.4
11.2
19.2
13.6
1 .8
1.8
9.9
0.9
10.8
<0.9
<1 .0
36.5
51 .1
9.6
10.4
19.2
9.6
3.6
9.9
0.9
11.7
<0.9
35.7
58.8
12.8
11.2
20.0
12.0
1.8
0.9
11.7
<0.9
9.9
<0.9
<1 .0
49.8
56.8
11.5
9.5
19.5
10.7
1.6
10.6
n.9
9.7
<0.9
<1.0
39.4
50.8
10.6
10.4
18.9
11.3
1.2
2.3
10.2
1.0
9.5
<0.9
0.5
173.5 165.3 177.9 165.7
162.4 166.8 158.3 140.8
169.5 163.4 1/7.6 182.5
167.0
170.6
6.2
157.1
11.4
173.3
8.5
167.0
'a^-- Not detected
-------
compounds into evacuated stainless steel cylinders and then pressurizing
with hydrocarbon-free air to a known pressure. Since the volume of the
liquid compound, the cylinder volume, and the final pressure of the mixture
were all accurately known, one can calculate the concentration of individual
species through this formula:
(I)(D)(1000) _ „
PV
where
I = Volume of compounds injected ((JL)
D = Density of liquid compound (g/mL)
P = Final pressure (atm)
V = Volume of container (m3)
€ = concentration of compound ([Jg/m3).
To convert from (jg/m3 to ppm,
. (2.45 x 104)
1 ug/m3j — = C
(M x i06) PP"1
where
M = Molecular weight.
In both the aromatic and aliphatic standard mixtures, 200 pi of each
compound were injected. Both containers were pressurized to 500 psi (34 atm).
The C2-C5 column was calibrated periodically with prepared mixtures
from Scott Environmental Laboratories as well as with an NBS propane (0.976
ppm) mixture, SRM #1660.
In the calibration of C2-C5, aliphatic, and aromatic compounds, the
cryogenic traps were replaced by 1-mL sample loops. The calibration mix-
tures did not need further concentrating, so they were injected directly
from the loops at room temperature. The use of the 1-mL loop slightly
affected the retention times of the compounds as compared to the cryogenic
trapping procedure. Therefore, the quantitative calibrations were done with
the 1-mL loops, while qualitative calibrations (peak elution times) were
done with diluted mixtures on the cryogenic traps.
The quantitative calibrations were performed at monthly intervals since
the responses of the FID's were not expected to change greatly. This sta-
92
-------
bility was shown by the fact that very few changes in response factors were
required in any of the recalibrations,
The qualitative calibrations were performed, on the average, at twice-
weekly intervals. Dilutions of the standard mixtures (approximately 50 ppb)
would be cryogenically trapped and analyzed to allow the C2-C5, aliphatic,
and aromatic elution times to be checked and adjusted.
The calibrations in all cases involved analyzing the standard mixtures
and entering the species concentration and/or retention time of each chroma-
togram peak into the computer. The computer then "manufactured" a standard
chromatogram to which subsequent analyses were compared. Thus, peaks were
automatically identified and quantified by their elution times and sizes.
93
-------
SECTION 6.0
DATA SUMMARIES
6.1 CONTENTS OF DATA SUMMARY SECTION
This section contains summaries of pollutant and meteorological param-
eters from the eight ground station monitoring sites in Tulsa, Oklahoma,
during the summer of 1977. Some summaries of ozone and wind data gathered
by the Tulsa City/County Health Department are also given. The data summar-
ies are divided into five categories: ozone; oxides of nitrogen and hydro-
carbons; meteorological parameters; summaries of hydrocarbon species; and
Tenax GC/MS results.
Individual hourly averages in SAROAD format for all pollutant and
meteorological parameters are in Volume II of this report. Volume II also
contains the following: annotated flight tracks of all aircraft flights;
computer printout of all flight data; pibal sounding data; listings of
concentrations for all individual hydrocarbon species; and a listing of all
species found in Tenax cartridges by GC/MS/COMP.
6.2 OZONE DATA SUMMARIES
6.2.1 Mean Daily Ozone Concentrations
Mean daily ozone concentrations, i.e., the average of 24 hourly values
each day, are given for each of the eight monitoring stations in Tables 6.1
through 6.8. The actual number of hourly observations is also listed. Mean
(by month of) daily maximum (by month of) hourly ozone concentrations are
given m Table 6.9. Maximum hourly ozone concentrations for each station
for each month are given in Tables 6.10, 6.11, and 6.12.
6-2.2 Ozone Cumulative Frequency Distributions
Cumulative frequency distributions, or percentile values, for the
3-month period for each monitoring site are shown in Table 6.13. The percen-
tiles shown are 10, 30, 50, 70, 95, 96, 97, 98, and 99. Also listed are the
maximum value, second and third maximum values, and the arithmetic mean.
94
-------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
able 6.1. Mean daily ozone concentration. July, August, September, 1977. Liberty Mounds
July
Auf
>ust
September
Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
Mean Dail
y
Number of Hourly
O3 Cone., ppm
Observations
O3 Cone., ppm
Observations
O3 Cone.,
ppm
Observations
0.030
24
0,042
20
0.031
23
0.032
23
0.061
2 3
0.034
24
0.036
24
0.063
23
0.043
24
0.040
24
0.072
23
0.052
23
0.049
23
0,078
23
0.037
18
0.053
24
0.055
23
0.037
24
0.044
23
0.056
24
0.034
20
0.050
24
0.059
23
0.031
24
0.046
24
0.056
24
0.031
23
0.039
23
0.054
23
0.030
24
0.043
23
0.047
23
0.035
24
0.039
23
0,055
23
0.043
24
0.033
20
0.040
23
0.027
24
0.042
23
0.053
24
0.025
19
0. 055
24
0,049
23
0.033
19
0.061
23
0.039
23
0.051
24
0.050
23
0.030
23
0.041
24
0.047
23
0,050
23
0.034
24
0.057
23
0.048
23
0.023
23
0.046
24
0,04/
23
0.033
21
0.040
23
0.050
24
0.055
24
0.031
24
0,044
23
0.066
23
0.042
24
0.051
23
0.045
24
0.046
24
0.049
24
0.036
23
0.061
24
0.053
23
0.040
24
0.047
23
0.051
24
0.035
24
0,023
23
0.040
23
0.039
24
0.037
23
0.027
22
0.037
24
0.059
2,4
0.032
23
0.036
24
0.050
22
0.035
-23
0.037
24
0.058
22
0.036
24
-------
Dat
1
2
3
4
5
6
7
8
9
10
II
12
13
14
15
16
1 7
18
19
20
21
22
23
24
25
26
27
28
29
30
O 1
-J-L
?able 6.2, Mean dally ozone concentration.
Office
July, August, September, 1977. Tulsa Post
July
Mean Daily Number of Hourly
O3 Cone., ppm
Observations
0.041
019
015
017
024
035
045
035
029
047
042
024
051
054
029
049
039
021
042
050
029
041
0
0
6
23
18
20
23
13
23
24
23
24
23
24
23
24
23
23
23
24
23
20
24
23
August
Mean Daily Number of Hourly
O3 Cone., ppm
Observations
0.027
0.047
0.031
0.02«
0.026
0.012
0.012
0.014
0.013
0.029
0.029
0.034
0.027
0.037
0.025
0.016
0.017
0.030
0.020
0.031
0.030
0.025
0.041
0.034
0.033
0,012
0.011
0.015
0.026
0.024
0.017
23
24
24
24
23
24
24
24
24
23
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
23
23
24
24
September
Mean Daily Number of Hourly
O3 Cone., ppm Observations
021
023
035
041
032
031
028
023
024
024
033
016
017
022
021
019
0.014
0.016
0.019
0.025
0.030
0.047
0.015
0.021
0.032
0.018
0.030
0.022
0.025
24
24
24
24
24
24
22
24
24
24
18
24
24
24
24
24
24
24
24
24
24
24
24
24
24
23
24
24
14
0
-------
Table 6. 3. Mean daily ozone concentration. July, August, September, 1977. Tulsa City/County
Health Department
July
Au
gust
September
Mean Daily Number of Hourly
Mean Daily
Number of Hourly
Mean Daily Number of Hourly
Date
03 Cone., ppm Observations
O3 Cone., ppm
Observations
O3 Cone., ppm Observations
1
0
0.026
24
0.025 24
2
0
0.053
22
0.029 24
3
0
0.051
23
0.036 24
4
0.050 15
0.049
23
0.049 23
5
0.047 15
0.058
23
0.031 24
6
0
0.042
22
0.031 24
7
0
0.048
24
0.029 24
8
0.037 6
0.048
23
0.031 24
9
0.033 23
0.049
23
0.033 23
10
0.040 14
0.051
23
0.026 23
11
0.045 15
0.033
23
0.031 24
12
0.036 18
0.040
21
0.038 24
13
0.032 23
0.029
23
0.021 24
14
0.043 23
0.039
24
0.025 23
15
0.052 23
0.039
23
0.022 24
16
0.054 24
0.029
14
0.036 24
17
0.052 24
0.021
13
0.035 24
18
0.045 24
0.037
23
0.033 24
19
0.053 23
0.037
23
0.022 23
20
0.045 24
0.029
23
0.027 24
21
0.037 23
0.032
24
0.050 23
22
0.049 23
0.028
23
0.067 1
23
0.054 24
0.047
23
0
24
0.049 18
0.036
23
0
25
0.052 13
0.038
24
0.048 17
26
0.040 14
0.039
24
0.024 24
27
0.020 24
0.030
23
0.028 23
28
0.041 22
0.021
24
0.020 23
29
0.060 23
0,022
23
0.022 23
30
0.046 23
0.023
23
0.012 8
31
0.042 24
0.029
24
-------
UcL L
1
2
3
4
5
6
7
8
9
10
li
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
e 6.4. Mean dally ozone concentration. July, August, September, 1977. Sperry
July
Aug
ust
September
Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
O3 Cone., ppra
Observat ions
O3 Cone ., pptn
Observations
O3 Cone., ppm
Observat ions
_
0
0.026
24
0.027
24
-
0
0.044
24
0.032
24
-
0
0.049
24
0.041
24
0.047
9
0.055
24
0.041
24
0.049
24
0.067
24
0.036
24
0.051
24
0.049
24
0.037
24
0.050
23
0.045
24
0.039
24
0.042
23
0.046
24
0.035
24
0.042
24
0.045
24
0.034
23
0.048
24
0.052
24
0.037
18
0.045
23
0.032
23
0.037
19
0.044
23
0.034
24
0.039
24
0.041
19
0.025
24
0.028
24
0.052
21
0.040
24
0.022.
16
0.043
12
0.041
24
0.024
24
0.057
22
0.040
24
0.040
24
0,047
23
0.029
24
0.040
24
0.045
23
0.043
24
0.033
24
0.054
24
0.026
24
0.023
24
0.053
24
0.042
24
0.026
24
0,046
23
0.027
24
0.049
24
0,047
23
0.043
24
0.057
24
0.047
24
0.052
24
0.037
24
0,052
24
0.044
24
0.028
24
0.064
24
0.041
21
0.034
24
0.042
24
0,041
24
0.028
23
0,023
19
0.035
24
0.037
24
0,011
8
0.030
24
0.025
24
0.061
15
0.026
24
0.028
24
0.052
2 4
0.026
24
0.029
24
0.042
24
0.031
24
-------
ate
1
o
£.
3
4
5
6
7
8
9
10
11
12
13
14
15
16
1?
18
19
20
21
22
23
24
25
26
27
28
29
30
31
'able 6.5. Mean daily ozone concentration. July, August, September, 1977. Skiatook Lake
July
August
September
Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
O3 Cone. , pprn
Observations
O3 Cone., ppm
Observations
O3 Cone., ppm
Observations
0.054
23
0.025
22
0.029
24
0.044
23
0.052
24
0.02 7
24
0.043
21
0.053
24
0,030
24
0.045
3
0.069
24
0.036
24
-
0
0.079
24
0.033
24
0.045
4
0.054
10
0.03/
23
-
0
-
0
0.032
24
-
0
-
0
0.031
24
0.046
10
0.049
9
0.030
23
0.039
24
0.052
23
0.039
24
0.041
22
0.036
22
0.034
23
0.034
22
0.034
24
0.049
24
0.025
22
0.026
24
0.030
24
0.029
22
0.040
24
0.033
24
0.035
23
0.046
24
0.028
24
0.048
22
0.041
24
0.045
23
0.036
24
0.030
24
0.044
24
0.034
23
0.043
24
0.037
24
0.045
23
0.029
24
0.023
24
0.038
22
0.037
24
0.027
24
0.038
21
0.025
24
0.060
24
0.047
23
0.039
24
0.062
23
0.042
24
0.037
24
0.046
24
0,049
24
0.044
24
0.028
24
0.064
23
0.037
24
0.037
34
0.043
24
0.041
24
0.036
24
0,031
24
0.033
23
0.045
24
0.043
' 24
0.029
24
0.030
24
0.042
24
0.021
23
0.037
23
0.045
24
0.023
24
0.037
24
0.035
24
0.033
24
-------
Dat
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
e 6.6.
Mean daily ozone concentration.
July, August, September, 197 7.
Vera
Mean Daily
O3 Cone., ppm
July
Number of Hourly
Observations
August
Mean Daily Number of Hourly
O3 Cone., ppm
Observations
0.031
0.022
0.026
0.027
0.031
0.039
0.041
0.039
0. 033
0.049
0. 046
0.037
0.034
0.057
0.060
0.063
0.054
0.044
0.054
0.054
0.044
0.051
0.05/1
0.053
0. 069
0.042
0.029
0. 059
0. 058
0.064
0. 048
24
23
24
21
21
24
23
23
24
23
23
23
22
21
2 3
23
24
23
23
23
23
23
23
24
23
23
23
23
21
22
24
0.034
0.048
0.059
0.058
0.067
0.053
0.052
0.048
0.049
0.052
0.036
0.040
0.033
0.045
0.038
0.035
0.028
0.041
0.034
0.042
0.027
0.038
0.052
0.050
0.042
0.044
0.037
0.029
0.025
0.029
0.029
23
23
23
23
23
23
24
23
23
21
2 3
23
24
23
23
23
24
23
24
23
24
23
23
24
23
24
21
24
24
24
24
September
Mean Daily Number of Hourly
O3 Cone., ppm
0.031
0.036
0.049
0.043
0.033
0.034
0.042
0.040
0.029
0.036
0.035
0.044
0.033
0.033
0.027
0.039
0.037
0.036
0.031
0.030
0.051
0.064
0.042
0.036
0.041
0.037
0.043
0.034
0.033
0.032
Observations
24
24
24
24
24
24
23
21
24
24
24
24
23
24
24
24
24
24
24
24
23
24
24
24
24
24
24
24
24
23
-------
ate
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
e 6,7, Mean dally ozone concentration. July, August, September, 1977. Wynona
Ju
iy
August
Sc
ptember
Mean Dally
Number of Hourly
j Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
O3 Cone., ppm
Observations
IO3 Cone., ppm
i
Observations
O3 Cone., ppm
Observations
0.058
24
! 0.043
24
0.034
24
0.047
23
0.068
24
0.035
24
0.052
22
0.072
24
0.044
24
0.045
.1
0.074
23
0.038
24
-
0
0.076
24
0.040
24
0.054
8
0.057
24
0.035
24
0.045
23
0.056
24
0.039
24
0.039
24
0.055
24
0.035
23
0.032.
23
0,054
24
0.028
24
0.035
24
0.053
24
0.036
24
0.043
23
0.037
23
0.033
24
0.042
22
0.039
24
0.044
24
0.033
23
0.037
24
0.032
24
0.040
22
0.046
24
0.034
24
0.040
9
0.052
24
0.029
24
-
0
0.043
24
0.048
24
-
0
0.037
24
0.048
24
-
0
0.046
24
0.039
24
0.0/1
21
0.040
24
0.025
24
0.059
22
0.047
24
0.032
24
0.043
24
0.040
24
0.058
24
0.062
24
0.052
24
0.064
24
0.058
23
0.050
24
0.047
24
0.065
24
0.050
24
0.035
24
0.082
24
0.044
24
0.040
24
0.052
24
0.052
24
0.040
24
0.044
24
0.041
24
0.041
23
0.054
24
0.035
23
0.030
24
0.061
24
0.028
24
0.035
24
0.064
22
0.028
24
0.037
24
0.047
24
0,032
24
-------
Dat
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
lable 6,8, Mean daily ozone concentration. July, August, September, 1977, Ochelata
July
11
UGt
September
Mean
Daily
Number of Hourly
; Mean Daily
Number of Hourly
Mean Daily
Number of Hourly
O3 Cone., ppm
Observations
jO3 Cone., ppm
Observations
O3 Cone., ppn
Observations
_
0
| 0
034
23
0
037
24
-
0
0
042
14
0
037
2L
-
0
0
074
15
0
045
24
-
0
0
062
23
0
045
24
_
0
0
071
23
0
040
24
0.063
11
0
054
23
0
040
24
0
055
23
0
04 7
23
0
051
24
0
050
23
0
046
24
0
052
24
0
045
24
0
048
20
0
031
23
0
049
23
0
048
24
0
034
22
0
046
23
0
032
23
0
034
24
0
046
22
0
037
23
0
043
24
0
040
23
0
030
24
0
034
24
0
045
23
0
044
24
0
033
24
0
055
20
0
041
24
0
028
23
0
055
23
0
038
21
0
04 9
23
0
052
24
0
031
24
0
043
24
0
047
23
0
041
23
0
040
24
0
054
23
0
031
24
0
032
24
0
051
23
0
045
24
0
035
24
0
052
23
0
036
24
0
053
24
0
054
23
0
04 7
24
0
064
23
0
052
23
0
048
24
0
044
24
0
051
24
0
045
23
0
039
24
0
064
2 3
0
042
24
0
046
24
0
042
23
0
040
24
0
039
24
0
033
23
0
035
24
0
045
23
0
048
21
0
029
24
0
028
24
0
049
2 3
0
024
23
0
038
24
0
036
13
0
029
22
0
036
24
0.
043
11
0
029
22
-------
Table 6.9. Mean daily maximum hourly ozone concentrations
Si te
July
Number
of
Days
August
Number
of
Days
September
Number
of
Days
Liberty Mounds
0.069
31
0.077
31
0.061
30
Public Health Dept.
0.074
26
0.066
31
0.061
26
Post Office - Tulsa
0.067
22
0.053
31
0.049
29
Sperry
0.079
28
0.073
31
0.062
30
Skiatook Lake
0.064
28
0.069
29
0.065
30
Vera Post Office
0.091
31
0.073
31
0.065
30
Ochelata
0.079
26
0.068
31
0.067
28
Wynona
0.075
27
0.075
31
0.063
30
Mohawk Blvd. 3J
0.087
31
0.076
31
0.075
30
Apache Street
0.089
31
0.079
31
0.065
29
— Concentrations may be at least 20 percent higher than the other
sites due to differences in calibration via NBKI procedure.
103
-------
T
lr,
00
01
02
03
04
05
06
07
08
09
10
1.1
12
.13
14
15
16
17
18
19
20
2.1
22
23
6.10. Maximum hourly ozone concentrations, pore. July, 1977
Liberty
Post
Health
Skiatook
Mounds
Office
Dept.
Sperrv
Lake
Vera
Wynona
Ochelata
0.068
0.051
0.048
0.058
0,056
0.053
0.059
0.065
0.068
0.049
0.049
0.052
0.056
0.048
0.058
0.063
0.060
0.045
0.046
0.052
0.057
0.044
0.057
0.066
0.058
0.043
0.045
0.052
0.058
0.035
0.052
0.073
0.053
0.048
0,048
0.052
0.050
0.045
0.052
0.070
0.043
0.045
0.043
0.047
0.051
0.035
0.047
0.078
0.043
0.035
0,043
0.042
0.049
0.036
0.047
0.078
0.050
0.030
0.048
0.049
0.047
0.043
0.052
0.090
0.060
0.073
0.083
0.089
0.086
0.086
0.089
0.091
0.055
0,072
0.075
0.092
0.105
0.127
0.107
0.100
0.055
0.080
0.121
0.119
0.104
0.124
0.124
0.102
0.073
0.091
0.101
0.099
0.106
0.110
0.094
0.087
0.055
0.059
0.091
0.080
0.081
0.081
0.092
0.091
0.056
0.075
0.123
0.135
0.128
0.135
0.125
0.114
0.062
0,074
0.085
0,092
0.091
0.101
0.101
0.091
0.108
0.118
0.133
0.143
0.146
0.146
0.158
0,158
0.124
0.127
0.117
0.091
0.073
0.070
0. 070
0.069
0.090
0.090
0.112
0.087
0.076
0.064
0.055
0.052
0. 096
0.090
0.092
0.063
0.058
0.055
0.055
0.048
0. 091
0.094
0.088
0.088
0.074
0.064
0.063
0.058
0.078
0.082
0.091
0.085
0.078
0.068
0.061
0.056
0.115
0.116
0.111
0.095
0.080
0.064
0.063
0.062
0.096
0.089
0,08^-
0.081
0.069
0.064
0.057
0.059
0.158
0.158
0.143
0.123
0.113
0.112
0.098
0.088
-------
T
r,
00
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
6.11. Maximum hourly ozone concentrations, pprc. August, 1977
Liberty
Post
Health
Skiatook
Mounds
Office
Dept.
Sperry
Lake
Vera
Wynona
Ochelata
0.078
0.031
0.062
0,070
0.076
0.058
0.079
0.061
0.072
0.035
0.072
0.064
0.073
0.059
0.076
0.060
0.068
0.044
0.072
0.060
0.067
0.054
0.074
0.062
0.064
0.036
0.075
0.056
0.063
0.048
0.072
0.061
0.050
0.033
0.073
0.051
0.057
0.053
0.068
0.053
0.051
0.028
0.074
0.043
0.055
0.054
0.069
0.054
0.073
0.023
0.068
0,039
0.056
0.049
0.059
0,051
0.050
0.027
0.062
0.041
0.047
0.045
0.054
0.044
0.062
0.050
0.052
0.054
0.062
0.054
0.063
0.049
0.072
0.051
0.054
0.075
0.074
0.059
0.068
0.084
0.093
0.065
0.077
0.115
0.080
0.098
0.093
0.094
0.106
0.082
0.093
0.102
0.087
0.099
0.099
0.091
0.105
0.085
0.107
0.107
0.106
0.103
0,106
0.099
0.104
0.080
0.111
0.135
0.112
0.128
0.111
0.114
0.108
0.085
0.096
0.100
0.120
0.151
0.108
0.114
0.114
0.084
0.087
0.103
0.111
0.133
0.115
0.106
0.102
0.080
0.081
0.103
0.107
0.104
0.121
0.101
0.106
0.101
0,085
0.108
0.101
0.103
0.113
0.096
0.117
0.096
0.086
0.093
0.096
0.089
0.105
0.089
0.100
0.087
0.058
0.075
0.085
0.068
0.099
0.077
0.085
0.070
0.046
0.069
0.077
0.06.1
0.082
0.061
0.075
0.050
0.074
0.055
0.074
0.054
0.072
0.053
0.078
0.044
0.058
0.064
0.075
0.054
0.071
0.056
0.081
0.035
0.063
0.073
0.076
0.056
0.075
0.059
-------
T
ir,
00
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
6.12. Maximum hourly ozone concentrations, ppm. September, 197 7
Liberty
Mounds
Post
Office
Health
Deot.
Sperry
Skiatook
Lake
Vera
Wynona
Ochelata
0.073
0.070
0.066
0.061
0.058
0.056
0.051
0.051
0.050
0.058
0.052
0.046
0.050
0.042
0.037
0.031
0.067
0.043
0.042
0.041
0.045
0.043
0.042
0.035
0.067
0.061
0.061
0.059
0.052
0.044
0.035
0.031
0.079
0.076
0.069
0.064
0.061
0.055
0.054
0.053
0.068
0.064
0.061
0.056
0.055
0.051
0.063
0.050
0.076
0.071
0.067
0.065
0.060
0.057
0.060
0.054
0.064
0.065
0.062
0.060
0.058
0.055
0.052
0.050
0.063
0.075
0.079
0.080
0.076
0.075
0.081
0.080
0.033
0.050
0.063
0.061
0.067
0.076
0.075
0.069
0.046
0.067
0.082
0.094
0.086
0.085
0.093
0.086
0.042
0.075
0.095
0.089
0.094
0.117
0.098
0.083
0.061
0.070
0.078
0.086
0.080
0.081
0.085
0.085
0.046
0.066
0.086
0.098
0.095
0.126
0.118
0.096
0.055
0.066
0.075
0.075
0.080
0.075
0.075
0.075
0.052
0.068
0.083
0.094
0.102
0.101
0.108
0.095
0.079
0. 089
0.081
0.079
0.079
0.079
0.079
0.074
0.067
0.081
0.079
0.076
0.070
0.070
0.051
0.057
0.066
0.064
0.050
0.060
0.073
0.072
0.069
0.067
0.080
0.075
0.076
0.068
0.064
0.069
0.065
0.071
0.080
0.072.
0.074
0.072
0.071
0.080
0.081
0.079
0.083
0.086
0.085
0.076
0.071
0.070
0.061
0.065
0.075
0.098
0.077
0.069
0.067
0.069
0.077
0.080
0.089
0.080
0.086
0.078
0.065
0.069
0.069
0.064
-------
Table 6.13. Percentile values, maximum values, and arithmetic mean for ozone, ppm. July -
September, 1977
Monitoring Site
Percentile
Max
2nd Max
3rd Max
Arith
Mean
10
30
50
70
90
95
9 ft
97
9fi
99
Liberty Mounds
0.019
0.032
0.043
0.055
0.071
0.079
0.081
0.083
0.086
0.093
0.127
0,124
0.117
0.044
Tulsa Post Office
0.005
0.015
0.023
0.035
0.055
0.065
0.068
0.072
0.077
0.085
0.127
0.112
0.107
0.028
Tulea City/County
Health Department
0.014
0.074
0.034
0.045
0.065
0.074
0.077
0.082
0.087
0.093
0.124
0.124
0.121
0.031
Sperty
0.012
0.026
0.037
0.052
0.072
0.080
0.083
0.088
0.092
0.098
0.135
0.117
0.115
0.040
Sklatook Lake
0.011
0.02 7
0.038
0.050
0.067
0.075
0.076
0.080
0.086
0,092
0.120
0.112
0.112
0,039
Vera
0.015
0.027
0.036
0.050
0.075
0.090
0.094
0.098
0.104
0.115
0. 1.51
0.135
0.135
0.042
Wynona
0.021
0.033
0.044
0.056
0,073
0.084
0.087
0.090
0.095
0.102
0.123
0.121
0.123
0.046
Ochelata
0.020
0.030
0.040
0.054
0.069
0.079
0.084
0.086
0.089
0.096
0.114
0.114
0.108
0.043
Mohawk Blvd. —
0.005
0. 075
0.038
0.056
0.083
0.093
0.096
0.099
0.105
0.110
0.142
0.133
0.128
0.042
Apache St, i!
0.013
0.028
0.041
0.055
0.078
0.089
0.092
0.097
0.107
0.120
0.166
0.166
0.163
0.043
— Concentrations at this site are 20 percent higher than the other sites as they are based on calibration via NBKI procedure.
-------
6.2.3 Frequency Pistnbution Plots
Frequency distributions of hourly ozone concentrations for each of the
eight monitoring stations are shown in a series of thirty-two bargraph
figures. Ozone concentrations are displayed in increments of 0.01 ppm. The
actual incremental steps are: 0.00 - 0.009; 0.01 - 0.019; 0.01 - 0.029,
0.03 - 0.039. etc. Both the number of hourly observations and the percentage
of the total observations are denoted on the figures. The figures present
frequency distributions for each site for each month and for the entire
3-month period.
Figures 6.1 through 6.8 are ozone frequency distributions for July 1977;
Figures 6.9 through 6.16 are ozone frequency distributions for August 1977;
Figures 6.17 through 6.24 are for September 1977; Figures 6.25 through 6.32
are frequency distributions for the entire 3-month period.
6.2.4 Mean Hourly Standard Deviation of Ozone Concentrations
Table 6.14 presents the mean hourly standard deviations for ozone
concentrations and number of values hy hour for the entire sampling period
for each monitoring site.
6.2.5 Percentage of Hourly Ozone Values >0.08 ppm
Table 6.15 lists each monitoring site and gives the number of hours and
percentage of all hours that exceeded a concentration of 0.08 ppm for each
month and for the 3-month period.
6.2.6 Diurnal Plots of Mean Ozone Hourly Concentrations
Mean diurnal ozone concentrations for the entire period of study are
plotted in Figure 6.33 for the Liberty Mounds, Tulsa Health Department, and
Tulsa Post Office monitoring sites. This allows comparison of the back-
ground ozone diurnal pattern and the in-city patterns. Figure 6.34 illus-
trates the mean diurnal ozone concentration pattern at the Sperry, Skiatook
Lake, and Wynona sites. Figure 6.35 shows the same information for the Vera
and Ochelata sites.
108
-------
150
o
CM
CO
o
v£>
100
CM
r-4
50
10
o
-j
as
co
<*-
r^
-ZL
J=5_
¦f
0 0.010.02 0.05 0.08 0.11
Ozone Concentration, ppm
r—\
xL
ro
O
0.15
0.16
Figure 6.1. Frequency distribution of hourly ozone concentrations,
Mounds. July, 1977.
Liberty
150
100
50
10
CJ
cr*
as
as
o
o
as
CM
tn oo
m o
oo
o
0 0.01 0.02 0,05 0.08 0.11
Ozone Concentration, ppm
0.15
0.18
Figure 6.2. Frequency distribution of hourly ozone concentrations.
Health Department. July 1977,
109
-------
.50
100
u
a
x>
50
10
\0
cr>
O kC
« i—i
OC
cr>
m vD
•
-------
150
100
c 50
10
CNJ
oo
o
CM
o
r~s
d
0.05 0.08 0.10
Ozone Concentration, ppm
0.15
Figure 6.6.
Frequency distribution of hourly ozone concentrations,
Wvnona. July, 1977.
Ill
-------
150
>
S100
50
10
Figure 6.
•sC
vD
m
04 in
c->
r- m
vD
cvi
LT,
cn
LTi
CN
CO r°.
O O
0 0.01
0.05 0.08 0.10
Ozone Concentration, ppnt
0.15
Frequency distribution of hourly ozone concentrationss
Vera. July, 1977.
150
3J100
10
m
"T~
0 0,01
r— O
vO
Cvj
in
Ch
GC
sD
C~S rH
CM Kf
O
0.05 0.08 0.10
Ozone Concentration, ppm
0,15
figure 6,8. Frequency distribution of nour.1v ozone3 concentrations.
Ochelata. July, 1977 .
112
-------
150
00
100-
•
^100
¦.p.
50
10
\D
o d
0 0.01 0.05 0,10
Ozone Concentration, ppm
0.15
Figure 6.10, Frequency distribution ot hourly ozone concentrations,
Tulsa City/County Health Department* August, 1977.
113
-------
200
150
100
ppm
I
0.15
Figure 6.11. Frequency distribution of hourly ozone conncnuratioiu
Tulsa Post Office, August. 1977,
150
>
v
£ 100
3
0)
50 -
10
O
r-- vD
O
Ol r-i
CPs 00
m on
o c.01 0.05 0.08 0.10
Ozone Concentration, ppm
0.15
Figure 6.12. Frequency distribution of hourly ozone concentrations,
Sperry. August, 1977.
114
-------
150
100
3
X
V-i
U
CJ
5:oo
50
U
-------
L50
.00
u
-------
u
CD
O
2S
150
'•D
100
50
10
CM
CN|
CO
rH
o
CM
o%
CN
\D r-i
o o
0 0.01 0.05 0.03
Ozone Concentration, ppm
—i
0.11
Figure 6.17. Frequency distribution of hourly ozona c.oncentrati
Liberty Mounds. September, 1977.
00
150
X
>
W 100
50
M
CM
-------
150
>
100
sD
CN
CN
cn
S3"
O
O
V
rO
£
5
2:
50
10
sO
tn
ON
o
0 0.01 3.08
Ozone Concentration, ppm
0.13
Lgure 6.IS. Frequency distribution ot hourly ozone concentrations,
Tulsa Post Office. September, 1977,
150
100
u
0)
*2
B
3
50
10
ro
ON
c o
r- O
0 0.01 0.08
Ozone concentration, ppm
0.13
iSure 6.20. Frequency distribution of hourly ozone concentrations,
Sperry. September, 1977.
118
-------
w
G
O
>
OJ
w
X)
150
100
o
vO
iA
U~)
LO
CM
O
oc
00
r--
oo
u
Of
.a
e
50
10
in
CI
rH
0 0.01 -0.05 0.08
Ozone concentrations ppm
Figure 6.21. Frequency distribution of hourly ozone concentrations,
Skiatook Lake. September, 1977.
QJ
£1
B
O
150
o
*r-i
u
» 100
c
u
p
o
50
10
CO
m
•
-------
180
150
CNJ
—I
u
\0
rH
100
CN|
o
QJ
e
50
10
sD
vO
m
ro
C\}
H _
o o
0.14
0 0.01 0.05 0.0B 0.10
Ozone Concentration, ppro
Figure 6.23. Frequency distribution or hourly ozone concentrations
Vejra. September, 1977
200
150
LOO
CNj
O
u
0)
50 h
ID
CQ
Csl
m
a\
-------
480
42 (
\D
00
300
240
u 150
% 120
I 90
* 60
30
ON
\D
O
o
CM
o
0 0.01
*ure 6.
480
r
=F=
0.05 0.08 0.12
Osone Concentration, ppm
0.18
25. Frequency 'i.ctributicn of hourly ozone concentrations,
Liberty Mounds. July, August, and September, 1977.
u
«
X)
u
3
~ 20
« 300
>>
240
150
120
90
60
30
¦ cr*
o
CN1
3 0.01 0.05 0.08
Ozone Concentration, ppm
ure 6.26. Frequency distribution of hourly ozone concentrations,
Tulsa City/County Health Department. July, August, and
September, 1977.
0.18
121
-------
510
~ ?o
a;
500
240 I-
1 50 |_
120
90
60
30
00
m
c
CM
o
GO
VO
<7 ON)
o o
-I 1 1
0 0.01 0.05 0.08 C.12
Ozone Concentration, ppm.
0.16
•"igure 6.27.
5 LI) r
x 420
Frequency distribution of hourly ozone concentrations. Tu.l;
Post Office. July, August and September, 1977.
z>
Si
300
£40
150
120
90
60
30
CO
-H CO
m
co
•£>
CNJ
CT\
CN
r-^
oo
vO
r-^
O
CN
3
0 0.01
0.12
0.16
Figure 6,28.
0.05 0.08
Ozone Concentrat ion , pp;u.
Frequency distribution cf hourly ozone concentrations. Sparry,
July, August auc Sep tember s 197 7 .
122
-------
420
300
KT
CO
O
\£>
240
150
120
90
60
30
vO
CO
0 0.01
en
GO
fO
o
0.05 0.0B 0.17
Ozone Concentration, ppm.
Figure 6.29. Frequency distribution of hourly ozone concentrations.
Lake, .July, August and September, 1977.
Skiatook
o
vO
\D
\D
rsj
.n
CN
o
CN
o
00
o
CO
O -
*—i
o
0 0.01 0.05 0.08 0.12 0.15 0.17
Ozone Concentration, ppn.
;"i»ure 6.10. Frequency distribution of hourly ozone concentrations, Wynona.
July, August and September, 1977.
123
-------
420
0 0-0.1
C. 12
ignre 6.31
0.05 0,08
Ozone Concentration, ppm.
Frequency distribution of hourly ozor.e concentrations
July, August and September, 19//.
0.17
V<-r fi,
420
00
3D
300
to
CO
vT
CT\
O
150
120
90
60
30
ignro 6.32.
vO
r-5
14
o
0 3-01 3.05 0.08 0.12 0.17
Ozone Concentration, pp;n.
Frequency distribution of hour.lv ozone concentrations. Oche.Lat
July, August and September, 1977.
124
-------
.ab 1
¦r,
00
01
02
03
0/.
05
06
07
08
09
10
11
12
13
14
1 5
16
17
18
19
20
21
22
23
Va
85
86
86
88
88
86
88
88
83
78
84
85
87
85
86
84
86
86
85
86
85
84
83
83
14. Mean hourly standard deviations and number o
sampling period.
f values by hour of oz
Liberty Mounds
Tulsa Post Office
mean
S,
No. Values
0.016
0.015
0.015
0.014
0.013
0.013
0.014
0.012
0.013
0.015
0.018
0.017
0.016
0.016
0.017
0.016
0.016
0.018
0.019
0.016
0.015
0.015
0.015
0.015
91
91
91
88
61
82
91
91
89
91
90
90
91
93
93
92
91
93
92
91
90
91
92
92
mean ^d No. Values
0.012
0.012
0.012
0.01.1
0.011.
0.010
0.008
0.008
0.013
0.015
0.018
0.020
0.021
0.022
0.020
0.019
0.018
0.020
0.022
0.020
0.017
0.015
0.013
0.013
79
80
80
80
80
70
81
81
81
76
78
78
80
80
81
79
78
76
78
80
78
79
79
79
Tulsa City/County
Health Department
S,
No. Values
0.013
0.012
0.012
0.01 2
0.012
0.012
0.012
0.012
0.013
0.016
0.021
0.022
0.021
0.022
0.020
0.018
0.016
0.017
0.017
0.015
0.0.14
0.014
0.013
0.013
78
77
77
77
77
78
78
79
73
53
76
79
79
81
79
77
78
77
77
77
77
78
79
78
-------
Table 6.14. Mean hourly standard deviations and number of values by hour of ozone for entire
sampling period. (cutidniii'd)
Skiatook Lake
Vera
K
ynona
Ochelata
Hour, CST
mean °d
No. Values
mean No.
Values
mean %
No.
Values
mean sd
No ,
Values
00
0. 017
87
0.013
92
0.016
86
0.012
84
01
0.017
83
0.013
92
0.016
36
0.012
80
02
0.017
87
0.012
91
0.015
84
0.012
84
03
0.017
85
0.012
87
0.014
88
0.01,2
85
04
0.015
85
0.012
92
0.014
88
0.011
84
05
0. (314
83
0.011
92
0.013
88
0.010
83
06
0.014
85
0.011
87
0.013
88
0.010
85
07
0. 012
S3
0.010
92
0.012
87
0. 010
85
08
0.012
83
0,011
87
0.014
81
0.012
71
09
0.012
82
0.013
78
0.014
86
0.013
80
10
0.015
83
0.020
90
0.016
86
0.01 5
86
11
0.015
84
0.02 2.
90
0.018
85
0.016
81
12
0.016
84
0.024
92
0.018
85
0.016
81
13
0.018
83
0.025
92
0.018
85
0.017
85
.14
0.01 7
8 5
0.025
93
0.017
87
0.018
86
15
0.015
83
0.022
91
0.017
86
0.017
84
16
0.016
78
0.019
91
0.0 1.8
8/
0.016
83
17
0.015
83
0.019
85
0.019
86
0.015
79
18
0.017
84
0.018
89
0.018
88
0.014
82
19
0. 016
86
0.016
92
0.017
88
0.013
84
20
0.016
88
0.014
92
o. o : 6
87
0.013
8£
21
0.016
86
0.013
92
0.016
88
0.011
85
22
0.017
88
0.012
93
0.016
88
0.012
84
23
0. 018
88
0.012
92
0.016
87
0.012
8^
-------
Table 6,13. Summary of hourly ozone concentrations >0.08 ppm* July - September, 1977
f-o
Liberty Mounds
Tulsa Post Office
Tulsa City/County
Health Department
Sperry
Sklatook Lake
Vera
Wynon.i
Orhe] ,*ita
Number
Hourr,
29
19
25
44
10
115
71
34
July
August
Total Percent
Number Hours
Hours >0,08
72!
4 74
5 24
597
592
710
575
561
4.0
4.0
4.8
7.4
1.7
16.2
12.4
6.1
Number Total Percent
Hours Number Hours
>0.08 Himrs >0.08
62
10
25
4?
40
33
52
31
716
7 39
698
740
660
720
741
704
8.7
1.4
3.6
5.7
6.1
4.6
7.0
4.4
Septepiber
Number Total Percent
Hours Number Hours
>0.08 Hours >0.08
3
1
8
11
6
22
3
28
691
67 7
617
699
714
713
718
713
0.4
0.1
J .3
1.6
0.8
3.1
0.4
3.9
Three Month IVrfoil
Number Total PprronC
Hours Number Hour?
>0.08 Hours "0.08
94
30
38
97
56
1 70
126
93
2128 4.4
1890 1.6
18 1"
2036
1966
2143
2034
1973
3.2
4.8
2.8
7.?
6. 2
4.7
-------
~ Tulsa City/County Heal th Department,
O Tulsa Post Office
® Liberty Mounds
0.08
0.06
0. 04
0.03
0.02
0.01
06 08 10 12 14 16 18 20 22 00 02 04
Hour (CST)
Figure 6.11. Mp;?n diurnal ozone concentrations at Liberty Mounds, Tulsa City/County
Health Department and Tulsa Post Office (July + August. + September, 1977 ).
-------
~ Wynona
O Skiatook Lake
• Sperry
J I L
J I L
J I L
J I L
06 08
10 12
14
16 18
Hour (CST)
20
22
00 02
04
Figure 6.34. Mean diurnal ozone concentration at Sperry, Skiatook Lake, and
Wynona (July + August + September, 1977).
-------
0.08
0.07
0.06
0.05
e
CL
CL
J 0.04
c
o
0.03
0.0?
0.01
0
~ Ochelata
O Vera
® Sperry
J I I 1 I i I J till L_J I 1 I 1 I I I I I 1
06 08 10 12 l/» 16 18 20 22 00 02 0^
Hour (CST)
Figure 6.35. Mean diurnal ozone concentration at Sperry, Vera, and Ochelata
(July + August + September, 1977).
-------
6.3 OXIDES OF NITROGEN AND HYDROCARBON DATA SUMMARIES
6-3.1 Mean 0600 to 0900 CDT Concentrations of NO and NMHC
x
The 0600 to 0900 local time (CDT) is of interest to air pollution
modelers and strategists. Average concentrations of NO (the sum of NO and
NO2) for this 3-hr period and the overall averages by month and for the
total period were computed. The pollutant parameter NMHC (as measured by
•-he Beckirian air quality chromatograph and as measured by summing the concen-
trations of individual hydrocarbon species) was also calculated for the same
time period. These values are shown in Table 6.16. The reader should note
that the data for NO, NO2, and NMHC (Beckinan) tabulated in Volume II of the
report are shown in central standard time (CST); the time frame 0600 to 0900
CDT corresponds to 0500 to 0800 CST.
6.3.2 Mean Hourly Standard Deviations for N02 and NMHC
Hourly means of nitrogen dioxide concentration and hourly standard
deviations, and the number of values are listed in Table 6.17 for all sites.
Average concentrations of NO2 at sites south or north of Tulsa are at or
near the minimum detectable limit for the analyzers used in this study.
Table 6.18 lists the same information for NMHC as recorded by the continual
Beckman 6800 chromatograph. NMHC concentrations were measured at the Wynona,
Tulsa Post Office, and Tulsa Health Department sites.
6.3.3 Mean Daily 0600 to 0900 CDT NMHC/N0_ Ratios
Mean daily 0600 to 0900 CDT NMHC/NO^ ratios for the three sites where
hydrocarbon species samples were collected and the three sites where NMHC
was measured by automated chromatograph are given in Table 6.19. The median,
maximum, and minimum ratios are also listed.
Values of NMHC/NO^ ratios (as determined using the automated chromato-
graph) are given for each day in Tables 6.20, 6.21, and 6.22 for the Post
Office site, the Health Department site, and the Wynona site, respectively.
Values of NMHC/NO ratios (as determined by summing individual hydro-
carbon species concentrations) are given in Tables 6.23, 6.24, and 6.25 for
the Liberty Mounds, Tulsa Post Office, and Tulsa Health Department sites.
131
-------
Table 6.16. Mean 0600 to 0900 CDT NO and NMHC concentrations
by month and entire period
Julv
August
September
Total
period
NO
Liberty Mounds
Tulsa Post Office
Tulsa City/County
Health Department
Sperry
Skiatook Lake
Vera
Wynona
Ochelata
0.009
0.065
0.019
0.016
0.005
0.006
0.006
0.011
0.006
0.073
0.028
0.016
0.005
0.012
0.006
0.007
0.005
0.055
0.034
0.020
0.004
0.012
0.004
0.005
0.007
0.065
0.027
0.017
0.005
0.011
0.005
0.007
Tulsa City/County
Health Department
Tulsa Post Office
Wynona
0. 138
0.471
NMHC, ppmC (Beckman)
0.176
0.703
0.230
0.348
0.571
0.231
0.607
0.530
NMHC, ppmC (species summation)
Liberty Mounds
(less ethylene)
Tulsa Post Office
Tulsa City/County
Health Department
0.248
0.430
0.257
0.231
0.681
0.407
0.209
0.437
0.268
0.228
0.534
0.317
132
-------
Tab
x, (
00
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
i do
Va
85
85
84
84
84
85
85
84
83
73
81
85
83
86
85
85
85
84
85
83
83
84
.17. Hourly mean, X, hourly standard deviation, c, and number of hours
p p in
Liberty Mounds
X C No. Values
0.004
0,005
88
0.004
0.005
88
0.004
0.004
88
0.004
0.004
86
0.003
0.004
65
0.005
0.005
88
0.006
0.005
90
0.005
0.004
90
0.004
0.003
84
0.004
0.004
87
0.004
0.004
88
0.004
0.004
88
0.004
0.004
90
0.003
0.003
88
0.004
0. 004
88
0.003
0.003
89
0.003
0.003
89
0.003
0.003
89
0.004
0.004
88
0.005
0.004
88
0.005
0.004
89
0.005
0.005
89
0.005
0.005
90
0.004
0.004
90
Tulsa Post Office
X a No. Values
0.025 0.013 76
0.024 0,011 76
0.023 0.014 75
0.021 0.011 75
0.020 0.011 66
0.025 0.010 77
0.029 0.010 79
0.032 0,012 79
0.031 0.012 72
0.031 0.013 78
0.031 0.014 77
0.030 0.015 78
0.026 0.013 78
0.026 0.013 79
0.027 0.015 78
0.029 0.016 77
0.029 0.016 77
0.029 0.017 76
0.028 0,016 76
0.028 0.015 77
0.028 0.013 77
0.029 0.013 77
0.028 0.013 76
0.025 0.012 77
Tulsa City/County
Health Department
X 0 No. Values
0.011 0,010 84
0.009 0.008 84
0.007 0.006 84
0.007 0.007 84
0.008 0.007 85
0.012 0.008 83
0.019 0.010 81
0.020 0.011 80
0.017 0.011 77
0.013 0.009 55
0.012 0.007 77
0.011 0.006 81
0.011 0.006 82
0.010 0.006 82
0.011 0.006 84
0.012 0.007 82
0.014 0.008 81
0.015 0.009 81
0.019 0.010 82
0.023 0.013 82
0.024 0.014 83
0.021 0.013 81
0.017 0.012 83
0.014 0,011 83
-------
Tab 1 6,17. Hourly mean, X, hourly standard deviation, a, and number of hours for nitrogen dioxide,
ppm (continued)
Skiatuok Lake Vera Wynona Ochelata
Hour:, CST
X
Q
'Z,
o
Values
X
a No.
Values
X
O
z
D
Values
X
C
s:
o
Values
00
0.005
0.003
89
0.008
0
004
84
0
004
0.004
83
0
006
0.003
84
01
0.005
0.003
84
0.007
0
004
84
0
004
0.003
84
0
006
0.003
79
02
0. 005
0.003
88
0.007
0
003
81
0
004
0.003
79
0
006
0.003
83
03
0.005
0.003
88
0.001
0
003
79
0
004
0.003
85
0
006
0.003
84
04
0.004
0.003
38
0.007
0
003
85
0
004
0.003
85
0
006
0.003
84
05
0.005
0.003
85
0.008
0
003
85
0
005
0.003
85
0
006
0.003
84
06
0.005
0.003
89
0.008
0
00 3
80
0
005
0.003
85
0
005
0.003
85
07
0.005
0.004
79
0.008
0
003
83
0
004
0.002
83
0
006
0.002
84
08
0.005
0,003
84
0.008
0
004
81
0
004
0.003
75
0
006
0.003
68
09
0.005
0.004
84
0.008
0
004
70
0
004
0.002
75
0
005
0.003
7 6
10
0.004
0,003
83
0.007
0
00A
80
0
004
0.003
83
0
005
0.002
83
11
0.004
0.003
85
0.006
0
003
80
0
003
0.003
83
0
004
0.002
79
12
0.003
0.002
84
0.006
0
003
83
0
003
0.003
81
0
004
0.002
76
13
0.003
0. 003
83
0.006
0
003
84
0
003
0.003
84
0
004
0.002
82
14
0.003
0.003
84
0.005
0
003
85
0
003
0.002
84
0
004
0.002
81
15
0.003
0.002
80
0.006
0
003
84
0
003
0.002
83
0
004
0.002
81
16
0.003
0.003
75
0.006
0
003
83
0
003
0.002
83
0
004
0.002
80
17
0.004
0,003
79
0.006
0
003
77
0
003
0.003
8 5
0
004
0.002
79
18
0.004
0.004
86
0.007
0
004
79
0
003
0.003
84
0
006
0.003
79
19
0.005
0.003
88
0.007
0
004
83
0
004
0.004
83
0
006
0.003
81
20
0.005
0.003
89
0.008
0
003
86
0
004
0.004
82
0
006
0.003
82
21
0.005
0.003
89
0.008
0
003
86
0
004
0.003
84
0
007
0.003
83
22
0.005
0.003
89
0,008
0
004
86
0
004
0.003
84
0
007
0,003
82
23
0.005
0.003
89
0.008
0
004
85
0
004
0.004
84
0
007
0.004
82
-------
_JL
oo
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
-18, Hourly mean, X, hourly standard deviation, O, and number of Injurs fur nnmru-M'hane hydro-
carbons, ppmC (Beckman 6800 data)
Tulsa City/County
Wynona Tulsa Post Office Health Department
X
a
No. Values
X
a
No. Values
X
a
No. Values
0. 434
0.415
26
0.302
0
.204
39
0.127
0.159
51
0.405
0.291
26
0. 337
0
283
39
0.121
0.164
50
0.460
0.404
26
0. 345
0
359
39
0.129
0.233
48
0.483
0.427
26
0. 373
0
338
38
0.132
0.201
48
0.490
0.435
25
0.460
0
371
22
0.151
0.223
48
0.593
0.572
25
0.562
0
766
39
0.154
0.171
50
0. 589
0.626
25
0.625
0
442
41
0.249
0.340
50
0. 398
0.346
26
0.639
0
378
41
0.286
0.297
52
0.225
0.082
26
0. 579
0
429
41
0.210
0.226
50
0.227
0.086
26
0.545
0
412
43
0.160
0.166
45
0.195
0.059
25
0.427
0
203
43
0.154
0.221
42
0.189
0.063
26
0.436
0
250
42
0.128
0.162
49
0.194
0.086
21
0.378
0
192
42
0.137
0.129
51
0.173
0.068
23
0.462
0
382
42
0.126
0.123
53
0.165
0.072
23
0. 504
0
522
41
0.152
0.136
52
0.156
0.060
23
0.422
0
272
41
0.174
0.139
50
0.147
0.050
24
0. 353
0
165
39
0.224
0.212
50
0.175
0.067
24
0. 323
0
267
40
0.271
0.393
50
0.230
0.098
24
0. 309
0
185
41
0.337
0.338
50
0. 352
0.359
24
0.397
0
510
41
0.370
0.323
51
0.351
0.283
24
0.334
0
215
41
0.367
0.439
51
0. 351
0.208
23
0.354
0
245
40
0.300
0.392
52
0.438
0.470
24
0.403
0.
498
39
0.181
0.214
52
0.411
0.359
26
0.326
0.
239
39
0.175
0. 31 7
50
-------
Table 6.19. Mean daily 0600 to 0900 CDT NMHC/NO ratios with standard deviations,
maximum, minimum, and median values
Mean ratio value
NMHC/NO
x
Standard deviation
NMHC/NO ratio
x
Median value of
NMHC/N0x ratios
Maximum ratio value
NMHC/NO
x
Minimum ratio value
NMHC/NO^
August
Mean ratio value
NMHC/NO
Standard deviation
NMHC/NO ratio
x
Median value of
NMHC/NO ratios
X
Maximum ratio value
NMHC/NO
X
Minimum ratio value
NMHC/NO
Liberty
Mounds
XHC datac
7 cases
33.9
32.4
20.0
103.5
10.2
24 cases
47.2
33.2
35.5
125.0
11.8
Tulsa
Post
Office
1HC data
15 cases
9. 1
4.5
8.2
22.6
4.1
28 cases
13.6
12.0
11.4
64.5
1.8
Tul sa
City/County
Health
Department
IHC data
15 cases
13.3
6.2
10.5
26.9
7.0
25 cases
20.7
23.5
12.8
121 .4
6.9
Tulsa
Post Office
Beckman 6800
Tulsa
City/County
Health
Department
Beckman 6800
17 cases
10.7
5.1
10.8
22.5
2.7
23 cases
13.2
8.7
12.8
31.0
1.7
3 cases
6.9
3.5
6.9
8.9
2.8
25 cases
7.9
5.9
6.1
24.7
0.9
Wynona
Beckman 6800
0 cases
0 cases
See footnote at end of table.
(continued)
-------
Table 6,19 (continued)
September
Mean ratio value
NMHC/NOx
Standard deviation
NMHC/NO ratios
Median value of
NMHC/NO^ ratios
Maximum ratio value
NMHC/NO^.
Minimum ratio value
NMHC/NO
x
Total Period
Mean ratio value
NMHC/NO
x
Standard deviation
NMHC/NO ratio
Median value of
NMHC/NO ratios
x
Maximum ratio value
NMHC/NO
x
Minimum ratio value
NMHC/NO
Liberty
Mounds_
IHC datac
Tulsa
Post
Office
IHC data
46.2
30.1
35.9
120.0
8.1
53 cases
45.0
31.5
34.4
125.0
8.1
9.2
3.3
9.2
16.2
10.9
>. 3
9.5
64.5
l.i
Tulsa
City/County
Health
Department
IHC data
22 rases 27 cases 27 cases
9.3
7.1
33.0
2.6 4.0
70 cases 67 cases
14.4
15.7
10.5
121.4
4.0
Tulsa
Post Office
Beckman 6800
0 cases
40 cases
12.1
7.4
11.4
31.0
1.7
Tulsa
City/County
Health
Department
Beckman 6800
16 cases
10.2
5.4
9.0
26.7
1.3
44 cases
8.7
5.7
8.4
26.7
0.9
Wynona
Beckman 6800
18 cases
155.2
85.9
153.3
352.0
47.5
19 cases
169.1
99.9
159.2
380.0
47.5
3Less ethylene.
-------
Table 6.20. Daily 0600-0900 CDT average NMHC (Beckraan 6800 gas
chromatograph) and NO , and ratio of NMHC to NO . Tulsa
Post Office
Average Average
N'MHC
6-9 CDT
NMHC
NMliC
6-9 CDT
NMHC
Date
ppnC
N0X , Dpi!!
N0X
Date
ppmC
NOx,ppm
N0X
7/15
0.
570
0.053
10.8
8/06
0.250
0.149
1.7
16
0
520
0.047
11.1
07
0. 380
0.209
1.8
17
0
130
0.027
4.8
08
0.600
0.192
3.1
18
0
650
0.045
14.4
09
0.690
0.137
5.0
19
0
580
0.051
11.4
10
0.810
—
-
20
0
560
0.038
14.7
11
0.470
0.030
15.7
21
0
360
0.073
4.9
12
0.320
0.025
12.8
22
0
340
0.027
12.6
13
0.350
0.042
8.3
23
0
620
0.036
] 7.2
14
0.330
0.0.12
27.5
24
0
350
0.128
2.7
15
0.940
0.074
12.7
25
0
870
0.090
9.7
16
_
0.102
—
26
0
530
O.C40
13. 3
17
—
0.027
-
27
0
280
0.026
10.8
13
0.740
3.052
14.2
28
0
360
0.016
22.5
19
0.710
0.047
15.1
29
0
540
0.068
7.9
20
0.530
0.037
14.3
30
0
540
0.150
3.6
21
0.833
0.029
28.6
31
0
200
0.023
8. 7
22
3.110
0.128
24.3
8/01
0
980
0.088
11.1
23
0.720
0.033
21.8
02
1
110
0.075
14.8
24
0.470
0.036
13.1
03
0
900
0.071
12.7
25
0.620
0.020
31.0
04
0
380
0.071
5.4
26
0.430
0.056
7.7
05
—
0.068
"—
27
C.200
0.116
1.7
138
-------
Table 6.21. Daily 0600-0900 CDT average NMHC (Beckman 6800 gas
chronatograph) and NO , arid ratio of NMHC to NO^. Tulsa
City/County Health Department
Averagp
Average
V,T* *1 {c
6-9 CDT
NMKC
NMHC
6-9 CDT
NMHC
Date
ppraC
N0V,ppro
NO,
Date
ppmC
NO^.ppn
N0X
7/25
0.050
0,018
2.8
8/26
0.030
0.014
2.1
26
-
0.029
—
27
0.0
0.005
—
2 7
-
0.041
—
28
0.0
0.003
—
28
0.160
0.018
8.9
29
0.070
0.026
2.7
29
0.340
0.038
8.9
10
0.190
0.025
7.6
30
0.0
0.018
—
31
0.130
0.011
11.8
31
—
0.026
—
8/01
—
0.078
—
9/01
0.260
0.040
6.5
02
0.800
0.055
14,5
02
0.420
0.055
7.6
03
0.080
0.028
2.9
03
0.320
0.040
8.0
04
0.620
0.047
13.2
04
0.120
0.009
13.3
05
0.240
0.026
9.2
05
0.110
0.012
9.2
06
0.150
0.010
15.0
06
0.420
0.039
10.8
07
0.050
0.005
10.0
07
0.450
0.050
9.0
08
0.170
0.010
17.0
08
0.780
0.073
10.7
09
0.130
0.014
9.3
09
0.430
0.027
15,9
10
0.220
0.018
12.2
10
0,260
0.026
10.0
11
0.270
0.027
10.0
11
0.160
0.006
26.7
12
0.060
—
—
12
0.210
0.024
8.7;
13
0.010
0.011
0.9
13
—
0.021
—
14
0.010
0,009
1.1
14
—
0.017
—
15
0.190
0.037
5.1
15
—
0.030
—
16
0. 040
0.011
3.6
16
0.650
0.098
6.6
17
0.150
0.024
6.3
17
0.010
0.008
1.3
18
0. 360
0.061
5.9
18
0.0
0.014
—
19
0.110
0.036
3.1
19
0.120
0.011
10.9
20
0.100
0.025
4.0
20
1.190
0.149
8.0
21
0.060
0.018
3. 3
2?
0.790
0.032
24.7
23
—
0.026
—
24
0.070
0.038
1.8
25
0.0
0.012
139
-------
Table 6.22. Daily 0600-09C0 CDT average NMHC (Beckman 6800 gas
chromatograph) and NO , and ratio of NMHC to NO . Vynona
Average
Average
NMHC
6-9 CDT
NMHC
NMHC
6-9 CDT
NMHC
Date
ppmC
N0V,ppm
" N0X
Datp.
ppmc.
N0vppm
" \'0V
8/29
0. 140
0.0
9/1 1
0. 290
0.006
48.3
30
o
00
o
0.001
380.0
12
0.150
0.0
-
31
0.170
0.0
—
13
0. 330
0.002
165.0
9/C1
0. 120
0.0
-
14
0.140
0.002
70.0
02
1.060
0.004
265.0
15
0.260
0.005
52.0
03
1.6 30
0.006
271 . 7
16
0.460
0.003
153.3
04
1. 340
0.008
167.5
17
0.150
0.0
-
05
0.150
0.0
—
18
0.200
0.003
66.7
06
0. 370
0.003
123.3
19
-
0.0
-
07
0.680
0.00 3
226. 7
20
1. 340
0.007
191.4
08
1. 760
0.005
352.0
21
0.260
0.002
130.0
09
0.900
0.005
180.0
22
0.410
0.004
102.5
.10
0.190
0.004
47.5
23
0.360
0.002
180.0
140
-------
Table 6.23.
0600-0900 CDT average NMHC (sum of individual hydro-
carbon species less ethylene) and N0X, and ratio of NMHC
Liberty Hounds
to NO,
Average
>:nmhg
6-S CDT
ENMHC
Date
ppmC
N0X,ppm
N0X
7/14
—
0.019
__
15
—
0.011
16
—
0.011
17
—
0.008
18
—
0.014
19
0.144
0.014
10.2
20
0.117
0.008
14.6
21
0.240
0.012
20.0
22
G.536
0.018
29.8
23
0. 327
0.008
40.9
Date
ENMHC
ppmC
Average
6-9 CDT
N0X> ppm
8/22
23
24
25
26
27
28
29
30
31
1.042
0.136
0.215
0.125
0.125
0.052
0.088
0.065
0.103
0.154
24
—
0.007
—
9/01
0.314
0
000
25
—
0.007
—
02
0.303
0
010
30.3
26
—
0.005
—
03
0.620
0
018
34.4
27
—
0.010
—
04
—
28
—
0.005
—
05
0.044
0
002
22.0
29
—
0.015
—
06
0.528
0
008
66.0
30
0.162
0.009
18.0
07
0.229
0
007
32. 7
31
0.207
0.002
103.5
08
C.596
0
020
29.8
8/01
—
—
—
09
0.160
0
009
17.8
02
0.424
0.012
35.3
10
0.065
0
008
8.1
03
0.209
0.017
12.3
11
0.120
0
001
120.0
04
0.097
0.008
12.1
12
0.106
0
002
53.0
05
—
0.004
—
13
0.095
0
002
47.5
06
—
—
—
14
0.129
0
000
—
07
0.077
0.003
25.7
15
0.081
0
000
—
08
0. 323
0.007
46.1
16
0.171
0
006
28.5
09
0.223
0.006
31.2
17
0.125
0
003
41. 7
10
0.216
0.015
14.4
18
0.068
0
003
22.7
11
0.228
0.007
32.3
19
0.149
0.
014
10.6
12
0.130
0.011
11.8
20
0.455
0
015
30.3
13
0.181
0.006
30.2
21
0.225
0
003
75.0
14
—
0.005
—
22
0.204
0
002
102.0
15
0.343
0,003
114.3
23
—
0
003
—
16
—
—
—
24
0.159
0
000
—
17
0.214
0.006
35.7
25
0.121
0
003
40.3
18
0.225
0.002
112.5
26
0.279
0
003
93.0
19
0.233
0.003
77.7
27
0.148
0
002
74.0
20
—
0.005
—
28
0.083
0
000
—
21
0.541
0.008
67.6
29
0.075
0
002
37.5
30
—
0
002
—
021
003
000
001
002
003
002
002
005
002
ENMHC
" n o~J"
49.6
45.3
125.0
62.5
17.3
44.0
32.5
20.6
77.0
141
-------
Table 6.2/4. 0600-C900 CDT average NMHCI (sum of i nri i vi riual hydro
carbon species) and N0X, and ratio of NMIIC to N0X.
Tulsa Post Office
Date
ZNMHC
mmC
Average
6-9 CDT
NOx,ppm
ENMHC
N0X
Date
ZNMHC
ppmC
Average
6-9 CDT
N0x,ppm
ENMHC
N0X
7/ 14
0.531
0.
077
6.9
8/22
3.684
0
128
28.7
15
0.392
0.
053
7.4
23
0.478
0
033
.14.5
16
0. 331
0
047
7.0
24
0.592
0
036
16.4
17
—
0
027
—
25
0.431
0
020
21.6
18
—
0
045
—
26
0.565
0
056
10.1
19
—
0
051
—
27
0.204
0
116
1.8
20
0.310
0
038
8.2
28
0.224
0
108
2.1
21
0.327
0
073
4.5
29
0.367
0
032
11.5
22
0.298
0
027
11.0
30
0.329
0
029
11.3
23
0.421
0
036
11. 7
31
0.571
0
105
5.4
24
0.528
0
128
4.1
9/01
0.348
0
037
9.4
25
0.687
0
090
7.6
02
0.640
0
063
10.2
26
0.364
0
040
9.1
03
0.367
0
031
11.8
27
0.288
0
026
11.1
04
0.175
0
018
9.7
28
0. 362
0
016
22.6
05
0.131
0
012
10.9
29
0.567
0
068
8.3
06
0.519
0
037
14.0
30
0.771
0
150
5.1
07
0.493
0
059
8.4
31
0.2 76
0
023
11.9
08
0.819
0
085
9.6
8/01
0.794
0
OSS
9.0
09
0.808
_
02
0.857
0
075
11.4
10
0.187
0
025
7.5
03
0.852
0
071
12.0
11
0.150
0
011
13.6
04
0.528
0
071
7.4
12
0.348
0
054
6.4
05
—
0
058
—
13
0.462
0
054
8.6
06
—
0
149
—
14
0.154
0
020
7.7
07
0.531
0
209
2.5
15
0.358
0
057
6.3
08
0.719
0
192
3.7
16
0.870
0
095
9.2
09
0.487
0
137
3.6
17
0.225
0
085
2.6
10
0.584
-
—
18
—
0
136
—
11
0.448
3
030
14.9
19
0.282
0
038
7.4
12
0.435
0
025
17.4
20
1.298
0
203
6.4
13
0.332
0
04 2
7.9
21
0.289
0
071
4.1
14
0. 774
0
012
64.5
22
0.508
0
035
14.5
15
1.065
0
074
14.4
23
0.393
0
089
4.4
16
1.161
0
102
11.4
24
0.172
0
021
8.2
17
0.404
0
027
15.0
25
0.390
0
030
13.0
18
0.535
0
052
10.3
26
0.653
0
082
8.0
19
0.507
0
047
10.8
27
0.300
0
032
9.4
20
0.536
0
037
14.5
28
0.278
0
025
11.1
21
0.767
0
029
26.4
29
0.614
0.
038
16.2
30
-
142
-------
Table 6.25. 0600-0900 CDT average NMHC (sum of individual hydro-
carbon species) and N0X, and ratio of NMHC to N0X.
Tulsa City/County Health Department
Average
Average
XNMHC
6-9 CDT
ENMHC
ENMHC
6-9 CDT
KNMHC
Date
ppmC
NO-y, ppm
N0X
Date
ppraC
NOx,ppm
NOx
7/14
0.234
0.029
8.1
8/22
1.127
0.132
8.5
15
0.242
0.013
18.6
23
-
0.026
-
16
-
0.012
-
24
0.425
0.038
11.2
17
0.215
0.008
26.9
25
1.457
0.012
121.4
18
-
0.026
-
26
0.389
0.014
27.8
19
0.279
-
-
27
0.163
0.005
32.6
20
0.294
0.012
24.5
28
-
0.003
-
21
0.239
0.019
12.6
29
0.332
0.026
12.8
22
0.251
0.031
8.1
30
0.222
0.025
8.9
23
0.335
0.032
10.5
31
0.136
0.011
12.4
24
0.176
0.009
19.6
9/01
0.217
0.040
5.4
25
0.270
0.018
15.0
02
0.393
0.055
7.1
26
0.242
0.029
8.3
03
0.285
0.040
7.1
27
0.289
0.041
7.0
04
-
0.009
28
0.173
0.018
9.6
05
0.140
0.012
11.7
29
0.397
0.038
10.4
06
0.1.94
0.039
5.0
30
0.179
0.018
9.9
07
0.288
0.050
5.8
31
0.289
0.026
11.1
08
0.519
0.073
7.1
3/01
0.537
0.078
6.9
09
0.290
0.027
10.7
02
0.559
0.055
10.2
10
0.103
0.026
4.0
03
0.343
0.028
12.2
11
-
0.006
-
04
0.396
0.047
8.4
12
0.163
0.024
6.8
05
0.223
0.026
8.6
13
0.255
0.021
12.1
06
-
0.010
-
14
0.117
0.017
6.9
07
0.270
0.005
54.0
15
0.283
0.030
9.4
03
0.010
-
16
0.566
0.098
5.8
09
0.193
0.014
13.8
17
0.105
0.008
13.1
10
0.477
0.018
26.5
18
0.069
0.014
4.9
11
0.330
0.027
12.2
19
0.154
0.011
14.0
12
-
-
-
20
0.885
0.149
5.9
.13
0.158
0.011
14.4
21
0.166
0.019
8.7
14
0.141
0.009
15.7
22
0.274
0.034
8.1
15
0.421
0.037
11.4
23
0.205
0.014
14.6
16
0.281
0.011
25. 5
24
0.228
0.022
10.4
17
0.309
0.024
12.9
25
0.165
0.005
33.0
18
0.444
0.061
7.3
26
0.516
0.078
6.6
19
-
0.036
-
27
0.100
0.016
6.2
20
0.368
0.025
14.7
28
0.122
0.025
4.9
21
0.476
0.018
26.4
2 9
0.44/
0.029
15.4
30
—
—
U3
-------
6.3.4 Diurnal Plots oj^Jlean Hourly THC, CII4 and NMHC Values
Mean diurnal patterns for total hydrocarbon measurements are shown in
Figure 6.36. Similar patterns for methane and nonmethane hydrocarbons are
shown in Figures 6.37 and 6.38.
6.4 METEOROLOGICAL DA'IA SUMMARIES
6.4.1 Tabulated Frequency of Wind Directions
Table 6.26 shows the tabulated case count and percentage of time the
wind direction is from successive 10° compass increments for the four sites
that monitored this parameter. The case count of calms (expressed as 0° for
wind speeds less than 1 mph) is also listed.
Tables 6.27, 6.28, 6.29, and 6.30 give similar information for 30°
increments of wind direction for the entire 3~month period.
6.4.2 Tabulated Frequency of Wind Speed
Hourly frequencies of wind speed for the 3-month period are given in
Tables 6.31, 6.32, 6.33, and 6.34. The increments of wind speed values (in
miles per hour) include a 0.0 to 0.9-mph range (i.e., calm periods) and
successive 5-mph increments
6.4.3 Precipitation and Maximum Temperatures
Daily maximum temperatures (°F) and 24-hr total precipitation (inches
water) for Tulsa are illustrated for the months of July, August, and Septem-
ber 1977 in Figures 6.39, 6.40, and 6.41.
6.5 INDIVIDUAL HYDROCARBON SPECIES DATA SUMMARY
Hydrocarbon samples were primarily collected at three site, Liberty
Mounds, Tulsa Health Department and Tulsa Post Office, during the 0600 to
0900 CDT period. Additional collections were made at other sites during the
period of airborne sampling. Table 3.3 summarizes the number of samples
taken at each site as well as the nurtber of samples successfully analyzed
for all species sought. Explanations of unsuccessful analyses are listed m
Volume II with the data printouts.
Average values, ppbC, for the 0600 to 0900 CDT time frame collection
for three sites are given in Table 6.35 for alkanes and Table 6.36 for
alkene, alkyne, and aromatic compounds.
144
-------
LOO
~ Wynona (August 29-September 22)
OTulsa Post Office (July 28-August 26)
#Tulsa City/County Health Department
(.July 28-Septenber 20)
2. 70
2.55
2.40
2.10
1 .95
1.80
i i i i i i i
j i i
00
06
22
Time (CST)
Figure 6.36. Mean diurnal r.onrentrations of total hydrocarbons at Wynona, Tulsa
Post Office, and Tulsa City/County Health Department
-------
4 0
30
20
10
00
90
80
70
,60
~ Wynona (August 29-September 22)
OTulsa Post Office (July 28-August 26)
® Tulsa City/County Health Department
(July 28-September 20)
>
06 08 10 12 14 16 18 20 22 00 02 04
Time (CS~)
Figure 6.37. Mean diurnal concentrations of methane at Wynona, Tulsa Post Office,
and Tulsa City/Countv Health Department
-------
0.66
y 0.60
r3
£ 0'45
Q)
U
P
O
u
0. 30
0.15
0.12
0.09
0.06
0.03
~ Wynona (August 29-September 22)
O Tulsa Post Office (July 28-August 26)
0 Tulsa City/County Health Department
J I I I I
J I
06
08
10
12
Ih
16
Time
20
22
00
02
04
Figure 6.38.
18
(CST)
Mean diurnal concentration of nonraeth^ne hydrocarbons at Wynona, Tulsa
Post Office, and "Tulsa City/County Health Department
-------
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
Table 6,26. Wind direction; tabulation frequency by
10° of direction increment for entire study period
Liberty
Mounds
Cases %
131
6,6
41
2.2
51
2.7
52 "
2.8
47
2.5
48
2.6
55
3.0
52
2.8
29
1.6
46
2.5
30
1.6
19
1.0
33
1.8
23
1.2
32
1.7
80
4.3
73
3.9
101
5.4
277
14.9
123
6.6
105
5.6
179
9.6
72
3.9
58
3.1
57
3.1
23
1.2
10
0.5
30
1.6
9
0.5
5
0.3
17
0.9
6
0.3
10
0.5
12
0.6
17
0.9
15
0.8
24
1.3
1992
1861
Health
Department Wvnona Ocnclata
Cases % Cases % Cases %
4
0
0
84
4
z.
236
11
4
16
0
8
89
4
6
42
2
3
18
0
9
69
3
6
81
4
4
37
1
8
79
4
1
76
4
1
68
3
3
39
2
0
65
3
5
48
2
3
55
2
9
57
3
1
50
2
4
62
3
2
18
1
0
16
0
8
30
1
6
28
1
5
22
1
1
25
1
3
32
1
7
68
3
3
44
2
3
24
1
3
30
1
4
36
1
9
24
1
3
10
0
5
40
2
1
20
1
1
20
1
0
28
1
5
10
0
5
83
4
0
30
1
6
17
0
9
51
2
4
66
3
4
26
1
4
50
2
4
81
4
2
22
1
2
101
4
8
163
8
5
36
2
0
137
6
6
198
10
3
57
3
1
587
28
0
275
14
3
128
7
0
205
9
8
99
5
2
343
18
6
126
6
0
110
5
7
387
21
0
54
2
6
27
1
4
94
5
1
49
2
3
18
0
9
28
1
5
15
0
7
20
1
0
15
0
8
10
0
5
23
1
2
15
0
8
9
0
4
11
0
6
6
0
3
8
0
4
7
0
4
14
0
8
31
1
5
17
0
9
10
0
5
3
0
1
5
0
3
11
0
6
5
0
2
8
0
4
7
0
4
1
0
17
0
9
12
0
7
25
1
2
5
0
3
11
0
6
5
0
2
9
0
5
18
1
0
1
0
22
1
1
21
1
1
2
0
1
39
2
0
21
1
1
4
0
2
66
3
4
25
1
4
126
6
0
6
0
3
30
1
6
2095
2002
2067
2091
1918
1831
148
-------
Table 6.27. Hourly frequencies of calms and wind direction by 30° increments for July-September,
1.977. 1/i.nerty Mounds
CST Cases Calms 10-30° 40-6D" 70-90" 1.00-120" 130-150° !<>(>•• ml" 190-210" 220-240" 250-270" 280-300° 300 3.10" 140-360"
Less
% A11
...
.. .. ..
"
... ..
....
"
A11
On I ii's
No.
C.-;S?S
No._
%
No.
7,
No.
X
No.
Z
No.
Z
No,
%
No.
7,
No,
%
No.
%
No
7.
No.
2
Ni.
00
S3
7 J
10
12.0
6
8. 2
7
9.6
3
4.1
1
1 .4
6
8.2
2 5
34 . 2
16
21.9
3
4,1
1
1.4
0
0.0
1
1 .4
3
5
0!
8 3
71
12
14.5
9
12.?
3
4.2
3
4.2
1
1 .4
h
8.4
19
26.8
21
29.6
2
2,8
4
5,6
0
0.0
I
1 .4
2
2
a
02
83
69
14
16.9
6
8.7
6
8.7
2
2.9
3
4.3
4
5.8
21
30.4
14
20.1
R
11.6
2
2.9
0
0.0
2
2.9
1
4
03
R3
72
11
1.3.2
8
11.1
3
4.2
3
4.2
4
5.5
5
6.9
1 i
2j.fi
15
20.8
1 1
1 5. 3
2
2.8
2
2.8
2
2,8
0
0
0
04
8 3
76
7
8.4
10
13.2
5
6.6
5
6.6
3
3.9
4
5.3
15
19.7
11
14.5
14
10.4
1
1 . 3
5
6.6
2
2.6
1
S
05
S3
71
12
14.5
8
11. 3
1
1 .4
7
9.9
2
2.S
5
7.0
16
22. 5
1 1
35.5
9
12.7
5
7.0
1
1 .4
1
1
)
II
06
83
?i
12
1.4.5
7
9.9
4
5.6
3
7.0
2
2.8
5
7.0
14
19.7
14
19. 7
7
9.9
3
4,2
4
5. ft
}
4.2
3
4
0 7
H3
71
1 2
14. 5
8
11.3
6
8.4
4
5.6
7
9.9
'«
5.6
14
19.7
1 3
18.3
7
9.9
2
2.8
2
2.8
2
2.8
2
2
8
08
82
72
11.
1 3.4
8
11.1
5
6.9
5
6.9
2
2.8
6.9
I 7
2 3.6
18
25.0
7
9.7
1
1,4
1
1.4
1
1 .4
1
)
4
09
83
79
4
4.8
6
7.6
9
11.4
4
5.1
8
ID. 1
5
6.3
] 2
15.2
16
20.3
14
17.7
1
1 . 3
1
1.3
0
0.1)
3
3
8
10
82
80
7.
2.4
6
7. 5
10
12.5
7
8.7
4
5.0
7
8.7
12
15.0
17
21,2
) 3
16.2
2
2.5
1
1.2
1
1.2
0
l)
0
11
'32
80
2
2.4
4
5.0
6
7.5
9
11.2
0
0.0
11
13.7
14
17.5
22
27.5
9
11.2
3
3.7
1
1 .2
0
o.;)
1
2
12
fl?
80
2
2.4
3
3.7
7
8.7
3
3.7
4
5.0
6
7.3
16
20.0
23
28.7
10
12.5
5
6.2
0
0.0
0
0.0
3
3
7
I 3
84
83
1
1 . 2
3
3.6
8
9.6
1
1.2
4
4.8
5
6.0
1 5
18. 1
25
2 5.0
12
14.4
4
4.8
1
1 .2
J
1.2
4
4
8
14
84
83
1
1.2
2
2,4
6
7.2
5
6.0
3
3.6
5
6.0
1 3
15. /
28
33. 7
8
9.6
6
7.2
2
2.4
2
2.4
3
3
6
15
84
82
2
2.4
5
6.1
3
3.7
8
9.8
0
0,0
7
8.5
1 7
20. 7
25
30.5
10
12.2
2
2.4
2
2.4
0
0.0
3
3
?
16
84
83
I
1.2
3
3.6
8
9.6
4
4.8
4
4.8
3
3.6
21
2 .4
1"
22.9
9
10.8
5
6.0
2
2.4
0
0.0
4
4
8
17
83
83
0
0.0
6
7.2
5
6.0
9
10,8
6
7.2
3
1.6
21
25.3
21
25.3
6
7.2
3
3.6
2
2.4
0
0.0
1
i
?
1H
84
84
0
0.0
5
5.9
5
5.9
11
13.1
5
5.9
4
4.8
24
28.6
16
19.0
6
7.1
2
2.4
1
1,2
2
2.4
2
2
4
19
83
83
0
0.0
5
6.0
6
7.7
11
) 3. 3
2
2.4
8
9.6
28
33.7
1 3
15.7
4
4.8
0
0.0
2
2.4
2
2.4
2
2
£
20
83
83
0
0.0
5
6.0
10
12.0
6
7.2
6
7.2
6
7.2
26
31 .3
12
14.5
6
7.2
1
1.2
1
1 .2
2
2.4
2
i
4
21
83
81
2
2.4
8
9.9
7
8.6
5
6.7
2
2.5
10
12.3
26
32.1
1 1
13.6
5
6.2
3
3.7
0
0,0
1
1.2
3
3
;
22
83
77
6
7.7
7
9.1
10
12.9
5
6.5
3
3.9
5
6.5
24
31.2
1 3
1.6.9
3
3.9
4
5.2
0
0.0
1
I . 3
2
2
6
23
83
76
7
8.4
6
7.9
10
13.2
2
2.6
5
6.6
7
9.2
23
30. 3
1 3
17.)
4
5.3
1
1 , 3
0
0,0
1
1.3
4
5
3
-------
Table 6.28. Hourly frequencies of calms and wind direction by 30° increments for Tulsa Cizy/
County Public ileal tli Department. July-.Scpte hdpr, 1,9 7 7
Hour
_CST
Cases
Calms
_?0-
30°
40
-6r
70-
_90°_
100;
¦120"
1.30
:1 50_°_
J.60
-180°
190
;2ir
220
•240"
2_50-
270°
280-
300"
30U;
_33U°_
340
360'
1
L a: i
AT 1
No,
Case.*?
No.
_JL
No,
Z
No._
Z
No._
(,
No.
Z
No.
x
No.
_I,
No.
A
No_-.
2
KO_;
X
No .
2
No .
X
00
87
87
0
0.0
0
o.o
10
I}.':
1
1 . 1
4
4
6
10
11.5
28
32.2
24
2 7.6
3
3.4
1
0
0.0
1
1 . 1
r
3.7
01
3/
87
{}
0.0
2
2.1
6
6.9
4
4.r,
4
4
6
8
9.2
27
31.0
25
28. 7
3
),4
1
1
1.1
>
7 . 3
1
4 . 6
oi
8?
86
3.
]. i
1
] .2
7
«. )
4
4.7
4
4
7
8
9.3
22
25.6
28
32.6
5
5.8
1
0
0.0
o
2 . 3
4
4. 7
0 1
8/
87
(5
0.0
I
j . 1
/,
4.6
5
5.7
3
3
4
12
! 3.8
2.1
24.1
25
28, /
8
9,2
0
I
1.1
2
2.3
5
5,7
0'«
67
8 7
0
0,0
5
3.7
2.3
j
3.4
3
3
4
8
9.2
24
27.6
31
35,6
3
3,4
2
0
0.0
2
2 . 3
4
4, 5
OS
87
87
0
0.0
2
2,3
8
9.2
1
3.4
2
2
3
6
6.9
26
29.9
28
32,2
3
3.4
2
2 . 3
1
1.1
1
1 .1
5
5. 7
0f>
sr,
86
0
o.o
5
5.8
9
10. 5
4
4.7
2
7
3
JO
ll.fi
20
2 3.3
29
33.7
4
4 .7
1
1 .2
0
0.0
7
2.3
0
0.0
07
86
86
0
0. o
u
q.7
?
8.1
4
4.7
C
0
0
1.0
11.6
18
20,9
29
33. 7
5
5.8
0
0.0
0
0.0
1
1 .2
8
9,3
08
8 7
87
0
0,0
U 6
6
6.9
5
5. 7
6
6
9
0
9.2
1 7
19.5
31
35.6
4
4 . 6
1
1 .1
1
1.1
0
0.0
l,
4.6
m
88
88
0
0.0
I
I. J
1.0
J1 .4
2
2. 3
2
2
3
9
10.2
14
15.9
29
33.0
14
15.9
2
2.3
1
1.1
0
0.0
3
3.4
io
88
88
0
0.0
i
2.3
10
11.4
6
6.8
)
1
)
5
5.7
1 0
11.4
32
36.4
14
15.9
5
5,7
0
0.0
0
O.o
3
3. 4
j
89
8')
0
0.0
2
2.2
1!
9.0
4
4 . 5
2
2
2
(¦
6.7
9
30.1
29
32.6
I 5
16.9
9
10.1
0
0.0
1
1. i
4
4 . 5
i ;;
HV
89
0
0.0
\
\ 1
3
9.0
3
3.4
4
4
5
3.4
1.9
21.3
26
29. 2
13
14.6
5
5.6
)
1.1
2
2.2
4.5
i ;
89
89
0
0.0
J
1.1
9
10.1
1
3.4
4
4
5
2
2.2
22
24.7
28
31 .5
8
9.0
1
1.1
2
2.2
4 . 5
5
5.6
1
9C
90
0
0.0
1.
i. I
?
10. 1)
4
4 . 4
4
/,
/.
3
3. 3
2fi
31. 1
22
24.4
6
6. 7
4
4 . 4
1
1 . 1
1
1. 1
7
7,8
i
91',
90
0
0.0
2
?.?.
9
10.0
2
2.2
4
4
4
5
3.6
26
28.9
26
2H. 9
5
5.6
2
2.2
0
0.0
2
2 . 2
7
1.8
16
88
88
0
0.0
2
2.3
7
R.I)
2
2.3
1
j
;
12
13.6
20
22.7
26
29. 5
3
3.4
1
1 . 1
1
1.1
2
2.3
1)
12.5
I
87
H7
0
0.0
0
0.0
8
9.2
4
4 . 6
3
3
4
1 2
13.3
21
24 . 1
23
26.4
1
1 . 1
2
2.3
0
0.0
2
2.3
I 1
12.6
} 8
87
87
(:
0.0
0
0,0
U
12. 6
4 .6
0
0
0
1 !
12.6
26
29,9
20
2 3.0
2
2.3
1
1 .1
1
1.1
2
2.3
9
10.3
19
86
80
0
0.0
0
o.o
12
14.0
2
2. 3
0
0
0
13
15.;
31
36.0
1 7
19.8
2
2.3
2
2.3
0
0.0
1
1.2
6
7.0
20
85
8r)
0
0.0
0
0.0
J 3
15.3
3
3.3
0
0
0
15
17.6
31
36 . 3
1
17.6
2
2.4
0
0.0
0
0.0
1
1 .2
5
5.9
sr>
86
0
0.0
0
0.0
12
14.0
!)
5.9
0
0
0
10
11,6
36
4 1.9
14
11. i
2
2.3
1
1 .2
0
0.0
0
0.0
6
7.0
22
86
86
0
0.0
0
0.0
8
9.:)
7
8.1
3
3
5
7
a. i
35
40.7
16
18.6
2
2.3
1
1.2
0
0. 0
0
0.0
7
8.1
2
8h
86
0
o.o
0
o.o
9
10. 5
4
4 . 7
3
3
3
10
1 1.. 6
32
37.2
21
24 .4
1
1.2
0
0.0
0
0.0
1
1.2
5
5.8
-- -
—
—
- _
,
—
^ . -
—
„
,
_
. _
-------
:i;V!r
CST
00
01
02
I)!!
1)6
05
06
07
08
09
10
1J
12
1 3
14
1.5
16
17
ia
19
20
21
22
23
Table 6,29, Hourly frequencies of calms and wind direction by 30° increments for V,'yjion;i, July-
aepteiuber, 1^77
Cases
C.-i
11 ms
10:
40-
;6u:_
/0-
•90"
) 00-
-.170°
.UP:
-150°
1 6.)
-180°
190-
-210"
220
-240"
250-
•27£°
280-
300"
300-
3.10 3
140
;360"
liPSS
T A 1 1
C.'i 1 m<;
N!L:
_ Cases
No.
Z_
No.
X
No.
Ni>.
?.
No.
Z
No.
Z
No._
%
_No_._
/,
No.
X
No.
2
N;>.
7
No .
7.
HA
81
3
3.6
12
14.8
'..9
3
3.7
/,
4.9
3
3.7
.31
38. 3
10
12.3
3
3.7
2
2.5
0
0.0
5
6.2
l>
!'. 9
84
80
4
4.8
12
15.0
7
8. B
3
3.8
3
3.8
1
1.3
28
35.0
12
15.0
2
2.5
J
1 . 3
2
2.5
1
3.H
6
t .
84
77
7
8.3
10
13.0
3
3.9
2
2.6
3
3.9
1
1. 3
28
36.4
14
18.2
3
3.9
1
1 . 3
1
1 . 3
1
3.9
8
10.4
8.'.
7 8
(.
/.I
11
14.1
2
2.6
4
5. !
4
5.1
5
ft. 4
25
32. 1
1 2
15.4
2
2.6
1
1 ,3
1
1. 3
3
3.8
8
10. 1
84
79
5
6.0
JO
12.7
7
8.9
1
1 . 1
4
5 .1
4
5. 1
29
"Hi. 7
12
15.2
0
0.0
0
0.0
2
2.5
1
1 . 3
9
11.4
84
79
5
6.0
12
15.2
3
6.3
6
7.6
3
3.8
6
7.6
25
31.6
<)
11 .4
2
2.5
0
0.0
0
0.0
2
2.5
9
11.4
m
80
4
4.8
13
16.3
9
11 . 3
6
7.5
i,
4.8
5
6.3
27
33.8
6
7.5
1
1 .3
0
0.0
2
2.5
2
2.5
5
6. 3
83
79
4
4.8
13
16.5
5
6.3
6
7.6
3
3.8
5
6.3
26
32.9
12
15.2
1
1 . 3
2
2.5
4
4.8
I
1.3
1
1 . 3
83
30
3
3.6
10
12.5
9
11.3
2
2.5
6
. 5
4
5.0
23
28.8
16
20.0
1
1.3
3
3.6
5
6.3
1
1.3
0
0.0
81
SO
1
1.2
11
13.8
8
10.0
4
5.0
3
3.6
5
6.3
18
22.5
1 5
18.8
10
12.5
2
2.5
2
2. 5
0
0.0
2
2.5
81
31
0
0.0
9
11.1
10
12.3
2
2.5
5
6.2
3
3.7
29
2 3.5
ia
22.2
6
7.4
2
2.5
2
2.5
3
3.7
2
2.5
82
SO
2
2.4
8
10.0
9
11.3
1
1 . J
3
3.6
3
3.6
25
31 . 3
18
22.5
7
8.8
1
1 .3
1
1 . 3
0
0.0
4
5 . U
83
S3
0
0.0
4
4.8
11
13.3
3
3.6
1
2.4
5
6.0
24
28.9
19
22.9
4
4.8
5
6.0
I
1.2
2
2,4
3
3.6
83
SI
2
2.4
6
7.4
6
7.4
7
8.6
2
2.5
5
6.2
2 5
30.9
15
18.5
.5
7/2
4
4.9
1
1.2
I
1.2
4
4.9
83
R1
2
2.4
1
B.6
/
8.6
6
2,4
3
3. /
9
11.1
29
35.8
8
9.9
4
4.9
3
3.7
0
0.0
0
0.0
<;
6. 2
H i
78
.?
6.0
5
6,4
5
6.4
7
9.0
3
3.8
7
9.0
36
46.2
4
5.1
2
2.6
3
3.8
3
3.8
0
0.0
3
3.8
8 4
83
1
1.2
7
8.4
7
8.4
7
8.4
3
3.6
12
14.5
30
36. 1
5
6.0
2
2.4
1
1.2
0
0.0
4
4.8
5
6.0
m
80
4
4.8
9
J1 . 3
9
11.3
5
6. 1
7
8.8
1 3
16.3
26
32.5
4
5.0
1
1 . 3
2
2.5
0
0.0
0
0.0
4
5.0
m
81
3
3.6
J1
J 3.6
5
6.2
6
7.4
.10
12.3
16
,19.8
2 5
30.9
3
3.7
2
2.5
0
0.0
:i
0.0
1
1.2
2
2.5
m
81
3
3.6
8
9.9
7
8.6
6
7.4
8
9.9
16
19.8
25
30.9
2
2.5
1.
1.2
1
1.2
2
2.5
0
0.0
5
6.2
m
80
4
4.8
10
12.5
9
11.3
2
s. 5
10
12.5
16
20.0
23
28,8
4
5.0
0
0.0
I
1.3
0
0.0
1.3
4
5.0
8 4
79
5
6.0
12
15.2
5
6.3
4
5.1
3
3.8
15
19.0
27
34.2
5
6.3
0
0.0
0
0.0
0
0.0
1 . 3
?
8.9
84
79
5
6.0
) 3
16.5
4
5.1
4
5.1.
4
5.1
11
13.9
30
38.0
5
6. 3
2
2.5
0
0.0
0
0.0
1
1.3
5
6.3
8'.
78
6
7.1
14
17.9
3
3.8
2
2.6
4
5.1
7
9.0
32
41.0
8
10. 3
0
0.0
0
0.0
I
1.3
1
.1. 3
6
7.7
-------
Table 6.30. Hourly frequencies of calms and wind direction by 30° increments for Ochelata, July -
September, 1977
. _
-
'
Huur
CST
Case s
Cn
1 ins
-J.P:
40-
-60"
70-
±0°._
100:
•120°
111:
_150°
160-
-180°
190;
-? iq';
220-
:240_'
250-
2B0r
3og;
300-
_310°
340;
:.wr
T A1 !
All.
_Caljw3
No.
Cases
No._
%
No.
%
No_.
No.
%
No,
%
!to._
1..
No
No ,
%
No.
N-'-:-.
X
No.
, ,
No.
X
00
86
66
20
30. 3
9
1 3.6
3
4.5
1
1.5
0
0.0
0
0.0
2
3.0
37
56.0
1.
1.5
3
4 . 5
1
1 .5
2
3.0
7
1C.6
01
86
61
25
40. 9
9
14.8
4
6.6
0
0.0
1
1 .6
0
0.0
2
.3.3
31
50.8
5
8.2
I
1 .6
0
0.0
3
4.9
5
8.2
02
86
66
20
30. 3
1.0
15.2
4
6.1
1
1 . 5
0
0.0
0
0.0
1
1.5
29
43.9
2
3.0
2
3.0
2
3.0
5
7.6
10
15.2
03
86
61
J 5
40. 9
u
21.0
2
3.3
0
0.0
1
1.6
0
0.0
3
4.9
24
39.3
3
4.9
3
4.9
I
1 .6
h
6 . 6
6
9.8
04
86
61
25
40.9
15
24.6
2
3. 3
3
4.9
0
0.0
1
1 .6
5
8.2
21
34 .4
3
4.9
2
3.3
2
3. 3
1
1 .6
6
9.8
05
86
66
20
30. 3
11
16. 7
7
10.6
2
3.0
0
0.0
1
1.5
2
3.0
26
39.4
0
0.0
2
3.0
3
4 . 3
2
3.0
10
15.2
06
86
67
19
28.4
15
22.4
5
7.5
3
4.5
0
0.0
1
1.5
8
J 1.9
27
40.3
2
3.0
1
1,5
0
0.0
1
! .5
4
6.0
07
86
68
8
11.8
11
16.2
9
13.2
4
5.9
3
4 . 4
3
4 , 4
13
19. 1
31
4 5.6
1
1 .5
0
0.0
0
0,0
0
0.0
3
4.4
08
86
81
5
6.2
9
11.1
5
6.2
5
6.2
2
2.5
5
6,2
15
18.5
37
45.7
0
0.0
I
1 .2
0
0.0
t
I .2
1
1.2
09
86
81
1
1.2
g
10.6
6
7.1
5
5.9
3
3.5
3
3.5
1 5
17.6
37
43.5
4
4.7
0
0.0
1
1.2
2
2.4
0
0.0
10
87
87
0
0.0
7
8.0
6
6.9
7
8.0
3
3.4
4
4.6
9
10.3
39
44.8
5
5.7
2
2.3
3
3.4
2
2.3
0
0.0
11
87
87
0
0.0
6
6.9
10
11.5
3
3.4
/,
4.6
5
5. 7
7
8.0
40
46.0
5
5.7
1
1.1
2
2.3
2
2.3
2
2.3
1 2
86
86
0
0.0
4
7
8.1
5
5.8
4
4.6
5
5.8
12
13,9
39
45.3
2
2.3
2
2.3
2
2,3
1
3. 5
1
1.2
13
36
86
0
0.0
4
4 . 7
7
8.1
4
4.7
5
5.8
5
5.8
13
] 5.1
38
44.2
1
1.2
3
3.5
3
3.5
1
1.2
2
2 . 3
14
87
87
0
0. 0
6
6.9
5
5. 7
7
8.0
7
8.0
3
3.4
1 4
16.1
39
44 ,8
3
3.4
0
0.0
2
2 . 3
1
I . 1
0
0.0
15
86
86
0
0.0
7
8.1
7
8. 1
5
5.8
3
3.5
4
4.7
17
19.8
38
44.2
1
1 .2
0
0.0
2
2,3
2
2.3
0
0.0
16
86
86
0
0.0
6
7.0
4
4.7
?
8.1
2
2.3
7
8.1
14
16.3
37
43,0
2
2.3
0
0.0
2
2.3
3
3.5
2
2.3
17
86
86
0
0.0
11
12.8
3
3.5
4
4.7
6
7.U
5
5.8
1 1
15.1
36
41.9
3
3.5
1
1.2
0
0.0
2
2.3
2
2.3
18
86
81
5
6.2
4
4.9
0
11.1
6
7.4
4
4.9
4
4.9
] 2
14,8
38
46,9
0
0.0
2
2.5
0
0.0
?
2.5
0
0.0
19
86
78
8
10. 3
5
6.4
8
10.3
5
6,4
2
2.6
3
3.8
1.6
20, 5
32
4] .0
5
6.4
0
0.0
0
n.n
0
0.0
2
2.6
20
86
!h
)U
13.2
8
10.5
6
7,9
3
3.9
3
3.9
0
0.0
1 ]
14.5
37
48,7
4
5.3
0
0.0
2
2.6
1
1 . 3
1
1 . .3
21
86
72
14
19.4
7
9. 7
8
11.1
2
2.8
0
0.0
3
4.2
6
8,3
38
52.R
1
1.4
1
] ,4
0
0.0
2
2.8
4
5.6
22
86
70
16
22.9
7
10.0
5
7.1
2
2.9
1
1.4
3
4.3
6
8.6
35
50.0
1
1.4
1
1.4
1.
1 .4
4
5.7
4
5.7
23
86
71
15
21.1
5
7.0
8
11.3
0
0.0
0
0.0
0
0.0
5
7.0
38
53.5
4
5.6
2
2.8
1
1.4
4
5.6
4
5.6
-------
Table 6.31. Hourly frequencies
of wind speed
Tor Liberty Hounds. JuJy-Seplember, 19/7
Hour, CST
0.0 - 0..9
No. Values
jnp.li
IVrcon t:
1.1) - 5
9 niph
6.0 -..10.
No. Values
.9 Jiudl
Percent
11.0 -
] 3 . 9. iiii?) i
s Percent
No. Va
- 20.9 mpli
tics I'lMccnt
2] ._ ()_
Nn . Va 1 ik'!
tnj>h
Percent
rot. ,-iJ.
No. Value
No . V.i 1 ur
; Percent
No. Value
00
4
4.9
57
70./.
1 5
18.5
6
6.9
1
1 . 2
0
0
81
01
5
6.2
5 3
6 5.'.
1 7
21.0
5
6.2
]
1.2
0
0
HI
m
]
1.2
54
66.7
18
22.2
7
8.6
]
J .2
0
0
8 1
01
1
1 . 2
59
72.8
16
19.8
6
6.9
1
1 .2
0
0
31
0/:
2
2.5
59
72.8
16
19.8
6
6.9
0
0.0
0
0
81
05
:i
3.7
58
7 ! . 6
15
18.5
5
6.2
0
0.0
0
0
81
0f>
l
1 . 2
61
7 5.3
16
19.8
'3
3.7
0
0.0
0
0
8)
07
/,
4.9
51
6 3.0
22
2/.2
3
3. /
1
1.2
0
{)
81
OH
3
3. 7
'.9
59.8
2 5
30. 5
u
6.9
1
1.0
0
0
82
09
2
2.4
/.I
50. 0
31
37 .8
8
9.8
0
0.0
0
0
82
] 0
2
2.5
34
42.0
30
37.0
3
16.0
o
2.3
0
0
81
11
1
1 . 2
31
38. 3
32
39. 5
6
19.8
]
1 . 2
0
0
81
12
0
0.0
21
2 5.3
4 3
CC
16
16.9
s
6.0
0
f)
8 3
1 .)
0
0.0
2 3
7.1.1
44
'33.0
n
13. 3
3
6.0
0
0
83
1*
0
0.0
23
27.7
1,7
SO. 6
.1/.
16.9
6
6.8
0
0
83
1 5
0
0.0
25
30.1
37
66. 6
15
18.1
6
7.2
0
0
83
] 6
0
0.0
27
32. 5
36
4 "J. 9
16
17.1
3
6.1
0
0
82
i;
0
0.0
20
2'.. U
44
33.0
16
19.3
3
3.6
0
0
83
18
0
0.0
23
27.7
4 5
56.2
3
13.7
2
2.6
0
0
8 3
19
0
0.0
23
28.0
4 5
36.9
13
13.9
1
1.2
0
0
82
20
0
0.0
39
4 7.6
3 3
60.2
')
] 1.0
1
1.2
0
0
82
21
0
0.0
49
59. R
26
31 . 7
7
8.3
0
0.0
0
0
82
77
7
2. U
4 8
58. 5
27
32.9
5
6.1
0
0.0
0
0
82
2 3
2
2.4
51
62.2
24
?9.3
6
6.9
1
1 .'?
0
0
82
-------
Table 6.32. Hourly frequencies
September, 197 7
of wind speed
for uJ sa City/County health Department
0.0 ¦¦ 0.9 mph
Nu. Values Percent
0.0
0.0
1.1
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
1.0 3.9 mph
No. Values Percent
23
2 3
24
26
2 3
23
.10
27
30
2 6
21
2 ]
21
20
19
If)
14
1 5
14
1 3
1 5
20
20
23
32 . 2
28. 7
2 7.6
29.9
32 .
28. 7
l'i. 5
31.. 0
3'.. 5
29. 3
26.:
23.9
23.9
22 . 7
2: . 3
17.8
15.
16.
15.
1 4.
2 3.0
2 3.0
2.6./.
6 ._0 - 10.9 mph
No. Values PercenL
38
39
40
4 2
4 3
4 3
4 0
4 1
3 /,
37
56
39
37
36
29
33
y>
33
39
38
•'.3
36
33
4 3.7
44.8
46.0
AH. 3
31.7
')1 . /
46.0
<•.7.1
39.1
42.0
40.9
4 3. R
4 1 .6
40.4
32.6
36. 7
38 .2.
38.2
3 7 . 3
44 . 3
4 3.7
4 9.4
41.4
40.2
J 1.0 - 15.9 mph
No. Values Percent
1 3
18
20
1 7
1 2
14
15
1 8
20
20
22
24
2 4
23
30
29
2 8
27
36
29
30
20
26
24
17.2
20.7
2 3.0
19.3
13.8
16. )
17.2
20. 7
>3.0
22. 7
2 3.0
2 7.3
27.0
2 3.8
13. 7
32.2
31.3
30. 3
4 0.9
33.0
34. 3
2 3.0
29.9
27.6
0 - 20.9 mj;h
3 3.7
3 3.7
3 i. 4
2 2.3
1 1 . I
3 3.4
3 . 7
6 6.8
4 4 . 3
4 4.3
7 7.9
9 KM
10 11.1
11 12.4
11 I ? . 4
5 3.7
7 8.
4 4 .
4 4.
2I_.0_^ -np;]
Nn. Va1ues Pe r'c mi '
1 . 1
0.0
:). :i
n.")
)
;>.D
!). 1
;;. o
.')
0.0
1. l
i. 1
3.'.
3.4
2.2
2 . 2
2 . 2
2.2
0.0
0.3
0. 1
0. J
0.')
.:)
-------
Table 6.33. Hourly frequencies of wind speed for Kynona. July-September 1977.
- . - •— - . -
—
— - — -
— —
-
...
- * ¦ • ~
...
~ -.1 ^
0,0 - 0.9
mph
1.0 5
9 ni| h
6J) - 10
9 n p '"i
11.0 - 15
. 9 mph
16J) _-_2U
.9 mph
2]_._0__-_
To (a 3
Hour. CST
No. Vol ues 1
i* remit
No . V;i 1 uu
i Percent
No. Valuer.
Per c em
No. V;lhlPS
Perrent
No. V,"s 1 >jcs
Percent
No. V.ilties
Perrent
No. Values
oi:«
a
9.4
53
62 . 4
19
22.4
4
4. 7
1
1.2
0
0
SS
01
8
9,4
54
63. 5
18
21 .2
r)
5.9
0
0.0
')
f)
ss
02
9
10.6
56
65."
15
J 7. 6
/,
4 , 7
1
1.2
0
0
$¦>
0 3
9
10.6
57
67.1
16
18.8
2-4
1
1.2
0
0
04
7
8.2
59
69.4
J 7
20.0
2.4
0
0.0
i)
0
8^
05
9
10.6
59
69.4
IS
17.6
2.4
0
0.0
0
0
as
06
7
8,2
55
64.7
18
21 .2
5
5.9
0
0.0
0
f)
1)7
1
1.2
48
57. 1
n
32. 1
8
<>.5
0
c.o
0
u
08
0
0.0
19
46.4
27
32.1
17
20.2
1
1 . 2
0
0
8-«
m
0
o.n
33
46. 3
25
>0.5
18
'.1.5
;
1 . 2
0
(}
8 2
10
0
0.0
30
36. 6
34
41.5
13
15.9
5
6. I
0
0
8?
) 1
0
0.0
25
30.1
38
45.8
16
19. 3
4
4.8
0
0
fH
12
0
0.0
29
3 '. .9
33
39.8
1 7
20. 5
4
4 .8
0
0
S3
1 3
0
0.0
27
32.5
32
38.6
18
21.7
6
7 , 4.
0
0
83
14
0
0.0
23
27.7
37
44.6
18
21.7
5
6.0
0
D
83
13
0
0.0
2 3
27.7
37
44.6
19
22.9
'«
4.8
0
0
3 3
16
0
0.0
28
33.3
32
38.1
20
23.8
/,
4.8
0
0
3-'.
1 /
0
0.0
33
39.3
28
3 1.3
20
2 3.8
3
3.6
0
0
R.'f
18
1
! . 2
34
4] .0
36
4 3,4
12
14.5
1
1.2
0
0
S 3
19
u
5.0
4 9
61 . 3
23
28.8
8
10.0
0
0.0
0
0
B0
20
5
6.3
53
67.1
23
29, ]
3
3.8
0
0.0
0
0
79
21
7
9. 1
49
63.6
23
29.9
5
6.5
0
0.0
0
0
77
22
6
7.5
55
68.8
19
23.8
4
5.0
0
0.0
0
0
no
21
9
12.0
53
70.7
17
22. 1
4
5.3
]
0.0
0
0
75
-------
Table 6.34. Hourly frequencies of wind speed for Oche.lata.
.]ul y - -Sep Lembrt r , .1977
—
;
J.._! _ 1!.._
. — ....
0.0 - 0
9 rnph
1_. 0 - 5
9 inpli
9 mpli
n_.o -
5.9 m p 11
16.0 - 20
9 mull
21.0 -
tnpli
Tot
] 7
23.6
6 3
59.7
1.2
16.7
0
0. 0
0
0.0
0
(i
72
03
1.8
26.7
30
68. 5
5
6.8
0
0.0
0
0. 0
0
0
7 3
06
16
21 .9
r-l
69. 9
6
8.2
0
o.r
0
0. 0
0
0
/ 3
05
1 7
2 3.3
69
67. 1
7
9.6
0
0.0
0
0.0
0
0
7 3
06
I 1
1 7.8
3.1
69. 9
9
12.3
0
0.1;
0
0 .0
0
0
73
07
j
6.8
58
79.5
10
1 !. I
0
0.0
0
9.0
0
0
7 3
(J8
¦
5.3
.w
78. 1
1.0
13.7
2
2 . 7
0
0.0
0
0
7 3
09
1
1. 6
5 2
71.2
1 7
2 1. 3
1
6 . 1
0
0.0
0
0
73
3 0
0
0.0
6 7
66 .6
2 6
32 . 9
2
2 . 7
0
3.3
0
0
7 3
)
0
0.0
6 3
59. 7
76
1
3
6.2
0
0.0
0
0
72
12
0
n. (i
6 3
60. H
27
36.5
j
1 .6
1 .'4
0
0
76
13
0
0.0
6],
55.6
31
6 1.9
¦j
2 . 7
0
o
o
0
0
76
16
0
0.0
37
30.0
36
68.6
i
1 6
0
3.0
0
0
76
1 5
0
0.0
6 2
57.5
30
6 1. 1
;
1 .6
0
o.o
0
0
/ i
16
0
0.0
38
52. 1
32
63.8
3
6 . 1
0
0.0
0
0
7 3
1
1)
U. 0
39
56 .2
32
6 6 .6
.1
1.6
0
3.0
0
0
72
18
3
6 . l
6/t
60. 3
2 6
36. 1
0
0.0
0
0.0
0
0
7 3
19
3
6.8
30
60.5
1.7
2 3.3
1
1 .6
0
3.0
0
0
7'i
20
0
11.0
6 5
61.. 6
20
2 7.6
0
0.0
0
3. 3
n
0
73
21
1 2
16.4
6 6
6 3.0
1 5
20. 5
n
0. 0
0
3.3
0
0
7 3
22
I i
17.8
6 5
61.6
15
20. 5
0
0.0
0
0.3
0
0
7 3
2 3
.1 ?
16.7
6 5
62.5
1.5
20.8
0
0.0
0
0.3
0
0
72
-------
.75
.,50
.25
.00
.75
.50
.25
0
110
100
90
80
70
60
Da
Ju
r~l.
i
1 3 5 7 9 11 13 15 1/ 19 21 23 25 27 29- 31
Day of Month
ily maximum temperature and 24-hour total precipitation, Tulsa International Airport,
/, 1977. Dflfa supplied by NOAA, Tulsa,
-------
2.00 p-
u
v
u
a
3
CO
0)
x:
u
c
"ri
1 - 75
1. 50
1,25
c
.21. oo
u
CO
u
£0.75
U
2 0.50
0.25
Ln
cc
rC.
no
fa 100
CD
&-<
u
0)
n<
70
13 5 7 9 11 13 15 17 19 21 23 25 27 29 31
Day of Month
Figure 6,40. Daily maximum temperature and 24-hour total precipitation, Tulsa International Airport,
August, 1977. Data supplied by NOAA, Tulsa.
-------
2.00 p-
1. 75
S 1. 50
x.
u
a
'H 1.25
c
•2 i.oo
d 0.75
H
U
-------
Table 6.35. Average concentrations
, ppbC, alkane hydrocarbon species,
0600 to 0900 CDT,
Tulsa,
Oklahoma,
monitoring sites
Site
liberty Mounds
Health Department
Post Off
ice
Compound class
Value
ppbC No,
samples
Value, ppbC
No.
samples
Value, ppbC No
. sa
Alkane
Ethane
36
4
70
26.5
77
39.8
78
Propane
54
9
63
23.1
77
38.9
78
Isobutane
1 1
4
70
10.9
77
24.8
78
n-Butane
25
7
70
26.6
77
69.3
78
Isopentane
17
4
69
31.3
76
58.8
78
n-Pentane + Cyclopentane
36
3
68
39. 1
73
41.5
78
2,2-Dimethylbutane
0
0
62
0.1
65
0.2
73
2-Methylpentane
4
0
31
8.5
49
11.6
70
3-Methylpentane
9
1
31
17.7
52
17.7
71
n-Hexane
3
1
61
5.5
69
10.4
74
2,4-Dimethylpentane
0
4
60
0.6
61
1 . 1
71
2-Methylhexane
1
5
56
5. 7
65
7.9
73
3-Methylhcxane
1
0
58
4.4
61
4. b
69
2,2, 4-Trimethylpentane
1
7
45
4.8
56
8.3
63
n-Heptane
0
7
55
3. 1
63
5 .1.
69
Methyleyelohexane
0
5
41
2. 1
60
1.6
62
2,3,4-Trimethylpentane
0
3
54
0.3
63
0.8
69
2-Methylheptane
2
6
56
8.9
71
13.8
71
3-Me thylhept a ne
0
4
59
1. 1
71
2.7
71
n-Octane
0
5
61
2.0
71
2.8
74
n-Nonane
0
2
63
0.3
71
1.2
74
n-Decane
0
0
62
0.0
71
0.2
74
n-Undecane
0
0
63
0.0
71
0.0
7 4
n-Dodecanc
0
0
63
0.0
69
0.0
73
-------
Table 6,36. Average concentrations, ppbC, alkene, alkyne, and aromatic hydrocarbon species,
0600 to 0900 CDT, Tulsa, Oklahoma, monitoring sites
Compound class
Liberty
Value, ppbC
Mou
"No"
rids
samples
Si te
Health Department
Value, ppbC No, samples
Value
Post
, ppbC
Office
No. san
Alkene
Ethylene
(a)
(a)
22
2
72
45
,0
78
Propylene
4
.2
70
I
3
77
10
7
78
t-2-Pentene + Isoprene
1
6
61
2
3
71
3
4
74
1-Hexene
0
2
61
0
1
68
0
6
70
p-Pinene
0
0
67
0
0
72
0
.0
76
Aromati c
Benzene
15
.3
66
23
.8
73
29
6
76
Toluene
7
.3
66
9
5
73
13
8
76
Ethylbenzene
3
4
65
5
9
72.
3
9
76
js-Xylene + «--Pinene
0
8
66
0
9
72
2
0
76
ra-Xylene
1
4
66
2
4
72
4
7
76
o-Xylene
0
.8
65
1
7
72
2
9
76
n-Propylbenzene
3
1
66
2
1
72
2
9
76
m-Ethyltoluene
1
.0
66
0
7
72
1
7
76
1,3,5-Trimethylbenzene
1
.0
66
0
6
72
1
8
76
t-Butylbenzene
0
8
66
0
1
72
1.
0
76
o-Ethyltoluene
0
8
66
0
3
72
1.
0
76
1,2,4-Trimethylbenzene
9
.4
66
11
0
72
18.
5
76
1,2,3-Trimethylbenzene
1
.0
66
1
0
72
3.
4
76
n-Butylbenzenc
0
9
66
1
9
72
5.
0
76
Alkyne
Acetylene
2
1
70
11
8
77
18,
5
78
(a)Invalid data; no computation.
-------
6.6 TENAX GC/MS/COMP RESULTS
The results obtained from the collection and analysis of volatile
organics by Tenax GC/MS/COMP are presented in tables and figures in Volume II
of this report. The ambient air sampling protocol for collection of the
five samples is given in Table 3.3 of this volume.
In these five samples, over 100 compounds were detected and identified.
The composition consisted of an assortment of alkanes, alkenes, alkyl aro-
matics, oxygenated compounds, halogenated hydrocarbons, and nitrogen-containing
substances. A general inspection of the profiles indicates a substantial
increase in the overall quantity of constituents between the sample collected
at Liberty Mounds and at the downtown Tulsa Post Office. The chromatographic
conditions used for the resolution of the constituents in these samples were
not precisely controlled and thus make it difficult to compare samples on a
quantitative basis.
Table 6.37 presents the quantitative comparison of volatile organics
that was made for ambient air 0600 to 0900 CDT samples from Liberty Mounds
and the Tulsa Post Office site, and a 1400 to 1700 CDT sample from Vera. A
significant increase in the relative quantity of alkanes, alkenes, alkyl
aromatics (including benzene and toluene) and ketones occurs as the ambient,
air is transported from Liberty Mounds through downtown Tulsa. Then the
concentrations decrease upon reaching Vera.
In Volume ITT. of this report, results of the Tenax GC/MS/COMP samples
are compared with those obtained from samples collected in stainless steel
cylinders and analyzed by GC/FID.
162
-------
Table 6,37. .Quantitative comparison of volatile organics in ambient air i'ram Liberty
Mounds, Tulsa, and Vera. GC/MS analysis
Site
Chemical Class Liberty Mounds Post Office, Tulsa Vera
alkanes (> C,)
_ ^
4.61
0.28
15.92
+
1.15
(3. 4)a
6.87
+
0. 74
(1.5)
alkenes (> C,)
— 0
4.56
+
0.06
11 .67
1. 20
(2.5)
5. 79
+
0.59
(1.3)
alkvl aromatics (> C0)
— O
3.36
+
0.62
10.82
+
0.99
(3.2)
3.64
1-
1.18
(1.1)
benzene
0. 25
+
0.13
0.43
+
0.01
(1.7)
0.10
+
0.01
(0.4)
to 1 up.ne
0.43
+
0.10
3. 74
+
0.46
(8.7)
0. 29
-r
0.03
(0.7)
cildehydes (> C,)
o
3.60
+
0.46
1 . 36
4*
0.07
(0.38)
0.72
0,28
(0.2)
ketones (_> C^)
0.51
+
0.06
1. 74
+
0.20
(3.4)
0.13
+
0.5
(0.2)
phenols (> C^)
2.34
+
0.26
1.38
+
0.03
(0.6)
1.82
+
0.46
(0.7)
misc. oxygenates (> C,)
1.91
+
0.39
0.89
•1
0.51
(0.5)
0.87
+
0. 30
(0.5)
light hydrocarbons (C^-C^)
0.81
+
0.07
0.39
+
0.06
(0.5)
0,12
+
0.07
(0.1)
3 3
Values in arbitrary units/m of air, numbers in parenthesis relative to Liberty Mounds.
-------
SECTION 7.0
REFERENCES
1. Uses, Limitations, and Technical Basis of Procedures for Quantifying
Relationships Between Photochemical Oxidants and Precursors, Environ-
mental Protection Agency, Report No. EPA-450/2-77-021a.
2. C. E. Decker, T. M. Royal, and J. B. Tommerdahl, Development and Testing
of an Air Monitoring System, Environmental Protection Agency, Report No.
EPA-650/2-74-019.
3. "Measurement Principle and Calibration Procedure for the Measurement
of Nitrogen Dioxide in the Atmosphere (Gas Phase Chemiluminescence),"
40 CFR, Part 50, Appendix F.
4. "Reference Method for Determination of Hydrocarbons Corrected for
Methane," 40 CFR, Part 50, Appendix E.
5. Research Triangle Institute, Ambient Monitoring Aloft of Ozone and
Precursors in the Vicinity and Downwind of a Major City, Environmental
Protection'Agency, Report No. EPA-450/3-77-099.
6. Research Triangle Institute, unpublished data, 1976.
7. R. A. Baker and R. C. Doerr, "Methods of Sampling and Storage of Air
Containing Vapors and Gases," Inter. J. Air Pollution, 2, 142-158 (1959).
8. Research Triangle Institute, Study of the Formation and Transport of
Ambient Oxidants in the Western Gulf Coast and North-Central and North-
east Regions of the United States, Environmental Protection Agency,
Report No. EPA-450/3-76-033.
9. G. W. Snedecor and W. G. Cochran, Statistical Methods, The Iowa State
University Press, Ames, Iowa, Sixth Edition, 1969.
10. D. Hardison, J. Harden, J. McGaughev, A. Sykes, and R. Denyszyn,
"Evaluation of Various Hydrocarbon Sampling Devices" (Proceedings of
the 71st Air Pollution Control Association Meeting, Houston, Texas)
June 1978.
164
-------
APPENDIX A
SAMPLING AND ANALYTICAL METHODOLOGY FOR GC-FID
IDENTIFICATION OF HYDROCARBONS
165
-------
APPENDIX A
SAMPLING AND ANALYTICAL METHODOLOGY FOR UC-FIJ
J.l)j£NTIP 1CATICN OP tiYi.SkOfiARRONR
KTI provided sample containers for the collection of ambient air samples
for subsequent analyses of trace organic volatiles. Samples were collected at
selected sites within the Tulsa study area. The overall methodology can be
broken down into two basic areas: (1) the collection of air samples, and (2)
the analysis of the air samples. These two are discussed in the following
subsections.
1.0 Sampling Criteria
Obtaining a representative air sample for analysis of trace organic
volatiles is not a trivial task. Three factors must be considered.
1. The air sample must be representative of the air mass. Two ap-
proaches can be used to accomplish this goal. The first is to
collect a multitude of short-term grab samples; the second is to
collect longer term integrated samples. From previous field ex-
perience, the latter approach provides less erratic data than the
former.
2. In order to characterize an area for its hydrocarbon background,
samples have to be collected at appropriate sites and times. For
example, if samples are collected between 6:OD and 9:00 a.m. LDT in
an urban center, the data will be strongly influenced by automotive
emissions. It would be difficult to determine the contributions of
other hydrocarbon emission sources to the urban air mass. Total
characterization of sources can only be accomplished by collecting
samples at different times of the day so that one emission source
does r.ot predominately influence the hydrocarbon background.
3. The sample must not be altered by either the collection device or
the sampling containers. This aspect has been evaluated in RTI
laboratories and our findings will be discussed in the next sec-
tions .
166
-------
1.1 Sampling Containers
A variety of sampling techniques have been employed to collect trace
hydrocarbon species, but two methods have prevailed. One involves the collec-
tion of trace volatiles on a solid adsorbent. The other involves collecting a
volume of air inside a container, then concentrating a part of that sample to
analyze for the trace constituents. RTI has had a great deal of experience in
both areas. Samples for GC/MS analyses were collected on Tenax GC (refer to
Appendix B) while samples for GC/FID, GC/EC were collected in treated stain-
less steel containers.
1.1.1 Construction and Leak Checking Stainless Containers
The containers utilized in this study were constructed of all stainless
steel components. The bodies of the containers as well as the tops were made
from 304 stainless steel. The container bodies were constructed from a 2-1
stainless steel beaker manufactured by Vollrath (Sheboygan, Wisconsin).
The tops of the containers were stamped from 304, 1/8" thick stainless steel.
The lips on the stainless steel beakers were cut with a wet cutting wheel
after the container had been electropolished. After the container was cut it
was cleaned with strong oxidizing reagents to remove any grease deposits on
the inside of the container.
A 1/4" x 2" stainless steel tube was heliarced to the top of each con-
tainer. The tops were then electropolished, and the tops and bodies of the
containers were joined by heliarcing under an inert atmosphere to prevent any
oxidation of the interior surfaces during this process. The containers were
then mounted with II series Nupro valves, constructed of stainless steel with
metal bellow seals. Each container was then engraved with a letter and num-
ber. The letter told the function of the container, e.g., source sampling or
ambient sampling, and the number identified the container.
The container was then ready for testing. It was first pressurized to 60
psi with zero air and leak checked under pressure. The container was immersed
in clear water and visually inspected for leaks. If there were no leaks, the
container was ready to be cleaned.
1.1.2 Cleaning Procedure for Stainless Steel Containers
The cleanup procedure for a new sample container being put into service
for the first time was identical to that for a container which was returned
167
-------
from the field. First, the container is evacuated to less than 0.5 rani' H'g
pressure. The bellows valve is closed and torqued' to 20 in-lb. This 20
in-lb torquing is repeated each time the valve is closed. Next, the con-
tainer was loosely connected to the clean air supply, and the compression
fitting connections were flushed with clean air. After approximately 1 min,
the compression fitting connection was tightened and the container valve
opened. When the container was pressurized to 60 psi, the valve was torqued
closed and the container was disconnected from the zero air supply. The
container was allowed to equilibrate lor 20 minutes, then heated to approxi-
mately 100° C and evacuated. The pressurization heat/evacuation process was
repeated. The bellows valves were torqued shut, and the container inlet port
was finally sealed with a brass plug to prevent any loss of vacuum. The
container was then ready for shipment to the field for sampling.
1.1.3 Shipping Procedure and Logging Procedure for Stainless
Steel Containers
After the container had been cleaned and sealed with a brass plug, a tag
containing the following informalion was aLlached to the tubing below the
valve:
Conta iner No. :
Sampling Date:
Sampling Starting Time:
Sampling Finishing Time:
Site:
Flow Rate - Start: Finish:
The container number was entered prior to shipping; the rest of the data
was entered by the sampling team. Sampling data, time and site are self-
explanatory. The flow rates were measured by attaching a soap film flow meter
to the end of the critical orifice while the pump was drawing in air from the
manifold. The starting flow rate was measured just prior to attaching the
sample container; the finish flow rate was taken immediately after the con-
tainer was removed. Thus, any large changes in flow rates, which could indi-
cated plugging of the orifice, could be detected.
The containers were packed in aluminum suitcases and shipped air freight
to Tulsa. Two couriers were used during the program: Eastern Airlines and
Federal Express.
168
-------
Prior to its departure, each container's number was entered on a master
log sheet to enable RT1 to keep track of each container's whereabouts. The
same log sheet had spaces to record the dates when the containers were returned
to RTI and when each analysis was performed.
1.2 Pumping System, Metal Bellows Pump
To collect ambient air samples with the stainless steel containers,
various approaches could have been taken. Since the containers were evacuated,
they could simply have been opened to the atmosphere and filled. To collect
an integrated sample over time, a critical orifice could have b«en mount.eel in
front of the valve, and the valve opened. The orifice would have maintained a
constant flow rate up to 0.5 atmosphere of vacuum, but beyond 0.5 atmosphere
the flow rate would no longer have been constant and would gradually fall to
zero until the container was filled (i.e., was at ambient pressure). This
method has two drawbacks: (l) it does not provide a constant flow rate during
the entire sampling period, and (2) it provides samples which are at atmospheric
pressure or under a partial vacuum.
To alleviate these problems the container needs to be pressurized.
Pressurizing the container without contaminating the sample air can only be
accomplished by employing a pump free of lubricants and polymeric diaphrams.
The only pump which provides this capability is the metal bellows pump which
is constructed of stainless steel and TFE Teflon, Such pumps can deliver
pressures of up to 40 psig.
1.2.1 Sampling Methodology Associated with the Stainless Steel
Containers
The approach described in Section 1.2 was employed by RTI to collect
samples in Tulsa, Figure A.1 is a schematic drawing of the system used. The
system consisted of two metal bellows pumps mounted on a 10" x 16" x 3/8"
piece of plywood. The piece of plywood was shock mounted with four rubber
feet.
The system was constructed to minimize the sample's residence time inside
the tubing. In order to pressure the container to 5 psig over a 3-hr period,
flow rates had to be approximately 15 ml/min. With a single pump long resid-
ence time inside the tubing connecting the MB (Metal Bellows Corporation) pump
and the sampling manifold would exist. To minimize the residence time, the
MB-21 or MB-41 pump pulled air from the station manifold at an elevated flow
169
-------
Station
Sampling
Manifold
1/.16" o.d. Tubing
Orifice Critical
0.010"i.d
Stainless
Steel
Tubing
Stainless
Steel Tee
Excess
MB 151
Metal Bellous
Metal Bellows
OUT
OUT
IN
Sampie
Container
MB 151
Metal Bellous
Pump
MB 2.1. or 41
Metal Bellows
Pump
Flexible
S.S. Section
1/4'' o.d.
Stainless
Steel
Tubing
figure A.1. Schematic of RTI's pumping system used to collect field samples.
170
-------
rate of 2-3 1/min. A stainless steel Swagelok tee connected the MB-151 pump
to the station manifold and the smaller metal bellows pump. The small metal
bellows pump was attached to the sampling manifold via 1/4" o.d. stainless
steel tubing connected to a 12" long piece of flexible stainless steel tubing
which absorved most of the vibrations. All connections were made with Swagelok
compression fittings.
The tubing connecting the Swagelok tee to the MB-151 pump was 1/16" o.d.,
0.030" i.d., to minimize the internal volume. The tubing connecting the
MB-151 and the stainless steel sampling container was 1/16" o.d. x 0.010" i.d.
The interior diameter of the tubing was further reduced by crimping the tubing
over a 6 - 8" length. This technique cut the flow rate from several hundred
ml/min to 10 - 30 ml/min. Prior to field deployment each system was tested.
This testing is described in more detail in the next section.
1.2.2 Pumping System Performance Checkout
The first checkout for the pumping system was designed to insure that it-
was leak free. Leaks in the MB-21 or 41 pumps were not as critical as for the
rest of the system, since the only purpose of the smaller pumps was to purge
the tubing connecting the MB-151 pump and the manifold. The fittings connect-
ing the MB-151 to the Swagelok tee were checked by plugging each arm of the
tee, then monitoring the flow rate at the output of the MB-151 with a soap
bubble flow meter. With such an arrangement, leaks of less than 0.1 ml/min
could easily be detected. The system was next tested by plugging the outlet
of the pump and attaching a bubble flow meter to the inlet. The fittings on
top of the pump were tested with a nonorganic base soap material ("Snoop") to
check for microscopic leaks.
After this inspection, the critical orifices on each pumping system were
tested for proper flow rate over a typical sampling period. Each pumping
system was attached to a mass flow meter with its output displayed on a strip
chart recorder. Each pumping system was tested for at least 2 hr. During
the testing period, it was noted that the flew rate decreased for the first
15 minutes, then stabilized. During this time period the pump attained
thermal equilibrium. Therefore, in the field, a 15-min warmup time was used
to purge the pumping system prior to beginning sample collection.
Another important test was to insure that a constant flow rate could be
maintained throughout Lhe sampling period. An experiment was set up with a
171
-------
mass flow meter in line between the stainless steel container and the critical
orifice. The output of the mass flow meter was again displayed on a strip
chart recorder. A printout of such a test is shown in Figure A.2.
To cheek for contamination of the samples by the pumps, and to insure the
integrity of the system, the pumping system was attached to RTI's clean air
source. The analysis of the pumping system output showed only ethylene, which
is shown tc be present in the clean air supply at approximately 0.2 ppb.
The final test was to check the effect of the pumping system on a variety
of hydrocarbons. A cosnplex mixture of C5 - Cjg hydrocarbons was prepared for
each compound at 10 -20 ppb (V/V). The mixture was analyzed to ascertain,,the
concentration of each compound. It was then sampled by the pumping system.
The output was analyzed, and the concentration of each compound was found to
be within the experimental error of the repeatability of the initial analyses.
After this test, the pumping systems were ready for field usage.
1.3 Deployment of RTI's Sampling Systems in Tulsa
Five pumping systems and associated critical orifices and stainless steel
tubing were provided for the Tulsa study. RTT personnel were trained in the
collection of samples with both stainless steel containers and Tenax cartridges.
2.0 Analytical Techniques
In this project, each sample was analyzed for three major groups of com-
pounds: C2 - Cr; light hydrocarbons; C5 - C12 aliphatics; and C6 - Cj.o aroraatics.
A packed column was used for the C2 - C5 light hydrocarbons analyses, while
the aliphatic and aromatic mixtures were separated on capillary columns. The
hydrocarbon compounds were detected by a flame ionization detector (FID). The
detector response was transmitted to a Hewlett-Packard Model 18652A analog to
digital converter and this signal was then transmitted to a Hewlett-Packard
3352B laboratory data system. All chromatograms were also displayed on Linear
Model 225 M or Perkin-Elmer Model 56 strip chart recorders. The Hewlett-Packard
data system has capability to store response factors for each individual com-
pound selected as well as identifying compounds on the basis of retention time.
Three analyses, C2 - C5, C5 - C10 aliphatic, and C6 - Ciq aromatic shared
the same pumping system for drawing samples from the sample containers through
the cryogenic trap. The pump, a Metal Bellows Corporation model MB 151, was
equipped with a critical orifice which controlled the flow rate at 100 ml/min.
172
-------
n
•H
s
16 •
12
8 -
0.5
1.0
HOURS
] . 5
-J
2.0
Figure A.2, Flow rate versus time for filling a 2-1 stainless steel container
by MB 151 metal bellows pump.
-------
Air from the outlet side of the pump was passed through a 1-1/revolution
American Meter Company wet test meter (model 802). The scale was graduated
in 10 mi divisions and the meter could easily be read to +2 ml.
A series of valves on the inlet side of the pump determined which of the
three systems would be monitored (see Figure A.3), The outlet side was also
controlled by an open-shut valve which prevented a backflow of air into the
partially evacuated bellows when the pump was turned off. It was desirable
to keep a partial vacuum on the bellows to avoid a lengthy bellows evacuation
time prior to the sample withdrawal.
The sampling procedures for these three analyses were similar. First,
the sample container was attached to the appropriate system by means of a
1/16" o,d. stainless steel tube. The container was then placed in a heated
oven and allowed to reach 60° - 70° C. The pump was turned on and the outlet
valve opened to allow the bellows to empty. On the Cy - and aromatic
analyses, the inlet valve of the container was also opened, since there was
another shut-off valve separating the pump from the sample container on these
systens. As the pump was emptying, the cryogenic trap was immersed in liquid
oxygen and allowed to cool. When the bellows had emptied, as evidenced by the
absence of movement on the wet test meter, the valve separating the pump and
sample container was opened. Approximately ten milliliters of sample was
allowed to bypass the trap in order to flush out the sample lines. Then, with
the proper arrangement of the multiport valves, the next 100 ml was routed
through the trap. Upon trapping out the desired volume of sample, the pump
was switched off and all inlet and outlet valves were closed in quick succes-
sion. The multiport valves were then arranged to close off the trap from the
rest of the system. The liquid oxygen v.-as removed, and the trap was immersed
in a 200° C silicone oil bath. After sufficient time to heat the trap (from
15 sec for C2 - C5 to 1.5 - 2 min for aliphatics), the sample was injected and
the analysis program commenced.
2.1 Cg - Gs Light Hydrocarbons Analysis
The C2 ~ C5 light hydrocarbon analysis system was made up of a Perkin-
Elmer model 900 gas chromatograph equipped with an 8' x 1/8' stainless steel
column packed with 100~120 mesh Durapak® phenylisocyanate. The column was
1 7 U
-------
VALVE POSITIONS
TRANSFER
Clean
Air Vent
Carrier
Oil a
TRAP POSITION
Column
Carrier
VS
Li^-ht Hydro-
carbons ,-v
^—0-
.Ca r r 1 o. r
Gas
Sample
Loop
S-c)o
A 1iphatics
Carrier
Oas
Col u;mv
Carrier.
Closed
To Pump
Carrier
C *Cif5
Sample
Loop
INJECT
Carrier Gns
Closed
Column
Sample
Figure A.3. Schematic diagram of the Cp-Cs light hydrocarbons, C5-C10
aliphatic, and Cg-C10 aromatic valving system.
-------
maintained a~ 18° C ~ 0.5° in a cold water bath. The analysis was terminated
after 30 min. Upon completion of the analysis, the multiport valves were
turned to the bypass-trap position in order to backflush the column. The
backflushing was assumed to be complete when the FID response returned to base-
line. This column was capable of separating ethane and ethylene at room tem-
perature. One of the drawbacks of the column is the poor separation between
cyclopentane anc n-pentane. Since these two compounds were not adequately
separated, they were reported as one component.
2.2 Cs - C]2 Aliphatic Analyses
The C5 - C|2 aliphatic analysis system consisted of a Perkin-F.lmer model
3920B gas chromatograph equipped with a 200 ft length SCOT 0V-101 capillary
column. This capillary column was chosen for its excellent separation of
aliphatic compounds in the C,. - C molecular weight range. The analysis was
started by injecting the sample into the column at 30° C. This temperature
was maintained for 8 min, then the column was temperature programmed at
a rate of 4° C/min until it reached 100° C. The column was held at this
temperature until the analysis was completed. The analysis ran for approxi-
mately 60 min; there was no need for backflush afterwards.
2.3 Cfi - Cio Aromatic Analyses
The analyses for C6 - Cjaromatic compounds were performed using the
same Perkin-Elmer model 900 gas chroir.atograph as used for the C2 - C5 analysis.
The aromatic compounds, however, were separated on a 200 ft SCOT MIMA capillary
column. The column was maintained at 90° C for 6 minutes, then temperature
programmed at 0.5°/min to 110° C. This temperature was held until the analysis
was completed. The program ran for approximately 60 min, and no backflush
was necessary after the completion of the analysis.
I 76
-------
APPENDIX B
SAMPLING AND ANALYSIS OF VOLATILE ORGANIC
COMPOUNDS IN AMBIENT AIR BY TENAX GC-MS/COMP
177
-------
APPENDIX B
SAMPLING AND ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN AMBIENT AIR
1.0 Principle of Method
Volatile organic compounds are concentrated from ambient air on
Tcnax GC in a short glass Lube (1-3). Recovery of the volatile organics
is accomplished by thermal desorpt ion and purging with helium into a
liquid nitrogen cooled nickel capillary trap (1,2,4). Then the vapors
are introduced into a high resolution glass gas chromatographic column
where the constituents are separated from each other (2,5). Charac-
terization and quantification of the constituents in the sample are
accomplished by mass spectrometry either by measuring the intensity of
the total ion current signal or mass fragmentography (2,6). The col-
lection and analysis systems are shown in Figure B.l.
2.0 Range and Sensitivity
The linear range for the analysis of volatile organic compounds
depends upon two principal features. The first is a function of the
breakthrough volume of each specific compound which is trapped on the
Tenax GC sampling cartridge. The second is related to the inherent
sensitivity of the mass spectrometer for each organic (2,7). Thus, the
range and sensitivity are a direct function of each compound which is
present in the original ambient air. The linear range for the quanti-
tation on the gas chromatograph/mass spectrometer/computer (GC/MS/COMT)
is generally three orders of magnitude. Table B.l lists the overall
theoretical sensitivity for some examples of volatile organics which is
based on these two principles (7).
The sensitivity of this technique for the very volatile organic
compounds (C^ to C^) is inadequate for the purpose of this study.
Alternate methods for their collection and analysis are suggested.
3.0 Interferences
The potential difficulties with this technique are primarily asso-
ciated with those cases where Isomeric forms of a particular substance
cannot be resolved by the high resolution chromatographic, column and at
the identical mass cracking pattern of each of the isomers. An example
of such a problem is seen with the C^-alkyl aromatics of which
178
-------
FLOW
/ME 7 E3
pl.vp
NEED
VALVc
CART3:0G5
GAS
ME7E2
GLASS
r IL7EH
VAPCR COLLECTION SYSTEM
FVP.Qz
GAS
T
C'JSHEV
GLASS
M A53
SEPARAT
ca
CAPILL-SY
4 j
GAS
E7EH
C!-PQMA7C0.=APt
CARRIES
GAS
COMPUTES
TWO
POSITION
valve
CaRKlcS
CAPILLAHY
TRAP
THEH'.'AL
DESCSPTiON
CHAM2E3
EXHAUST
PLCTTE3
analytical system
Figure B.I. Vapor collection and analytical system for
analysis of organic vapors in ambient air.
179
-------
Table 8.1-. OVERALL THK3RKTICAL SENS IT TV WT OF HIGH RESOLUTION
GAS CHROMATOGRAPHY/kXsfS' SPfifcTRCifl?rftT/tiO^OTER ANALYSIS
FOR ATMOSPHERIC POLLUTANTS
Chemical
Class
Estimated Detection
Limita
rtg/m~
ppt
Haloftenatcd
hyd rocarhon
Vinyl bromide
250
57
nroinofomt
O.lKiO
0.03
Biomodichloromethune
1 .300
0.22
Dibromoclilorome thane
0,667
0.07
]-Bromo-2-chloroethane
1,00
0.67
Allyl bromide
5.00
1.0-'i
l-Broniopropnne
5.200
1.06
1 - C h 1 o r a - 3 - b r u i r. o p r o 11 > r?
0,1.50
0.01
l-Chloro-2,3-d Lbroinopropane
-0.100
<0.01
2,l-Dibromo-2-chloropropane
-0.100
<0.01
I j 2-D i uruii'OetliaiH:
0.330
0.07
L, 3-1) i.bromo pro pane
-0.100
-0.01
Epiehloroiiydr in
9.600
2.50
(1-Ciilci o-2, 3~epoxyprcpane)
Epi bromobydi r in
0,300
0.05
(1 -l5ro;mi-2, 3-epoxy Mrepr.ne)
BroinubeiUtirin
0.100
0.02
Methyl bromide
500
135
M-';hvl c.liLoridc
2000
1C00
VLnyl chloride
800
333
Methylene chloride
700
200
Chloroform
200
^0
Carbon tetrachloride
250
400
(continued)
-------
Table B.1, (cont'd)
Chemical
Class
Compound
Estimated Detection
Llmita
ppt
H:«lojje.na'. ed
hydrocarbon
(cont'd)
1,2-D1 chlorcethrine
1,1, Jt-Tr .ir.hJ oroeth.me
Tetrachlorosliiylene
Trichloroethylene
l-Chlovc-2-iuethyl propane
3™(!hlQro-2-mnt;hy] propene
32
66
_ , J
10
62
62
8.15
12.45
0.33
1.92
21.5
21.5
3-Ch lor o-l-hut
Allyl chloride
4-Clil oro-l-bu tent
l-Cliloro-2-bu tene
83
83
3S
13
28.8
28.8
13.2
ChloroDenzer.e
£"l)j.cl)lorobaii?.e'-.e
m-1) j. c h lo r o ben z en e
J.'cnzyichioride
2.10
1 .00
0.75
0.65
0.47
0.06
0.01
0.01
Halogonaf.C'l
el hers
?-Chloroorhyl ethyl ether
B i m-(e: 11o r ome t hy1)e t he r
4.15
1.0
0.97
1.10
Nitrosaminos
Oxygenated
N-MJtrosodimethylamine
N-Mitrosodiethylamine
Acrolein
Clyr. idaldehyde
Propylene oxide
Butadiene diepoxl.de
5.0
3.0
-100
-59
-60
~20
1.67
0.74
56.5
19.5
25.5
6.7
(continued)
-------
Table B.i, (cont'd)
Estimated Detection
Limita
Chemical
Class Compound ng/m ppt
Oxygenated
Cyclohexane oxide
-10
2.5
hydrocarbons
Styrpne oxide
2
0,415
(continued)
Ace tophenonc
-2
-0.415
0-Prop:Lolaetone
-3
-1.2
Nitrogenous
Nitromathane
8
-2.4
Compounds
Aniline
3,0
0,78
Sulfur
Diethyl sulfate
-50
_
Compounds
Ethyl methane sulfate
-5.0
»
Q
Limits are calculated on the basis of the breakthrough volume for 2,2 g of Tenax OC, (at 70°F),
capillary column performance and sensitivity of the mass spectrometer to that compound in the
mass fragmentography mode of most intense ion.
-------
there are 53 isomers. As the number of carbon atoms Increases to the
hydrocarbons and aromatics, the number of potential isomers beeoaes
increasingly large and difficult to completely resolve by gas chroma-
tography and and/or by their corresponding mass cracking pat-terns. • However,
differentiation between the hydrocarbons; that is alkanes, alkenes,
aromatics, oxygenated, etc., can be made.
4 • 0 Reproducibility
The reproducibility of this method has been determined to range
from ±10 to ±30% of the relative standard deviation for different subs-
tances when replicate sampling cartridges are examined (5). The inherent
analytical errors are a function of several factors: [1] the ability to
accurately determine the breakthrough volume for each of the identified
organic compounds, [2] the accurate measurement of the ambient air
volume sampled, [3] the percent recovery of the organic from the sampling
cartridge after a period of storage, [4] the reproducibility of thermal
desorpt ion for a compound from the cartridge and its introduction into
the analytical system, [5] the accuracy of determining the relative
molar response ratios between the identified substance and the external
standard used for calibrating the analytical system, [6] the reproducibi-
lity of transmitting the sample through the high resolution gas chromato-
graphic column and, [7] the day-to-day reliability of the MS/COMP system
(1-8).
The accuracy of analysis is generally ±30%; however, the accuracy
of analysis is dependent on the chemical and physical nature of the
compound (2,8).
5.0 Advantages and Disadvantages of the Method
The gas chromatograph/mass spectrometer interfaced with a glass jet
separator, is extremely sensitive and specific for the analysis of many
volatile organic compounds in ambient air. High resolution gas chroma-
tographic separation provides adequate resolution of the substances
found in ambient air for the air subsequent quantification. The com-
bination of the high resolution gas chromatographic column and the
selection of specific or unique ions representing the various compounds
183
-------
of interest identified in the air samples yields a relatively specific
assay method for these compounds (1-8),
Collected samples can be stored up to one month with less than 10%
losses for most of the chemical classes (2,8). Because some of the
compounds of interest may be hazardous to man, it is extremely important
to exercise safety precautions in the preparation and disposal of liquia
and gas standards, cleaning of used glassware, etc. in the analysis of
air samples.
Since the mass spectrometer cannot be conveniently mobilized,
sampling must be carried out away from the instrument.
The efficiency of air sampling increases as the ambient air decreases
(i.e., sensitivity increases) (8).
The retention of water by Tenax is low; its thermal stability is
high; and its background is negligible allowing sensitivity analysis
(1,2,5,8).
6.0 Appa ratus
6.1 Sampling Cartridges
The sampling tubes are prepared by packing a ten centimeter long by
1.5 cm i.d. glass tube containing 6 cm of 35/60 mesh Tenax GC with glass
wool in the ends to provide support (2,5). Virgin Tenax (or material to
be recycled) is extracted in a Soxhlet apparatus for a minimum of 18
hours each time with acetone and hexane prior to preparation of cartridge
samplers (2,5). After purification of the Tenax GC sorbent and drying
in a vacuum oven at 100°C for 3 to 5 hours at 28 inches of water, all
the sorbent material is meshed to provide a 35/60 particle si2e range.
Cartridge samplers are then prepared and conditioned at 270°C with
helium flow at 30 ml/min for 30 min. The conditioned cartridges are trans-
ferred to Kimax (2.5 cm x 150 cm) culture tubes immediately sealed
using Teflon-lined caps and cooled. This procedure is performed in
order to avoid recontamination of the sorbent bed (2,5).
Cartridge samplers with longer beds of sorbent may be prepared
using a proportional increased amount, of Tenax in order to achieve a
larger breakthrough volume for compounds of interest, and thus increasing
the overall sensitivity of the technique (8).
-------
6.2 Gas Chromatographic Column
A 0.35 mm i.d. x 100 m glass SCOT capillary column coated with SE-
30 stationary phase and 0.1% benzyltriphenylphosphonium chloride is used
for effecting the resolution of the volatile organic compounds (5). The
capillary volume is conditioned for 48 hr at 245° at 2.25 ml/min of
helium flow.
A glass jet separator on a Varian MAT CH-7 GC/MS/COMP system is
employed to interface the glass capillary column to the mass spectrometer.
The glass jet separator is maintained at 240°C (2,5).
6.3 Inlet Manifold
An inlet manifold for thermally recovering vapors trapped on Tenax
sampling cartridges is used and is shown in Figure B.l (1,2,4,5).
6.4 Gas Chromatograph
A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet manifold (Figure B.l).
6.5 Mass Spectrometry/Computer
A Varian MAT CH-7 mass spectrometer with a resolution of 2,000
equipped with a single ion monitoring capability is used in tandem with
a gas chromatograph (Figure B.l).. The mass spectrometer is interfaced to
a Varian 620/L computer (Figure B.l).
7.0 Reagents and Materials
All reagents used are analytical reagent grade.
8.0 Procedure
8.1 Cleaning of Glassware
All glassware, sampling tubes, cartridge holders, etc. are washed
in Isoclean/water, rinsed with deionized distilled water and acetone, and
air dried. Glassware is heated to 450-500°C for 2 hr to insure that
all organic material has been removed prior to its use.
8 . 2 Preparation of Tenax GC
Virgin Tenax GC is extracted in a Soxhlet apparatus for a minimum
of 18 hr with acetone or methanol piror to its use. The Tenax GC sor-
bent is dried in a vacuum oven at 100°C for 3-5 hr and then sieved
to provide a fraction corresponding to 35/60 mesh. This fraction is
used for preparing sampling cartridges. In those cases where sampling
185
-------
cartridges of Tenax GC are recycled, the sorbent is extracted in a
Soxhlet apparatus with acetone or methanol as described for the virgin
material, but the sorbent is further extracted with a nonpolar solvent,
hexane, in order to remove the relatively nonpolar and nonvolatile
materials which might have accumulated on the sorbent bed during previous
sampling periods.
8.3 Collection of Volatile Organics in Ambient Air
Continuous sampling of ambient air is accomplished using a Nutech
Model 221-A portable sampler (Nutech Corp., Durham, NC, see Figure B.l
Reference 2). Flow rates between 1-10 1/inin are available with this
sampling system. Flow raLes are generally maintained at 1 1 using
critical orifices, and the total flow is monitored through a calibrated
flow meter. The total flow is also registered by a dry gas meter.
Concomitant with these parameters the temperature is continuously recorded
with a Meterological Research, Inc. Weather Station since the breakthrough
volume is important in order to obtain quantitative data on the volatile
organics. This portable sampling unit operates on a 12 volt storage
battery and is capable of continuous operation up to a period of 24
hr. However, in most cases at the rates which are employed in the
field, the sampling period is generally 1-3 hr. This portable sampling
unit is generally utilized for obtaining "high volume" samples. Duplicate
cartridges are deployed on each sampling unit utilizing a sampling head
as shown in Figure B.2.
In addition to the Nutech samplers, DuPont personnel samplers are
also used to acquire "low volumes" of ambient air as well as long-term
integrated samples (12-36 hr). Identical Tenax FC sampling cartridges
are employed in this case, and the sampling is conducted in duplicate.
The flow rate is balanced between duplicate cartridges using critical
orifices to maintain a rate of 25-100 ml/min per cartridge.
For large sample volumes, it is important to realize that a total
volume of air may cause the elution of compounds through the sampling
tube if their breakthrough volume is exceeded. The breakthrough volumes
of some of the volatile organics are shown in Table B.2 (2,4,7,8). These
breakthrough volumes have been determined by a previously described
186
-------
I
Figure B.2„ Sampling head for hou.sing cartridge sampling train.
187
-------
Table B.2. TENAX GC BREAKTHROUGH VOLUMES FOR SEVERAL ATMOSPHERIC POLLUTANTS1
Temperature (°F)
Chemical
Class Compound
b, p,
(°C) 50 60 70 80 90 TOO
halcgenated
hvdroearbon
methyl chloride
-24
8
6
5
4
3
2.5
methyl bromide
3,5
3
2
2
1
J.
0.9
vinyl chloride
13
2
1.5
1.25
1.0
0.8
0.6
methylene chloride
41
11
9
7
5
4
3
ch1e reform
61
42
31
24
18
13
10
carbon tetrachloride
77
34
27
21
16
13
10
1,2-dichloroethane
S3
53
41
31
23
18
14
1,1,1-tri ch1oroetihane
75
23
18
15
12
9
7
tetrachloroethyleae
121
361
267
196
144
106
73
trichlorouthylene
87
90
67
50
38
28
21
1-chloro-2-methylpropene
68
26
20
16
12
9
7
3-chloro-2-nielhylproperie
72
29
22
17
13
10
8
1, 2-d ichloropropane
95
229
152
1J 5
81
58
41
1,3-dichloropropane
121
343
253
184
134
97
70
epiehiorohydrin (1-chloro-
2,3-epoxypropane)
116
200
144
104
74
54
39
3-chloro-l-but ene
64
19
15
12
9
7
6
allyl chloride
45
21
16
12
9
6
5
4-chloro-l-butene
75
47
36
27
20
15
12
1-chloro-2~bu teiui
04
146
106
77
56
40
29
chlorobenzene
132
899
653
473
344
249
181
_o~dichlorobenzenc
181
1,531
1
,153
867
656
494
372
m-d j.chlorobcnzena
173
2,393
1
,758
1,291
948
697
5)0
benzyl chloride
179
2,792
2
,061
1,520
1,125
83C
612
br O'iiO t orin
149
50/
336
294
2 24
1/1
130
ethylene <11 bromide
131
348
255
28b
138
10 JL
74
bro;i.obenzene
155
2,] 44
1
,521
1,07 9
764
54 2
384
-------
Table B.2. (cont'd)
Temperature (°?)
Chemical
Class
Compound
b.p,
Cc)
50
60
70
80
90
100
halogenated
2-chloroethyl ethyl ether
108
468
336
241
234
124
89
ethers
Bis-(ehloromethy1)ether
-
995
674
456
309
209
142
nitrosamlnes
N-nitrosodimethylamine
151
385
280
204
163
148
107
N-nitrosodiethylamine
177
2,529
1,836
1,330
966
700
508
Oxygenated
acrolein
53
19
14
10
8
6
4
hydrocarbons
glycidaldehyde
_
364
247
168
114
77
52
propylene oxide
34
35
24
17
11
8
5
butadiene diepoxide
-
1,426
1,009
714
506
358
253
cyclohexene oxide
132
2,339
1,644
1,153
811
570
400
styrene oxide
194
5,370
3,926
2,870
2,094
1,531
1,119
phenol
183
2,071
1,490
1,072
769
554
398
ocotophenone
202
3,191
2,382
1,778
1,327
991
740
g-propiolactone
57
721
514
366
261
186
132
nitrogenous
nicromethane
101
45
34
25
19
14
11
hydrocarbons
aniline
184
3,864
2,831
2,075
1,520
1,114
817
sulfur
diethyl sulfate
208
40
29
21
15
11
8
compounds
ethyl methane sulfate
86
5,093
3,681
2,564
1,914
1,384
998
amines
dimethylamine
7.4
9
6
4
3
2
1
isobtitylamine
69
71
47
34
23
16
11
t-butylamine
89
6
5
4
3
2
1
di-(n-butyl)amine
159
9,506
7,096
4,775
3,105
2,168
1,462
pyridine
115
378
267
189
134
95
67
ani]ine
134
8,128
5,559
3,793
2,588
1,766
1,205
ethers
diethyl ether
34.6
29
21
15
11
8
5
propylene oxide
35
13
9
7
5
4
3
-------
Tabic B. 2. (cont'd)
Temperature (°F)
Chemical
Class
Compound
b.p.
(°C)
50
60
70
80
90
100
esters
ethyl acetate
77
162
108
72
48
32
22
methyl acrvlate
80
164
111
75
50
34
23
methyl nethacrylate
100
736
484
318
209
137
90
ketones
acetone
56
25
17
12
8
6
4
methyl ethyl ketone
80-2
82
57
39
27
19
13
methyl vinyl ketone
81
84
58
40
28
19
14
acetophenone
202
5,346
3
,855
2,767
2,
000
1,439
1,037
aldehydes
acetaldehyde
20
3
2
2
1
0.9
0.7
benzald ehyd e
179
7,586
5
,152
3,507
2,
382
1,622
1 ,101
alcohols
methanol
64.7
1
1
0.8
0.6
0.4
0.3
n-propanol
97 .4
27
20
14
10
7
5
allyl alcohol
97
32
23
16
11
8
6
aromatics
benzene
80.1
108
77
54
38
27
19
toluene
110,6
494
348
245
173
122
86
ethylbenzene
136,2
1,393
984
693
487
344
243
cumenc
152. 4
3,076
2
, 163
1,525
1,
067
750
527
hydrocarbons
n-hexane
68.7
32
2 3
17
12
9
6
n-lieptane
98.4
143
104
75
55
39
29
1-hexene
63.5
28
20
15
11
8
6
1-heptene
93.6
286
196
135
93
64
4 4
2, 2-diniethylbutane
49.7
0.5
0.4
0.3
0.2
0.2
0.1
2, 4-dimethylpentane
80.5
435
25 2
146
84
49
28
4-methyI-1-pentene
53.8
14
10
8
6
4
3
cycloliexane
80.7
49
36
26
19
14
10
-------
Tabic B.2. (cont'd)
Temperature (°F)
Chemical
Class
Compound
b. p.
(°C)
50
60
70
80
90
100
inorganic
nitric oxide
0
0
0
0
0
0
gases
nitrogen dioxide
-
0
0
0
0
0
0
chlorine
-
0
0
0
0
0
0
sulfur dioxide
-
0.06
0.05
0.03
0,02
0.02
0.01
water
100
0.06
0.05
0.04
0.03
0.01
0
Breakthrough volume is given in 1/2.2 g Tenax GC used in sampling cartridges
-------
technique (2). The breakthrough volume is defined as that point at
which 50% of 3 discreet sample introduced into the cartridge is lost.
Although the identity of a compound during ambient air sampling is not
known (therefore, also its breakthrough volume), the compound can still
be quantified after identification by GC/MS/COMP once the breakthrough
volume has subsequently been established. Thus, the last portion of the
sampling period is selected which represents the volume of air sampled
prior to breakthrough for calculating their concentration. For cases
when the identity of volatile organic compound is not known until after
GLC/MS, the breakthrough volume is subsequently determined.
Previous experiments have shown that the organic vapors collected
on Tenax GC sorbent are stable and can be quantitatively recovered from
the cartridge samplers up to 4 weeks after sampling when they are
tightly closed in cartridge holders and placed in a second container
that can be sealed, protected from light, and scored at 0° C (1,2).
8.4 Analysis of Samples
The instrumental conditions for the analysis of volatile organics
on the sorbent Tenax GC sampling cartridge are shown in'"Table:.B.3. SThe
thermal desorption chamber in the six-port valco valve is maltvt&inied'• a£
270° and 240°, respectively. The glass jet separator is maintained at
240°. The mass spectrometer is set to scan the mass range from 25-350.
The helium purge gas through the desorption chamber is adjusted to 15-2C
ml/min. The nickel capillary trap on the inlet manifold is cooled with
liquid nitrogen. In a typical thermal desorption cycle, a sampling
cartridge is placed in the preheated desorption chamber and the helium
gas is channeled through the cartridge to purge the vapors into the
liquid nitrogen capillary trap [the inert activity of the trap has been
shown in a previous study (5)]. After the desorption has been completed,
the six-port valve is rotated and the temperature on the capillary loop
is rapidly raised (greater than 10o/min); the carrier gas then introduces
the vapors onto the high resolution GLC column. The glass capillary
column is temperature programmed from ambient to 240° c at 4° C/'min and
held at the upper limit for a minimum of 10 min. After all the
192
-------
Table B.3.- OPERATING PARAMETERS TOR GLC-MS-CGMP SYSTEM
Parameter
Settins
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
270°C
220°C
-195°C
+180°C
4 min
GLC
100 m glass SC0T-SE-30
carrier (He) flow
transfer line to ms
25-240°C, 4/C° min
*^3 ml/min
240°C
MS
scan range
scan rate, automatic-cyclic
filament current
multiplier
ion source vacuum
m/e 20 -~ 300
1 sec/decade
300 pA
6-° _fi
^4 x 10 torr
193
-------
components have been eluted from the capillary column, the analytical
column is then cooled to ambient temperature and the next sample is
processed (2).
An example of the analysis of volatile organics ia ambient air is
shown-in Figure B.3 and the background from a hlaak Cfilftrifig©
Figure B.4. The high resolution glass capillary column was coated with
SE-30 stationary which is capable of resolving a multitude of compounds
to allow their subsequent identification by MS/COMP techniques; in this
case over 120 compounds were identified in this chromatograph.
8.4.1 Operation of the MS/COHP System (Figtire B«5)
Typically, the mass spectrometer is first set to operate in the
repetitive scanning mode. In this mode the magnet is automatically
scanned exponentially upward from a preset low mass to a high mass
value. Although the scan range may be varied depending on the particular
sample, typically the range is set from m/e 25 to m/e 300. The scan is
completed in approximately 1.8 sec. At this time che instrument
automatically resets itself to the low mass position in preparation for
the next scan, and the information is accumulated by an on-line 620/L
computer and written onto magnetic tapes or the dual disk system. The
reset period requires approximately 2.0 sec. Thus, a continuous
scan cycle of 3.8 sec/scan is maintained and repetitively executed
throughout the chromatographic run. The result is the accumulation of
a continuous series of mass spectra throughout the chromatographic run
in sequential fashion.
Prior to running unknown samples, the system is calibrated by
introducing a standard substance, perfluorokerosene, into the instrument
and determining the time of appearance of the known standard peaks in
relation to the scanning magnetic field. The calibration curve which is
thus generated is stored in the 620/L computer memory. This calibration
serves only to calibrate the mass ion over the mass scanning range.
While the magnet is continuously scanning, the sample is injected
and automatic data acquisition is initiated. As each spectrum is acquired
by the computer, each peak which exceeds a preset threshold is recognized
and reduced to centroid time and peak intensity. This information is
194
-------
90
*3
03
7C'-
20
CO:
CO
50'
LJ
JV-'V
TCvrES.VlJHt: tcC)
\:z ic--i
Oft
to
on
44
30
TIV-E
Figure B.3. Profile of ambient air pollutants for Wood River, IL using high resolution gas
chromatography/mass spectrometry/computer.
-------
Figure B.4
i,2o
/
5-3
63 DO S2
TEMPERATURE (°C)
104
115
140
I5<
Background profile for Tenax GC cartridge blank
-------
v£>
•Vj
TIT
Varian
620L
computer
Modem
interface
Sample
inlet/
manifold
Separator
1200 Baud
modem
Telephone
States
plotter
Random
access
disk
9-track
magnetic
tape
Gc column
(capillary)
Varlan CH-7
mass
spec trometer
Cyphernetics
time shared
PDP/10
Figure 1.5,
Schematic diagram of GC-MS computer system.
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stored in the computer core while the scan is in progress. In addition,
approximately 30 total ion current values and an equal number of Hall
probe signals are stored in the core of the computer as they are acquired.
During the 2-second period between scans this spectral infornation,
along with the spectrum number, is written sequentially on disks, and
the computer is reset for the acquisition of the next spectrum.
This procedure continues until the entire GC run is completed. By
this time there are from 800-1400 spectra on the disk which are then
subsequently processed. Depending on the information required, that day
may then either be processed immediately or additional samples may be
run, stored on magnetic tape, and the results examined at a "later time.
The mass spectral data are processed in the following manner.
First, the original spectra are scanned and the total ion current (TIC)
information is extracted. Then the TIC intensities are plotted against
the spectrum number on the Statos 31 recorder. The information will
generally indicate whether the run is suitable for further processing,
since it provides some idea of the number of unknowns in the sample and
the resolution obtained using the particular GLC column conditions.
The next stage of the processing involves the mass conversion of
the spectral peak times to peak masses, which is done directly via the
dual disk system. The mass conversion is accomplished by use of the
calibration table obtained previously using perfluorokerosene. Normally
one set of the calibration data is sufficient for an entire day's data
processing since the characteristics of the Hall probe are such that the
variation in calibration is less than 0.2 atomic mass units/day. A
typical time required for this conversion process for 1,000 spectra is
approximately 30 min.
After the spectra are obtained in mass converted form, processing
proceeds either manually or by computer. In the manual mode, the full
spectra of scans for the GC run are recorded on the Statos 31 plotter.
The TIC information available at this time is most useful for deciding
which spectra are to be analyzed. At the beginning of the runs where
peaks are very sharp nearly every spectrum must he inspected
198
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individually to determine the identity of the component. Later in the
chromatographic run when the peaks are broader only selected scans need
to be analyzed.
Identification of resolved components is achieved by comparing the
mass cracking patterns of the unknown mass spectra to an eight major
peak index of mass spectra. (9). Individual difficult and unknowns are
searched by the use of the Cornell University STIRS and PBM systems.
Unknowns are also submitted to EPA MSSS system for identification. When
feasible, the identification of unknowns are confirmed by comparing the
cracking pattern and elution temperatures for two different chroma-
tographic columns (SE-30 and Carbowax SCOT capillaries) for the unknown
and authentic compounds. The relationship between the boiling point of
the identified halogenated hydrocarbon and the elution temperature on a
nonpolar column (the order of elution of constituents is predictable in
homologous series since the SE-30 SCOT capillary separates primarily on
the basis of boiling point) is carefully considered in making structure
assignments.
Mass spectral search programs are operational at the Triangle
Universities Computation Center (TUCC). RTI maintains twice daily
service to TUCC, which is one-quarter mile distance from the RTI campus.
Additional information about each magnetic tape containing the mass
spectra of halogenated hydrocarbons is entered directly into the TUCC
job stream using a remote job entry processing. This is normally done
at TUCC using one of the five terminals located within the Analytical
Sciences Laboratory. The control information contains selected spectrum
numbers of instructions to process entire gc runs. The computer program
systems compare simultaneously either the entire library of 25,000
compounds or some subset of this library. The complete reports showing
the best fits for each of the unknowns is produced at TUCC and printed
out at the high speed terminals located on the RTI campus of TUCC.
Thus, the processing of the mass spectral data obtained for the halogena
ted hydrocarbons in the samples collected is processed by one of three
routes. Each consists of a different level of effort. The first level
is strictly a manual interpretation process which proves to be the most
199
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thorough approach. The second level is executed when the interpretation
at the first level has not yielded conclusive results.
8.4.2 Quantitative Analysis
In many cases the estimation of the level of pollutants by capil-
lary gas chromatography in combination with mass spectrometry is not
feasible utilizing only the total ion current monitor (See Figure B.3 fur
example). Since baseline resolution between peaks is not always achieved,
we employ the techniques which have been previously developed under
contract whereby full spectra are obtained during the chromatographic
separation step and the selected ions are presented as mass fragmentograms
using computer software programs which allow the possibility of deconvolu-
ting constituents which were not resolved in the total ion current
chromatogram (6). Examples are depicted in Figures B.6 and B,7 which
represent an ambient air sample with a TIC profile as in Figure B.3.
In our GC/MS/COMP system, we request from the Varian 62G/L dedicated
computer mass fragmentograms for any combination of m/e ions when full
mass spectra are obtained during chromatography. Thus, selectivity is
obtained by selecting the unique ion for that particular organic substance,
and this is represented vs. time with subsequent use of that ion intensity
for quantitation. Also, quantification with external standards is easily
achieved using the intensity of the total ion current monitor or the use
of a unique mass cracking ion in a mass spectrum of the external standard.
Thus, we use mass fragmentography for the quantitation of organics in
ambient air when the tota1 ion current monitor is inadequate because of
the lack of complete resolution between components in the mixture.
As described previously, the quantitation of constituents in ambient
air samples is accomplished either by utilizing the total ion current
monitor or, where necessary, the use of mass fragmentograms. In order to
eliminate the need to obtain complete calibration curves for each com-
pound for which quantitative information is desired, we use the method
of relative molar response (RMR) factors (10). Successful use of this
method requires information on the exact amount of standard added and
the relationship of RMR (unknown) to the RMR (standards). The method of
calculations is as follows:
200
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m/e 146
1
•»/© 166
m/e 117.
1
CC1,
Jl
1_j 1 i I i I j I i 1 i ! i I'll ' I i I i I ¦ 1 i i I i I i I i I i i 1. i Lj I i Lj I i_l i_l i 1 i.l i 1 j I
50
100 150 200
MASS SPECTRUM NO.
250
300
Figure B.6, Mass fragmentograms of characteristic ions representing carbon tetrachloride
(in/e 117), tetrachloroethylene (m/e 166) and m-dichlorobenzene (m/e 146)
in ambient air.
-------
methylene chloride
m/e 49.
K iV-A.
K)
O
ro
m/e 83
5
^ I
VJ
_A^
. 1 .. .1 i t ¦ > , i, J
J I L 1 !_]_J J 1 I L_J_
50
100 150
MASS SPECTRUM NO.
: jl_J j_J t L..1 j, ...i i 1. i—L
200 250
Figure B.7. Mass fragmentogranis of characteristic ion representing methylene chloride
(m/e 49) and chloroform (m/e 83) in ambient air.
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A /Moles ,
(1) RMR = EOJi
unknown/standard A ,/Moles
std stc
A = peak area, determined by integration or triangulation.
ihe value of RMR is determined frotr. at least three independent
analyses.
A /g /GMW .
(2) RMR . , , =
unk/std A ,/g / GMW
std std std
A = peak area, as above
8 = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
_ Aunk G,ft"unk ®std
Sunk A "•GMW " •RMR " ,
std std unk/std
The standard added can be added as an internal standard during
sampling, however, since the volume of air taken to produce a given
sample is accurately known, it is also possible and more practical to
use an external standard whereby the standard is introduced into the
cartridge prior to its analysis. Two standards, hexafluorobenzene and
perfluorotoluene, are used for the purpose of calculating RMR's. From
previous research it has been determined that the retention times for
these two compounds are such that they elute from the glass capillary
column (SE-30) at a temperature and retention time which does not inter-
fere with the analysis of unknown compounds in ambient air samples.
Since the volume of air taken to produce a given sample is accura-
tely known and an external standard is added to the sample, then the
weight can be determined per cartridge and hence the concentration of
the unknown. The approach for quantitating ambient air pollutants
requires that the RMR is determined for each constituent of interest.
This means that when an ambient air sample is taken, the external standard
is added during the analysis at a known concentration. It is not impera-
tive at this point to know what the RMR of each of the constituents in
203
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the sample happens to be, however, after the unknowns are identified.
Then the RMR can be subsequently determined and the unknown concen-
tration calculated in the original sample using the RMR. in this manner
it is possible to obtain qualitative and quantitative information on the
same sample with a minimum of effort,
9.0 References
1. Pellizzari, E. D., Development of Method for Carcinogenic Vapor
Analysis in Ambient Atmospheres, Publication No. EPA-650/2-74-121,
Contract No. 68-02-1228, 148 pp., July, 1974.
2. Pellizzari, E. D., Development of Analytical Techniques for
Measuring Ambient Atmospheric Carcinogenic Vapors. Publication No.
EPA-600/2-75-075, Contract No. 68-02-1228, 187 pp., November, 1975.
3. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Sawicki,
Envirou. Sci. Tech., 9, 552 (1975).
4. Pellizzari, E. D., B, II. Carpenter, J. E. Bunch and E. Sawicki,
Environ. Sci. Tech., 9, 556 (1975).
5. Pellizzari, E. D., The Measurement of Carcinogenic Vapors in
Ambient Atmospheres. Publication No. EPA-600/7-77-055, Contract
No. 68-02-1228, 288 pp., June, 1977.
6. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae,
Anal. Chem., 48, 803 (1976).
7. Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No.
68-02-2262, February, 1976.
8. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae,
Anal. Lett., 9, 45 (1976).
9. "Eight Peak Index of Mass Spectra", Vol. 1, (Tables 1 and 2) and
II (Table 3), Mass Spect romet ry Data Centre, AWRE, Aldermaston,
Reading, RT74PR, UP, 1970.
10. Pellizzari, E. D., Quarterly Report No. 3, EPA Contract No.
68-02-2262, in preparation.
Analytical protocol revised 1/24/77.
204
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TECHNICAL REPORT DATA
(/'lease read Instructions on the reverse before completing)
1 REPORT NO.
EPA-450/4-79-008a
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Study of "he Nature of Ozone, Oxides of Nitrogen,
5. REPORT DATE
and Nonmethane Hydrocarbons in Tulsa, Oklahoma -
Volume I: Project Description and Data Summaries
6. PERFORMING ORGANIZATION CODE
7. ALTHOR(S>
W, C. Eaton and F. E. Dimmock
8, PERFORMING ORGANIZATION REPORT NO.
0. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
1 1. CONTRACT/GRANT NO. 1
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
1 3. 1 YPfc Oh HfcPORT AND PER.OD COVERED
14. SPONSORING AGENCY CODE
1 G. SUPPLEMENTARY NOTES
EPA
Project Officer: Norman C. Possiel, Jr.
16. ABSTRACT
During the summer of 1977, Research Triangle Institute (RTI) conducted a field
measurements program entitled "Study of the Nature of Ozone, Nonmethane Hydrocarbons,
and Oxides of Nitrogen in Tulsa, Oklahoma." This volume of the report describes the
project and summarizes the data. The monitoring network consisted of eight RTI
ground sites and two Tulsa City/County Health Department sites. An airborne measure-
ments program employing a Piper Navaho B was an integral part of the study and is
described in detail.
Surface data are summarized through tables of mean daily concentrations, cumulative
frequency distributions, and diurnal plots, etc. Also included in this volume are:
descriptions and results of the quality control and quality assurance aspects of the
field study; an appendix describing the sampling and analytical methodology for GC/FID
identification of hydrocarbons; and an appendix describing the sampling and analysis
by GC/MS of volatile organic compounds collected on TENAX-GC polymer.
KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.lDENTJRERS/OPEN ENDED TERMS
c. cosati Field/Group
Ozone
Oxides of Nitrogen
Non-Methane Hydrocarbons
Pollutant Transport
18. DISTRIBUTION STATEMENT
Unlimited
19, SECURITY CLASS (This Report)
21. NO. OF PAGES
20. SECURITY CLASS (This page)
22. PRICE
EPA Form 2220-1 (Rev. 4-77) previous edition is obsolete
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