&EPA
United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Research Triangle Park NC 27711
EPA-600 4-80 006
January 1980
Research and Development
Regional Air
Pollution Study
Gas Chromatography
Laboratory Operation
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U S Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are
1 Environmental Health Effects Research
2 Environmental Protection Technology
3 Ecological Research
4 Environmental Monitoring
5 Socioeconomic Environmental Studies
6 Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8 "Special" Reports
9 Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL MONITORING series
This series describes research conducted to develop-new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations It also includes
studies to determine the ambient concentrations of pollutants m the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161
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ABSTRACT
A gas chromatography laboratory was set up to analyze air samples col-
lected in 100-liter Teflon bags and 8-liter stainless steel tanks. Samples
were analyzed for total hydrocarbons (THC), methane, and CO on a Beckman
Model 6800 gas chromatograph, and for C2-C-|0 hydrocarbons on a Perkin-Elmer
Model 900 gas chromatograph equipped with dual columns, connected to a PEP-1
data system. A phenyl isocyanate column resolved the Cp-Cr compounds and a
support-coated-open-tubular squalane column was used for Cfi-Cln compounds.
Experiments were performed to establish optimun temperature programming,flow
rates, and column lengths to yield good compound resolution within reasonable
elution times.
A total of 455 samples including replicates, were analyzed during the
summer and fall, 1976. Of these samples, 292 were collected at 12 of the
Regional Air Monitoring System (RAMS) sites to yield data on spatial and tem-
poral distributions of hydrocarbons. All were analyzed for THC, methane, CO,
and Cp-Cr hydrocarbons. In addition, early morning (0600-0800) samples were
analyzed for Cg-C-,g compounds. Portions of these data are included in this
report. Sampling results indicate excessive concentration of ethylene within
some of the RAMS stations, probably from the ozone monitoring system used at
all RAMS sites. Some samples collected during roadway studies were re-
analyzed on subsequent days; results showed good reproducibility using the
Teflon bags. System reproducibility from quality control checks was good;
with analyses of standards indicating deviations generally less than 5 per-
cent.
All data, including the sums of paraffins, olefins, aromatics and
total non-methane hydrocarbons are stored in the RAPS Data Bank at Research
Triangle Park, North Carolina.
m
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CONTENTS
Abstract iii
Figures vii
Tables viii
1.0 Introduction 1
2.0 Summary 2
3.0 Development of the Squalane Column 4
3.1 Literature Search 4
3.2 Development of the 60.96 and 30.48 Meter Columns 6
3.2.1 Preliminary Experiments 6
3.2.2 C?-Cr Analysis on the Phenyl Isocyanate
(Dura Pak) Column 7
3.2.3 Use of Dual Columns 7
3.2.4 Response Factors for Hydrocarbons Cg-C-m 12
4.0 Analysis of RAMS Stations Samples During the Summer and Fall
Intensives of 1976 16
4.1 Selection of Sampling Bags and Tanks 16
4.2 Ambient Air Sampling 19
4.2.1 Bag Preparation and Sample Collection 19
4.3 Ambient Air Sampling 22
4.4 Data Validation, Interpretation and Distribution 22
5.0 Special Studies 27
5.1 Collection and Analyses of Roadway Samples 27
5.2 Ethylene Studies 29
5.3 Special Audits 29
5.3.1 Total Hydrocarbon, Methane and Carbon Monoxide Audits . .31
5.3.2 Isobutane, Normal Hexane and Synthetic Bag
Mixture Audits 33
5.4 Special Studies at RAMS 103 and 107 33
5.5 Data Validation, Interpretation and Distribution 34
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CONTENTS (continued)
6.0 Quality Control 38
6.1 Standards for Beckman 6800 38
6.2 Standards for Perkin Elmer 900 38
6.3 Daily Standards 38
7.0 Data Processing 42
7.1 Data Tabulation 42
7.2 Keypunching and Processing 42
Literature Cited 44
Appendices
A. Operation of Beckman 6800 Gas Chromatograph 45
B. Operation of the Perkin Elmer 900 Gas Chromatograph 52
C. Data from Summer and Fall Intensives 65
D. Special Studies 117
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FIGURES
Number Page
1 Squalane Column Analysis of Atmospheric Sample for
^2 ~ ^10 Hydrocarbons 5
2 Laboratory Air - Phenyl Isocyanate Column 10/14/76
(New Method) 8
3 Sample of Ambient Air on the Squalane Column (New Method) . . 9
4 Hydrocarbons C2 - C5 on Dura Pak, 3 Minutes at 0°,
Programmed at 6°/Minute (Old Method) 10
5 Atmospheric Organics Analysis System - P.E. 900 11
6 Quantitative Study of Hydrocarbons C5 - CIQ 6/17/76 .... 13
7 Bag 17 Analyzed on the Phenyl Isocyanate Column 6/9/76. . . 17
8 Bag 17 Analyzed on Squalane Column 6/19/76 18
9 Background of Stainless Steel Tank 20
10 RAMS Bag Sampling System Flow Diagram 21
11 Five Point Calibration of Beckman Model 6800 Gas
Chromatograph 32
vn
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TABLES
Number Page
1 Experimentally Determined Response Factors for
Co - CIQ Hydrocarbons 14
2 Estimated Response Factors for Cfi - C,« Hydrocarbons. ... 15
3 Ambient Air Samples Analyzed in the Gas Chromatography
Laboratory 1976 23
4 Summary of Summer and Fall Intensives 1976 25
5 Average Carbon Monoxide to Acetylene Ratios 26
6 Carbon Monoxide to Acetylene Ratios of Roadway Samples. . . 28
7 Storage of Roadside Samples in Teflon Bags 30
8 Carbon Monoxide Audits 31
9 Methane Audits 31
10 Isobutane, N-Hexane and Special Bag Audits 33
11 Quantitative Studies at RAMS 103 and 107 35
12 Propane Standard 40
13 Toluene Standard 41
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1.0 INTRODUCTION
The Regional Air Pollution Study (RAPS) is directed toward a quantita-
tive understanding of urban pollution, including the monitoring of ambient
levels of pollution, the gathering of micro-meteorological data and of a
comprehensive emission inventory.
The gas chromatography laboratory was established to support these
investigations. In particular it was charged with the collection and
analysis of samples of hydrocarbons C-, - C-.Q, carbon monoxide and tracer
gases in ambient air. In order to find a more accurate and selective
method for identifying hydrocarbons C~ - C,Q, modifications were made on
the Perkin Elmer 900 Gas Chromatograph such that detailed analyses of these
hydrocarbons in the parts-per-billion range could be performed. Samples
were run and the results were tabulated and classified.
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2.0 SUMMARY
The gas chromatography laboratory modified the analysis of C2 - C,«
hydrocarbons from the methods described in the final reports of Task Orders
53 and 103. A Perkin Elmer (P.E.) Model 900 gas chromatograph equipped with
dual columns and a PEP-1 data system was used. A phenyl isocyanate (Dura
Pak) column gave good resolution for C~ - Cr compounds and a Support-Coated-
Open-Tubular (SCOT) squalane column was used to analyze hydrocarbons Cfi -
C,n< The modifications included shortening the SCOT squalane column from
30.48 meters to 15.24 meters and raising the initial temperature from -3°C
to 25°C. These changes permitted the accurate and methodical identification
of hydrocarbons Cfi - C,Q on the squalane column with an analysis time of 55
minutes. As result of these modifications the precision of the analyses done
on the squalene column was improved as indicated by the reproducibility of the
analysis of a toulene standard over a three month interval.
A total of 455 samples of ambient air (including triplicate analyses)
was analyzed during the summer and fall intensives and for special studies
during this task order period. These samples were collected from RAMS sta-
tions and roadside locations and were analyzed for total hydrocarbons (THC),
carbon monoxide (CO) and methane (CH.) on the Beckman Model 6800 gas chro-
matograph and hydrocarbons C? - C,« on the P.E. 900 gas chromatograph.
Two hundred and ninety-two ambient air samples from twelve RAMS sites
were analyzed during the summer and fall intensives. All of the samples were
analyzed for THC, CH., and CO (Beckman 6800) and C2 - C5 hydrocarbons (P.E.
900). The 0600-0800 (CST) samples were analyzed for THC, GIL and CO and C?
- C-,^ hydrocarbons (P.E. 900). Tables containing a portion of these data are
in Appendix C.
High concentrations of ethylene at RAMS sites 101 and 124 led to a
special study of ethylene concentration. The samples were collected in 100
litre Teflon bags (5 mil thickness) and 8 litre stainless steel tanks, in
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and around the stations as requested by the EPA Task Coordinator. The results
of this special study indicate that in certain cases the values reported for
ethylene may be biased by fugitive emission of ethylene from the ozone monitor
and associated hardware found in each of the RAMS stations.
Roadway samples were analyzed by the gas chromatography laboratory for
a special study conducted by the EPA Task Coordinator. Some of the samples
were reanalyzed on subsequent days. Relatively good reproducibility was obtained
using the 5 mil Teflon bags.
To insure quality control, standards were run daily and records main-
tained of the areas and peak heights. The triplicate analyses of the first
bag sample each day showed a standard deviation of less than 2.0 ppbC for the
task order period.
All of these data, including the sums of the paraffins, olefins, aromatics
and total non-methane hydrocarbons, were processed and prepared for entry into
the RAPS Computer Data Bank, Research Triangle Park (RTP), North Carolina.
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3.0 DEVELOPMENT OF THE SQUALANE COLUMN
In the past, the gas chromatography laboratory experienced some diffi-
culty in the analysis of C,- - C,~ compounds on the squalane column. During
Task Orders 53 and 103 periods the initial 60.96 meters x 0.05 cm squalane
SCOT column was reduced to 30.48 meters because of excessive column bleed
(1, 2). A Carbowax 20M-TPA on Chromosorb W-AW post column was added during
Task Order 53 but was replaced with glass beads during Task Order 103
because of the problems incurred with the Carbowax column. A potassium
carbonate (K?CO.,) pretrap was added during Task Order 53 in order to minimize
the effect of water and polar compounds in the squalane system. Figure 1
is an example of hydrocarbons C2 - C,Q analyzed during both task order
periods. Because of the length of time required for analysis and the broaden-
ing of the peaks, Cq - C,- were not really identified. Alternate methods of
analysis were explored.
The literature was searched and the problem examined in a systematic
manner with the aim of developing a method of analysis that: (1) provided a
reliable basis for identification of hydrocarbons on the squalane SCOT column;
(2) could be easily incorporated in the equipment of the laboratory; and (3)
preferably employed only one column for the analyses of compounds C? - Clfr
3.1 LITERATURE SEARCH
Extensive work on the squalane SCOT column has been reported in the
literature. W. 0. McReynolds (3) and others described the analyses of
hydrocarbons C,-, - C,n on 60.96 and 30.48 meters x 0,05 cm columns. The
problem encountered was the length of time required to complete the analyses
since in some cases five or more hours were required, L. S. Ettre (4)
described the analysis of C-, - CQ hydrocarbons on a 30.48 meter x 0.05 CM
column requiring only 35 minutes. The method, although attractive, had
some shortcomings: it did not identify all the compounds in which the gas
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N-Bu-C6Hs
M.P-XYL.
0-XYL.
E~-C.H5
2,3,5TM-CSH9 N-C8H18
2,3,3TM-C5H9
2,3.4TM-CSH,,
Toluene
2,5DM-C«H12
2 2 4TM-
^' '
2,4DM-CSHIO
2,3DM-C4H8
-CSH
3M-1-C5H9
2,2DM-C4H6
N-C,H«
Sn12
1-CsHT'
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chromatography laboratory was interested, e.g. ethyl benzene, the xylenes
and decanes; therefore, modifications had to be made.
3.2 DEVELOPMENT OF THE 60.96 AND 30.^8 METER COLUMNS
3.2.1 Preliminary Experiments
Two 100 litre Teflon bags were filled with 50 litres of Scotl-Marrin
ultrapure air by using a mass flow meter which was corrected for standard
temperature and pressure. Bag 1 was injected with 10 ml of each of the
following gases using the appropriate size precision sampling syringe:
methane (CH.), ethane (C^Hg), ethylene (C2H,), propane (C-I-L), acetylene
(C2H0), isobutane (I-C.H,Q), normal butane (N-C.H,Q); and 0.05 ml each of
the following liquids: isopentane (I-Cj.H,?), normal pentane (N-C,-H,2),
hexane (CCH,.), heptane (C7H,C), toluene (C-,H0), octane (C0H,0), ethyl
014- / IO / O O IO
benzene (CoH,»), rneta xylene (CoH,Q), ortho xylene (CRH,n), nonane (CgH,,-.),
mesitylene (CgH,2) and decane (C,QH22). After equilibration, one milliliter
of this mixture was injected into Bag 2 (dilution bag). The diluted
contents of Bag 2 were analyzed on the 60.96 and 30.^8 meters x 0.05 cm
squalane columns.
The 60.96 and 30.48 meters squalane columns provided acceptable
separation for hydrocarbons C, - C.,; but, the heavier hydrocarbons (Co -
C,n) took an exceptionally long time to elute. The physical conditions
(flow rate and temperature) were the same as described in the final report for
Task Orders 53 and 103. In an attempt to overcome the elution problem with
the heavier hydrocarbons, the initial oven temperature was varied from -3°C to
0°, 3°, 15° and 25°C and the final temperature from 75°C to 90°C and 115°C.
The carrier gas flow rate was increased from 12 cc/min. to 15 cc/min. The
results of these changes were not satisfactory; an increase in temperature
and carrier gas flow rate yielded no data on C, - Cfi hydrocarbons (they
eluted in the initial 15 seconds) and the higher temperatures yielded
significant shifts in the baseline of the chromatograph at 90°C and above.
These changes had little or no effect on the heavier hydrocarbons.
The 15.24 meter squalane SCOT column was then employed and was found
suitable for the analyses of Cfi - C,~ hydrocarbons. It was found that
hydrocarbons C, - Cj. elute too fast (within the first two minutes) to be
-------
properly identified. The hydrocarbons were analyzed under the same physical
conditions (temperatures and flow rates) as described for the 60.96 and
30.48 meters columns. The initial temperature was increased to 25°C and
the final temperature increased to 90°C; the carrier gas flow rate remained
at 12 cc/min. These conditions proved ideal for the analysis of hexane,
which eluted at 3.6 minutes, through normal butyl benzene, which eluted at
55 minutes. It was then decided to continue to employ two columns in the
P.E. 900 in the analyses of hydrocarbons C^ - C,Q. Figures 2 and 3 show
typical examples of ambient air analyzed with the two columns employed in
the P.E. 900 gas chromatograph.
3.2.2 C2 - Cr Analysis on the Phenyl Isocyanate (Dura Pak) Column
During the preceding task order period (103) C? - C,- hydrocarbons were
analyzed on the 1.83 meter x 0.63 cm ID phenyl isocyanate (Dura Pak)
column where the initial oven temperature was held at 0° for 3 minutes then
programmed at a rate of 6°/minute until normal pentane (N-C^H-,,,), the last
compound analyzed on the column, eluted. The whole analysis took 13 minutes
to complete.
With the modified procedure, initial oven temperature at 25°C for 8
minutes, the programmed at a rate of 2°/minute and employing the Dura Pak
column, normal pentane elutes in 10 minutes. Figures 2 and 4 show that the
change in environment had no adverse effect on the C^ - C,- analysis.
3.2.3 Use of Dual Columns
The analysis of hydrocarbons Cp - C-.Q was accomplished by using two
columns connected to two flame ionization detectors in the Perkin Elmer
Model 900 gas chromatograph (Figure 5 shows the schematic diagram of the
analysis system). Hydrocarbons Cp - C,- were analyzed on a 1.83 meter x
0.63 cm ID phenyl isocyanate (Dura Pak) column that was conditioned by
heating it at 115°C with helium flowing through over a 24 hour period.
Hydrocarbons Cg - C,Q were analyzed on a 15.24 meter x 0.05 crn ID squalane
SCOT column that was conditioned at 115°C with helium flowing through over
a 60 hour period. Both columns shared the same oven which was held at 25°C
for eight minutes, then programmed at a rate of 2°C per minute until the
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Tnm IT i i jw ~~
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FIGURE 2. LABORATORY AIR - PHENYL ISOCYANATE
COLUMN 10/14/76 (NEW METHOD)
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MINUTES 1 23 4 5 6 7 8 9 10 11 12 13
TEMPERATURE °Ck 0 *t 6 12 18 24 30 36 42 48 54 60
FIGURE 4. HYDROCARBONS C0 - Cc ON DURA PAK , 3 MINUTES AT Oc
d. b
PROGRAMMED AT 6°/MINUTE (Old Method)
10
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system reached 90°C, where it was held for the remainder of the analysis.
The total analysis times were 10 minutes for hydrocarbons C9 - Cr on the
L, O
Dura Pak column and 55 minutes for hydrocarbons C, - C,n on the squalane
column.
3.2.4 Response Factors For Hydrocarbons C^ - C,~
In order to obtain accurate response factors (RF) for Cr - C1A hydro-
b I U
carbons for the squalane column, two synthetic mixtures of the various
compounds were carefully prepared, using the procedure described in Section
3.2.1, then analyzed on the P.E. 900 gas chromatograph. The concentrations
of the liquid compounds were computed in the following manner.
Example: Toluene
22.4 x I/mole x g i x 0.8669 - x 0.05 ml
Bag-1 -- - = 228 ppm
50 litres of ultrapure air
n 0 1 ml of contents of Bag 1 x 228 ppm -, , . 01 n . r
Bag-2 - - - a - nL- x 7 carbon number = 31.9 ppbC
50 litres of ultrapure air
The PEP-1 computer was programmed in such a manner (area normalization)
that only the areas of the selected compounds were computed. The response
factors for the hydrocarbons were calculated in the following manner.
Example: Toluene
concentration
RF =
RF =
area x 5
31.9
2.044 x5
RF = 3.12
Figure 6 shows an example of a chromatograph that was used in calculating
the response factors for hydrocarbons Cg - C,,,. It was observed that
although equivalent amounts of each hydrocarbon were in the final mixture,
the detector of the P.E. 900 indicated varying integrated peak areas. Table
1 shows experimentally determined response factors for C? - C,n hydrocarbons.
In instances where the pure compound could not be obtained for analysis,
the response factors were estimated (Table 2).
12
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TABLE 1. EXPERIMENTALLY DETERMINED RESPONSE FACTORS
FOR
- C1Q HYDROCARBONS
COMPOUNDS
Ethane
Ethyl ene
Propane
Acetylene
Isobutane
N-Butane
Propylene
Iso-Pentane
N-Pentane
N-Hexane
Trans 2-Hexene
Cis 2-Hexene
Cyclobexane
N-Heptane
Toluene
Octane
Ethyl Benzene
Methyl Xylene
Ortho Xylene
Nonane
N-Propyl Benzene
Mesitylene
N-Decane
N-Butyl Benzene
RESPONSE FACTOR (RF)
3.91
3.85
4.12
4.84
4.50
4.16
4.36
4.11
4.10
4.24
3.72
3.72
3.74
2.98
3.12
3.26
3.39
3.61
3.67
2.99
3.94
3.88
4.34
4.16
14
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TABLE 2. ESTIMATED RESPONSE FACTORS FOR C, - C1n HYDROCARBONS
o KJ
COMPOUNDS RESPONSE FACTOR (RF)
Olefins Cg to CIQ 3.70
Paraffins Cft to Cin 3.50
0 ID
Alkyl Aromatics 3.80
15
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4.0 ANALYSIS OF RAMS STATIONS SAMPLES DURING THE
SUMMER AND FALL INTENSIVES OF 1976
During the period of performance of Task Order 113, the gas chromatography
laboratory analyzed atmospheric samples from various RAMS stations. Sampling
commenced on 23 June 1976 with a collection of two or four samples per site,
five sites per day, two days per week. The choice of sites and times of
sampling were determined by the EPA Task Coordinator. The sampling period
ended on 18 November 1976.
4.1 SELECTION OF SAMPLING BAGS AND TANKS
Ambient air samples were collected in Teflon bags and stainless steel
tanks. The 100 litre Teflon bags (5 mil thickness) were checked for leaks
by filling the bags with approximately 60 litres of helium, then gotng over
them thoroughly (especially the seams and Teflon fittings) with a Gow Mac
helium leak detector. The detector was zeroed, then the detector's nozzle
was passed over the bag. If the gauge remained at zero, the bag was leak
free; but, if the gauge moved from zero, the bag contained a leak. Leaks
that occurred around the fittings were repaired by tightening them. Bags
with leaks in their seams were set aside to be repaired at RTP in Durham,
N.C. The "leak free" bags, filled to capacity with helium, were left on
the shelves overnight, then again checked for leaks. These bags were
purged three times with helium then filled with approximately 60 litres of
ultrapure air and again left on the shelves overnight. The bags were
analyzed on the Beckman 6800 for THC, CH4 and CO and the P.E. 900 for
C2 " C10 nydrocarbons- Ba9s possessing more than 2 ppbC of hydrocarbons
were put aside; those having less than 2 ppbC hydrocarbon contamination
were placed into circulation to be used in the RAMS sampling system. A
supply of at least 25 "good bags" were kept in the system at all times.
Bags were replaced in the system as needed. Figures 7 and 8 show the
background chromatographs of a typical good bag.
16
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FIGURE 8. BAG 17 ANALYZED ON SQUALANE COLUMN 6/19/76
18
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During the 1976 fall intensive and special studies periods, four 8
litre stainless steel tanks were introduced into the sampling system. The
tanks were fitted with a vacuum gauge on the rear and a two way needle
valve on the front. The tanks were purged with helium, pressurized to approxi-
mately 30 psi with ultrapure air, and left to stand overnight in order to
ascertain the amount of leakage and the degree of hydrocarbon contamination.
The contents of the tank were analyzed on the P.E. 900 gas chromatograph
the following day. The air in the tanks was removed by attaching a regulator
with a quick connect fitting to the two-way valve. The valve was opened all
the way so that fractionating of the gases would not occur and the regulator
was partially opened. The quick connect fitting was joined to its counterpart
on the P.E. 900 in injection mode (see Figure 5). Three of the four tank3
were found suitable for sampling. Figure 9 shows an example of a chromato-
gram of a hydrocarbon-free stainless steel tank.
4.2 AMBIENT AIR SAMPLING
The gas chromatography laboratory was responsible for the bag prepara-
tion, placing bags at the RAMS stations, sample transportation, sample
analyses, data validation and computer tape and printout distribution of
the data. These were accomplished as follows:
4.2.1 Bag Preparation and Sample Collection
In order for the Teflon bags to be in place at the RAMS stations at
0600 hours CST, they were purged three times with helium and stored in a box
at 0400 on the sampling day. The bags were transported to the various sites
in a van and placed in the bag boxes at the RAMS stations. Figure 10 shows
the sampling system and the flow diagram of the system at each site. A glass
wool filter was used for the removal of ozone and particulants.
One bag was placed at each site in each bag box and upon command from
the central computer at 0600 CST, the port between 1 and 2 would open on
box 1 (see Figure 10) and air would flow through for two hours at an approxi-
mate rate of 833 cc/minute. (This rate varied somew twhat from station
to station owing to the idiosyncrasy of the equipment at that station.) The
port between 1 and 2 would open and ambient air would flow through 2
19
-------
ffi"
m
IQ/27/7&
FIGURE 9. BACKGROUND OF STAINLESS STEEL TANK
20
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SAMPLING MANIFOLD
3 PORT
SOLENOID
VALVE
GLASS WOOL
FILTER
VACUUM
BOX
TOO LITRE
5 MIL TEFLON
BAG
FLOW METER
NEEDLE VALVE
VACUUM
MANIFOLD
5
VACUUM
PRESSURE
METER
FIGURE 10. RAMS BAG SAMPLING SYSTEM FLOW DIAGRAM
21
RELIEF VACUUM EXHAUST
VALVE PUMP
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to 1, then into the bag. Although port 3 was closed, the vacuum pump con-
tinued to evacuate the air in the air box; this caused the ambient air
to fill the bag.
After two hours, a command from central would shut off the air flow on
box 1 and turn on the air flow of box 2 and the procedure would be repeated.
The 0600 ambient air samples were removed and an empty bag put in its
place in order to collect a sample at 1000-1200 hours. This procedure con-
tinued until the final samples were collected at all stations at 1200-1400
hours. The ambient air samples, protected from direct sunlight, were trans-
ported back to the laboratory for analyses.
4.3 AMBIENT AIR SAMPLING
Ambient air samples, which were collected in the 100 litre Teflon bags
at the RAMS stations over a two hour period of time, were analyzed for THC,
CH. and CO on the Beckman 6800 and for hydrocarbons C~ - C,n on the Perkin
Elmer 900 (procedures are described in Appendices A and B). Initially all
bag samples were analyzed for all compounds but this proved too difficult due
to the late arrivals of the 0600-0800 and 0800-1000 samples at the laboratory
(13:00-14:00 hours), the number of samples (maximum of 16) and the time
required to complete the squalane analysis (1.5 hours including printout
and turnaround times). The following changes were made by the EPA Task
Coordinator: ambient air samples that were collected at 0600-0800 hours
were analyzed for THC, CO and C, - C,Q and subsequent bags were analyzed
for THC, CO and C, - C,-. Table 3 shows the number of ambient air samples
analyzed by the gas chromatography laboratory during this Task Order period.
The analyses commenced immediately upon arrival of the bags at the laboratory
and continued until all analyses were complete for all samples, which required
the operation of two shifts at the laboratory.
4.4 DATA VALIDATION, INTERPRETATION AND DISTRIBUTION
Each chromatogram of ambient air samples of the summer and fall inten-
sive was visually analyzed by the EPA Task Coordinator and laboratory per-
sonnel working together. At the conclusion of the Intensive and data valida-
tion, the arithmetic mean and standard deviation of the concentrations of all
time segments were calculated for total hydrocarbons (THC), methane (CHA),
22
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TABLE 3. AMBIENT AIR SAMPLES ANALYZED IN THE
GAS CHROMATOGRAPHY LABORATORY 1976
MONTH NUMBER
June 20
July 98
August 96
September 9
October 0
November _69_
TOTAL 292
23
-------
carbon monoxide (CO) and acetylene (C?H?). Table 4 shows data on a station by
station basis. The sums of the parafins, olefins, aromatics and total non-
methane hydrocarbons per sample were calculated and recorded. The validated
data, on one copy of a 600 foot, 9 track, 800 BPI, odd parity magnetic data
tape, along with two copies of the printout were given to the EPA Task Coordi-
nator. Appendix C contains some of the results of the data collected during
the summer and fall intensives.
The carbon monoxide to acetylene ratios were computed from the arith-
metic mean for each station where acetylene was consistently analyzed.
These data are shown in Table 5. It should be noted that acetylene was not
present in sufficient quantities to be analyzed at all times for many of
the RAMS sites.
24
-------
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25
-------
TABLE 5. AVERAGE CARBON MONOXIDE TO ACETYLENE RATIOS
RAMS STATION
Summer 101
Summer 103
Summer 114
Summer 115
Summer 118
Summer 122
Summer 124
Fall 101
Fall 103
Fall 114
Fall 115
RATIO OF CO TO C0H0
L. C.
96
177
84
143
142
127
196
"X = 1 38 S =40
X
56
72
62
71
I = 65 S = 8
X
26
-------
5.0 SPECIAL STUDIES
Special studies and audits were carried out by the gas chromatography
laboratory, as requested by the EPA Task Coordinator. These included road-
way sampling, ethylene concentration verifications and audits on various gas
samples.
5.1 COLLECTION AND ANALYSES OF ROADWAY SAMPLES
The EPA Task Coordinator requested and collected roadway samples for the
gas chromatography laboratory to analyze THC, CO and C, - C,n hydrocarbons.
A mobile air monitoring laboratory was used as the vehicle from which the
samples were collected from heavily traveled thoroughfares during the morning
rush hours. The bags used as containers for ambient air samples were purged
three times with'helium, filled with approximately 60 litres of helium,
then left with the EPA Task Coordinator the day prior to sampling. Prior to
sampling, a metal bellows pump was used to purge the bag of the helium, fill
the bag with approximately 60 litres of ambient air, then purge the bag
again. The 50-60 litre ambient air sample for analysis was collected by
using the metal bellows pump with a Teflon sample line (~ 1.2 m long) extended
out of the driver's side of the mobile laboratory for periods of 5-10 minutes.
The samples were transported back to the laboratory for analysis. These
roadway samples were collected mainly from 1-270, 1-40, Olive Road, Manchester
Road and Babler Park. Detailed analytical results are contained in Appendix D.
The carbon monoxide to acetylene ratios were computed for each sample
collected. The arithmetic mean of the ratio, 68.5, (Table 6) is similar to the
carbon monoxide to acetylene ratio (63.4 ji6.1) computed for automobile
emissions in the Lincoln Tunnel by EPA researchers (5).
27
-------
TABLE 6. CARBON MONOXIDE TO ACETYLENE RATIOS OF ROADWAY SAMPLES
Location
Manchester Road
1-40
1-270
N on 1-270 (1-40 to Olive)*
W on Manchester
W on Olive
N on 1-270 Olive to Page
W on Manchester (1-270 to
Date
9/22/76
9/22/76
9/22/76
9/27/76
9/27/76
9/27/76
9/27/76
Ratio of CO to C0H0
i- L
70
78
60
(41)
55
76
83
Weidman Road) 10/29/76 60
W on Manchester
Weidman Road to Ries Rd. 10/29/76
S
N
on 1-270 (Manchester to 1-44) 10/29/76
on 1-270 (1-44 to
Babler Park**
01
ive to Eatherton
Manchester) 10/29/76
9/22/76
(west of airport)**9/22/76
61
67
75
1= 68.5 S = 9.35
X
96
61
* Extremely high acetylene - not used in determining X and S
f
**Rural Samples
28
-------
In order to ascertain the quality of data obtained from ambient air
samples stored in Teflon bags over a period of time, the EPA Task Coordin-
ator requested that some of the roadway samples be analyzed on the day
collected and again 48 and 168 hours later. Table 7 shows samples collected
from Manchester Road, 1-40 and 1-270 at the requested times.
5.2 ETHYLENE STUDIES
Ethylene studies were carried out at RAMS stations 101 and 124 on 20,
22, 28 and 31 October 1976 and 1 and 4 November 1976 because of periodic
abnormally high concentrations of that compound found in these stations
during the summer intensive. Ethylene was of particular interest because
of its use with the ozone analyzers at the RAMS stations. For these studies,
the ambient air samples were collected in 100 litre Teflon bags and in 8
litre stainless steel tanks. The samples were taken from the following
locations on various days:
A. From RAMS station bag box with a sample taken outside simulta-
neously, 10-17 meters upwind and 2-3 meters above the ground using
a metal bellows pump.
B. Inside the station between the pump box and bag box.
C. From the outlet of the center most blower of the pump box.
D. From the outlet of the vacuum pump in pump box.
The bags and tanks were immediately transported back to the laboratory
and analyzed on the phenyl isocyanate column of the Perkin Elmer Model 900
gas chromatograph for C2-Cj- hydrocarbons. Detailed analytical results are
contained in Appendix D.
5.3 SPECIAL AUDITS
At the request of the EPA Task Coordinator, the cylinders MM11435,
MM11437, MM11436 (from Scott-Marrin) and cylinder number FF3753 (from AIRCO
Industrial Co.) were analyzed for CO, THC and CH. and RSG-80-4802 and
RSG-80-7384 (from AIRCO Industrial Co.) for isobutane and normal hexane
respectively. The audits were done in the following manner.
29
-------
TABLE 7. STORAGE OF ROADSIDE SAMPLES IN TEFLON BAGS*
MANCHESTER ROAD INTERSTATE 40
tC9/22/76
§A9/22/76 A9/24/76 A9/28/76 A9/22/76 A9/24/76
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N"C4H10
C3H6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N-C7H16
Toluene
N-CgHlg
E"C6H5
M-XYL
0-XYL
N"C9H20
N-P-Cx-H,-
0 0
N-C1QH22
22.3
157.1
27.6
111.5
15.2
91.0
73.7
125.0
68.0
46.0
15.0
72.0
12.0
30.0
77.0
30.0
4.0
5.0
16.0
22.2
148.6
26.7
99.5
14.5
88.0
69.8
119.0
64.0
41.0
15.0
71.0
14.0
36.0
93.0
36.0
4.0
8.0
9.0
24.0 18.9
158.5 127.3
29.0 14.4
105.4 83.1
15.8 11.3
94.0 68.0
74.2 60.3
130.0 84.0
72.0 41.0
64.0
32.0
165.0
16.0
68.0
136.0
65.0
4.0
6.0
19.1
12V.O
14.2
78.0
11.1
66.0
57.3
81.0
38.0
27.0
14.0
67.0
12.0
37.0
90.0
32.0
1.0
2.0
5.0
INTERSTATE 1-270
A9/22/76 A9/24/76 A9/28/76
42.0
253.0
54.8
190.1
19.8
131.0
112.7
172.0
86.0
38.0
51.0
239.0
45.0
107.0
277.0
91.0
21.0
18.0
41.0
47.1
280.1
61.5
208.2
24.2
149.0
125.0
191.0
85.0
87.0
28.0
140.0
25.0
66.0
131.0
56.0
10.0
10.0
25.0
44.9
254.4
56.8
185.0
22.0
137.0
113.5
179.0
94.0
* Concentration in ppbC
t C - Collected
§ A - Analyzed
30
-------
5.3.1 Total Hydrocarbon, Methane and Carbon Monoxide Audits
A five point calibration (Figure 11) was performed on the Beckman 6800
as described in Appendix A. The tanks to.be audited were analyzed on the
gas chromatograph and their concentrations determined from the 5-point
calibration curve.
The results of the audit on 10/21/76 are shown in Tables 8 and 9.
TABLE 8. CARBON MONOXIDE AUDITS
Manufacturer's
Tank # Cone, in ppm
MM11435 1
MM11436
MM11437
*FF3753
L-2359
L-1749
*Tank prepared
5.35
8.00
5.02
5.06
5.11
by EPA at
Manufacturer's
Tank # Cone, in ppm
MM11435
MM11436
MM! 1437
*FF3753
L-1749
L-2359
8.04
4.98
2.02
1.99
1.95
Rock we!
Cone, in
16.24
8.31
5.23
21.62
5.33
RTF
TABLE 9
Rockwel
Cone, in
7.81
4.83
1.95
5.85
1.81
1.82
% Difference
1 Rockwell vs.
ppm Manufacturer
5.5
3.7
4.0
5.1
. METHANE AUDITS
% Difference
1 Rockwell vs.
ppm Manufacturer
2.9
3.0
3.5
9.0
6.7
EPA
Cone, in ppm
15.56
8.17
5.16
20.32
5.29
5.34
EPA
Cone, in ppm
8.35
5.23
2.08
6.33
2.09
2.20
% Difference
Rockwell vs.
EPA
4.2
1.7
1.3
6.0
0.7
I Difference
Rockwell vs.
EPA
6.5
7.6
6.3
7.6
13.4
17.3
*Tank prepared by EPA at RTP
31
-------
160-
140-
120-
100-1
80H
60-
40-
20-
T
2
T
3
r
4
r
5
THC
©CH4
SCO
FIGURE 11. FIVE POINT CALIBRATION OF BECKMAN
MODEL 6800 GAS CHROMATOGRAPH
32
-------
5.3.2 Isobutane, Normal Hexane and Synthetic Bag Mixture Audits
Audits were performed on AIRCO cylinders RGS-80-7384 and RGS-80-4802
containing isobutane and normal hexane respectively in nitrogen and on a
synthetic mixture of carbon monocide and methane in ultrapure air. In order
to perform these audits, primary standards were prepared of I-C.H,^ and
N-CgH,. as described in Appendix B and a 5-point calibration was performed
to facilitate the analysis of the synthetic bag mixture of CO and CH. whfch
was prepared by the EPA Task Coordinator, The results are given in Table 10.
TABLE 10. ISOBUTANE, N-HEXANE AND SPECIAL BAG AUDITS
AIRCO RGS-8Q-7384 AIRCO RGS-80-4802
Isobutane Hexane
Cone, in ppm Cone, in ppm
Manufacturer 57.0 50.0
Rockwell 62.1 36.5
EPA 58.4 47.0
The results of the special bag samples are;
Value of
Measured EPA Std,
CO
4.5
8.9
4.59
9.32
5.4 SPECIAL STUDIES AT RAMS 103 AND 107
Special studies were conducted at RAMS stations 103 and 107 in order to
compare concentrations of compounds collected simultaneously in Teflon bags
and stainless steel tanks; determine contamination at stations by collect-r-
ing samples upwind; and to ascertain the accuracy of the data obtained from
the gas chromatography laboratory. The samples were analyzed using the
Dura Pak Column.
The bag and tank samples were collected by the same methods described
in sections 4.2.1 and 4.1 respectively. The actual collection time varied from
sample to sample, but bag and tank samples that were collected simultaneously
33
-------
were collected over the same time interval. Tank samples were collected upwind
of the stations.
Table 11 shows the results of replicate analyses of the samples-, a compar-
isons of duplicate bag samples, and a comparison of station and upwind samples.
5.5 DATA VALIDATION, INTERPRETATION AND DISTRIBUTION
Each chromatogram of ambient air samples collected for the roadway,
ethylene and special studies at RAMS 103 and 107 was visually analyzed 5y
the EPA Task Coordinator and laboratory personnel jointly. The validated
data on one copy of a 6800 foot, 9 track, 800 BPI, odd parity magnetic data
tape, along with 2 copies of the printout were given to the EPA Task
Coordinator. These data contain the sums of the paraffins, oleftns, aromatics
and total non-methane hydrocarbons per sample and are furnished in Appendix D
of this text.
34
-------
TABLE 11. QUANTITATIVE STUDIES AT RAMS 103 and 107
A. Reproducibility
RAMS 103
Sample 103-1
Collection Time
Dura Pak Column.
First
Compound Analysis
CQH, 20.0
L 0
C2H4 48.7
C,HQ 56.4
0 O
f H ?9 5
00 *
I-C4H1Q 16.1
N-C H 53 1
i* ^ A T r\ \j *j t i
C H 96
w o' '/T ^ U
I-C5H]2 43.7
N-C5H]2 15.1
RAMS 107
Sample 107-1
Collection Time
Dura Pak Column.
First
Compound Analysis
C2H6 14.7
C2H4 47.3
C3H8 12'2
C2H2 37.3
I-C4H1Q 9.2
N-C4H1Q 41.4
C3Hg 13.8
I-C5H12 40.5
Nr u ico
-Li-Hip 1 0. L
of Analyses
and Date: 7:15 -
Concentrations
Repeat
Analysis
19.7
48.3
55.4
26.6
16.6
54.5
11.3
44.8
17.2
and Date: 7:22 -
Concentrations
Repeat
Analysis
14.5
46.9
11.7
38.8
8.9
40.8
12.9
40.6
15.7
9:05, November 24,
in ppbC
Duplicate
Analysis
20.2
49.6
57.3
28.4
17.0
55.2
12.8
45.5
15.7
9:12, November 30,
in ppbC
Duplicate
Analysis
14.8
47.6
12.1
43.1
9.2
42.3
14.2
40.6
18.3
1976
Average
20.0
48.9
56.4
28.2
16.6
54.3
11.2
44.7
16.0
1976
Average
14.7
47.3
12.0
39.7
9.1
41.5
13.7
40.6
16.8
Standard
Deviation
0.25
0.67
0.95
1.46
0.45
1.07
1.60
0.90
1.08
Standard
Deviation
0.17
0.30
0.29
3.01
0.17
0.75
0.71
0.06
1.40
(continued)
35
-------
TABLE 11 (continued)
B. Duplication of Samples
RAMS 107
Samples 107-1, 107-2
Collection Time and Date:
7:22 - 9
Dura Pak Column. Concentrations in
Compound Bag #1
C2H6 29.3
C2H4 76.2
C,H0 25.3
J O
C2H2 72.3
I-C,H,n 23.5
4 10
N-C4H]0 94.0
C3H6 27.5
I-C5H12 84.9
N-C5H]2 35.2
RAMS 107
Samples 107-1, 107-2
Collection Time and Date:
Bag #2
29.8
74.8
25.7
72.6
20.6
90.4
28.4
82.3
34.9
7:22 - 9
Dura Pak Column. Concentrations in
Compound Bag #1
C2H6 14.8
C2H4 47.3
C3H8 12.2
C2H2 37.3
T-f H Q 9
L v> /i 1 1 1 /-i J t (
4 10
N-C,Hin 41.4
4 10
C0HC 13.8
J o
I-C5H]2 40.6
N-CcH19 16.2
O 1 £-
Bag #2
14.7
56.1
12.9
38.1
8.8
41.1
13.4
40.1
15.9
:12, November 24, 1976
ppbC
Average
29.6
75.5
25.5
72.5
22.1
94.2
28.0
83.6
35.1
:12, November 30, 1976
ppbC
Average
14.8
51.7
12.6
37.7
9.0
41.3
13.6
40.4
16.1
Standard
Deviation
0.35
0.99
0.28
0.21
2.05
2.54
0.64
1.83
0.21
Standard
Deviation
0.07
6.22
0.49
0.56
0.28
0.21
0.28
0.35
0.21
(continued)
36
-------
TABLE 11 (continued)
C. Comparison of Upwind and Station Data
RAMS 103
Samples 103-1 (average), 103 Tank
Collection Time
and Date: 7:15 - 9:
Upwind Sample Collected in Stainless
Dura Pak Column
Compound
C2H6
C2H4
C3H8
C2H2
NC4H10
N-C4H1Q
C3H6
I-C5H12
N-C5H12
RAMS 107
. Concentrations in
Station Sample
(average)
20.0
48.9
56.4
28.2
16.6
54.3
11.2
44.7
16.0
05, November 23, 1976
Steel Tank
ppbC
Upwind
(S.S.
19.
27.
52.
26.
14.
47.
11.
41.
15.
Sample
Tank)
5
5
3
7
1
0
1
7
0
% A
2.5
43.7
7.3
5.3
15.1
13.4
0.9
6.7
6.2
Samples 107-1 (average), 107 Tank
Collection Time
and Date: 7:22 - 9:
Upwind Sample Collected in Stainless
Dura Pak Column
Station
Compound Sample
C0H, 29.6
d. b
C H 75 5
\tr\\ 1 /i /
-------
6.0 QUALITY CONTROL
To insure accurate results for all analyses done in the laboratory,
quality control procedures were employed. The instruments were standard-
ized using standard gases from Scott-Marrin for the Beckman 6800 and
accurately prepared laboratory standards for the P.E. 900. (See Appendix B,
Sec. 1.3) Records of area sizes and peak heights were maintained and checked
daily, duplicate and repeat analyses were performed on the samples that were
collected.
The first daily sample was analyzed three times in order to insure
that the Perkin Elmer 900 was functioning properly. The first repeat
analysis came directly after the original analysis, to provide a check on
reproducibility of the machine; the second duplicate analyses were performed
at the end of the day in order to ascertain whether the gas chromatograph
maintained its stability. These duplications were usually within +_ 5% of
each other; if not, the samples were reanalyzed.
6.1 STANDARDS FOR BECKMAN 6800
Scott-Marrin gases were chosen as standards because of the good
reputation of the company and the availability of the THC, CH», and CO gases
in stable all-aluminum cylinders. EPA Quality Assurance Branch at the Research
Triangle Park provided the calibrations used to determine the concentrations
of the gases used as primary and secondary standards.
6.2 STANDARDS FOR PERKIN ELMER 900
Appendix B describes the methods employed to prepare standards. Propane
was used on the phenyl isocyanate column and toluene on the squalane column in
the P.E. 900 gas chromatograph. The gases were stored in an stainless steel
cylinders in order to insure their stability.
6.3 DAILY STANDARDS
A tank containing laboratory air was used as a secondary standard.
38
-------
Its composition was checked against the primary standards. The tank was
refilled periodically because of the size of the cylinder and the volume of
gas used per analysis, reanalyzed, then standardized against the primary
standards.
Tables 12 and 13 show that from 20 July 1976 through 30 November 1976,
the standard deviation of the analysis of propane, in two tank standards,
were 0.08 ppbC and 1.07 ppbC with a standard error of 0.02 ppbC and 0.32
ppbC, respectively. For the same period, toluene exhibits a standard deviat-
ion of 0.58 ppbC and a standard error of 0.15 ppbC.
The comparison of areas of the standards was used as a quality control
criterion as well as to detect the presence of leaks in the system. This
approach provided a high level of confidence for the work done over this task
order period.
39
-------
TABLE 12. PROPANE STANDARD*
DATE
7/20/76
7/22/76
7/27/76
7/29/76
8/3/76
8/4/76
8/5/76
8/10/76
8/12/76
8/17/76
8/19/76
AREA
14.7193
13.7971
16.7500
16.7449
16.7033
17.0707
16.9472
17.1686
16.7462
16.5964
16.7571
I = 16.36
S = 1.07
X
S- = 0.32
X
DATE
8/24/76
8/26/76
8/31/76
9/2/76
9/22/76
9/24/76
9/27/76
9/28/76
10/20/76
10/22/76
10/28/76
10/29/76
11/1/76
11/2/76
11/3/76
11/4/76
11/8/76
11/10/76
11/12/76
11/16/76
11/18/76
11/24/76
11/30/76
AREA
2.2904
2.3351
2.3192
2.3775
2.3649
2.4480
2.3218
2.2637
2.1580
2.1924
2.2105
2.2111
2.1606
2.2017
2.1917
2.2104
2.2781
2.2583
2.2524
2.1953
2.2167
2.1489
2.2672
I =2.26
S = 0.08
X
S- = 0.02
X
* These areas are directly proportional to the response factors and
the concentrations. Areas in arbitrary units.
40
-------
TABLE 13. TOLUENE STANDARD*
DATE
7/20/76
7/22/76
7/27/76
8/3/76
8/5/76
8/12/76
8/17/76
8/19/76
AREA
0.9344
1.0363
1.8308
1 . 4842
1.6171
0.9089
1.4664
0.8082
X = 1.26
Sx = 0.38
S-=0.14
DATE
8/26/76
8/31/76
9/2/76
9/22/76
9/24/76
9/27/76
10/29/76
11/8/76
11/10/76
11/12/76
11/16/76
11/18/76
11/29/76
11/30/76
AREA
12.9900
13.2486
13.0400
13.0912
13.1302
13.2902
13.1078
12.6534
12.6560
12.5260
12.1836
13.0540
14.1280
14.3846
X" = 13.1100
Sx = 0.58
S-= 0.15
* These areas are directly proportional to the response factors and
the concentrations. Areas in arbitrary units.
41
-------
7.0 DATA PROCESSING
Data generated by the RAPS Gas Chromatography Laboratory were processed
and submitted to the RAPS Computer Data Bank, Research Triangle Park (RTP),
North Carolina. Data processing from analysis to submission to the data
bank was performed as described in the following sections.
7.1 DATA TABULATION
It was planned to perform approximately thirty-two analyses per week
for up to sixty components. The data were initially recorded in the form
of strip chart chromatograms, punched tape and/or teletype printouts.
Next, the data were given a first quality review by visiually inspecting the
data for general chromatographic form. Quantitative values for each component
were then established. Following review and approval, the data were tabulated
on a special preprinted form for keypunching.
7.2 KEYPUNCHING AND PROCESSING
At the end of the analysis period, the data forms were presented to
the EPA Task Coordinator for review and approval and subsequently keypunched
and keypunch validated. Keypunching errors were corrected by computer opera-
tors at the RAMS Computer Facility.
Data processing entailed checking the cards for index number consistency,
as provided for by the form, and then producing a triple copy printout of
labelling information: the name, code number, concentration CPPB), ratio
relative to CO, and flags if the concentration or ratio was outside an upper
and lower set of limits provided by EPA. Four quantities aggregated by the
software were treated as components in all respects: sum of nonmethane
paraffins, olefins, aromatics, and nonmethane hydrocarbons. Validation of the
data was carried out by visual inspection and comparison of the data with the
chromatogram and original tabulated data. Also, special attention was direc-
ted to flagged data for validity and proper annotation.
42
-------
Upon completion of data validation, three copies of a 600 foot, 9 track,
800 BPI, odd-parity magnetic data tape were prepared. One copy was sent to
RTP, along with a copy of the printout. The other copy of the tape and a
printout was delivered to the EPA Task Order Coordinator (St. Louis) and a
third copy of the printout and tape retained by the RAMS Central Computer
Facility.
43
-------
LITERATURE CITED
1. Mindrup, R. F., RAPS Final Report, Task Order 53, pg. 5-10.
2. Seeger, G. and Hern, D., RAPS Final Report, Task Order 103, pg. 20-30.
3. McReynolds, W. 0., Gas Chromatograph Retention Data, pg. 22-26,
154-155.
4. Ettre, L. S., Open Tubular Columns, Perkin Elmer 1973, pg. 32-33.
5. Lonneman, et al, Environmental Science and Technology, VI. 8, pg. 231,
44
-------
APPENDIX A
OPERATION OF BECKMAN 6800 GAS CHROMATOGRAPH
45
-------
CONTENTS
A.O Total Hydrocarbons, Carbon Monoxide and Methane Analyses 48
A.I Reproducibility of the Beckman 6800 48
A.2 Linearity of Detector Response 48
A.3 Primary Standard 49
A.4 Secondary Standards 49
A.5 Calculations 49
46
-------
TABLES
Number Page
A-l Tank 1-2327 - Tank Standard for 6800 51
47
-------
A.O TOTAL HYDROCARCONS, CARBON MONOXIDE AND METHANE ANALYSES
Analyses of CO, THC and CH. were done on a Beckman Model 6800 Gas
Chromatograph in the following manner:
The recorder was turned on, set at 10 mv range and zeroed with the zero
volt button. The auto-zero switch was actuated in order to zero the electro-
meter of the chromatograph. The pump on the back of the chromatograph was
turned on and a sample bag was connected to commence analyses.
To analyze total hydrocarbons, the attenuation was normally set at 4
and the range at 10 and the valve B toggle switch was actuated for approxi-
mately 15-20 seconds. The recorder was allowed to return to zero, aided
with the auto-zero toggle switch. The attenuation was changed from 4 to 1
for the methane and carbon monoxide analyses and the valve A toggle switch
actuated for 45 seconds.
A.I REPRODUCIBILITY OF THE BECKMAN 6800
Reproducibility of the results of the analyses of THC, CH, and CO was
checked by running duplicate analyses; that is, the first sample and the
standard were rerun after the analysis of all other samples. During the
course of this task order, these duplicates agreed closely with the initial
analysis (+5%).
A.2 LINEARITY OF DETECTOR RESPONSE
Five point calibrations were carried out in duplicate to insure that
the detector response was linear with respect to sample concentration. The
tests were performed for THC, CH. and CO. These checks were determined
from synthetic bag mixtures prepared in the laboratory. The procedure was
as fol 1ows:
48
-------
Five bags were prepared. The bags were labeled and filled with 100 liters
of zero air using a mass flow meter. The appropriate amounts of CH. and CO
were injected into each bag using a gas-tight calibrated syringe and allowed
to diffuse throughout the bag. The bags were then analyzed. The make-up of
the mixtures is shown below:
BAG # ZERO AIR CH, CO CONC.
1
2
3
4
5
100 litres
100 litres
100 litres
100 litres
100 litres
t
0.1 ml
0.2 ml
0.3 ml
0.4 ml
0.5 ml
0.1 ml
0.2 ml
0.3 ml
0.4 ml
0.5 ml
1 ppm
2 ppm
3 ppm
4 ppm
5 ppm
A.3 PRIMARY STANDARD
A cylinder containing small amounts of methane and carbon monoxide in
air (Scott-Marrin L 1749) was analyzed by the EPA at Research Triangle Park,
North Carolina. Its concentrations was computed to be 5.33 ppm CO and 1.99
ppm CH.. This cylinder served as the primary standard for the Beckman 6800
and was used to calibrate other tanks.
A.4 SECONDARY STANDARDS
Two other cylinders (Scott-Marrin L 2327 and L 2359) served as secon-
dary standards for the Beckman 6800 during this task order period. When
analyzed against the primary standard Scott-Marrin L 1749, their concentra-
tions were computed to be 5.28 ppm CO, 4.38 ppm CH. and THC for Scott
L 2327 and 5.29 ppm CO and ppm CH4 and 2.20 ppm CH4 and THC for Scott L 2349.
The secondary standards were checked against the primary ones once a month.
A.5 CALCULATIONS
Calculations of the concentrations of THC, CH. and CO in various
samples are straight forward and were done by hand. When analyses were to
be performed, the secondary standard was analyzed; that is, its peak height
was measured. Since its concentration was known, it was possible to compute
the concentration of unknown once its peak height was measured:
Standard concentration in ppm . hninlt+ nf ,nt,nnt ,- concentration
Peak height of standard In im X peak height of unknown in m ~ of unknown
49
-------
Initially, a sample of standard gas was injected into a Teflon bag, then
analyzed on the Beckman 6800. It was observed that the peak height varied as
much as 42.6% for THC, 9.7% for CH4 and 58% for CO. These variations were
unacceptable; therefore, another method was devised by which the standard gas
was passed directly into the Beckman 6800. With this procedure, maximum peak
height variation for THC was 8.4%, CH4 was 14.9%, and CO was 17.9%. The
standard deviations were computed to be 4.88 mm (3.8%) for THC, 7.25 mm (6.5%)
for CH and 9.89 mm (9.2%) for CO as shown in Table A-l.
50
-------
TABLE A-l. TANK L-2327 - TANK STANDARD FOR 6800
DATE
6/23/76
6/28/76
7/06/76
7/08/76
7/13/76
7/15/76
7/20/76
7/22/76
7/27/76
7/29/76 am
7/29/76 pm
8/03/76 am
8/03/76 pm
8/03/76
8/05/76
8/10/76 am
8/10/76 pm
8/12/76 am
8/12/76 pm
8/24/76
8/26/76 am
8/26/76 pm
THC
129.5*
127.0
127.0
142.5
132.0
115.5
130.0
129.5
122.6
124.8
124.7
126.4
129.1
125.8
126.4
132.9
130.1
128.4
127.1
127.0
125.1
125.1
X" = 127.7
Sx = 4.88
S-= 1.04
CH,
105.0
103.5
106.5
104.0
102.0
97.0
106.0
112.0
117.3
106.6
121.8
115.1
115.0
116.5
116.9
102.3
112.5
120.9
118.3
117.2
117.5
118.7
I = 111.48
Sx = 7.25
S-- 1.54
CO
102.0
100.5
92.0
98.5
85.5
86.8
103.8
110.7
117.0
96.7
122.4
112.8
109.0
114.6
116.5
106.5
106.9
121.0
119.1
113.3
114.7
115.8
I = 108.00
Sx= 9.89
S-= 2.11
* Response in mm
51
-------
APPENDIX B
OPERATION OF THE PERKIN ELMER 900 GAS CHROMATOGRAPH
52
-------
CONTENTS
B.O C2 - CIQ Analysis 56
B.I General Procedures 56
B.2 Reproducibility of the Phenyl Isocyanate Column 57
B.3 Linearity of Detector Response of Phenyl Isocyanate Column . 57
B.4 PEP-1 Computer Calculations for P.E. 900 62
B.4.1 Reference Peak(s) 62
B.4.2 Relative Retention Times 62
B.4.3 Response Factor 63
B.4.4 Response Ractor Update 64
B.5 Calculations Used to Determine Standard Concentrations ... 64
B.6 Primary Standards (Propane and Toluene) P.E. 900 64
B.7 Secondary Standards (Propane and Toluene) P.E. 900 64
53
-------
FIGURES
Number Page
B-l Five Point Calibration of Propane on Perkin Elmer 900
Gas Chromatograph 59
B-2 Five Point Calibration of Toluene on Perkin Elmer 900
Gas Chromatograph 60
54
-------
TABLES
Number Page
B-l Five Point Calibration of Propane 61
B-2 Five Point Calibration of Toluene 61
55
-------
B.O C2 - CIQ HYDROCARBON ANALYSIS
The RAMS bag samples were analyzed for C2-C-,0 hydrocarbons on the PE 900
gas chromatograph. The ambient air samples were analyzed and the concen-
trations of the compounds determined by comparing the samples to the standard.
One sample was analyzed in duplicate and in some cases triplicate to insure
the reproducibility of the entire set of samples and the precision and accu^
racy of the gas chromatograph.
B.I GENERAL PROCEDURES
The hydrogen and air sources were turned on and the flame ionization
detectors lighted. The oven was cooled from 90°C (overnight and weekend
temperature) to 25°C by turning on the liquid nitrogen. The recorders were
turned on, checked for positive response, then zeroed; the vacuum line was
turned on. Directives of identification and sampling time were entered on
the teletype to the PEP-1 integrator.
The stainless steel concentration trap was placed in a Dewar flask
which contained liquid oxygen. The appropriate vacuum line was connected
to the vacuum source and the bag or tank connected to the inlet line. The
vacuum source was opened and a small sample was drawn through the inlet
line to purge the line of any air from a previous sample. The inlet valve
was switched to the trapping mode and a measured volume of the sample was
cold-trapped into the liquid oxygen cooled concentration trap.
After the sample was trapped, the ready light on the PEP-1 interface was
actuated, the valve switched to the injection mode and a Dewar flask of hot
water applied to the concentration trap. The "ready light" on the gas chroma-
tograph was immediately pressed to initiate the temperature programming. The
chromatograph was programmed to hold 25°C for 8 minutes. The temperature was
then raised at a rate of 2°C per minute to 90°C, where it was held for the
remainder of the run. The valve was returned from the injection mode to the
backflush (neutral) position after 2 minutes. The analyses times were 10
56
-------
minutes for the phenyl isocyanate column (Cp-Cg) and 55 minutes for the
squalane column (CJ--C,Q).
Upon completion of the analyses, the PEP-1 integrator tabulated the
area measured, the concentration and the identification of peaks. The reset
button on the gas chromatograph was pressed and the above procedure was
repeated. The analyses and turnaround time for trapping sample, analysis
and computer printout times for C2-Cr were approximately 0.5 hours on the
phenyl isocyanate column and 1.35 hours for C5-C,Q on the squalane column.
The files of the memory bank of the PEP-1 computer were normally erased at
the end of the working day.
B.2 REPRODUCIBILITY OF THE PHENYL ISOCYANATE COLUMN
To ascertain and maintain reproducibility of this column, the propane
standard and triplicate sample analyses were used as indicators. Any major
change in the area size of the propane standard or major deviation from the
concentrations of nine compounds analyzed on the column signaled problems in
the system. The magnetic tapes and the computer printouts demonstrate the
reproducibility of the triplicate analyses done on the first datly bag samples.
The reproducibility of the daily duplicate and triplicate analyses were
generally within +_ 5%.
B.3 LINEARITY OF DETECTOR RESPONSE OF PHENYL ISOCYANATE COLUMN
Five point calibrations were carried out on the P.E. 900 is insure
that the detector response was linear with respect to sample concentration.
Five mil (0.005 inch) Teflon bags were filled with ultrapure air and injected
with accurately measured quantities of propane and toluene. After allowing
half an hour for diffusion, samples were withdrawn from this bag ("A") and
injected into five other bags, each of which had been filled wtth 50 1 of
ultrapure air according to the schedule shown on the following page:
57
-------
Bag # Zero Air
C3HC(99% purity)
Cone. Toluene (99% purity) Cone.
A 50 liters 5 ml of propane
1 50 litres 1 ml from Bag A
2 50 litres 2 ml from Bag A
3 50 litres 3 ml from Bag A
4 50 litres 4 ml from Bag A
5 50 litres 5 ml from Bag A
100 ppm
6 ppbC
12 ppbC
18 ppbC
24 ppbC
30 ppbC
0.05 ml toluene
1 ml from Bag A
2 ml from Bag A
3 ml from Bag A
4 ml from Bag A
5 ml from Bag A
226.9 ppm
31.9 ppbC
63.8 ppbC
95.7 ppbC
127.6 ppbC
159.5 ppbC
The bags were analyzed in descending order, then reanalyzed in the same
order for duplicate analyses. Figures B-l and B-2 and Tables B-l and B-2
are examples of the 5 point calibrations of propane and toluene respectively.
58
-------
30 -
25 -
.0
Q.
Q.
5 20
o
<
CtL
LiJ
O
15 -
5 -
. i
1 .2 .3 .4 .5 .6 .7 .8
AVERAGE AREA IN ARBITRARY UNITS
FIGURE B-1. FIVE POINT CALIBRATION OF PROPANE ON
PERKIN ELMER 900 GAS CHROMATOGRAPH
59
-------
co
o
LU Q-
Z «t
LJJ a:
rD co
_i o
o h-
(- <
£ u-o
Hi o a:
~_ ii CO
o: i <:
rf < tO
S cc
L± CQ O
r; H-O
CQ I CTl
2 So:
-------
TABLE B-l. FIVE POINT CALIBRATION OF PROPANE
Bag A:
Bag 1 to
Number
1
2
3
4
5
5.0 ml gas SOL
5: 50 litres of
Amount
Injected
From Bag A
1.0 ml
2.0 ml
3.0 ml
4.0 ml
5.0 ml
of ultrapure air
ultrapure air each
Run - 1
0.0642
0.1068
0.1631
0.2288
0.3080
AREA
Run - 2 Average
0.0641
0.1061
0.1652
0.2297
0.3082
TABLE B-2. FIVE POINT CALIBRATION OF
Bag A:
Bag 1 to
Number
1
2
3
4
5
0.0500 ml liquid
5: 50 litres of
Amount
Injected
From Bag A
1.0 ml
2.0 ml
3.0 ml
4.0 ml
5.0 ml
50L of ultrapure
ultrapure air each
Run - 1
3.5380
4.4350
6.6937
8.5107
10.9798
air
0.0641
0.1064
0.1641
0.2292
0.3081
TOLUENE
AREA
Run - 2 Average
--
4.4036
6.4601
8.1254
10.7468
3.5380
4.4193
6.5769
8.3181
10.8633
Cone.
6 ppbC
"i2 ppbC
18 ppbC
24 ppbC
30 ppbC
Cone.
31.9 ppbC
63.8 ppbC
95.7 ppbC
127.6 ppbC
159.5 ppbC
61
-------
B.4 PEP-1 COMPUTER CALCULATIONS FOR P.E. 900
The PEP-1 computer was programmed in such a manner that it could detect,
file, store, compute the concentration of selected compounds and print out
pertinent data of samples that were analyzed on the P.E. 900.
In order to accurately compute the concentrations of the label com-
pounds, the following information was input to the computer:
1) reference peak(s)
2) relative retention times for all compounds
3) response factor for all compounds
4) response factor update
B.I.4.1 Reference Peak(s)
N-Butane and toluene were chosen as the reference peaks for the phenyl
isocyanate and squalane columns respectively because both compounds occur
abundantly in ambient air samples and no large peaks appear nearby, making
identification easy. When writing the programs for the phenyl isocyanate
and squalane columns, n-butane was assigned a reference number of one (1)
and toluene was assigned a reference number of five (5). Along with the
reference numbers, time spans for the elutions of the two compounds were
provided.
B.4.2 Relative Retention Times
Relative retention times may be obtained two ways: manual computation
or the PEP-1 system. The G. C. Laboratory employs both methods; the pro-
cedure and results of both are identical. As an example, the calculation
of RRT of C9H, is as follows:
c. b
X = Relative retention time of n-butane = 1.0.
T = The elution time in minutes of n-butane =2.5 minutes.
X = The unknown relative retention time of C0HC.
, 2 6
T = The known elution time of the C0HC = 0.87 minutes.
L b
62
-------
x _ x]
T ~ T1
x .87 = X1
2.5
X1 = .348
It should be noted here that once the reference peak has been desig-
nated and its elution time standardized, the PEP-1 automatically assigned
the relative retention times to all other compounds occurring in each sample.
The same procedure was used for toluene.
B.4.3 Response Factor
To obtain response factors (RF) for hydrocarbons Cp - C,0 a primary
standard was made up and analyzed in the laboratory. The PEP-1 was pro-
grammed in such a manner that only the areas of the selected compounds were
computed. After manually calculating the concentrations of the hydrocarbons
and obtaining the various areas from the computer, it was possible to cal-
culate the response factors for each compound.
The PEP-1 used the following formula:
Area x response factor x 5 = concentration
To calculate the response factors of the hydrocarbons:
Concentration
RF =
Area x 5
Example: Toluene
RF= 31'9
2.0440 x 5
RF = 3.12
Response factors for all selected Cp - C,n hydrocarbons were determined in
the above fashion.
After all of the calculations are done and the computer has been
properly programmed, the PEP-1 uses; area x response factor x 5 to compute
the concentrations of unknowns against the concentration of a standard.
63
-------
B.4.4 Response Factor Update
Once the concentration of the standard was calculated and an acceptable
range (+_ 3%) for propane and +_ 3% for toluene) for the area size of each com-
pound had been established, the response factor update feature of the PEP-1
data system was used to correct the small changes that occur in the detector
from day to day. The daily computed concentrations for the propane and
toluene standards were compared to the calculated value for these standards;
the relative change was fed to the computer and the response factor for each
compound that is analyzed is multiplied by that factor. During this task
order period, the detectors showed little or no change. The changes that
occurred were random with a standard deviation of less than +_ 3%.
B.5 CALCULATIONS USED TO DETERMINE STANDARD CONCENTRATIONS
The preparation of primary standards and the secondary standard was
done at the same time. Only one secondary standard was needed because
ambient air contains the propane and toluene that was used by the Gas
Chromatography Laboratory on the phenyl isocyanate and squalane columns,
respectively. The PEP-1 computer system uses the area x response factor x
5 method for computing the concentrations of compounds,
B.6 PRIMARY STANDARDS (Propane and Toluene) P.E. 900
The primary standards for the P.E. 900 were synthetically prepared in
the laboratory by using the same reagents and equipment described in Section
B.3 of this appendix. It should be noted here that only one dilution bag
was used.
B.7 SECONDARY STANDARDS (Propane and Toluene) P.E. 900
Since the hydrocarbons to be analyzed occurred in laboratory air,
secondary standards were prepared by simply storing a pressurized sample of
ambient air in an 8 litre stainless steel tank, equipped with the appropri-
ate valves. A sample of the secondary standard was then analyzed and the
concentration of propane and toluene computed.
64
-------
APPENDIX C
DATA FROM SUMMER AND FALL INTENSIVES
65
-------
CONTENTS
C.O Introduction 69
66
-------
FIGURES
Number Page
C-l Listing of all compounds recorded on magnetic tapes .... 70
67
-------
TABLES
Number Page
C-l RAMS Station 101 "Summer Intensive" 73
C-2 RAMS Station 102 "Summer Intensive" 81
C-3 RAMS Station 103 "Summer Intensive" 82
C-4 RAMS Station 108 "Summer Intensive" 88
C-5 RAMS Station 113 "Summer Intensive" 89
C-6 RAMS Station 114 "Summer Intensive" 90
C-7 RAMS Station 115 "Summer Intensive" 95
C-8 RAMS Station 118 "Summer Intensive" 97
C-9 RAMS Station 121 "Summer Intensive" 99
C-10 RAMS Station 122 "Summer Intensive" 100
C-ll RAMS Station 124 "Summer Intensive" 103
C-12 RAMS Station 101 "Fall Intensive" 105
C-l3 RAMS Station 103 "Fall Intensive" 108
C-14 RAMS Station 114 "Fall Intensive" Ill
C-l5 RAMS Station 115 "Fall Intensive" 114
68
-------
C.O INTRODUCTION
Appendix C contains data obtained from samplings at RAMS stations. The
results are in table form in order to provide an overview of the data from
RAMS stations. The arithmetic mean (X) and standard deviation (S ) were
A
calculated for total hydrocarbon (THC), methane (CH^), carbon monoxide (CO)
and acetylene (C2H2) for each table so that comparisons could be made between
and among the RAMS stations. Not all compounds are listed in these tables.
The magnetic tape of data delivered to the EPA contains the concentration for
all compounds as well as sums for olefins, paraffins, etc. The following
marks and abbreviations were used: "Trace" indicates less than 1 ppbC in the
squalane analyses, "BDL" below detection limits, "MM" not measurable (because
of interference, etc.). All concentrations in the following tables are in
ppbC and the time of samples is Central Daylight Time (CDT) from April 25
to October 30 and Central Standard Time (CST) after October 30.
Figure C-l shows the header for that tape and lists the various com-
pounds which are reported.
69
-------
081TOTAL SULFUR
002HYDROGEN SULFIDE
003SULFUR DIOXIDE
304METHYL MERCAPTAN
005N1TROGEN OXIDES (HOX)
006SULFUR HEXAFLUORIDE
007TR1CHLORO-FLUORO METHANE
008DICHLORQ-DIFLUQRO METHANE
009TOTftL ORGANICS
010METHANE
011CARBON MONOXIDE
012ETHYLENE
013ETHANE
014ACETYLENE
015PROPANE
016PROPYLENE
017ISOBUTAHE
018ISOBUTYLENE + BUTENE-1
019N-BUTANE
020T-2-BUTENE
021C-2-BUTENE
0223-il-l BUTENE
023ISOPENTANE
924PENTENE~1
0252-M-l BUTENE
026N-PENTANE
027T-2-PENTENE
028C-2-PENTENE
0292-M-2 BUTENE
8302,2-DM-BUTANE
031CYCLOPENTENE
0323-M-l-PENTENE + 4-M-l-PENTENE
0334-M-C-2-PENTENE
034CYCLOPENTANE
0352,3-DM-BUTANE + 4-M-T-2 PENTENE
0362--M-PENTANE
9372-M-l-PENTENE
0383-M-PENTAHE +
039T-3-HEXENE
0402-M-2-PF.NTENE
0413-M-C-2 PENTENE
042N-HEXfiNE
043T-2-HEXENE
044C-2-HEXENE
0453-M-T-2-PENTENE
04SMETHYLCYCLOPENTANE + 3,3-DM-l-PENTENE
047BENZENE
0482,4~DM-PENTENE
0492,2,3-TM-BUTANE
0502,4-DM-i-PENTENE
0511-METHYLCYCLOPENTENE + 2-M-C-3-HEXENE
0522,4-DM-2-PENTENE + 3-E-l-PENTENE + 3-H-l-HEXENE
0532-M-T-3-HEXENE + 5-M-l-HEXENE
054CYCLOHEXANE + 4-M-C-2-HEXENE
HEXEHE-1 + 2-E-l-BUTENE
+ 3-M-CYCLOPENTANE
(continued)
FIGURE C-l. LISTING OF ALL COMPOUNDS RECORDED ON MAGNETIC TAPES
70
-------
0554-M-1-H3XENE + 4-M-T-2-HEXENE
0563-M-2-t-'--BUTEHE + 5-M-T-2-HEXENE
057CYCLOHEXEN::
0532-h-HEXSl!I: -> 5-M-C-2-HEXEHG
0592,3-DM-PEMTftNi + 1, i-DM-CYCLOPEHTANE
0603-M-HEX-'il;£
9611-C-3-lJ.":-CVCLG?ENTAKE + 2-M-i-HEXANE
362 1 -T-3-- ;;-!-! ''ILOPENTHh'E -:- i-KIPTENF -!- 2-E-l-PENTftNE
9633-E-PENTqf-jr ,;, s-M-r-
36SC-3-HEPTEHE
0663-M-C-3-HEXENE + />M-2-Hr.XENE -r ?-M~T~3-Hir.XcHE
068N-HEPTANE
B692,3-DI1-2-PENT?t!E + C-2-HEPTnHE
9701-C-2-DM-CYCLCPCNTPHE
071M-CYCLOHEXriN£ + 2,2-DM-HEXrtMi£ + 1, U3-TM-CYCLOFHHTflNE
0724-M-CYCLOHEXEf-^
0732,5~DM-HEXfiNc
077 1-T-2-C -^-Th-'-YCJLOPENTANE
078TOLUENE
0792,3,4-T>:-PENTPNE
0S22-M-HEP"--it-!E
3, 4-Df1~HEXHHE + 1-C-2-T-4-TM CY^LDPENTflNE
0853-M-HEPTPHE ' 3-M-j-E-PENTflHE
0862,2,5-rr1-HE;-:nNE + 1-C-2~C-4-TM CYCinPINTftN'E
0371-T-4-DM-CYCLOHEX9ME
083 l-M-T-3 -E-CYC-OPENTftHE
3892,2,4-TN-HEXhlwE
090CYCLOHEPTftNE + 1-M-l-E-CYCLOPENTflNE
091 l-T-2-DM-CYCLOHEXANE + l-C~2-C-3-TM-CYCLQPENTflNE
393 l-T-3-Dh-CYCLOHEXflHE
0952,3,5-T.l-HEXfiNE
9962,2-DM-HFPTftNE
9972,4-rtl-HEPTRNE + 2,2,3~TM-HEXftNE
0992,2-D:i--;-P:ZHTf-1NE + 2-N-4~E-HEX^NE
9992,6-Ph-i-aPTfiNE -I- l-L>2-J)N-CYCl.nHEXANE
100N-PROPYLCYCLOP£NTANE
101!£THYLCYCLOHE>:ANE
1(522,, 5-DM-HEPTfiNE + 3^5-DM-HEnANE
103ETHYLBENZENE
1043,3-DM-HEPTPiHE
1052, 3, 3- m- HEPTANE
106P-XYLENE
107M-XYLEME
1884-M-OCTrtNt (continued)
FIGURE C-l (continued)
71
-------
1032-M-QCTP.NE
1L33-E-H~.PTPNE
1113-M-QCTANE
1120--XYLENE
1132.2,4-Th-HEPTPME
1142,2,5-TM-HEPTfiNE
iS52,5,5IT<1~HEPTfiNE
liSN-HONhNC
117N-PROPVL9ZNZENE
1132,2,3,3-TM-HEXP.NE
li9i-M-2-E-BEHZENE
129!., 3, 5-Th- BENZENE
121TERT-E'UTYLBENZENE
123SEC-BUT-'L.BEHiL;SE + ISOBLTYLBEMZENE
124H-DECPHE
1251,2,3~TM-3EN2EME + )-M-4-ISnPRO°YLBEN2ENE
126N-BUTYL3iZNZEHL:
12?PflRftFFI!-i5
1280LEFIMS
129AROM?rriCS
liaTGTflL MOM-METHfiHE HYDPOCftRSDHS
FIGURE C-l (continued)
72
-------
TABLE C-l. RAMS STATION 101
SUMMER INTENSIVE
Mean Standard Deviation
THC
CH4
CO
2 2
Date
Dura Pak
C2H6
C3H8
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
Beckman 6800
THC
CH4
CO
3720 ppbC
2016 ppbC
1621 ppbC
19.8 ppbC
6/23/76 6/23/76 6/23/76 6/23/76 7/13/76
7-9 9-11 11-13 13-15 9-11
8.7
996.5
22.8
8.7
12.6
62.6
2.4
55.0
14.0
2690 2600 3550 2540 3850
1960 1940 1900 1900 2060
1520 1010 1050 1220 2210
494 ppbC
262 ppbC
634 ppbC
11 ppbC
7/15/76
7-9
8.0
967.5
8.2
8.6
4.1
17.7
3.0
22.0
9.0
3640
2030
1280
7/15/76
9-11
5.9
18.8
5.3
5.0
4.5
17.3
BDL*
14.0
7.0
2730
2090
1460
* Below detection limits
(continued)
73
-------
TABLE C-l (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H]0
N-C.H,n-
4 10
C3H6
IsoCcH10
5 12
N-C5H]2
Squalane
N"C6H14
N-C^H,,
7 16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N-C9H2Q
N-P-C6H5
N"C10H22
Beckman 6800
THC
CH4
CO
7/15/76
11-13
5.3
1055.6
6.0
4.5
3.5
12.6
1.3
14.0
7.0
3680
1960
730
7/15/76
13-15
4.1
12.7
3.4
6.3
4.1
15.6
1.0
13.0
4.6
2470
1870
700
7/20/76
7-9
8.4
1345.9
10.4
10.9
7.2
32.7
6.3
36.0
18.0
12
5
50
15
18
88
19
40
1
189
3690
1920
1320
7/20/76
0-11
8.0
30.0
9.7
5.5
6.4
24.5
3.0
25.0
8.0
7950
1800
926
7/20/76
11-13
4.9
1253.4
5.2
4.8
5.4
32.3
BDL*
26.0
8.0
3560
1780
712
7/20/76
13-15
4.5
11.7
4.1
2.1
4.1
21.3
BDL*
18.0
6.0
2270
1720
610
7/22/76
7-9
12.6
1553.2
16.7
19.3
15.1
72.9
11.5
73.0
28.5
27
9
62
5
25
67
22
2
3
5
3960
1920
2120
* Below detection limits
(continued)
74
-------
TABLE C-l (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
Cnll/j
IsoC4H1Q
N"C4H10
C3H6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N"C7H16
Toluene
N-C8H]8
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-CCH,
0 0
N-C1QH22
Beckman 6800
THC
CH4
CO
7/22/76
9-11
9.4
33.5
9.1
10.8
6.6
27.3
3.6
28.0
19.0
2370
1870
1060
7/22/76
13-15
5.8
21.9
5.5
4.2
6.2
28.9
BDL*
24.0
10.0
2520
1800
525
7/27/76
7-9
14.5
1240.8
23.4
17.3
13.8
45.6
34.0
43.0
17.0
10
4
48
3
13
40
11
2
1
4010
1630
1130
7/27/76
9-11
10.4
30.1
18.6
11.9
12.4
36.9
43.0
30.0
11.0
2600
1480
796
7/27/76
11-13
12.3
1137.4
12.0
11.2
5.0
22.1
66.0
22.0
10.0
4860
2110
758
7/27/76
13-15
8.7
14.3
9.0
8.5
4.4
23.3
25.0
21.0
6.0
2260
1710
781
7/29/76
7-9
11.3
1044.0
12.0
12.4
4.4
24.2
15.0
26.0
9.9
13
2
117
4
30
73
24
3
2
3
3630
2080
1190
* Below detection limits
(continued)
75
-------
TABLE C-l (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
NTH
"~U4 10
C3H6
IsoC5H12
NTH
5 12
Squalane
NTH
614
N-C7H,fi
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N-CgH20
N-P-CCHC
0 0
N-C1QH22
Beckman 6800
THC
CH4
CO
7/29/76
9-11
11.7
26.9
16.5
12.7
8.5
43.3
11.5
38.0
15.0
3320
2000
1250
7/29/76
11-13
12.2
1402.6
19.2
13.4
10.4
63.6
14.0
50.0
18.0
2960
1740
1070
7/29/76
13-15
14.1
41.3
20.8
12.9
10.3
53.0
8.0
42.0
18.0
6440
1710
1120
8/3/76
7-9
9.8
1345.6
17.7
10.7
4.2
22.7
6.8
23.0
12.0
8
2
81
4
9
24
8
1
BDL*
2
4060
2090
1040
8/3/76
9-11
6.6
22.9
11.4
5.6
4.2
15.1
3.1
10.0
5.0
2470
1920
754
8/3/76
11-13
5.0
1151.5
7.2
3.7
2.7
10.6
1.5
9.2
4.3
3180
1680
585
8/3/76
13-15
6.0
20.7
8.6
4.7
6.1
22.2
1.3
19.0
9.0
2240
1720
645
* Below detection limits
(continued)
76
-------
TABLE C-l (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N-C4H]0
C3H6
ISOCrH-,,
5 12
N-CrH19
5 12
Squalane
N-C6HU
N-C7H,C
7 16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C H
"65
N-C1QH22
Beckman 6800
THC
CH4
CO
8/5/76
7-9
9.0
1321.0
11.2
14.4
8.2
48.3
5.1
49.0
21.0
9
3
32
2
9
32
12
1
1
3
3810
1820
1220
8/5/76
9-11
7.0
14.9
7.3
8.3
5.0
26.7
2.5
29.0
11.0
2350
1730
811
8/5/76
11-13
6.1
15.8
5.5
6.5
6.7
41.0
1.0
30.0
13.0
2300
1720
770
8/5/76
13-15
6.0
19.9
4.9
6.2
5.1
28.0
1.1
25.0
11.0
2200
1720
635
8/12/76
7-9
8.6
24.9
19.4
29.7
14.0
70.6
7.3
54.0
28.0
23
7
73
8
55
199
47
8
3
20
3110
1820
1810
8/12/76 8/12/76
9-11
8.
1864.
18.
10.
14.
47.
3.
30.
13.
3790
1690
850
11-13
9 8.3
0 43.8
4 7.7
3 7.4
0 5.5
2 24.9
4 1.8
0 23.0
0 10.0
2390
1740
630
(continued)
77
-------
TABLE C-l (continued)
Date
Dura Pak
CoH/-
d. b
2^4
C3H8
C2H2
IsoC4H]0
N-C4H1Q
C,H,
3 6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N-C7H]6
Toluene
N-CgH18
E-C,H,-
6 5
M-XYL
0-XYL
N"C9H20
N-P-CCHK
6 5
N-C10H22
8/17/76
7-9
14.1
158.1
21.0
21.6
10.7
43.8
11.2
40.0
19.0
18
8
48
5
14
39
8
5
2
25
8/17/76 8/17/76 8/19/76
9-11 11-13 7-9
Repeat
Analysis
7.9 5.6 19.5
83.1 79.4 108.3
11.7 6.6 32.8
13.5 6.6 19.6
7.2 3.0 9.1
30.4 14.2 37.7
8.4 2.3 11.0
29.0 13.0 31.0
13.0 6.0 25.0
8/19/76 8/19/76
7-9 11-13
19.2 8.2
108.1 30.8
32.9 9.0
18.5 7.5
9.0 4.8
37.4 21.2
11.1 2.3
35.0 19.0
21.0 10.0
13
8
57
6
25
42
13
4
2
19
(continued)
78
-------
TABLE C-l (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C,Hnn
4 10
C3H6
IsoCrH19
b \L
N-C5H]2
Squalane
6 14
N-C7H1C
7 16
Toluene
N-CgHlg
E-C6H5
M-XYL
0-XYL
N-CnHon
B 20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
8/24/76
7-9
30.2
65.5
70.8
23.3
88.6
240.2
34.8
163.0
98.0
4570
2600
2020
8/24/76
9-11
10.0
35.4
13.4
10.9
8.3
35.2
3.5
24.0
14.0
2750
1960
780
8/24/76
11-13
9.0
103.5
9.6
9.9
6.6
41.3
2.0
25.0
14.0
2490
1880
860
8/24/76
13-15
7.0
17.3
9.3
8.0
5.0
29.8
0.8
19.0
10.0
2060
1740
460
8/26/76
7-9
18.6
89.3
23.9
48.1
27.2
144.3
19.8
147.0
61.0
26
8
59
6
23
66
23
5
4
14
3750
2310
3180
8/26/76
9-11
12.3
117.4
14.4
20.9
14.7
98.9
7.9
80.0
33.0
3200
1940
1520
8/26/76
11-13
10.3
31.1
12.9
14.0
10.9
61.8
3.7
49.0
21.0
2760
1960
1200
(continued)
79
-------
Dote
,-nra Pak
C. "r
9 9
12.2
6800
1840
1010
-------
TABLE C-2. RAMS STATION 102
SUMMER INTENSIVE
Mean
THC 2660 ppbC
CH4 1972 ppbC
CO 935 ppbC
Standard Deviation
306 ppbC
97 ppbC
214 ppbC
Date 6/23/76 6/23/76 6/23/76 6/23/76
7-9 9-11 11-13 13-15
Beckman 6800
THC
CH4
CO
3010
1970
1100
2820
2110
1140
2440
1900
750
2370
1910
750
81
-------
TABLE C-3. RAMS STATION 103
SUMMER INTENSIVE
Mean Standard Deviation
THC 2327 ppbC 424 ppbC
CH4 1860 ppbC 273 ppbC
CO 763 ppbC 412 ppbC
CH 4 ppbC 2 ppbC
Date 6/28/76 6/28/76 6/28/76 6/28/76 6/30/76 6/30/76 6/30/76
7-9 9-11 11-13 13-15 7-9 9-11 11-13
Beckman 6800
THC
CH4
CO
3670
3200
1400
2530
1920
870
2280
1900
880
2350
1850
750
2210
1900
740
2070
1880
630
2140
1820
660
(continued)
82
-------
TABLE C-3 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
S qua lane
N"C6H14
N-C7H]6
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
6/30/76 7/13/76
13-15 11-13
5.8
26.2
10.9
3.3
3.4
12.7
BDL*
9.0
1.0
2090 2090
1840 1910
370 610
7/13/76
13-15
7.5
14.3
13.4
4.7
7.3
31.8
Trace
22.0
9.0
2240
1870
800
7/15/76
7-9
8.6
23.8
7.6
5.0
4.2
18.2
BDL*
14.0
4.5
2470
2030
1220
7/15/76
9-11
5.7
1128.0
5.9
2.1
2.0
8.5
BDL*
6.5
1.4
3570
1990
840
7/20/76
7-9
6.9
26.8
9.0
5.6
6.5
42.8
3.7
27.0
8.0
NM**
2
49
2
31
138
27
2
BDL*
36
2730
1880
1170
7/20/76
9-11
7.2
224.2
8.6
3.7
3.7
17.5
BDL*
12.0
4.8
2650
1780
990
* Below detection limits
** Not measurable (because of interference etc.)
(continued)
83
-------
TABLE C-3 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N"C4H10
C3H6
IsoCcH,,,
b 1 L
N-C,H1?
D 1 L
Squalane
N-CcH-i /.
6 14
N-C7H,,
7 16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N-CgH20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CH
7/20/76
11-13
4.8
38.9
4.9
1.5
3.7
15.8
BDL*
10.0
4.8
2340
1760
380
7/20/76
13-15
3.9
13.6
3.9
1.5
3.1
13.6
BDL*
8.0
3.0
2160
1720
430
7/22/76
7-9
10.7
69.0
34.8
9.1
23.1
62.9
5.9
38.0
15.0
25
211
586
1008
1262
1695
3423
1426
6
24
1390
2000
2510
7/22/76
9-11
8.1
32.8
16.5
5.5
4.5
18.4
2.8
15.0
6.0
2310
1800
1050
7/22/76
13-15
5.2
26.5
18.0
2.2
2.6
13.1
BDL*
5.0
4.0
1980
1760
440
7/27/76
7-9
11.8
20.1
37.9
6.6
15.6
37.8
49.8
26.0
13.0
11
3
16
2
14
39
10
2
2
BDL*
2500
1520
550
7/27/76
9-11
6.9
19.9
11.5
4.3
6.7
19.1
40.4
15.0
6.0
2180
1470
410
* Below detection limits
(continued)
84
-------
TABLE C-3 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoCKH,,
5 1 L
N"C5H12
Squalane
N"C6H14
N"C7H16
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-CgH5
N-C1QH22
Beckman 6800
THC
CH4
CO
7/27/76
11-13
7.1
15.2
13.0
4.0
2.8 .
9.8
35.6
7.8
3.0
2690
1740
410
7/27/76
13-15
6.5
13.7
8.9
3.0
2.3
7.6
20.4
4.0
1.0
2090
1680
390
Special
7/29/76
0800-
0815
55.4
68.6
19.2
Bags
7/29/76
1515-
1530
55.3
61.4
18.9
t 7.9 t 7.0
11.2
117.7
8.9
88.0
15.0
t 2650
1970
2070
9.5
98.9
1.8
64.0
14.0
2790
1760
2230
7/29/76
7-9
9.7
24.7
19.3
7.6
5.6
19.2
12.2
19.0
7.3
5
1
27
2
10
29
8
2
2
2
2190
1880
810
7/29/76
9-11
10.1
27.6
18.0
7.0
5.2
18.1
12.7
18.0
7.7
2220
1920
840
7/29/76
11-13
12.0
48.8
19.8
8.5
8.0
30.9
10.0
26.0
11.0
2420
1710
811
tValues are not included in calculations
(continued)
85
-------
TABLE C-3 (continued)
Date
Dura Pak
C2H6
C2H4
CoHQ
o o
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
NO 11
^ C T O
Squalane
N"C6H14
N-C7H1C
7 16
Toluene
N-CgH18
E-CCHC
6 5
M-XYL
0-XYL
N-CgH20
N-P-C.H,
b b
N-C1QH22
Beckman 6800
THC
CH4
CO
8/3/76
7-9
11.2
37.3
24.3
4.1
3.5
11.5
5.1
10.0
4.0
3
1
8
BDL*
4
13
2
Trace
Trace
1
2270
1920
570
8/3/76
9-11
4.7
18.3
7.2
2.9
2.5
9.5
11.8
8.0
3.0
1940
1750
530
8/3/76
11-13
4.0
8.4
4.9
2.2
2.3
7.2
2.2
3.0
NM**
1950
1830
450
8/3/76
13-15
5.9
19.5
7.5
2.7
4.8
4.8
4.0
6.0
3.0
2100
1710
560
8/5/76
7-9
6.8
8.4
31.0
3.3
15.8
47.6
2.0
40.0
9.0
38
1
16
3
7
29
5
1
1
3
2360
1800
670
8/5/76
9-11
8.4
29.4
17.6
5.8
8.0
59.2
2.0
32.0
10.0
2360
1770
820
8/5/76
11-13
6.0
17.9
12.4
3.4
6.6
22.4
1.0
17.0
8.0
2360
1720
660
* Rplnw rlpfprtinn limit1? (rnnt i miprl }
** Not measurable (because of interference etc.)
86
-------
TABLE C-3 (continued)
Date 8/5/76
13-15
Dura Pak
C2H6 5.3
C2H4 19.2
C^HQ s.5
C2H2 2.5
IsoC4H10 4.9
N-C4H1Q 26.2
C3H6 1.0
12 18.0
6.0
87
-------
TABLE C-4.
RAMS STATION 108
SUMMER INTENSIVE
THC
CH4
CO
Date
Beckman 6800
THC
CH4
CO
Date
Beckman 6800
THC
CH4
CO
6/23/76
7-9
2870
2130
1480
6/30/76
7-9
2190
1880
410
6/23/76
11-13
2260
1840
680
6/30/76
9-11
2100
1820
740
Mean
2223 ppbC
1872 ppbC
603 ppbC
6/23/76
13-15
2210
1840
520
6/30/76
11-13
1980
1840
180
Standard Deviation
6/28/76
9-11
2260
1840
680
6/30/76
13-15
1930
1820
180
270 ppbC
98 ppbC
388 ppbC
6/28/76
11-13
2210
1840
560
-------
TABLE C-5. RAMS STATION 113
SUMMER INTENSIVE
THC
CH4
CO
Date 7/6/76
7-9
Beckman 6800
THC 1963
CH4 1995
CO 1150
Mean
1874 ppbC
1912 ppbC
957 ppbC
7/6/76 7/6/76
9-11 13-15
1816 1843
1912 1830
861 861
Standard Deviation
78 ppbC
82 ppbC
167 ppbC
89
-------
TABLE C-6. RAMS STATION 114
THC
CH4
CO
C0H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC/iHin
4 10
N-C.H,n
4 10
C3H6
IsoC5H12
N-C,H19
5 12
Beckman 6800
THC
CH4
CO
SUMMER INTENSIVE
Mean
2613 ppbC
1851 ppbC
599 ppbC
7.1 ppbC
6/23/76 6/23/76 6/23/76 7/15/76
9-11 11-13 13-15 9-11
4.8
16.4
4.8
1.7
1.0
6.1
BDL*
5.0
1.0
2200 2750 2160 2450
1820 1840 1840 1960
520 560 540 550
Standard Deviation
91
31
2 ppbC
0 ppbC
302 ppbC
8.
7/15/76
11-13
4.6
21.8
4.8
1.4
1.0
6.6
BDL*
4.0
1.0
2330
1920
400
9 ppbC
7/15/76
13-15
2.4
10.9
2.8
0.7
1.0
4.4
0.5
2.0
1.0
2350
1650
330
7/20/76
9-11
5.7
20.5
6.3
3.0t
3.6
15.4
BDL*
10.5
2.3
2490
1760
460
* Below detection limits
(continued)
90
-------
TABLE C-6 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC/iHin
4 10
N"C4H10
C3H6
IsoC5H12
N"C5H12
Beckman 6800
THC
CH4
CO
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N"C4H10
C3H6
IsoC5H12
N~C5H12
Beckman 6800
THC
CH4
CO
7/20/76
11-13
5.0
32.6
4.9
2.0
3.0
12.8
BDL*
10.0
3.0
2650
1740
410
7/27/76
13-15
6.8
39.9
8.8
2.0
2.5
8.4
35.0
2.0
3.0
7/20/76
13-15
3.9
9.7
3.7
2.0
1.8
9.8
BDL*
6.8
3.0
2240
1610
480
7/29/77
11-13
14.9
29.6
25.8
5.6
14.3
35.7
13.0
25.0
11.0
2300
1680
510
7/22/76
9-11
8.2
15.5
8.9
4.7
4.1
14.2
0.7
14.0
5.0
2080
1820
660
8/3/76
11-13
7.7
113.3
18.6
2.8
16.2
48.1
24.5
27.0
14.0
2450
1790
340
7/22/76
11-13
7.5
41.9
7.6
2.9
2.6
12.4
BDL*
10.0
4.0
2040
1800
410
8/3/76
13-15
5.5
17.0
11.2
2.4
13.1
35.2
10.3
35.0
11.0
3870
2230
650
7/22/76
13-15
5.5
10.8
4.9
1.0
2.1
11.2
BDL*
9.0
3.0
1950
1760
480
8/5/76
9-11
13.3
52.9
12.1
11.5
7.4
34.9
4.5
31.0
15.0
2110
1710
840
7/27/76
9-11
7.5
19.2
14.7
3.7
8.6
19.0
31.0
11.0
6.0
2090
1390
340
8/5/76
11-13
5.7
102.5
5.5
5.3
3.8
17.3
6.5
13.0
7.0
2740
1720
840
7/27/76
11-13
6.6
27.8
10.1
2.6
3.3
9.9
51.7
4.0
6.0
2470
1660
340
8/5/76
13-15
4.6
10.5
3.5
2.7
1.8
8.5
BDL*
6.0
3.0
2120
1670
730
* Below detection limits
(continued)
91
-------
TABLE C-6 (continued)
Date 8/10/76 8/10/76 8/10/76
9-11 11-13 13-15
Dura Pak
C2Hg 5.5 51.9 4.2
C2H4 19.6 26.6 10.2
C3Hg 6.1 26.9 7.5
C2H2 5.7 49.4 3.8
IsoC4H1Q 4.0 21.6 4.6
N-C4H1Q 18.7 56.3 19.8
C3Hg 0.9 13.0 BDL*
IsoCcH,,, 15.0 59.0 14.0
b 1 £
N-C5H12 6.0 53.0 6.0
Squalane
N"C6H14
N-C7H1C
7 16
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
Q 9f)
M P p U
IN Y L6M5
N-C1QH22
Beckman 6800
THC
CH4
CO
* Below detection limits
** Nnt mpaciirahlo fhprancp nf i ntpvfovpi
8/12/76
7-9
37.6
20.5
19.8
18.1
9.1
29.0
6.0
26.0
39.0
9
14
45
3
30
89
24
3
1
8.
2370
1880
590
8/12/76
9-11
6.7
20.8
7.4
6.7
3.0
12.5
1.5
11.0
5.0
2110
1690
580
8/12/76
13-15
5.4
11.5
5.7
21.7
1.0
4.7
BDL*
3.0
2.0
2090
1670
290
8/17/76
7-9
6.2
26.1
15.1
5.3
7.1
27.4
2.2
13.0
9.0
9
3
14
1
5
19
5
1
NM**
1
(continued)
irp otr ^
92
-------
TABLE C-6 (continued)
Date
Dura Pak
C9H,
2 6
M/L
c. 4
C3H8
C2H2
IsoC4H1Q
N-C4H1Q
C3H6
IsoCrH,0
o 1
-------
TABLE C-6 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4Hin
1 ID
N-Cy,Hln
4 10
C3H6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N-C7H16
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C6H5
N"C10H22
Beckman 6800
THC
CH4
CO
8/26/76
7-9
15.8
35.4
19.5
10.1
8.3
30.0
3.9
25.0
11.0
11
2
23
2
11
32
9
1
1
8
2850
2290
830
8/26/76
9-11
14.2
37.0
15.9
15.3
7.8
37.0
4.7
32.0
14.0
2910
2200
1200
8/31/76
7-9
57.3
24.9
40.1
21.5
38.0
173.3
10.7
193.0
98.0
15
5
56
4
52
131
37
2
11
7
6140
3100
1330
8/31/76
9-11
13.7
55.0
35.6
16.3
23.8
61.1
6.1
52.0
25.0
3000
2220
1540
9/2/76
7-9
15.4
18.2
51.1
3.2
73.9
210.2
19.7
95.0
69.0
36
15
21
2
17
55
14
2
2
1
2800
1690
450
9/2/76
9-11
7.6
25.3
24.4
2.0
20.1
77.6
73.9
45.0
19.0
2020
1720
350
9/2/76
13-15
4.6
31.6
5.1
2.3
2.0
7.5
0.7
8.0
2.0
1780
1690
410
94
-------
TABLE C-7. RAMS STATION 115
SUMMER INTENSIVE
THC
CH4
CO
C2H2
Date
Beckman 6800
THC
CH4
CO
Date
Dura Pak
C2H6
C3H8
IsoC4H10
C3H6 ^
IsoC5H12
Beckman 6800
THC
CH4
CO
6/28/76
9-11
2660
1880
550
7/13/76
13-15
7.6
20.6
14.8
3.0
4.9
10.9
2.0
8.0
2.9
2160
1870
860
6/28/76
11-13
2490
1880
650
7/15/76
9-11
4.7
33.9
4.6
1.7
1.5
5.6
BDL*
3.0
1.0
2520
1930
490
Mean
2427 ppbC
1788 ppbC
498 ppbC
3 ppbC
6/28/76
13-15
2550
1900
430
7/15/76
11-13
3.4
28.5
3.1
2.2
1.4
5.3
BDL*
2.0
BDL*
2260
1870
330
Standard Deviation
6/30/76
9-11
2310
1840
630
7/15/76
13-15
2.5
36.2
2.1
0.9
0.9
4.2
BDL*
3.0
BDL*
2140
1830
610
908
147
213
2
6/30/76
11-13
2330
1800
260
7/20/76
9-11
5.7
34.0
6.6
2.5
3.1
12.9
BDL*
5.0
3.0
2220
1760
690
ppbC
ppbC
ppbC
ppbC
6/30/76
13-15
2120
1840
260
7/20/76
11-13
4.8
52.8
5.0
2.3
2.0
8.4
BDL*
7.0
2.0
2170
1720
410
7/20/76
13-15
4.2
31.2
4.3
2.4
2.3
9.6
BDL*
8.0
2.0
2090
1720
410
Below detection limits
(continued)
95
-------
TABLE C-7 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC.Hln
4 10
N-C4H1Q
C3H6
IsoC5H12
N-C5H12
Beckman 6800
THC
CH4
CO
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N-C4H1Q
C3H6
IsoC5H12
N-C5H12
Beckman 6800
THC
CH4
CO
7/22/76
9-11
9.9
38.8
14.6
6.3
7.0
24.1
BDL*
19.0
9.0
2210
1920
160
7/29/76
13-15
11.3
12.9
16.9
4.5
8.0
23.7
8.1
14.0
7.0
1060
1670
440
7/22/76
13-15
6.0
24.2
5.2
1.3
2.1
10.6
BDL*
9.0
2.0
2010
1770
380
8/3/76
9-11
3.2
21.6
3.1
2.6
2.1
10.9
14.4
10.0
3.0
1980
1690
700
7/27/76
9-11
6.6
33.2
9.0
3.1
4.8
12.1
44.9
6.0
2.0
3830
1350
280
8/3/76
11-13
8.0
36.0
5.2
10.4
6.0
37.1
2890.9
28.0
6.0
6200
1980
350
7/27/76
11-13
6.8
39.9
8.8
2.0
2.5
8.4
35.0
2.0
4.0
2460
1610
330
8/3/76
13-15
2.9
17.0
1.9
1.9
2.0
7.3
6.7
3.0
2.0
2000
1800
560
7/27/76
13-15
5.7
17.6
5.1
1.5
1.2
4.8
19.3
2.0
BDL*
2080
1580
330
8/5/76
9-11
7.4
27.8
10.1
6.8
4.0
22.6
19.2
18.0
9.0
2230
1790
940
7/29/76 7/29/76
9-11 11-13
13.9 11.0
19.8 25.4
22.8 16.2
6.9 3.9
9.4 7.8
27.9 22.5
14.2 11.0
26.0 15.0
10.0 7.0
2030 2860
2060 1650
950 450
* Below detection limits
96
-------
TABLE C-8. RAMS STATION 118
SUMMER INTENSIVE
Mean
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC.Hln
4 10
N-C»Hln
4 10
C3H6
IsoCKH19
5 12
5 12
Squalane
w r u
N'VH
N-C-,H,,
7 16
Toluene
N-C8H]8
E-C6H5
M-XYL
0-XYL
N-C9H2Q
N-P-C.Hp-
0 0
N-C1QH22
Beckman 6800
THC
CH4
CO
2791
1770
479
3.4
7/13/76 7/15/76 7/15/76
13-15 7-9 13-15
6.2 5.0 2.1
41.4 15.0 7.9
27.6 6.8 2.0
8.5 2.7 0.6
2.4 1.2 0.5
6.6 7.9 2.4
BDL BDL BDL
3.0 5.0 1.0
1.0 2.0
3850 2330 2280
1870 1900 1870
1380 580 210
ppbC
ppbC
ppbC
ppbC
7/20/76
7-9
4.8
24.8
4.6
1.5
1.1
6.4
BDL
2.0
NM
lilt
8
26
23
19
84
21
37
1
126
2340
1820
356
Standard Deviation
1311 ppbC
133 ppbC
301 ppbC
2.3 ppbC
7/22/76 7/22/76
7-9 13-15
6.6 4.6
9.3 13.5
8.3 3.9
1.1 0.2
2.4 1.2
9.7 3.9
BDL 0.7
4.0 2.0
14.0 1.0
2670
1740
191
7/27/76
7-9
6.3
18.2
7.7
5.6
3.3
14.6
12.7
8.0
2.0
2
1
4
1
5
18
6
Trace
Trace
1
2080
1480
380
(continued)
-------
TABLE C-8 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N-C5H12
Squalane
N-C6H14
N"C7H16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N-CgH20
N-P-C.H,-
b D
N-C1QH22
Beckman 6800
THC
CH4
CO
7/27/76
13-15
7.8
4.3
5.5
4.1
1.8
7.8
10.0
6.0
1.0
6070
1990
460
7/29/76
7-9
6.4
25.2
7.6
4.7
2.8
15.3
24.4
11.0
2.0
2
1
13
2
10
43
9
1
1
21
2030
1780
490
7/29/76
13-15
8.4
22.7
10.2
5.0
3.1
15.8
19.4
11.0
3.0
2610
1610
430
8/03/76
7-9
6.2
32.5
22.7
5.2
6.5
20.0
92.0
12.0
9.0
5
2
6
2
3
11
4
1
Trace
2
2280
1810
530
8/03/76
13-15
3.8
11.2
7.0
2.8
3.5
13.5
BDL*
9.0
4.0
2130
1750
590
8/05/76
7-9
5.3
27.2
4.7
1.9
1.8
5.6
BDL*
3.0
5.2
1
Trace
3
1
3
17
2
Trace
BDL*
1
2060
1720
410
8/05/76
13-15
4.2
12.6
3.0
1.3
0.8
3.2
BDL*
2.0
1.2
2100
1670
230
* Below detection limits
98
-------
TABLE C-9. RAMS STATION 121
THC
CH4
CO
SUMMER INTENSIVE
Mean
1960 ppbC
1872 ppbC
364 ppbC
Standard Deviation
311 ppbC
43 ppbC
183 ppbC
Date
Beckman 6800
THC
CH4
CO
7/6/76
9-11
1790
1870
660
7/6/76
11-13
1880
1930
370
7/6/76
13-15
2500
1830
717
7/8/76
9-11
1910
1900
350
7/8/76
13-15
1720
1830
270
99
-------
TABLE C-10. RAMS STATION 122
SUMMER INTENSIVE
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N"C4H10
C3H6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N-C,H,e
7 16
Toluene
N-CgH18
E-C5H5
M-XYL
0-XYL
N-C9H2Q
N-p-c.H,
0 0
N"C10H22
Beckman 6800
THC
CH4
CO
Mean
2939 ppbC
1864 ppbC
607 ppbC
5 ppbC
8/10/76 8/12/76
13-15 7-9
4.5 12.3
6.4 15.4
6.0 26.1
5.0 8.4
3.3 20.4
15.8 47.2
BDL* 4.9
12.0 36.0
4.0 18.0
2070 2580
1810 1840
450 650
Standard Deviation
8/12/76
13-15
7.4
16.1
6.8
4.4
2.3
7.8
1.0
7.0
3.0
1950
1670
300
1771
212
240
3
8/17/76
7-9
4.2
6.6
8.5
4.1
2.3
9.1
1.1
6.0
2.0
2
3
12
Trace
8
28
5
Trace
1
2
ppbC
ppbC
ppbC
ppbC
8/17/76 8/19/76
13-15 13-15
2.9 4.9
5.3 6.5
3.4 4.3
2.0 2.4
0.9 1.3
3.4 4.2
BDL* BDL*
1.9 2.0
0.8 2.0
* Below detection limits
(continued)
100
-------
TABLE C-10 (continued)
Date
Dura Pak
C2H6
24
CoHn
6 o
C2H2
IsoC-,H1n
4 10
N-C/,H,n
4 10
C3H6
IsoCKH19
5 12
N-C5H12
Squalane
N"C6H14
N-C7H1C
7 16
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
N-C9H2Q
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
8/24/76
7-9
7.5
18.9
10.1
3.9
2.0
7.8
0.7
5.0
3.0
2270
1890
460
8/24/76
13-15
5.8
8.1
4.6
3.0
1.7
4.1
BDL*
3.0
2.0
2080
1690
400
8/26/76
7-9
9.4
43.3
10.0
10.0
7.1
31.2
1.3
22.0
13.0
6
2
18
1
16
48
14
1
2
8
2520
1900
760
8/26/76
13-15
7.7
25.6
7.4
3.9
2.1
6.7
0.4
5.0
2.0
2210
1800
490
8/31/76
7-9
18.1
16.8
29.1
10.6
12.4
43.1
5.3
37.0
17.0
10
2
24
2
12
31
10
1
1
5
2750
2390
970
8/31/76
13-15
8.4
5.7
28.2
5.3
23.4
76.3
1.1
46.0
27.0
2160
1800
620
9/2/76
7-9
0.7
3.1
4.4
1.3
1.0
4.2
0.1
2.0
7.0
5
5
4
1
5
16
4
1
1
2
1600
1650
310
* Below detection limits
(continued)
101
-------
TABLE C-10 (continued)
Date 9/2/76
13-15
Dura Pak
C0H, 4.7
L 0
C2H4 5.1
C3H8 5.2
C2H2 1.9
IsoC4H1Q 1.9
N-C4H1Q 5.8
C3H6
12 3.0
2.0
102
-------
TABLE C-ll. RAMS STATION 124
SUMMER INTENSIVE
Mean Standard Deviation
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
Squalane
N"C6H14
N-C,H1C
7 16
Toluene
N-CQH
8 18
M-XYL
0-XYL
N-C9H2Q
N-P-C.H,-
o b
Beckman 6800
THC
CH4
CO
2264 ppbC 382
1931 ppbC 402
579 ppbC 214
3 ppbC 2
8/12/76 8/12/76 8/17/76 8/24/76 8/26/76
7-9 13-15 11-13 7-9 7-9
4.8 7.6 8.4 10.4 6.0
255.8 40.0 112.9 54.1 151.7
5.5 6.9 15.6 14.8 5.9
2.5 2.6 2.6 7.1 2.6
1.8 3.1 5.2 1.1
4.4 4.3 11.7 30.8 4.5
1.9 0.9
3.0 3.0 4.0 14.0 3.0
2.0 2.0 3.0 6.0 3.0
2380 1950 2270 2630
1720 1670 1890 1900
290 300 460 4fin
ppbC
ppbC
ppbC
ppbC
8/26/76
13-15
7.2
113.5
5.9
1.7
1.7
6.2
0.5
5.0
4.0
2210
1930
snn
8/31/76
7-9
a. 8
38.5
5.7
3.5
1.5
8.4
1.6
5.0
3.0
(continued)
103
-------
TABLE C-11 (continued)
Date
Dura Pak
C2H6
C3H8
IsoC4H1Q
N-C4H1Q
C3H6
N-C5H12
Squalane
1 1 w T n *i f
1 16
Toluene
E-C6H58
M-XYL
0-XYL
N-CgH20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
8/31/76
13-15
6.3
278.6
4.3
2.9
2.0
6.9
0.7
5.0
3.0
2900
2140
620
9/2/76
7-9
6.9
111.0
13.1
2.4
3.2
10.5
0.9
5.0
3.0
1910
1750
280
9/2/76
13-15
5.4
180.8
7.7
1.6
2.4
7.1
0.5
5.0
3.0
1850
1690
220
104
-------
TABLE C-12. RAMS STATION 101
FALL INTENSIVE
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
Squalane
N-C6H14
N-C?H16
Toluene
N-C8H18
E-CgH5
M-XYL
0-XYL
N"C9H20
N-P-C.H,
0 0
N~C10H22
Beckman 6800
THC
CH4
CO
11/8/76 11/10/76
13-15 7-9
18.0 11.9
46.4 24.3
11.4 6.8
40.3 25.8
11.8 6.7
47.5 29.6
12.4 7.0
44.0 28.0
22.0 13.0
NM
3
38
14
11
27
9
43
2
370
2690
2040
2115
Mean
2906 ppbC
1734 ppbC
1815 ppbC
33 ppbC
11/10/76 11/10/76
9-11 11-13
10.4 7.9
20.4 10.7
8.8 5.2
13.6 5.3
5.0 3.1
22.8 15.4
6.0 3.4
18.0 9.0
9.0 6.0
Standard Deviation
789 ppbC
240 ppbC
1322 ppbC
26 ppbC
11/10/76 11
/12/76 11/12/76
13-15 9-11 13:30-15
6.4 9
7.7 21
4.9 9
5.7 18
3.3 4
16.0 20
2.1 4
10.0 14
5.0 6
7
4
42
3
15
37
10
2
1
4
2330
1580
740
.2 7.6
.1 16.5
.0 6.6
.2 10.2
.9 3.1
.9 12.8
.1 1.5
.0 9.0
.0 5.0
1990
1470
250
(continued)
105
-------
TABLE C-12 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N~C4H10
C3H6
IsoC5H12
N"C5H12
Squalane
N"C6H14
N"C7H16
Toluene
N-C8H]8
E-C6H5
M-XYL
0-XYL
N-C9H2Q
N-P-CCHK
b b
N-C1QH22
Beckman 6800
THC
CH4
CO
11/16/76
7-9
40.0
87.9
37.0
71.2
23.0
101.3
26.0
92.0
38.0
29
13
87
10
31
68
28
3
4
15
3900
2120
3660
11/16/76 11/16/76
9-11 11-13
33.5 30.0
185.5 120.3
43.5 31.3
62.8 87.2
33.4 47.6
160.8 187.2
24.5 57.5
108.0 161.0
46.0 76.0
4020
1980
3810
11/16/76
13-15
10.7
19.7
14.8
14.2
8.4
30.8
5.8
23.0
11.0
2310
1490
710
11/18/76
7-9
75.6
57.4
75.5
60.1
32.0
134.2
22.2
99.0
54.0
31
5
49
15
16
40
17
35
3
10
3860
1970
3100
11/18/76
9-11
66.4
40.5
73.4
42.0
27.8
103.2
15.1
71.0
37.0
3300
1830
2250
11/18/76
11-13
23.8
28.7
27.0
16.7
21.0
95.0
8.8
61.0
28.0
2540
1470
900
(continued)
106
-------
TABLE C-12 (continued)
Date 11/18/76
13-15
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N-C5H]2
Beckman 6800
THC
CH4
CO
46.2
20.2
53.3
17.2
22.5
99.4
9.5
58.0
28.0
2670
1610
900
107
-------
TABLE C-13. RAMS STATION 103
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N-C4H1Q
C3H6
IsoC5H]2
N-C5H12
Squalane
N-C6H14
N"C7H16
Toluene
N-CQH1Q
8 18
E-C6H5
M-XYL
0-XYL
N-CgH20
N-P-C6H5
N"C10H22
Beckman 6800
THC
CH4
CO
11/8/76
7-9
19.1
47.2
13.5
26.0
6.8
31.5
7.7
30.0
14.0
11
3
90
14
21
37
15
38
3
258
3066
2270
1560
FALL INTENSIVE
Mean
2676 ppbC
1739 ppbC
1073 ppbC
15 ppbC
11/8/76 11/8/76 11/10/76
11-13 13-15 7-9
5.0 45.2 9.7
15.4 9.4 31.0
4.8 65.7 7.6
3.9 7.5 17.7
2.8 17.7 4.5
9.1 63.8 22.2
2.5 2.4 6.1
6.0 30.0 17.0
3.0 10.0 7.0
16
2
41
2
9
22
9
2
1
5
1785 1850
1683 1767
281 336
Standard Deviation
817 ppbC
367 ppbC
844 ppbC
14 ppbC
11/10/76 11/10/76 11/10/76
9-11 11-13 13-15
6.4 9.0 7.8
20.1 15.7 16.0
7.8 6.0 6.6
8.2 5.0 6.6
3.2 4.9 2.8
12.0 43.0 18.4
3.0 4.3 3.9
10.0 19.0 7.0
4.0 7.0 5.0
(continued)
108
-------
TABLE C-13 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N~C4H10
C3H6
IsoC5H12
N-C5H]2
Squalane
N"C6H14
N"C7H16
Toluene
N-C8H]8
E-C6H5
M-XYL
0-XYL
N-C9H2Q
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
11/12/76
9-11
7.0
11.9
7.7
7.9
2.7
11.8
2.2
11.0
1.0
2
1
6
1
4
10
4
1
1
2010
1500
490
11/12/76
1130-
1330
6.7
9.2
6.5
4.5
2.9
11.5
1.5
9.1
1.2
1990
1480
250
11/12/76
1330-
1530
6.3
9.2
6.4
4.8
2.1
7.6
1.2
6.4
1.0
2960
1470
280
11/16/76
7-9
42.1
121.6
223.8
51.0
65.0
174.9
24.6
118.0
43.0
48
6
40
5
21
48
16
3
3
11
4470
2550
2640
11/16/76
9-11
30.4
54.7
105.7
39.0
30.7
148.2
14.4
75.0
31.0
3360
1890
2160
11/16/76
11-13
9.0
7.8
18.7
6.0
5.7
24.9
1.5
11.0
4.0
2090
1440
410
11/16/76
13-15
11.4
13.2
34.1
8.4
8.8
43.8
2.4
17.0
6.0
2280
1480
530
(continued)
109
-------
TABLE C-13 (continued)
Date
Dura Pak
C2H5
C2H4
C3H8
CSH2
IsoC4H1Q
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
Squalane
N"C6H14
N"C7H16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH,
4
CO
11/18/76
7-9
58.6
23.2
69.1
15.9
31.6
197.3
6.3
57.0
30.0
6
2
24
2
4
16
4
2
1
5
2920
1740
1350
11/18/76
9-11
60.6
28.3
84.8
22.7
28.5
139.8
7.8
55.0
28.0
*
2990
1740
1690
no
-------
TABLE C-14. RAMS STATION 114
FALL INTENSIVE
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C4H1Q
C3H6
IsoC5H12
N"C5H12
Squalane
N'C6H14
N-C7H,,
7 16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
11/8/76
7-9
11.7
9.6
8.0
9.0
5.0
12.2
3.9
10.0
10.0
8
3
19
1
7
15
6
1
1
2
2654
2140
1330
11/8/76
13-15
6.7
10.7
11.2
8.0
6.1
29.6
2.3
17.0
8.0
2254
1863
536
Mean
2451 ppbC
1541 ppbC
1187 ppbC
19 ppbC
11/10/76
7-9
9.4
16.6
7.9
15.1
4.4
16.4
4.1
15.0
6.0
6
2
13
1
5
16
8
BDL*
1
1
Standard Deviation
11/10/76
7-9
Tank
(Upwind)
6.9
7.8
6.4
9.2
3.4
12.2
2.9
10.0
4.0
3
1
9
1
9
26
10
1
1
2
1299 ppbC
581 ppbC
1392 ppbC
22 ppbC
11/10/76 11/10/76 11/10/76
9-11 11-13 13-15
Tank
(Upwind)
5.1 9.9 4.9
3.6 5.6 7.0
7.2 8.1 4.7
2.3 1.7 1.6
1.1 2.4 4.0
3.8 11.1 16.8
1.9 0.9
2.0 11.0 9.0
2.0 6.0 2.0
* Below detection limits
(continued)
111
-------
TABLE C-14 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H1Q
N"C4H10
C3H6
IsoC5H12
N"C5H12
Squalane
N'C6H14
N"C7H16
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C,H,
b b
N-C1QH22
Beckman 6800
THC
CH4
CO
11/12/76
7-9
7.8
11.0
9.6
7.4
1.7
7.8
1.6
4.0
4.0
NM**
1
4
1
3
11
3
Trace
Trace
1
2030
1540
350
11/12/76
0930-
1130
6.2
8.3
6.8
3.9
1.2
6.2
1.1
4.0
2.0
10
3
1
1
4
1
Trace
Trace
1
1890
1470
210
11/12/76
1130-
1330
5.7
19.5
3.4
28.2
2.8
7.0
1.1
5.0
3.0
2060
1460
170
11/12/76
1330-
1530
5.4
4.9
5.3
9.3
1.7
5.0
1.1
4.0
2.0
1970
1450
220
Tank
11/12/76
7-9
(Upwind)
8.2
5.3
10.3
8.2
1.8
5.9
2.6
4.0
3.0
2
1
5
1
7
23
9
BDL*
1
2
Tank
11/12/76
9-11
(Upwind)
6.5
3.3
7.4
4.8
1.4
4.3
1.9
3.0
2.0
5
3
1
5
18
5
BDL*
BDL*
1
11/16/76
7-9
37.0
94.2
39.4
72.8
78.0
235.9
36.1
156.0
71.0
5170
1880
4010
* Below detection limits
** Not measurable (because of interference etc.)
(continued)
112
-------
TABLE C-14 (continued)
Date
Dura Pak
C2H6
C2H2
C3H8
C2H2
IsoC4H10
N"C4H10
C.H,
3 6
IsoC5H12
N-C5H]2
Squalane
N-C6H14
N-C7H16
Toluene
N-CgH18
L. "" w f li r~
6 5
M-XYL
0-XYL
N-C9H2Q
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
11/16/76
9-11
40.3
72.9
69.1
25.3
108.9
23.0
84.0
39.0
9
57
6
17
43
17
4
4
10
4010
2190
3280
11/16/76 11/18/76
13-15 7-9
6.1 66.2
38.4 80.2
5.3 69.6
16.7 37.1
6.8 19.6
24.2 67.2
7.1 8.7
18.0 43.0
10.0 25.0
24
4
39
3
12
27
12
2
1
NM*
2990
1770
1550
Tank
11/18/76
7-9
(Upwind)
63.0
23.9
66.4
32.1
17.3
57.1
10.0
34.0
19.0
13
4
37
2
8
23
8
1
1
2
* Not measurable (because of interference etc.)
113
-------
TABLE C-15. RAMS STATION 115
FALL INTENSIVE
THC
CH4
CO
C2H2
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N"C4H10
C3H6
IsoC5H12
N-C5H12
Squalane
6 14
N-C7Hn/I
7 14
Toluene
N-C8H18
E-C6H5
M-XYL
0-XYL
N-CQHQn
9 20
N-P-C.H,
0 0
N~C10H22
Beckman 6800
THC
CH4
CO
11/8/76
7-9:45
11.7
40.7
20.5
14.9
8.6
24.9
5.7
19.0
9.0
8
2
12
1
3
12
5
1
1
4
2285
2152
768
Mean
2321
1637
666
9
ppbC
ppbC
ppbC
ppbC
11/8/76 11/10/76 11/10/76
13-15 7-9
5.4 8.4
27.6 33.4
5.4 10.3
3.8 7.3
1.7 5.4
8.1 15.1
1.2 3.2
6.0 11.0
3.0 4.0
17
1
9
1
5
17
6
1
1
5
1967
1841
350
9-11
6.4
32.5
7.0
2.1
3.2
8.9
0.9
6.0
3.0
Standard Deviation
417 ppbC
225 ppbC
388 ppbC
7 ppbC
11/10/76 11/10/76
11-13 13-15
4.8 5.7
42.6 45.2
5.3 5.8
2.7 2.5
1.8 2.2
7.9 12.9
BDL* BDL*
2.0 8.0
2.0 3.0
11/12/76
9:30 -
11:30
13.0
28.1
63.7
7.4
28.5
53.1
17.5
33.0
14.0
14
2
9
2
4
9
3
1
TRACE
2
2360
1500
350
* Below detection limits
(continued)
114
-------
TABLE C-15 (continued)
Date
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N-C.H1n
4 10
C3H6
IsoCrH10
b \d.
N"C5H12
Squalane
N"C6H14
N-C7H,,
7 16
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
N-CgH2Q
N-P-H5
N-C]0H22
Beckman 6800
THC
CH4
CO
11/12/76
1130-
1330
8.3
24.4
16.4
6.2
14.5
20.9
4.1
13.0
5.0
2000
1450
300
11/12/76
1330-
1530
8.1
60.0
19.9
6.7
19.0
30.9
5.8
21.0
8.0
11/16/76
7-9
23.9
54.2
48.5
24.5
11.6
41.4
10.6
32.0
16.0
8
3
15
3
6
18
8
1
1
4
2620
1710
1070
11/16/76
9-11
15.0
30.9
26.9
13.8
8.0
32.5
5.0
16.0
9.0 .
2500
1580
840
11/16/76
11-13
9.2
30.1
20.6
5.8
6.0
21.0
1.2
12.0
4.0
2100
1450
430
11/16/76
13-15
10.6
32.1
19.6
8.6
5.5
19.4
2.1
13.0
5.0
2150
1500
470
11/18/76
7-9
65.8
37.9
91.0
17.2
24.0
66.9
12.2
33.0
19.0
8
3
14
2
6
15
5
1
1
3
2720
1770
980
(continued)
115
-------
TABLE C-15 (continued)
Date
Dura Pak
CA
C. 0
C2H4
C3H8
C2H2
IsoC4H1Q
M F* II
j\ If]
C3H6
IsoC5H12
N-C5H12
Squalane
N-C6HH
N"C7H16
Toluene
N-C8H18
M6H5
M-XYL
0-XYL
N-CgH22
N-P-C,H,
6 5
N-C1QH22
Beckman 6800
THC
CH4
CO
11/18/76
9-11
65.1
74.7
91.2
26.1
24.3
85.5
7.0
46.0
27.0
3020
1830
1610
11/18/76
11-13
48.4
65.6
65.7
11.1
16.5
55.8
4.5
27.0
14.0
2580
1710
690
Bag Box 1
11/18/76
13-15
28.1
35.1
35.2
5.7
11.0
40.2
1.3
21.0
10.0
2350
1580
450
Tank
11/18/76
13-15
(Upwind)
27.9
6.9
35.5
5.7
10.6
36.9
2.6
18.0
8.0
30
1
10
1
5
17
5
1
1
2
Bag Box 2
11/18/76
13-15
27.8
19.6
35.2
6.7
10.8
36.7
1 .0
21.0
6.0
21
1
12
1
6
19
5
1
1
2
2270
1560
410
116
-------
APPENDIX D
SPECIAL STUDIES
117
-------
CONTENTS
1.0 INTRODUCTION
Page
. 120
118
-------
TABLES
Number Page
D-l Roadway Samples Collected and Analyzed 9/22/76 . . 121
D-2 Roadway Samples Collected 9/22/76 Analyzed 9/24/76 123
D-3 Roadway Samples Collected and Analyzed 9/27/76 124
D-4 Roadway Samples Collected and Analyzed 10/29/76 125
D-5 CpH. Bag Samples at Station 101 Collected and
Analyzed 10/22/76 127
D-6 Ethylene Bag Sampling at Station 101 (with sampling pump). . 128
D-7 Ethylene Bag Sampling at Station 124 (with sampling pump). . 129
D-8 Ethylene Bag Sampling at Station 124 (with sampling pump). . 130
119
-------
D.O INTRODUCTION
Appendix D contains the results obtained from special studies in table
form in order to provide an overview of the data.
120
-------
TABLE D-l. ROADWAY SAMPLES COLLECTED AND ANALYZED 9/22/76 *_
Babler Park
# 5
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC H1n
4 10
N-C,H,n
4 1 0
C3H6
IsoC5H12
N-CRH19
5 12
Squalane
N"C6H14
N-C7Hn,
7 16
Toluene
N-C8H,8
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
4.1
5.2
5.7
3.0
0.8
3.4
1.8
1.7
1.5
6
1
9
30
4
Trace
BDL**
NMt
1930
1850
290
Babler Park Manchester
Repeat Road
3.7 22.3
5.4 157.1
5.3 27.6
3.2 111.5
0.8 15.2
3.3 84.1
1.4 73.7
1.8 125.0
1.5 68.0
46.0
15.0
72.0
12.0
30
78
30
4
5
16
4010
2270
7850
Ultrapure
Air
0.3
2.2
0.3
0.9t
BDL**
1.2
0.7
0.6
BDL**
NMt
NMt
9
Trace
10
33
6
Trace
1
1
210
240
Interstate
40 »
18.9
127.3
14.4
83.2
11.3
62.7
60.3
84.0
41.0
64
32
165
16
68
136
65
4
6
NMt
3450
1960
6510
* Concentrations in ppbC
**Below detection limits
t Not measurable (because of interference etc.)
(continued)
121
-------
TABLE D-l (continued)*
Interstate
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H10
N"C4H10
C3H6
IsoC5H12
N-C5H]2
Squalane
N-C6H14
N-C7H]6
Toluene
N-CgH18
E-C6H5
M-XYL
0-XYL
N"C9H20
N-P-CCHC
0 D
N-C1QH22
Beckman 6800
THC
CHA
4
CO
270
42.0
253.0
54.9
190.1
19.8
121.4
112.7
159.1
79.7
38
51
239
45
107
277
91
21
18
41
6250
3280
11360
Babler
Duplicate
4.6
5.6
5.6
3.3
0.8
5.3
1.8
2.9
1.5
* Concentrations in ppbC
122
-------
TABLE D-2. ROADWAY SAMPLES COLLECTED 9/22/76 ANALYZED 9/24/76*
Dura Pak
C9H,
2 6
Con/,
2 4
C,HQ
3 8
C2H2
IsoC4H-|0
N-C4H1Q
C3H6
IsoCKH19
b 1
-------
TABLE D-3. ROADWAY SAMPLES COLLECTED AND ANALYZED 9/27/76 *
Dura Pak
C2H6
C2H4
C3H8
C2H2
IsoC4H]0
N-C4H1Q
C3H6
IsoC5H12
N-C5H12
Squalane
N-C6HH
N-C7H]6
Toluene
N-C8H]8
E-C6H5
M-XYL
0-XYL
N-CQH9n
9 20
N-P-C6H5
N-C1QH22
Beckman
THC
CH4
CO
Bag 3
Bag 3 N. on 270
No. on 270 Repeat
38.6 38.4
306.6 305.3
16.6 16.6
355.4 361.0
33.5 33.0
180.3 179.1
141.2 141.4
136.0 243.0
135.0 134.0
91
31
126
21
55
123
61
6
22
16
6800
6000
1910
14600
Bag 1
West on
Manchester
16.1
94.0
12.0
105.5
12.0
57.6
39.1
75.0
42.0
45
11
44
52
93
88
27
135
894
4331
9000
1800
5850
Bag 4
West on
Olive
17.1
72.9
12.4
68.7
8.4
32.0
26.4
38.0
19.8
30
6
30
6
14
40
14
2
6
3
2900
1850
5190
Bag 5
N. on 270
(Olive-Page)
21.4
115.9
14.1
67.1
13.3
60.8
49.0
73.5
43.4
27
11
51
10
22
98
22
3
5
5
3500
1940
5540
Bag 1 (Dupl)
West on
Manchester
16.0
93.9
12.2
109.6
12.0
57.5
39.2
60.0
36.4
10020
1840
5890
* Concentrations in ppbC
124
-------
TABLE D-4. ROADWAY SAMPLES COLLECTED AND ANALYZED 10/29/76*
Dura Pak
C2H6
CnH/i
2 4
L» jn n
3 8
C2H2
Iso-C4H1Q
N-C4H1Q
C,H,
3 6
IsoC5H12
N-C5H12
Squalane
N"C6H14
N-C?H16
Toluene
N-C8H18
E-C.H,
6 5
M-XYL
0-XYL
N-C9H20
N-P-C6H5
N-C1QH22
Beckman 6800
THC
CH4
CO
W. on Manchester
1-270 to Weidman
36.1
215.1
47.0
205.4
32.0
153.3
95.6
145.2
61.4
38
19
94
12
38
90
47
5
7
9
5230
2350
12360
W. on Manchester
Weidman to Ries
53.6
259.1
40.5
257.8
33.0
194.3
114.1
182.6
75.8
74
25
119
20
41
129
52
8
12
15
6410
2690
15660
S. on 1-270
Manchester to 1-44
33.0
207.9
48.5
134.7
19.9
114.8
93.7
116.7
62.9
44
20
83
20
24
74
41
31
6
NM**
5000
2090
8970
* Concentration in ppbC
** Not measurable (because of interference etc.)
(continued)
125
-------
TABLE D-4 (continued)*
Dura Pak
C9H,
2 6
C2H4
C3H8
C2H2
Iso-C4H1Q
N-C4H1Q
CoH/-
3 0
IsoC5H12
N"C5H12
Squalane
N"C6H14
N"C7H16
Toluene
N-C8H18
E-C,H,
6 5
M-XYL
0-XYL
N'C9H20
N-P-C,H,
6 5
N"C10H22
Beckman 6800
THC
CH4
CO
W. on Olive
1-44 to Manchester
29.8
206.0
42.3
127.4
17.1
95.5
95.9
99.5
51.0
28
15
68
10
21
62
34
4
9
14
4290
1990
9580
W. on Olive
1-270 to Eatherton
5.3
6.6
11.8
5.8
2.2
7.7
2.4
9.8
2.2
BDL
1
5
2
3
5
5
1
NM**
MM**
2030
1720
350
Dupl . Analysis
W. on Manchester
1-270 to Weidman
37.3
220.4
47.8
208.4
33.0
156.8
95.2
148.9
61.0
38
21
99
13
32
88
39
5
3
8
- -
- -
- -
* Concentration in ppbC
** Not measurable (because of interference etc.)
126
-------
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse Dcfore completing)
1. REPORT NO.
EPA-600/4-80-006
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
5 REPORT DATE
REGIONAL AIR POLLUTION STUDY
Gas Chromatography Laboratory Operation
January 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
G. Cardwell
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Rockwell International
Environmental Monitoring & Services Center
11640 Administration Drive
Creve Coeur. MO 63141
10. PROGRAM ELEMENT NO.
1AA603 AA-126 (FY-79)
11. CONTRACT/GRANT NO.
68-02-2093
Task Order 113
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, N.C.
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park. N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final ..
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A gas chromatography laboratory was set up to analyze air samples collected in Teflon
bags and stainless steel tanks. Samples were analyzed for total hydrocarbons,
methane, CO, and C9-C1n hydrocarbons. A total of 455 samples, including replicates,
were analyzed during the summer and fall of 1976. Many samples were collected at
12 of the Regional Air Monitoring Systems (RAMS) sites to yield data on spatial and
temporal distributions of hydrocarbons. Additional sampling was performed to study
ethylene contamination in and around RAMS stations. Roadway samples were collected
to determine the composition of freshly emitted vehicular pollution. Quality control
audits indicated good system performance during the study. Replicate samples indi-
cated good reproducibility for samples stored for as long as six days in the Teflon
bags.
All data, including sums of paraffins, olefins, aromatic, and total non-methane
hydrocarbons are stored in the RAPS Data Bank at Research Triangle Park, North
Carolina.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
*Air pollution
*Hydrocarbons
*Carbon monoxide
*Gas chromatography
*Chemical laboratories
Regional Air Pollution
Study
St. Louis, MO
13B
07C
07B
07D
14D
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19 SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
139
20 SECURITY CLASS (This page/
UNCLASSIFIED
22 PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
131
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