Environmental Monitoring Series
REGIONAL AIR POLLUTION STUDY:
Gas Chromatography Laboratory Operations
Environmental Sciences Research Laboratory
Office of.Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology ^-
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the 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 in 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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EPA-600/4-76-040
July 1976
REGIONAL AIR POLLUTION STUDY:
GAS CHROMATOGRAPH LABORATORY OPERATIONS
By
A.C. Jones
Raymond F. Mindrup, Jr.
Air Monitoring Center
Rockwell International
Creve Coeur, MO 63141
Contract 68-02-1801
Task Orders 3, 21, and 53
Project Officer
Francis A. Schiermeier
Regional Air Pollution Study
Environmental Sciences Research Laboratory
Creve Coeur, MO 63141
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, N.C. 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for use.
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TABLE OF CONTENTS
PAGE
PART I: ESTABLISHMENT OF THE GAS CHROMATOGRAPH
LABORATORY (Task Order 3)
PART II: OPERATIONAL PROCEDURES (Task Order 21) 19
PART III: DEVELOPMENT OF METHODS AND ANALYSES OF
ATMOSPHERIC POLLUTANTS (Task Order 53) 53
ill
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PART I: ESTABLISHMENT OF THE
GAS CHROMATOGRAPH LABORATORY
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TABLE OF CONTENTS
PAGE
1. INTRODUCTION .. 4
2. TASK ORDER REQUIREMENTS 4
3. WORK PERFORMED 5
3.1 PERKIN ELMER, MODEL 900B CHROMATOGRAPH 7
3.1.1 COLUMN SELCTION FOR ANALYSIS OF
C - C WITH THE PE900B 8
3.1.2 SAMPLE CONCENTRATION DEVELOPMENT 8
3.2 BECKMAN, MODEL 6800 CHROMATOGRAPH 16
4. SUMMARY 17
5. REFERENCES 18
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LIST OF FIGURES
NUMBER PAGE
1 SAMPLE ANALYSIS FLOW DIAGRAM 6
CHROMATOGRAM OF AUTOMOBILE EXHAUSE GAS
OPERATED WITH PREMIUM LEADED FUEL
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1.
INTRODUCTION
To accomplish the objectives of the Regional Air Pollu-
tion Study (RAPS) it is necessary to perform continuous and
selective intensive monitoring and analysis of atmospheric
pollutants. The collection and monitoring of these pollu-
tants is performed by the 25 remotely operated Regional Air
Monitoring Systems (RAMS) stations, mobile laboratories, air-
borne laboratories and other bag sample collection techniques.
Analysis of the collected atmospheric bag samples is to be
performed at the RAPS Central Facility in a gas chromatography
laboratory to be established for this purpose. It was the
objective of this Task Order to set up and initiate opera-
tion of the RAPS Gas Chromatography Laboratory. The fol-
lowing sections of this report present a. summary of the ini-
tial effort performed under Task Order No. 3 to establish the
RAPS Gas Chromatography! Laboratory.
2. TASK ORDER REQUIREMENTS
Under this Task Order the contractor was to provide the
necessary manpower, materials and services to perform the fol-
lowing:
Services: Establish and operate a gas chromatography lab-
oratory, collect gas samples and perform quan-
tative analysis for nitrogen oxides, carbon
monoxide, Cl to CIQ hydrocarbons, total hydro-
carbons and other organic pollutants. A gov-
ernment furnished Perkin Elmer,Model 9003 gas
chromatograph with a PEP-1 data system and a
Beckman Model 6800 gas chromatograph were to
be provided. A government furnished analyzer
to perform analysis for nitrogen oxides was
also to be provided. Samples were to be col-
lected in Tedlar plastic bags, gas bottles, or
absorbing traps. Precautions were to be taken
to prevent condensation of vapors in sample
bags and sample bottles. Ambient air samples
were to be collected continuously for periods
ranging from 15 minutes to three' hoursJ. Pro-
vide EPA with a monthly report containing re-
duced data.
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2. TASK ORDER REQUIREMENTS (CONTINUED)
Personnel: Provide the following personnel; one expert
gas chromatographer, one technician exper-
ienced in source sampling
Equipment: Furnish equipment for gas chromatograph oper-
ations, including analytical columns, sample
valves, sample collection systems, operating
gases, calibration mixes, etc.
Period of
Performance:Start-September 1, 1973
Completion-February 28, 1974
3. WORK PERFORMED
In September 1973 a contract agreement was entered into
with McDonnell Douglas Electronics Company, St. Louis, Missouri
to provide the services of Dr. John Q. Walker as the gas chro-
matographic expert for the RAPS laboratory. Dr. Walker's first
action was to set up the gas chromatography laboratory. The gov-
ernment furnished analyzers were unpacked and assembled. Neces-
sary laboratory supplies, gases, tools and instruments were de-
termined and ordered. In November 1973 the laboratory was estab-
lished to the degree that functional check out and calibration
of the Perkin Elmer, Model 900B and Beckman, Model 6800 chro-
matographs could begin. Various laboratory operational pro-
cedures were studied for sample analysis based upon the meth-
odology depicted in Figure 1, Sample Analysis Flow Diagram.
Specific work performed setting up the gas analyzers for
routine operation and analysis during the remaining period of
this Task Order follows:
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GAS
SAMPLES
CALIBRATION
METHODS
SAMPLE
CONCENTRATION
BECKMAN
6800
ANALYZER
PERKIN ELMER
900-B
ANALYZER
OTHER
ANALYZERS
DATA
VALIDATION
Kb
w
Hfs>
DApC
DATA
BANK
SAMPLE ANALYSIS FLOW DIAGRAM
FIGURE 1
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3.1 PERKIN ELMER, MODEL 900B CHROMATOGRAPH
The high resolution gas chromatograph system to be set
up and made operational was comprised of three major compo-
nents: 1) Perkin Elmer, Model 900B chromatograph 2) Perkin
Elmer, Model PEP-1 Laboratory Computer System and 3) a Houston
Omni Scribe, Model 5213-4 dual pen recorder.
The initial objective was to adapt previously developed
methods for analysis of atmospheric samples using this dual
column instrument to conduct two simultaneous analyses of Ci
through CIQ hydrocarbons including compound type separations
(i.e. saturates from unsaturates and aromatics). Early in
the program it was recognized that the existence of a single
column with this capability would streamline operations over
the multiple column methods previously used (Reference 1 and
2). An additional developmental goal was to establish methods
for analyzing key compounds related to the internal combustion
engine's contribution to air pollution in concentrations less
than 1 ppm (i.e. acetylene, acetaldehyde, and aromatic hydrocar-
bons) . ?.. '• ' .
Dr. Walker's knowledge of the gas chromatograph methods
used at'the Shell Research Laboratories for analysis of complex
hydrocarbons during production of gasoline appeared to offer
a unique opportunity applicable to the needs of the RAPS pro-
gram. It was not fully recognized at the outset however, that
the hydrocarbon composition of gasoline samples differed from
atmospheric samples. Atmospheric sample complexity is increas-
ed because of the presence of reasonably large quantaties of
both polar and non-polar compounds; water, aldehydes and al-
cohol are typical examples.
Early attempts to place the system in operation were con-
fronted with several problems:
1) Late delivery of required laboratory equipment
for the sample injection system (solenoid valves,
valve oven, fittings, absolute pressure gauge,
molecular sieve, etc.).
2) The Perkin Elmer service representative had to
be called in to repair both the PE 900Bchroma-
tograph and PEP-1 computer.
3) Late delivery of gases for preparation of stand-
ards, etc.
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3.1.1 COLUMN SELECTION FOR ANALYSIS OF GI - CIQ WITH THE PE900B
During November and December 1973 literature surveys were
made in conjunction with experimental tests to define and ver-
ify procedures for routine sample analysis of Ci thru C^Q hydro-
carbons utilyzing a single column. The results of this effort
determined that adequate separation and resolution for reason-
able analysis times could not be achieved. For example, Shell
Oil uses a 200 ft. x 0.01 inch I.D. squalane column, temperature
programmed from -5 to 95° C. The disadvantages of this method
are the very long sample analysis time and poor separation of the
Ci - C4 compounds. A typical chromatogram for hydrocarbon iden-
tification performed by the Shell Research Laboratories is pre-
sented in Figure 2 and Table 1.
A test was run on the PE90CBusing a 150 ft. x 0.02 inch I.D.
support-coated open tubular squalane column programmed over a 0°
to 90° C temperature range. A. analysis (75 min) of both natural, gas
-and_ the.. €.3 . - Ci2 hydrocarbons of full range gasoline was achieved.
With this success, development of a method for concentrating atmo-
spheric samples was initiated.
3.1.2 SAMPLE CONCENTRATION DEVELOPMENT
Following meetings with W.A. Lonneman, Chromatography Lab-
oratory, EPA, Research Triangle Park, North Carolina and others,
it was decided to evaluate a sampling trap with concentration
capability similar to that developed by T.A. Bellar, EPA, Cin-
cinnati, Ohio.
Materials were ordered and a trap constructed of 18 inch x
1/4 inch O.D. stainless steel containing 5 cm of OY-17 on chro-
mosorb, 15cm of silica gel, 10 cm of 13A molecular sieve and 10
cm of 5A molecular sieve. This column required 3 to 5 minutes
for desorption at 225° C which is too slow. Furthermore, the
size of the column was not compatible with high resolution gas
chromatography. A similar column made of 1/8 inch stainless steel
was fabricated and similar unsatisfactory performance character-
istics were found.
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MINUTES
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1
100
I 1
110
1 1
120
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TABLE 1-A
PEAK BOILING
NUMBER COMPONENT POINT, <>C
1 Methane 161.49
2 Ethylene 103.71
3 Acetylene 84
4 Ethane 88.63
5 Propylene 47.70
6 Propane 42.07
7 Methylacetylene 23.22
+Propadiene 34.5
8 Isobutane 11.73
9 Isobutylene 6.90
+Butene-l 6.26
10 n-Butane 0.50
11 Trans-2-Butene 0.88
12 Neopentane 9.50
13 Cis-2-Butene 3.72
14 3-Methyl-l-Butene 20.06
15 Isopentane 27.85
16 Pentene-1 29.97
17 2-Methyl-l-Butene 31.16
18 2-Methyl-l,3-Butadiene 34.07
19 n-Pentane 36.07
20 Trans-2-Pentene 36.33
21 Cis-2-Pentene 36.94
22 2-Methyl-2-Bitene 38.57
23 3,3-Dimethyl-l-Butene — 41.24
24 2,2-Dimethylbutane 49.74
25 Cyclopentene 44.24
26 3-Methyl-l-Pentene 54.14
+4-Methyl-l-Pentene 53.88
27 4-Methyl-Cis-2-Pentene 56.30
28 2,3-Dimethyl-l-Butene 55.67
29 Cyclopentane 49.26
30 4-Methyl-lrTrans-2-Pentene 58.55
31 2,3-Dimethylbutane 57.99
32 2-Methylpentane 60.27
33 2-Methyl-l-Pentene 60.72
34 3-Methylpentane 63.28
+ (Hexene-1) 63.49
+ (2-Ethyl-l-Butene) 64.66
35 Cis-3-Hexene 66.47
36 Trans-3-Hexene 67.08
37 3-Methylcyclopentene 65.0
+2-Methyl-2-Pentene 67.29
10
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'iABLE 1-B
PEAK - BOILING
NUMBER COMPONENT POINT, °C
38 3-Methyl-Cis-2-Pentene 67.70
39 n-Hexane 68.74
+ (4,4-Dimethyl-l-Pentene) 72.49
40 Trans-2-Hexene 67.87
41 Cis-2-Hexene 68.84
42 3-Methyl-Trans-2-Pentene 70.44
43 4,4-Dimethyl-Trans-2-Pentene 76.75
44 Methylcyclopentane 71.81
+ 3,3-Dimethyl-l-Pentene 77.57
45 2,2-Dimethylpentane 79.20
+ 2,3-Dimethyl-2-Butene 73.21
+ (2,3,3,-Trimethyl-l-Butene) 77.87
46 Benzene 80.10
47 2,4-Dimethylpentane 80.50
48 4,4-Dimethyl-Cis-2-Pentene 80.42
49 2,2,3-Trimethylbutane 80.88
50 2,4-Dimethyl-l-Pentene 81.64
51 1-Methylcyclopentene 75.8
+ 2-Methyl-Cis-3-Hexene 86
52 2,4-Dimethyl-2-Pentene 83.26
+ 3-Ethyl-l-Pentene 84.11
+ 3-Methyl-l-Hexene 84
53 2,3-Dimethyl-l-Pentene 84.28
54 2-Methyl-Trans-3-Hexene 86
+ 5-Methyl-1-Hexene 85.31
55 3,3-Dimethylpentane 86.06
56 Cyclohexane 80.74
+ (4-Methyl-Cis-2-Hexene) 87.31
57 4-Methyl-1-Hexene 86.73
+ 4-Methyl-Trans-2-Hexene 87.56
58 3-Methyl-2-Ethyl-l-Butene 86.1
+ 5-Methyl-Trans-2-Hexene 88.11
59 Cyclohexene 82.98
60 2-Methylhexane 90.05
+ (5-Methyl-Cis-2-Hexene) 89.5
61 2,3-Dimethylpentane 89.78
+ (1,1-Dimethylcyclopentane) 87.85
+ (3,4-Dimethyl-Cis-2-Pentene) 87.9
62 3-Methylhexane 91.85
63 l-Cis-3-Dimethylcyclopentane 91.73
+2-Methyl-l-Hexene 91.95
+ 3,4-Dimethyl-Trans-2-Pentene 90.5
64 l-Trans-3-Dimethylcyclopentane 90.77
+l-Heptene 93.64
+2-Ethyl-l-Pentene 94
11
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TABLE 1-C
PEAK BOILING
NUMBER COMPONENT POINT,°C
65 3 Ethylpentane 93.48
+3-Methyl-Trans-2-Hexene 94
66 l-Trans-2-Dimethylcyclopentane 91.87
67 2,2,4-Trimethylpentane 99.24
+ (Trans-3-Heptene) 95.67
68 Cis-3-Heptene 95.75
69 3-Methyl-Cis-3-Hexene 95.33
+2-Methyl-2-Hexene 95.44
+3-Methyl-Trans-3-Hexene 93.53
70 3-Ethyl-2-Pentene 96.01
71 Trans-2-Heptene 97.95
72 n-Heptane 98.43
+ (3-Methyl-Cis-2-Hexene) 94
73 2,3-Dimethyl-2-Pentene 97.40
+ Cis-2-Heptene 98.5
74 l-Cis-2-Dimethylcyclopentane 99.57
75 Methylcyclohexane 100.93
+2,2-Dimethylhexane 106.84
+ 1,13-Trimethylcyclopentane 104.89
76 4-Methyleyelohexene 102.74
77 2,5-Dimethylhexane 109.10
+ Ethylcyclopentane 103.47
78 2,4-Dimethylhexane 109.43
79 2,2,2,-Trimethylpentane 109.84
80 l-Trans-2-Cis-4-Trimethylcyclopentane 109.29
81 Toulene 110.63
+3,3-Dimethylhexane 111.97
82 l-Trans-2-Cis-3-Trimethylcyclopentane 110.2
83 2,3,4-Trimethylpentane 113.47
84 2,3,3-Trimethylpentane 114.76
85 1,1,2-Trimethylcyclopentane 113.73
86 2,3-Dimethylhexane 115.61
+2 -Methyl-3-Ethylpentane 115.65
87 2-Methylheptane 117.65
88 4-Methylheptane 117.71
89 3,4-Dimethylhexane 117.73
+ (l-Cis-2-Trans-4-Trimethylcyclopentane) 116.73
90 3-Methylheptane 118.93
+ (S-Methyl-S-Ethylpentane) 118.26
91 2,2,5-Trimethylhexane 124.08
+ • (l-Cis-2-Cis-4-Trimethylcyclopentane) 118
92 1,1-Dimethyleyelohexane 119.54
+l-Trans-4-Dimethylcyclohexane 119.35
93 l-Cis-3-Dimethylcyclohexane 120.09
94 l-Methyl-Trans-3-Ethylcyclopentane 120.8
95 2,2,4-Trimethylhexane 126.54
12
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TABLE 1-D
PEAK BOILING
NUMBER COMPONENT ' POINT,°C
96 1-MethylTrans-2-Ethylcyclopentane 121.2
+l-Methyl-Cis-3-Ethylcyclopentane 121.4
97 Cycloheptane 118.79
+ 1-Methyl-1-Ethylcyclopentane 121.52
98 l-Trans-2-Dimethylcyclohexane 123.42
+ l-Cis-2-Cis-3-Triraethylcyclopentane 123.0
99 n-Octane 125.67
100 l-Cis-4-Dimethylcyclohexane 124.32
101 l-Trans-3-Dimethylcyclohexane 124.45
102 2,4,4 -Trimethylhexane 130.65
103 Isopropylcyclopentane 126.42
104 2,3,5-Trimethylhexane 131.34
105 2,2-Dimethylheptane 132.69
106 l-Methyl-Cis-2-Ethylcyclopentane 128.05
107 2,4-Dimethylheptane 133.5
+ 2,2,3-Trimethylhexane 133.6
108 2,2-Dimethyl 3Ethylpentane 133.83
+• 2-Methyl-4-Ethylhexane 133.8
109 Z,.6-Dimethylheptane 135.21
+ (l-Cis-2-Dimethylcyclohexane) 129.73
110 n-Propylcyclopentane 130.95
111 Ethylcyclohexane 131.78
+ 2,5-Dimethylheptane 136.0
+ 3,5-Dimethylheptane 136.0
112 Ethylbenzene 136.19
113 2,4-Dimethyl-3-Ethylpentane . 136.73
114 3,3-Dimethylheptane 137.3
115 1,1,3-Trimethylcyclohexane 136.63
116 2,3,3-Trimethylhexane 137.68
117 l-Cis-3-Cis-5-Trimethylcyclohexane 138.41
118 2-Methyl-3-Ethylhexane 138.0
119 p-Xylene 138.35
120 m-Xylene 139.10
+ (3,3,4-Trimethylhexane) 140.46
121 2,3-Dimethylheptane 140.5
122 3,4-Dimethylheptane 140.6
123 4-Methyloctane 142.48
124 2-Methyloctane 143.26
125 3-Ethylheptane 143.0
126 3-Methyloctane 144.18
127 0-Xylene 144.41
+ (2,2,4,5-Tetramethylhexane) 147.88
128 2,2,4-Trimethylheptane 147.8
129 2,2,5-Trimethylheptane 148
+ 2,2,6-Trimethylheptane 148
13
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TABLE 1-E
PEAK BOILING
NUMBER COMPONENT POINT, °C
130 2,5,5-Trimethylheptane 152.80
+ 2,4,4-Trimethylheptane 153
131 Isopropylbenzene 152.39
132 n-Nonane 150.80
133 3,3,5-Trimethylheptane 155.68
134 2,4,5-Trimethylheptane 157
+2,3,5-Trimethylheptane 157
135 n-Proplybenzene 159.22
136 2,2,3,3-Tetramethylhexane 160.31
+ 2,6-Dimethyloctane 158.54
137 l-Methyl-3-Ethylbenzene 161.31
138 l-Methyl-4-Ethylbenzene 161.99
139 3,3,4-Trimethylheptane 164
+ 3,4,4-Trimethylheptane 164
+ 3,4,5-Trimethylheptane 164
140 l-Methyl-2-Ethylbenzene 165.15
+• 5-Methylnonane 165.1
141 4-Methylnonane 165.7
142 1,3,5-Trimethylbenzene 164.72
143 2-Methylnonane 166.8
144 Tert-Butylbenzene 169.12
145 3-Methylnonane 167.8
146 Unidentified CIQ Alkylate Peak
147 1,2,4-Trimethylbenzene 169.35
148 Sec-Butylbenzene 173.31
+ Isobutylbenzene 172.76
149 l-Methyl-3-Isopropylbenzene 175.14
150 n-Decane 174.12
151 1,2,3-Trimethylbenzene 176.08
+l-Methyl-4-Isopropylbenzene 177.10
152 l-Methyl-2-Isopropylbenzene 178.15
+ Indane 177
153 Unidentified GH Alkylate Peak
154 1,3-Diethylbenzene 181.10
155 Unidentified Gil Alkylate Peak
156 l-Methyl-3-n-Propylbenzene 181.80
157 n-Butylbenzene 183.27
158 1,2-Diethylbenzene 183.42
+ l-Methyl-4-n-Propylbenzene 183.75
159 1,4-Diethylbenzene 183.30
160 l-Methyl-2-n-Propylbenzene 184.80
161 l,3-Dimethyl-5-Ethylbenzene 183.75
162 Unidentified Gil Alkylate Peak
163 2-Methylindane 184
164 1,4-Dimethyl 2-Ethylbenzene 186.91
165 1-Methylindane 186.5
14
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T. IE 1-F
PEAK BOILING
NUMBER COMPOUND POINT, °C
166 l-Methyl-3-Tert-Butylbenzene 189.26
HJnidentified Cll Alkylate Peak
167 l,3-Dimethyl-4-Ethylbenzene 188.41
168 l,3-Dimethyl-2-Ethylbenzene 190.01
+ l,2-Dimethyl-4-Ethylbenzene 189.75
169 l-Methyl-4-Tert-Butylbenzene 192.76
+ Unidentified Cn Alkylate Peak
170 l,2-Dimethyl-3-Ethylbenzene 193.91
171 n-Undecane 195.89
172 1,2,4,5-Tetramethylbenzene 196.8
173 1,2,3,5-Tetramethylbenzene 198.0
174 Isopentylbenzene 198.9
175 5-Methylindane 199
176 4-Methylindane 203
177 n-Pentylbenzene 205.46
178 1,2,3,4-Tetramethylbenzene 205.4
179 Tetraline 205.57
180 Naphthalene 217.96
181 l,3-Dimethyl-5-Tert-Butybenzene . 205.1
182 n-Dodecane 216.28
( ) Designates minor component
15
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To overcome the long desorptibn time and improve the reso-
lution a two step concentration procedure was next implemented.
The 18 inch x 1/4 inch concentration column (previously dis-
cussed) was interfaced to a smaller volume ( 20 inch x 0.02 inch
I.D.) column coated with OV101 silicone oil and cooled to liq-
uid nitrogen temperature. The effluent from this concentration-
column was then fed into the squalane analytical column. This
concentration configuration was set up for evaluation using the
following analysis conditions and procedures:
1) Isothermal at 0° for 12 minutes, then
2) Temperature programmed at 2° C to 90° C, then
3) Flow programmed at 1 pound per minute from 15 to
40 psig.
4) Eighty minutes (* 15 sec.) are required for the
elution of normal decane. Following this the
column flow is reversed (opening the back flush
valve) to elute the "nCio plus" flaction.
Just prior to initiation of testing with this configuration,
the squalane column deteriorated to an unusable point. Normal
procedures were tried to regenerate the column efficiency with no
success.
Procurement of a replacement 200 ft. x 0.02 inch I.D. was in-
itiated. This concluded the effort performed on the PE 900Bchro-
matograph analysis development during the period of performance
on this Task Order.
3.2 BECKMAN, MODEL 6800 CHROMATOGRAPH
Initial operation and check out of this instrument began in
November 1973. Due to damage received during shipment the instru-
ment would not separate C2 hydrocarbons (ethane, ethylene and a-
cetylene). A Beckman service engineer was called in and the unit
repaired. Several printed circuit boards were found out of align-
ment with their connectors and the molecular sieve column was par-
tially deactivated.
Check out and calibration of the chromatograph was next ini-
tiated. A 140 ft3 gas blend of 45 ppm CO, 5 ppm CH4, 5 ppm C2 H4
and 5 ppm C2 H2 in nitrogen was prepared to be used as a reference
standard with a commercially prepared 5 ppm CH4 in nitrogen mixture.
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Early analysis results showed very poor repeatability. The prob-
lem was found to be caused by a contaminated cylinder of ultra
pure hydrogen. The was replaced with a new cylinder and satis-
factory operation was then achieved.
4. SUMMARY
During the six month period covered by this Task Order the
RAPS, St. Louis, Gas ChromatographyLaboratory was established.
The services of a professional gas chromatographer, Dr. John Q.
Walker were acquired. Equipment and supplies were procured to
support laboratory operations. Two analyzers were set up and
tests initiated to establish operational procedures for sample
insertion techniques.
Plans were developed for a one year follow on to this initial
gas chromatographylaboratory effort. A schedule was developed to
place the laboratory in operation and begin routine sample bag
analysis in the near future. Additional laboratory staffing and
equipment.pxacurement was also planned.
17
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References
"Analysis of the Atmosphere for Light Hydrocarbons," by Edgar
R. Stephens and Frank R. Burleson; Journal of the Air Pollution
Control Association, (March 1967)
"Hydrocarbon Composition of Urban Air Pollution," by W.A. Lonneman,
S.L. Kopczynski, P.E. Darley and F.D. Sutterfield; Environmental
Science and Technology, (March 1974)
IS
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PART. II: OPERATIONAL PROCEDURES
19
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TABLE OF CONTENTS
PAGE
1.0 INTRODUCTION 23
2.0 TASK ORDER REQUIREMENTS 24
2.1 SERVICES 24
2.2 PERSONNEL 25
2.3 EQUIPMENT 25
2.4 PERIOD OF PERFORMANCE 25
3.0 WORK PERFORMED 26
3.1 PERSONNEL 26
3.2 LABORATORY EQUIPMENT 26
3.3 WORK PLAN 27
3.4 GAS CHROMATOGRAPHIC ANALYSIS DEVELOPMENT 27
3.4.1 Perkin Elmer, Model 900 B Chromatograph 28
3.4.1.1 Column Development 29
3.4.1.2 Concentration Trap Development 35
3.4.1.3 Analysis 35
3.4.2 Beckman Model 6800 Chromatograph 38
3.4.2.1 Chromatograph Modification 39
3.4.2.2 Beckman 6800 Chromatograph
Reproducibility 39
3.4.2.3 Efficiency Check of Carbon
Monoxide - Methane Conversion 41
3.4.2.4 Standard Bag Preparation and
Diffusion Losses 41
3.4.2.5 Calibration of Instruments 44
3.4.2.6 Analysis 44
3.4.3 Varian, Model 940 Gas Chromatograph 44
3.4.4 Bendix, Model 8101-B NO Analyzer 45
3.4.5 Tracor, Model 270, Sulfur Chromatograph 45
3.4.6 Bendix, Pure Air System 45
3.4.7 Bendix, Dynamic Calibration System 45
4.0 SAMPLE BAG ANALYSIS AND TESTING 47
4.1 SAMPLE BAG CLEANING 47
4.2 SAMPLE BAG LEAK TESTING 47
4.3 SAMPLE BAG CONTAMINATION TESTING 48
5.0 REFERENCES 52
20
-------
FIGURES
NUMBER PAGE
- C HYDROCARBON ANALYSIS ON PORASIL B COLUMN 31
C - C HYDROCARBON ANALYSIS ON DURAPAK N-OCTANE COLUMN 32
C^ - C,. HYDROCARBON ANALYSIS ON DURAPAK PHENYL
2 4
ISOCYANATE COLUMN 33
RETENTION TIME OF C - C HYDROCARBONS 36
BECKMAN MODEL 6800 BAG SAMPLING SYSTEM 40
CALIBRATION CURVE, TRACOR 270, SULFUR CHROMATOGRAPH 46
DECAY OF SELECTED MATERIALS THROUGH A 5 MIL. TEFLON BAG 49
LOSS"OF SELECTED MATERIALS THROUGH.A 2 MIL. TEFLON BAG 50
21
-------
TABLES
NUMBER PAGE
1 REPRODUCIBILITY OF COMPLEX AUTO EXHAUST USING PE 900
GAS CHROMATOGRAPH 34
2 REPRODUCIBILITY OF PE 900 ANALYSIS 37
3 STANDARD DEVIATION BECKMAN MODEL 6800 42
4 STANDARD BAG PREPARATION AND DIFFUSION LOSSES 43
5 HYDROCARBON RETENTION TEST USING TEDLAR BAG MATERIALS 51
22
-------
1.0 INTRODUCTION
To accomplish the objectives of the Regional Air Pollution Study (RAPS),
it is necessary to perform both continuous and selective intensive periodic
monitoring of atmospheric pollutants. The gas chromatography laboratory lo-
cated within the RAPS Central Facility has been established to support a
variety of studies under the RAPS program. The laboratory will assist in the
evaluation of the Regional Air Monitoring System (RAMS) station performance,
validation of automotive emissions inventory submodels, defining the composi-
tion of emissions from significant sources, tracking plumes, and developing
and validating photochemical submodels, particularly those involving the
contribution of the hydrocarbon-nitrogen oxide atmospheric reaction system to
the photoxidation of sulfur dioxide to sulfate.
The gas chromatography laboratory collects and analyzes atmospheric
samples for a variety of pollutants, including hydrocarbons, carbon monoxide,
and atmospheric, tracer gases. Supplemental analyses for sulfur compounds and
nitrogen-oxides-are also to be run on many samples using government furnished
analyzers.
Data from all analyses are recorded and entered into the RAMS/RAPS com-
puter data bank.
The objective-of the task order was to continue with the establishment
of the gas chromatography laboratory and develop operational procedures pre-
viously initiated by Task Order No. 3. The following sections of this report
present a summary of the work performed under Task Order No. 21, Gas Chro-
matography Laboratory Operation.
23
-------
2.0 TASK ORDER REQUIREMENTS
Under this task order the contractor was to provide the necessary man-
power, materials and services to perform a variety of studies as directed by
the RAPS Field Coordinator. A summary of specific activities to be performed
is presented in the following task specification:
2.1 SERVICES
1. The contractor shall prepare and submit to the RAPS Field Coordinator
for approval a work plan for operation of the Gas Chromatography Laboratory.
The plan shall include schedules, man-power estimates, and milestones for
bringing the gas chromatography lab into a state of complete readiness for
analysis of atmospheric samples. The work plan shall include the operation
and calibration of all government furnished (GFE) instruments, data process-
.ing, analysis, and reporting. It shall also consider the entry and retrieval
of data into/from the RAMS/RAPS data bank.
2. The contractor shall develop analytical configurations and methods
for gas chromatographic analysis of atmospheric samples for C-| - C-.Q hydro-
carbons, CO, methyl mercaptan, and atmospheric tracer gases, such as SFg and
fluorocarbons. Except for methane, hydrocarbons must be measured at concen-
trations down to one part per billion carbon (ppb C). Sulfur compounds to
0.1 ppb, and tracer gases to 1 part per trillion.
3. Sampling shall be done at the RAMS monitoring stations, from heli-
copters, from mobile vehicles, and at various sites in the St. Louis area.-
The contractor shall pick up and deliver to the gas chromatography lab all
bag samples collected at the RAMS stations. The bags shall be shielded from
sunlight during pickup and delivery. The contractor shall replace filled
bags at the RAMS stations with clean, leak-tight bags.
4. The contractor shall concentrate and analyze atmospheric samples for
specific experiments conducted by RAPS investigators.
24
-------
5. The contractor shall analyze about 400 or more atmospheric samples
for individual hydrocarbons (C-| - C10 inclusive), total nonmethane hydro-
carbons (NMHC), CO, NO, and NOX- Of these samples, the contractor shall
additionally analyze 100 of the samples for H2S, SOp, total sulfur, and
methyl mercaptan; and for atmospheric tracer gases (SFg, fluorocarbons).
6. The contractor shall validate all analyses, record and report con-
centrations for all chemical species specified above as well as sum of par-
affins less methane, sum of olefins, and sum of aromatics.
7. The contractor shall operate all laboratory equipment, and perform
instrument calibrations, routine service, and maintenance. EPA will pro-
vide necessary replacement of major parts and emergency services normally
performed by instrument manufacturers for all GFE instruments.
8. The contractor shall provide all necessary administrative and opera-
tional support for contract personnel assigned to this task.
9. The contractor shall provide each month a technical and financial
progress report.
2.2 PERSONNEL
1. The contractor is to provide the following personnel as a minimum:
a. One expert gas chromatographer.
b. One laboratory technician experienced in quantitative analysis
of gases.
2.3 EQUIPMENT
The contractor shall furnish all necessary equipment and supplies re-
quired for efficient and effective operation of the gas chromatography
laboratory.
2.4 PERIOD OF PERFORMANCE
Start 1 March 1974
Completion 30 November 1974
25
-------
3.0 WORK PERFORMED
At the time of initiation of effort on this task order, the gas chro-
matography laboratory was still in the early stages of development. Laboratory
tools, supplies and equipment were still being procured.
Instruments and analyzers were still being received, set up in the lab-
oratory and operational methods and procedures developed. The Perkin Elmer,
Model 900 B Chromatograph had been set up with its companion Perkin Elmer,
PEP-1 Computer and dual pen recorder. This Chromatograph, however, still re-
quired considerable development work to establish the capability for routine
C-j through C,Q hydrocarbon analysis. The Beckman Model 6800 Chromatograph
had been set up, calibrated and was ready to start routine analysis.
The activity that transpired for nine months in support of this task
order follows:
3.1 PERSONNEL
In early March 1974 a new contract agreement was entered into with
McDonnell Douglas Electronics Company, St. Louis, Missouri for the continued
services of John Q. Walker. Mr. Walker would continue to serve as the senior
gas chromatographer. In May 1974 Mr. Raymond Mindrup was hired as the gas
chromatographer engineer for the laboratory. A part time laboratory tech-
nician was hired in April to assist in the laboratory as required. This
completed the staffing of the laboratory for the period of this task effort.
3.2 LABORATORY EQUIPMENT
1. The analyzers to be used in the laboratory were all government fur-
nished equipment (GFE) consisting of the following major instruments:
a. Perkin Elmer, Model 900 Chromatograph
b. Beckman, Model 6800 Chromatograph
c. Varian, Model 940, Gas Chromatograph
d. Bendix, Model 8101-B, NOX Analyzer
26
-------
2. The Beckman 6800 Gas Chromatograph can perform specific methane anal-
ysis with high resolution and sensitivity in a short sampling period.
3.4.1.1 Column Development
Four support coated open tubular columns were evaluated for separation
of hydrocarbon compounds in the C2 to C,Q range. Separation and temperature
stability performance for each of the tested columns were as follows:
Liquid Phase Separation Temp Analysis Limits
Polyphenyl ether^ ' good for aromatics good to 200°C
Carbowax 1540 good for aromatics good to 150°C
OV101 Silicone Oil^ fair for most HC good to 160°C
Squalane C~ - Co poor separation good to only 65°C
C* - Cg acceptable
separation
Cg - CIQ peak broadening
The OV101 silicone oil column satisfied the temperature requirements for
separation of Co to C-.Q hydrocarbons; however, only poor quantitative resolu-
tion was feasible. The squalane column did not adequately resolve Co to C^
hydrocarbons (poor separation) or Cg to C-|Q due to the peak broadening at the
low temperature. Acceptable resolution was achieved for the C* to Cg hydro-
carbons.
In July 1974 tests were run to investigate the use of a Porasil "B" pre-
column ahead of the OV101 and squalane capillary columns. Specific improve-
ment in the resolution of Co to C* hydrocarbons was thought possible. The
results of this configuration testing found that a loss of resolution de-
veloped in the C^ to Cg analysis and the required analysis time was exces-
sive.
Next a dibutyl maleate column'5^ 50 ft. of 1/8 inch OD copper, was fabrv
cated for evaluation. It was believed that this configured column would re-
solve Cr through Cg hydrocarbons. Tests conducted at 0°C demonstrated poor
resolution (broad peaks), hence, this column was not considered suitable for
operational application.
29
-------
In mid July 1974 a meeting was held with the EPA Project Officer,
Rockwell's Principal Investigator and supporting staff personnel. The objec-
tives of the meeting were twofold:
1. Review the current analysis capability of the RAPS gas chromatograph
laboratory in support of the Summer 1974 Intensive and
2. Review the progress to date, problems, and establish a plan of action
to bring the Perkin Elmer PE 900 Chromatograph into operational service.
At this meeting it was agreed to drop further development work aimed at the
use of a single column for hydrocarbon analysis for compounds C2 through C-|Q.
Thus the capability for simultaneous analysis of two samples would no longer be
feasible. One channel of the dual chromatograph was to be used for separation
and analysis of the light gas compounds C2 through C^, and the second channel
for the heavy compounds C^ through C^Q.
Three packed columns, Porasil Er ' and two Durapcks: n-octane and phenyl iso-
cyanates, ' were investigated to provide the Cp - C. hydrocarbon analysis. The
Porasil B column gave the best separation of the three, resolving all the C2 - C^
hydrocarbons of interest above 5 ppb. concentration. Figures 1, 2, and 3 illus-
trate the respective separation of a mixture of C2 - C^ hydrocarbons on each
column. Reproducibility of the Porasil B analysis and trapping system was de-
termined with a sample of auto exhaust collected in a Teflon bag. The results
of this study are tabulated in Table 1, inferring the reproducibility of trap-
ping heavy hydrocarbon to be as good or better than the light C2's trapped in
this test. Limitations involved with the Porasil B are the lack of complete
resolution of C2 compounds at high concentrations and the peak broadening of
compounds whose elution time is greater than five minutes. These problems can
be seen in Figure 1.
For C. through C10 hydrocarbon analysis, a squalane SCOT (Support Coated
Open Tubular) capillary column was investigated. Temperature programming from
0° to 65° did not separate the C2 and C3 hydrocarbons but did minimize the
bleed of the squalane liquid phase. To facilitate the C-.Q hydrocarbon resolu-
tion, an Analabs flow programmer was used to flow program (from 10 to 40 cc
per- ninute) the column after the column temperature reached 65°C. This con-
figuration provided acceptable resolution of C. to Cg hydrocar'
-------
. r i .1.':. . r,.. ,L , .
Helicopter Sampling Over Site 109
1100 to 750 feet
11/29/75 9:08 AM
10 Win.
3 divisions = 5 minutes- - -
FIGURE 1
C2 - C4 HYDROCARBON ANALYSIS ON PORASIL B COLUMN
31
-------
O)
c
O
i-
D-
u
.0
O
I/)
Operator.. TTT.^.' ................ Date .
Column No ............ Length . A\ ..... .Dla. .V|$*A ----
Coating . &StYAf .feJ6 ........ Concn ................
Support M.-.6GTfetlC . ............. Mesh .........
TEMP: Col: Init PlVwV\C»4.ir.DC Final .......... .°C
Rate ...... .°C/min. Det. . .V.V.^. .°C Inj. . . )^SJ. .°C
CARRIER GAS .Bft- ......... Rate . .H. Ad. . . . ml./min.
Pressures: In'eV . . ?. .......... Outlet . . .
Hydrogen . /lp. . fe<^& ml./min. Ai
DETECTOR: E.C ............ T.C ........ F.I.D .......
Scavenger .............. Rate ............... ml./min.
Sens ................ Rec.Ra,nge ................. mv.
SAMPLE ?V\vVhf.S . )Aft-. ?TV\*. ....... Size ..........
Solvent ... ............... Concn .................. .
mUmin.
5-Min.
10-Min.
FIGURE 2
C2 - C4 HYDROCARBON ANALYSIS ON DURAPAK N-OCTANE COLUMN
32
-------
Od
O
I/I
Q.
L
Operator ):*«
Date?'. fi\O.«4 .....
ColumnNo ............ Length ..ft ...... Dia.fg*. .......
Genoa
. C
Final .......... C
°C Inj. ..
Coating .'
Support
TEMP: Col: I nit
RatelT?*.... C/min. Det.
CARRIER GAS ^l& RateCt.. <4ft ..... ml./min.
Pressures: Inlet . .13*5* Outlet
Hydrogen . iO*.^ ... ml./min. Air.W^.... mUmin.
DETECTOR: E.C.0*'?^'^?"! . . T.C F.I.D. X. ...
Scavenger Rate ml./min.
Sens Rec.Range mv.
SAMPLE ?>>
01
C
<0
+J
C
O)
o.
I
o
I/)
5-Min.
10-Min.
FIGURE 3
C4 HYDROCARBON ANALYSIS ON DURAPAK PHENYL ISOCYANATE COLUMN
33
-------
TABLE 1
REPRODUCIBILITY OF COMPLEX AUTO EXHAUST (72 VW) USING PE 900 GAS CHROMATOGRAPH
STANDARD
COMPONENTS PEAK AREAS* AVERAGE DEVIATION
- 0.01
- .081
- 0.003
- 0.015
- 0.005
- 0.011
- 0.031
NOTES:
A. Sample of auto exhaust was 1:3 of auto exhaust to ambient outside air.
B. Engine was cold.
C. Porasil B Column used.
2
* Calculated as peak ht, x peak width at half-height, inches .
Ethane
Ethyl ene
Propane
Acetylene
Isobutane
n-Butane
Propylene
0.20
0.65
0.05
0.28
0.19
0.61
0.37
0.20
0.51
0.05
0.31
0.20
0.59
0.35
0.18
0.65
0.045
0.29
0.19
0.61
0.41
0.19
0.60
0.05
0.30
0.19
0.60
0.38
-------
two minutes. See Figure 4 for an example of relative retention times of
C4 ~ C8 nydrocarbons- Reproducibility of the PE 900 system was determined
with repetitive analyses of a site sample (105, 4-6 AM, 8/25/74). Fourteen
compounds, C3 to Cg hydrocarbons, their peak area measured with the PEP-1 da-
ta processor, were compared and the standard deviation determined for each
compound. The results of this study are contained in Table 2.
3.4.1.2 Concentration Trap Development
When the previous multi-stage concentration trap was proven ineffective,
an investigation was conducted to determine the parameters that effect trap-
ping efficiency; such as, trap material, coolant, and size. Copper was chosen
over steel for heat transfer; liquid oxygen vs^ liquid nitrogen to minimize the
oxygen build up that extinguishes the flame, and 1/4 in. OD tubing with 60/80
mesh glass beads to 1/8 in. to prevent water freezing out. Two traps were used,
one to collect the sample (0.250 in. OD x 0.155 in. ID x copper, filled with
60/80 mesh glass beads) and the other (0.125 in. OD 0/065 in. ID copper, empty)
to inject the sample as a slug into the analytical sample column. The dual
trapping system was incorporated because of the time necessary to flush the
collected sample from the glass bead trap, which does not allow quantitative
introduction of the sample. Both traps were coated internally with SE 550
methyl silicone oil to prevent interaction of the sample with the active cop-
per surface. Trapping efficiency is shown both in Table 1 and 2, relating to
the analysis on the Porasil B and squalane columns.
3.4.1.3 Analysis
Routine analysis operation with the PE 900 initiated in August 1974 and
continued thru completion of the Summer 1974 intensive (25 July thru 28 August
1974). During this period a total of 205 analyses were performed using this
chromatograph. Of this total, 141 C2 - C^ analyses on Porasil B were per-
formed on helicopter samples and bag samples collected in support of the Long
Path Monitoring and Pollutant Variability Studies (Mr. Lou Chaney). Sixty-
four (64) analyses were performed for C^ - Cg using the squalane column.
35
-------
L- 0 I 0 J u U
I I) '.- a U U U U i: I! U II i. U (I (.
'I li '.I I) 0 I) tl
•J U ri !l U I) J 0 Q. 0 I I I I I t I I J 0 I I I I J '-butane1
101(1
FIGURE 4 - RETENTION TIME OF C
- Cg HYDROCARBONS
-------
TABLE 2
REPRODUCIBILITY OF PE 900 ANALYSIS
8-25-74
LO
ANALYZED 9-17
COMPONENTS
Propane
Propylene
iso-butane
isobutylene
n-butane
iso-pentane
n-pentane
2-methyl pentane
2-4 dimethyl pentane
Toluene
Ethyl Benzene
p-xylene
m-xylene
o-xylene
1:25 PM
0.366
1.663
0.461
0.337
1.914
1.599
2.135
29.225
5.691
7.771
7.726
11.258
23.629
5.837
3:30 PM
0.258
2.516
1.109
0.201
3.177
1.581
1.132
28.317
6.413
7.524
7.511
10.958
23.684
5.619
ANALYZED 9-18
SAM
0.435
1.762
0.500
0.243
1.994
1.505
1.889
31.215
5.970
7.577
7.392
1 1 . 598
22.432
5.488
10:35
*
*
*
*
*
*
*
35.007
6.469
7.618
8.119
11.842
25.114
5.833
AM 2:40 PM SAM
*
*
*
*
*
*
*
34.524
6.308
7.888
8.361
12.083
24.964
5.873
0.235
4.338^
1.336
0.195
4.530?*
1.631
1.349
28.600
8.607
6.724
6.660
9.911
20.813
5.071
ANALYZED 9-19
10:45
0.247
2.001
0.618
0.216
2.329
1.218
1.254
30.565
6.970
7.092
7.535
11.320
22.599
5.724
AM 1PM
0.221
1.096
0.333
0.314
1.357
0.999
1.070
26.228
6.724
18.243
7.915
9.558
19.936
6.006
3:40
0.336
1.798
0.441
0.321
1.703
1.177
1.261
31.593
7.537
7.382
7.430
11.070
22.459
5.493
PM ANG
0.300
1.806
0.685
0.261
2.079
1.387
1.441
30.586
6.743
7.447
7.628
11.066
22.848
5.660
o
.080
.464
.378
.062
.627
.224
.406
2.881
0.883
0.379
0.496
0.828
1.730
0.280
* Computer did not give area measurement
t Exceeds 2a limit
-------
During the entire period of this task order, including the summer 1974 in-
tensive period, 82 RAMS site samples were analyzed on both the 6800 and the sil-
ica gel analysis. Squalane analysis was performed on 38 on these samples.
Following the completion of the gas analysis in support of the 1974
Summer Intensive Study, it was decided by EPA that better resolution for the
&2 ~ C4 analysis was necessary and that better resolution and extension to
CIQ hydrocarbons was necessary for the heavier hydrocarbons analysis. Prior
to the November 74 Intensive, the Porasil B packed column was substituted
with the phenyl-isocyanate Durapak column, when the former column was found to
be affected by components in the air causing peak broadening at low concentra-
tions. Twenty-four (24) analyses of helicopter samples were performed for
C,£ - C^ hydrocarbons using the phenyl-isocyanate column during the November
Intensive. No further effort was expended investigating improved column con-
figurations due to the fact that Mr. Walker's services were discontinued, and
also the requirement existed to support the forthcoming November 74 Intensive.
3.4.2 Beckman Model 6800 Chromatograph
The Model 6800 Chromatograph is designed for monitoring six air pollutants,
total hydrocarbons, methane, carbon monoxide, ethane, ethylene and acetylene.
It is composed of a flame ionization detector, a pressure actuated valve intro-
duction system, and a three column analysis system.
The three columns are:
1. A prestripper column of Triton X-350 combined with silica gel for
removal of H^O, CO^j and hydrocarbons, other than methane.
2. Molecular sieve 5A, used for the separation of methane (CH*) and
carbon monoxide (CO) after the sample elutes from the prestripper
column.
3. Porapak N provides the separation of the £.£ hydrocarbons.
Total hydrocarbon analysis (THC) is directly analyzed from a sample loop
into the flame detector.
38
-------
Zero grade air (99.9999% purity) is supplied from certified bottled gas
and is prepurified by catalytic oxidizer for use as the carrier gas in the
THC analysis, C2 analysis, and as support air for the flame detector. Hy-
drogen is supplied from a hydrogen generator (99.9999% purity) through a
molecular sieve 5A trap for carrier gas in the CO-CH* analysis and as fuel
for the flame detector.
3.4.2.1 Chromatograph Modification
At the time work was initiated on this task order the Beckman 6800 Chro-
matograph had been set up in the laboratory and was operational. This chro-
matograph, as normally designed, will detect hydrocarbons as low as 20 ppb.
However, the RAPS requirements were to measure ethylene and acetylene in the
1 to 6 ppb range.
The sensitivity for C2 hydrocarbons was later approximately doubled by
changing the value of the input resistor on the amplifier and increasing sam-
ple loop size and/or flow rate. In this configuration, normal bag analysis
required about 40 to 60 liters of sample gas for two or three CH^, CO, THC
and Cp hydrocarbon analysis. To conserve sample gas, the excess sample gas
not normally routed through the three sample loops was re-routed back to the
sample bag as depicted in Figure 5.
In November, a further modification to the pumping system was incorporated
by establishing the pump downstream of the sample loops and to pull the sample
through rather than pump it^ '. This will allow a smaller sample to be removed
from the bag sample and prevent possible dilution of the sample with air from
the pump.
3.4.2.2 Beckman 6800 Chromatograph Reproducibility
To determine the reproducibility of the 6800 Chromatograph a Teflon bag
was filled with hydrocarbon free air, CO (3.0 ppm), CH, (3.0 ppm), C2H. (1.0 ppm)
and CoHo (1-0 ppm). The bags were analyzed ten times and peak heights measured.
From these measurements, the standard deviation for each compound was calculated.
39
-------
Return sample
FIGURE 5
Beckman Model 6800 Bag Sampling System
40
-------
The results are presented in Table 3. These results indicated that satis-
factory reproducibility (a = 1.5% or better) could be obtained.
3.4.2.3 Efficiency Check of Carbon Monoxide - Methane Conversion
In the analysis of carbon monoxide by the 6800 chromatograph, the carbon
monoxide is catalytically converted to methane and its concentration deter-
mined as the methane response on the flame ionization detector. A comparison
of equal concentrations of methane and carbon monoxide as peak area response
indicated only a six percent difference, but based on peak height measurement,
a 51 percent variation was found in the response.
3.4.2.4 Standard Bag Preparation and Diffusion Losses
To determine the consistency between bag standards prepared by different
laboratory technicians, three different personnel prepared the same mixture
of five compounds (C2H2, C2H», CO, C2Hg and CH^) in standard bags. Two tech-
nicians used 100 liter Teflon bags and the other used a 100 liter Tedlar.
The results as presented in Table 4 indicate:
1. The method of bag preparation was reproducible to - 10% between
operators. Note: One exception due to operator error concerning
acetylene.
2. Similar results were obtained with both Tedlar and Teflon bag
materials.
3. For these materials (Tedlar and Teflon), loss via infusion or
adsorption did not appear significant over twelve hours. This is
assuming that significant adsorption occurs only when adsorption
exceeds the - 10% error in the preparation of standards.
It should be recognized that these results, as they relate to bag per-
formance, are to be considered preliminary and applicable only to these test
conditions. As additional experience with bags was obtained, bag history and
origin were determined also to be important.
-------
TABLE 3
STANDARD DEVIATION BECKMAN MODEL 6800
i KG = Total Hydrocarbons
CO = Carbon Monoxide
C-Hp = Acetylene
C2H4 = Ethylene
N = No. of Measurement X = Arthmetic Mean
X = Measured Values a = Standard Deviation
THC (10 X 2 )
N X (ran)
1 155.4
2 157.0
3 156.0
4 157.0
5 156.8
6 158.0
7 158.2
8 160.3
9 161.3
10 162.5
Total 1582.5
cabs = |50.
(x - x)
2.9
1.3
2.3
1.3
1.5
0.3
0.1
2.0
3.0
4.2
(x - x)2
8.41
1.69
5.29
1.69
2.25
0.09
0.01
4.00
9.00
17.64
50.07
07 = 2.36 mm
•vjio - i
orel =2.36 =1
158.
3 x 100
.49% THC
C2H4 (10 X. 1)
N X (mm)
1 51
2 51
3 51
4 52
5 52
5 51
7 50
8 bO
(x - x)
0
0
0
1
1
0
1
1
9 51 i 0
] C 51
0
To-;"; 510.0
oabs = |4
"N10 -
orel = .67 X
57
= . 67 mm
100 = 1.31%
(x - x)2
0
0
0
1
1
0
1
1
0
0
4
C2H4
CO (10 X 1)
X (mm)
185
185
186
186
186
184
186
188
185
184
1855.0
oabs =
(x - I)
.5
.5
.5
.5
.5
1.5
.5
2.5
.5
1.5-
fT2T50 = 1
orel = 1.18
(x - x)2
.25
.25
.25
.25
.25
2.25 -
.25
6.25
.25
2.25
12.50
.18 mm
= .63% CO
185.5 x 100
C2H2 (10 X 1)
X (mm)
88
88
88
87
87
89
89
:87
88
87
(x - x)
.2
.2
.2
.8
.8
1.2
1 .2
- .8
.2
.8
873.0 1
oabs =
ore! = .
5.6 = .
10 - 1
79 X 100
87.8
(x - x)2
.04
.04
.04
.64
.64
1.44
1.44
.64
.04
.64
5.60
79 mm
= .89% C2H2
42
-------
TABLE 4
STANDARD BAG PREPARATION AND DIFFUSION LOSSES
TEDLAR STD. MIX - MADE 8/28/74
Analysis of 8/28/74 5:15 PM
Component
THC 10 x 8
CH4 10 x 2
CO 10 x 2
C?H4 10 x 1
C2Hg 10 x 1
C-H- 10 x 1
Pk. Ht. (mm)
202.67
180.33
127.33
66.67
93.33
109.67
Cone, (ppm-c)
8
5
5
1
1
1
Analysis of 8/29/74 8:45 AM
Component
THC 10 x 8
CH4 10 x 2
CO 10 x 2
C2H4 10 x 1
C2Hg 10 x 1
C2H2 10 x 1
Pk. Ht. (mm)
202.0
168.0
122.5
58.0
81.0
100.5
Cone, (ppm-c)
7.974
4.658
4.810
0.869
0.868
0.916
TEFLON STD. MIX - MADE 8/28/74
Analysis of 8/28/74 9:20 PM
Component
THC 10 x 8
CH4 10 x 2
CO 10x2
C2H4 10 x 1
C2H6 10 x 1
C2H2 10 x 1
Pk. Ht. (mm)
197.25
182.25
122.25
64.50
86.50
113.00
Cone, (ppm-c)
8
5
5
1
1
1
Analysis of 8/29/74 9:15 AM
Component
THC 10 x 8
CH4 10 x 2
CO 10 x 2
C2H4 10 x 1
C2Hg 10 x 1
C2H2 10 x 1
Pk. Ht. (mm)
192.25
177.50
118.50
61.50
84.00
99.50
Cone, (ppm-c)
7.797
4.870
4.847
0.953
0.971
0.881
TEFLON STD. MIX - MADE 8/29/74
Analysis of 8/29/74 2:45 PM
Component
THC 10 x 8
CH4 10 x 2
CO 10 x 2
C2H4 10 x 1
C2Hg 10 x 1
C2H2 10 x 1
Pk. Ht. (mm)
207.25
194.00
134.50
74.50
87.50
89.00
Cone, (ppm-c)
8
5
5
1
1
1
Analysis of 3/30/74 10:00 AM
Component
THC 10 x 8
CH4 10 x 2
CO 10 x 2
C2H4 10 x 1
C,H, 10 x 1
C D
C2H2 10 x 1
Pk. Ht. (mm)
201.00
189.00
131.00
73.00
86.00
87.00
Cone, (ppm-c)
7.759
4.871
4.870
0.980
0.983
0.978
SUMMARY
STD PREP REPRODUCIBILITY
Average THC = 202.39 - 5 mm, - 2.47%
Average CH4 = 184.53 - 7.4 mm, - 4.0%
Average CO = 128.03 - 6.2 mm, - 4.8%
Average C2H4 = 68.56 - 5.2 tan', i 7.7%
Average C2HC = 89.11 - 3.2 mm, - 4.1%
Average C,h
ADSORPTION REPRODUCIBILITY
AC (%) o(%)
103.89 - 13 mm, - 12.5%
Note
Average THC
Average CH4
Average CO
Average C?H4
Average C_Hg
Average C.,H2
- 1.9
- 4.0
- 3.2
- 6.6
- 5.9
- 7.5
1.4
2.4
0.6
5.7
6.3
4.9
Beckman 6800 Chromatograph Was Used.
43
-------
3.4.2.5 Calibration of Instruments
The standards for the Beckman 6800 were synthetic standards consisting of
CO and CH4 at approximate ambient concentrations (i.e. CH^ = 4 ppm and CO =
2 ppm). Any deviation from these concentrations for an unknown gas sample
could be calculated using the fact that the unknown concentration is direct-
ly proportional to its peak height. These standards were prepared on the day
of the analysis.
The standards for the P-E 900 were prepared weekly. The gases involved
were eight different hydrocarbons spread out over the entire C2 to Cg range.
The unknown samples were calculated from the fact that the area of the peak
is directly proportional to its concentration.
All above standards were prepared in a Teflon bag filled with a known
amount of Linde zero air. Precision syringes were used to inject known amounts
of standard gases from their respective tanks of pure known gases.
3.4.2.6 Analysis
During the period of performance on this task order, the Beckman 6800
Chromatograph analyzed 201 gas samples collected from the RAMS network, RAPS
helicopters, Winnebago mobile laboratory, portable samplers and various spe-
cial samples.
3.4.3 Varian, Model 940 Gas Chromatograph
Analysis of halogenated compounds of SFg fluorocarbons 11 and 12 were to
be performed in the gas Chromatograph laboratory using a Varian, Model 940 gas
Chromatograph. This instrument was received in late August minus the detector.
Application for license from the Atomic Energy Commission (AEC) had been ap-
plied for previously in July for the isotope detector. After the license was
granted in September, the detector was received and installed. Two columns
were prepared for analysis of SFg and fluorocarbons. Due to other higher pri-
ority effort, no further effort was expended on this instrument during the re-
maining period of this task order.
44
-------
3.4.4 Bendix, Model 8101-B, NOX Analyzer
This instrument was received late in October 1974. No effort was ex-
pended setting the analyzer up for use during the period of performance of
this task order.
3.4.5 Tracer, Model 270, Sulfur Chromatograph
The determination of total sulfur, sulfur dioxide, hydrogen sulfide and
methyl mercaptan in air samples were to be made using a Tracer, Model 270,
Sulfur Chromatograph. This instrument was received in August 1974 and set up
by the manufacturer's field representative. Initial checkout and testing found
a suspected bad analytical column which was returned to the factory for re-
placement. The problem was found to lie in the temperature setting of the anal-
ysis column and in: October the Chromatograph was placed back in operation and
calibrated. Figure 6 depicts the relationship of response for concentrations
of 45 to 180 pph..af-S02 in air.
During calibration, it was noted that there was some degradation in the re-
producibility of S02 data. Subsequent testing revealed that-the Teflon bags used
for sample collection must be preconditioned before use. Also, due to the short
"half-life" of SO^-in Teflon bags used for sulfur analysis, immediate analysis
after collection-is essential. Because of the instability of S02 in a gas sam-
ple bag, further work with the sulfur Chromatograph for the November Intensive
was terminated.
3.4.6 Bendix, Pure Air System
The Bendix pure air system was not set up or used during the period of
this task order.
3.4.7 Bendix Dynamic Calibration System
The Bendix calibration system was not set up or used during the period
of this task order.
45
-------
FIGURE 6
MODEL 270 SULFUR CHROMATOGRAPH ^L^sti^
CALIBRATION CURVE
(0-200 PPB RANGEl
-j—- i .. — ;. -i— -» • < ^ —- r,r*^. -.
60 90 " TZCT
CONCENTRATION S02 (PPB)
46
-------
4.0 SAMPLE BAG ANALYSIS AND TESTING
Operation and use of the RAMS gas bag collection system was initiated in
April 1974. Analysis of these early samples found that there was significant
bag contamination over and above the "total hydrocarbon" as measured by the
Beckman 6800 Chromatograph in the RAMS station. To alleviate this problem,
investigations into methods of bag decontamination were studied.
4.1 BAG CLEANING
Initial bag cleaning methods studied were by the use of heating and
vacuum. Four, new bags, 2 Teflon and 2 Tedlar, were "polluted" with a standard
mixture of 6 ppm and C-j - C^ hydrocarbons. Two bags, one Teflon "A" and one
Tedlar "B" were placed in a 65° oven with their inlets open for 60 minutes.
After removal from the oven and cooling, the bags were filled with HC free air,
and their total hydrocarbons immediately measured. Bag "A" contained 4.5 ppm
THC and bag "B" 4.3 ppm THC. Next the vacuum cleaning test was run. The re-
maining two bags (Teflon, bag "C" and Tedlar, bag "D") were held at vacuum
for fifteen minutes. The bags were then filled with hydrocarbon free air af-
ter vacuum treatment and immediately analyzed. Bag "C" measured 0.15 THC and
bag "D" 0.20 ppm THC. From these results it was decided to use the vacuum
method for bag cleaning in the future. All new and used bags were cleaned by
this procedure before use and sample collection.
4.2 BAG LEAK TESTING
From the initiation of bag sample collection and analysis, the major
problems experienced were with leaking sample bags. New bags as well as used
bags were found to leak. To minimize the loss of samples, all bags were given
a leak test prior to use and installation in a RAMS station. New bags found
to leak were returned to the supplier for repairs or replacement and used bags
were resealed (when possible) and leak tested before they were placed into
service.
47
-------
Leak testing consisted of filling each 100 liter bag with approximately
80 liters of air. The bag was next left to sit for 24 hours, preloaded by
placing a book (about 1 Ib.) on top. If there was less than a 10% loss of air,
the bag was considered suitable for service.
4.3 BAG CONTAMINATION TESTING
In August 1974 tests were performed to investigate diffusion losses through
bags. Three standard bag samples were prepared, two in Teflon bags and one in
Tedlar. Analysis was performed on each bag immediately after preparation and
again the next day. The results are shown in Table 4. Additional experiments
dealing with bag material losses were performed and the results are shown
graphically in Figures 7 and 8.
In October 1974 a test was conducted to investigate variation of hydro-
carbon concentration with time in Tedlar bags. New Tedlar bags (36 x 40 inches)
were made up, leak tested and cleaned. A Scott standard blend used for this
investigation was compared with a laboratory prepared standard to determine
each component concentration. The test was initiated with duplicate bags on
23 October and analyzed periodically through October. The result of this bag
test is presented in Table 5. In general, with the exception of THC, no sig-
nificant changes in concentration were found after sixty-nine hours. The in-
dicated loss of C2 hydrocarbons in bag "A" late in the test was due to deple-
tion of the sample.
48
-------
DFCAY OF SELECTED MATERIALS THROUGH A 5 MIL TEFLON BAG
SloDfi.hr*1
VOLUME OF BAG: 100 LITERS
. TEMPERATURE: 23.2C
time, nrs.
49
-------
Ul
o
iiLBiiiiiiuiyiioi!
LOSS OF SELECTED MATERIALS THROUGH A 2 MIL TEFLON BAG
I'DATA OF 8-15-74 •;„•
time, hrs.
-------
TABLE 5
HYDROCARBON RETENTION TEST USING
TEDLAR BAG MATERIALS
Sampl e
Bag A
Bag B
Time
(hours)
0
2.25
5.33
22.50
26.00
45.75
54.00
69.75
0.50
2.85
5.00
22.00
26.50
45.00
54.50
69.00
93.00
Total
Hydrocarbons
1.96
2.02
2.04
2.22
2.11
2.14
2.46
2.59
1.83
1.88
1.89
2.04
2.03
1.88
2.28
2.26
2.37
Methane
(ppm)
1.83
1.79
1.79
1.81
1.77
1.74
1.74
1.71
1.73
1.78
1.77
1.79 >
1.81
1.74
1.74
1.73
2.12
Carbon
Monoxide
I ppm)
3.71
3.43
3.51
3.60
3.54
3.68
3.63
3.55
3.51
3.45
3.45
3.57
3.57
3.63
3.68
3.65
4.34
Ethyl ene
(ppm)
0.444
0.441
0.448
0.456
0.456
0.442
0.436
0.350
0.444
0.451
0.448
0.460
0.456
0.442
0.447
0.436
0.486
Ethane
(ppm)
0.423
0.430
0.424
0.432
0.439
0.426
0.420
0.333
0.428
0.423
0.429
0.440
0.440
0.429
0.428
0.416
0.464
Acetylene
(ppm)
0.300
0.302
0.201
0.307
0.313
0.298 ,
0.290
0.232
0.303
0.304
0.304
0.313
0.311
0.300
0.298
0.292
0.317
Concentration of Scott
Standard Blend
Analyzed 10-21 1.631 1.756 3.737 0.490 0.453 0.320
10-29 2.070 1.830 3.630 0.482 0.482 0.348
Average
1.850
1.790
3.683
0.486
0.486
0.334
-------
5.0 REFERENCES
PAGE NO.
1. Non-cryogenic Trapping Techniques for Gas Chromatography 9
Thomas A. Bellar and John E. Sigsby, Jr.
Unpublished Report
2. Capillary Gas Chromatographic Method for Determining the 9
C3 - C-|2 Hydrocarbons in Full Range Motor Gasolines.
W.N. Sanders and J.B. Maynard
Analytical Chemistry Vol. 40, No. 3, March 1968 pp 527-535
3. Aromatic Hydrocarbons in the Atmosphere of the Los Angeles Basin 10
W.A. Lonneman, T.A. Bellar, and A.P. Altshuller
Environmental. Science and Technology Vol. 2, No. 11.
November 1968 pp 1017, 1020
4. Need for Standard Referee G.C. Methods in Atmospheric Hydrocarbon 10
Analyses
R.A. Rasmusson, H.H. Westberg, M. Holdren
Presented at the 26th Annual Summer Symposium on Analytical Chem-
istry, June 1973
5. Hydrocarbon Composition of Urban Air Pollution 10
W.A. Lonneman, S.L. Kopczynski, P.E. Dai ley and F.D. Sutterfield
Environmental Science and Technology Vol 8, No. 3, March 1974
pp 229-236
6. Waters Associates, Inc. Technical Bulletin of Gas Chromatographic 11
Column Packings.
7. Same as 4 above. 11
8. Atmospheric Sample Pumps - A Possible Source of Error in Total 20
Hydrocarbon, Methane and Carbon Monoxide Measurement
J. Hi!born
Note in Journal of the Air Pollution Control, October 1974 Vol.
24, No. 10 pp 963-964
52
-------
PART III: DEVELOPMENT OF METHODS
AND
ANALYSES OF ATMOSPHERIC POLLUTANTS
53
-------
TABLE OF CONTENTS
Page
1.0 INTRODUCTION 58
2.0 TASK ORDER REQUIREMENTS 59
2.1 SERVICES 59
2.1.1 Work Plan 59
2.1.2 Methodology 59
2.1.3 Sampling 59
2.1.4 Special Analysis 59
2.1.5 Routine Analysis 59
2.1.6 Analysis Reports 60
2.1.7 Laboratory Operation 60
2.1.8 Administration 60
2.1.9 Reports of Work 60
2.2 PERSONNEL 60
2. 3 EQUIPMENT 61
2.4 PERIOD OF PERFORMANCE 61
3.0 WORK PERFORMED 62
3.1 PERKIN ELMER, MODEL 900B GAS CHROMATOGRAPH 62
3.1.1 New Sampling System 62
3.1.2 C to C Hydrocarbon Analysis 65
3.1.3 C to C Hydrocarbon Analysis 65
3.1.4 Reproducibility Study of PE900
Chromatograph 65
3.1.5 Calibration for C to Cin Hydrocarbon
Analysis 67
3.2 BECKMAN 6800 - AIR MONITORING CHROMATOGRAPH 67
3.2.1 Reproducibility Study of Beckman 6800
Chromatograph 67
3.2.2 Determination of Precision of Beckman 6800
Chromatograph 67
3.2.3 Effect of Sample Characteristics on Flame
lonization Detector 67
3.2.4 Effects of Total Hydrocarbon Analysis by
Tedlar Bag 75
3.2.5 Effects on CO-CH Analysis by Contaminated
Hydrogen Carrier Gas 75
3. 3 BENDIX TOTAL OXIDES OF NITROGEN (NO ) ANALYZER 75
X
3.3.1 Improvements in Response and Accuracy 75
54
-------
TABLE OF CONTENTS (continued)
Page
3.4 TRACOR 270 - SULFUR CHROMATOGRAPH 75
3.5 VARIAN 460 CHROMATOGRAPH - ELECTRON CAPTURE
DETECTOR 78
3.6 BENDIX DYNAMIC CALIBRATION SYSTEM AND PURE
AIR SYSTEM 78
3.7 EVALUATION OF SAMPLE BAG MATERIALS 78
3.7.1 Tedlar Material Evaluation 78
3.7.2 Teflon Material Evaluation 85
3.7.3 Bag Leak Test Modification 85
3.8 QUALITY CONTROL 85
3.8.1 Carbon Monoxide Depletion/Time in
Quality Control Standards 85
4.0 SUMMARY
APPENDIX I -- WORK PLAN
55
-------
FIGURES
Number Page
ATMOSPHERIC ORGANIC ANALYSIS SYSTEM - PE900 66
2 SILICA GEL COLUMN ANALYSIS OF ATMOSPHERIC SAMPLE
FOR C - C HYDROCARBONS 68
3 SQUALANE COLUMN ANALYSIS OF ATMOSPHERIC SAMPLE FOR
C - C HYDROCARBONS 69
4 FIVE POINT CALIBRATION OF TOTAL HYDROCARBON ANALYSIS 73
5 FIVE POINT CALIBRATION OF CO AND CH,, ANALYSIS 74
4
6 EFFECTS OF SAMPLE MATRIX ON TOTAL HYDROCARBON ANALYSIS 76
7 DEPLETION RATE/TIME OF SO IN TEDLAR BAG 79
8 SF -FLUOROCARBON ANALYSIS CONFIGURATION 81
6
9 CHROMATOGRAM OF SF^ ANALYSIS 83
o
10 CHROMATOGRAM OF FLUOROCARBONS 11 and 12 ANALYSIS 84
11 CALIBRATION OF BENDIX DYNAMIC CALIBRATOR CAPILLARY
SYSTEM 85
12 CALIBRATION OF BENDIX DYNAMIC CALIBRATOR 86
13 CARBON MONOXIDE LOSS/TIME IN STEEL CYLINDER 91
14. GAS CHROTOGRAPHY LABORATORY DATA SHEETS 113
56
-------
TABLES
Number Page
1 GAS CHROMATOGRAPHY LABORATORY PERFORMANCE FROM
2 DECEMBER - 15 AUGUST . 63
2 REPRODUCIBILITY STUDY OF PE900 CHROMATOGRAPH 70
3 RESPONSE FACTOR DETERMINATIONS FOR PE900 CHROMATOGRAPH 72
4 REPRODUCIBILITY STUDY OF BECKMAN 6800 CHROMATOGRAPH 75
5 TOTAL HYDROCARBON RESPONSE DIFFERENCES/MOLECULAR
WEIGHT 78
6 RESULTS OF TEDLAR BAG DESORPTION/TIME 87
7 RESULTS OF TEFLON BAG EVALUATION 89
57
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1.0 INTRODUCTION
The St. Louis Regional Air Pollution Study is being conducted to develop,
evaluate and validate air-quality simulation models for both urban and rural
areas of stationary and mobile pollution sources. The RAPS Gas Chromato-
graphy Laboratory supports a variety of studies under the program; e.g.
A. Evaluation of the Regional Air Monitoring Stations (RAMS) sites.
B. Validation of Automotive Emissions Inventory Submodels.
C. Defining the composition of emissions from significant sources.
D. Tracking plumes.
E. Developing and Validating Photochemical Submodels.
The objective of this Task Order was to provide support of the various
RAPS programs through the development of methods and analyses of atmos-
pheric pollutants. Data from all analyses are recoraed and entered into
the RAMS/RAPS Data Computer Bank.
58
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2.0 TASK ORDER REQUIREMENTS
Under the Task Order the contractor was to provide the necessary man-
power, materials and services to perform the following:
2.1 SERVICES
2.1.1 Work Plan
The contractor shall prepare and submit for approval to the RAPS Field
Coordinator a work plan for operation of the Gas Chromatography Labora-
tory. The plan shall include schedules, manpower estimates, and mile-
stones for bringing the Gas Chromatography Lab operational for analysis
of atmospheric samples. The work plan shall include quality control,
sample handling, operation and calibration procedures for all govern-
ment furnished (GFE) instruments. It shall also include procedures
for entry and retrieval of data (into/from) the RAMS/RAPS data bank.
2.1.2 Methodology
The contractor shall establish and conduct analyses for Cl - CIQ hydro-
carbons, CO, total hydrocarbons, NOx, total sulfur, S02, H2S, CH3SH, and
atmospheric tracer gases, such as SF6> and fluorocarbons 11 and 12. Ex-
cept for methane, hydrocarbons must be measured at concentrations down to
one part per billion carbon (ppb C), CO to 0.01 ppm, sulfur compounds to
0.1 ppb, and tracer gases to 1 pp trillion. Measurements shall also be
made for total sulfur and NOx at atmospheric levels.
2.1.3 Sampling
Sampling shall be conducted at the RAMS monitoring stations from helicopters,
from mobile vehicles, and at various sites in the St. Louis area. The
contractor shall pick up and deliver to the Gas Chromatography Lab all
bag samples collected at the RAMS stations. The bags shall be shielded
from sunlight during pick-up and delivery. The contractor shall replace
filled bags at the RAMS stations with clean, leak-tight bags.
2.1.4 Special Analysis
The contractor shall concentrate and analyze atmospheric samples for
specific experiments conducted by RAPS investigators.
59
-------
2.1.5 Routine Analysis
The contractor shall analyze about 700 atmospheric samples for in-
dividual hydrocarbon (Cl - Clo inclusive), total non-methane hydro-
carbons (NMHC), CO and NOx, and total sulfur, H2S, S02 and CH3SH,
and for atmospheric tracer gases (SFs, fluorocarbons 11 and 12).
2.1.6 Analysis Reports
The contractor shall validate all analyses, record and report con-
centrations for all chemical species specified above as well as sum
of paraffins less methane, sum of olefins, and sum of aromatics.
2.1.7 Laboratory Operation
The contractor shall operate all laboratory equipment, perform in-
strument calibrations, routine service and maintenance. EPA will
provide necessary replacement of major parts and emergency services
normally performed by instrument manufacturers for all GFE instru-
ments.
2.1.8 Administration
The contractor shall provide all necessary administrative and opera-
tional support for contract personnel assigned to tiiis task.
2.1.9 Reports of Work
The contractor shall provide each month a technical and financial
progress report.
2.2 PERSONNEL
The contractor is to provide the following personnel as a minimum:
a. One gas chromatographer.
b. One laboratory technician experienced in quantitative analysis
of gases.
c. Part-time laboratory assistant for sample collection.
60
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2.3 EQUIPMENT
The contractor shall furnish all necessary equipment and supplies
required for efficient and effective operation of the Gas Chro-
ma tography Laboratory.
2.4 PERIOD OF PERFORMANCE
Start: 1 December 1974
Completion: 15 August 1975
61
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3.0 WORK PERFORMED
During the Task Order period, the Gas Chromatography Laboratory continued
to develop methods and analyze atmospheric samples per the work plan in
Appendix I. Sampling was initiated at five of the RAMS sites, oredeter-
mined by the RAPS Field Coordinator, on 2 December with collection of two
samples per site, five sites per day, at three day intervals. During Jan-
uary the number of RAMS sites sampled was increased to seven to insure a
minimum of ten samples of acceptable volume for analysis. In February, the
sampling of the RAMS sites was coordinated with hi-vol filter collection
at six sites per sampling day. This schedule was adhered to except for the
intervals of 9 to 19 March, 1 to 9 May, and 14 June through 14 July, when
time was spent correcting problems in the C2 - ClO hydrocarbon analysis.
Table 1 contains the Gas Chromatography Laboratory's performance record
during the Task Order period, subdivided to illustrate the number of spe-
cific analyses per sample.
All analyses from the task order inception to 28 February 1975 have been tab-
ulated and given to EPA on magnetic tape. Analyses from 3 March 1975 to 9
March 1975 have been tabulated, but not key punched pending approval of data
by the Project Monitor. Analyses from 22 March 1975 to 14 June 1975 have
been tabulated and given to EPA on magnetic tape. The remaining task order
data from 9 July 1975 to 15 August 1975 have been tabulated and are awaiting
data processing instruction from EPA.
With the acquisition of the second laboratory technician, G. Seeger, in Jan-
uary, the remaining instruments in the laboratory were established operation-
al; e.g. Bendix NOX Analyzer, Tracor 270 Sulfur Chromatograph, Bendix Pure
Air and Dynamic Calibration System. The work performed on each of these an-
alyzers during the period of this Task Order follows:
3.1 PERKIN ELMER, MODEL 900B GAS CHROMATOGRAPH
This high resolution gas chromatograph was used in conjunction with a concen-
tration system of liquid oxygen and two chromatographic columns to determine
C2 - CIQ hydrocarbon concentrations to one part per billion. The C2 - C5 hy-
drocarbons are determined with a silica gel packed column, while the C4 - Cio
hydrocarbon analyses is achieved with a squalane SCOT (support coated open tub-
ular) capillary column.
3.1.1 New Sampling System
On 11 December, W. Lonneman, EPA Senior Chemist, arrived in St. Louis to as-
sist in establishing a column system to achieve the separation of C2 - ClO
hydrocarbons. A new sample concentration and injection system was incorporat-
ed, allowing backflushing of the sample trap between sampling. Figure 1 con-
tains a diagram of the sampling system, depicting the concentration of the
sample and the injection of the sample onto the chromatographic column.
62
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TABLE 1 - GAS CHROMATOGRAPHY LABORATORY PERFORMANCE
FROM 2 DECEMBER - 15 AUGUST
type of
Sample
101
102
103
104
105
106
107
108
109
1
2
H
1
2
H
1
2
H
1
2
H
1
2
H
1
2
H
1
2
H
1
2
H
1
2
H
Max. Number
Samples
Possible
10
10
13
20
7
53
59
19
10
10
32
39
5
8
8
8
10
10
6
6
5
6
6'
5
# Samples
Collected
10
10
13
20
7
50
58
19
10
10
32
38
5
8
8
8
10
10
5
5
5
6
6
5
Number of Samples Analyzed/Analysis
Total
5
6
6
10
7
36
39
19
8
4
26
28
5
8
7
7
8
6
4
5
5
3
2
5
N0x
1
0
2
8
6
28
33
14
1
1
18
23
5
6
6
8
1
1
0
0
5
0
0
1
CO
5
6
6
10
6
36
39
19
8
4
26
28
5
8
6
8
8
6
4
5
5
3
2
5
CH4
5
6
b
10
7
36
39
19
8
4
26
28
5
8
6
8
8
6
4
5
5
3
2
5
THC
5
6
6
10
7
36
39
19
8
4
26
28
5
8
6
8
8
6
4
5
5
3
2
5
SGe1ca
5
6
6
10
7
29
31
14
8
4
23
25
5
8
6
8
8
6
4
5
5
3
2
5
Squalane
1
4
1
8
1
5
Status of Sample Data
foW/Wcf
5
6
6
10
7
36
39
19
8
4
26
28
5
8
7
7
8
6
4
5
5
3
2
5
PJHcWXg
5
6
5
3
7
35
31
16
8
4
25
25
5 .
8
7
7
8
6
4
5
0
3
2
5
WuSftl!8
-------
TABLE 1 (Cont'd)
Type of
Sample
111
112
113
114
115
116
118
119
120
1
2
A
1
2
H
1
?
H
1
2
H
1
2
H
1
2
H
1
?
H
1
?
H
1
?
H
Max. Number
Samples
Possible
12
12
12
12
13
20
4
17
24
9
21
26
1?
6
6
10
10
4
3
12
12
?
^Samples
Collected
12
12
8
9
13
19
4 , .
17
24
?
21
26
1?
5
5
10
10
4
3
10
9
2
Number of Samples Analyzed/Analysis
Total
11
7
8
7
10
16
4.
12
11
?
20
24
1?
5
4
8
8
4
1
8
6
2
NOX
11
4
8
7
3
9
4
11
11
l
10
20
2.
8
8
3
2,
8
6
2
CO
11
7
8
7
10
16
4
12
11
?
20
24
1?
5
4
8
8
4
V
8
6
2
CH4
11
7
8
8
10
16
4
12
11
?
20
24
12
5
4
8
8
4
3
8
6
2
THC
11
7
8
7
10
16
4
12
11
?
20
24
1?
5
4
8
8
4
3
8
6
o
Silica
Gel
7
4
6
5
10
16
4
7
9
1
16
17
q
5
4
8
8
2
3
6
5
2
Squalane
3
7
2
5
3
12
Status of Sample Data
fJWPSncI
11
7
8
7
10
16
4
12
11
2
20
24
12
5
4
8
8
4
3
8
6
2
pjRcRffiq
11
7
8
7
9
10
3
7
10
2
18
17
12
5
4
8
8
4
3
8
6
2
WB»
-------
TABLE 1 (Cont'd)
Type of
Sample
121
122
123
124
125
Other
Helico
^amnlp
L.Chan
QC Ck.
Grisco
Total
_L
?
H
J_
2
4
1
?
H
JL
2
H
1
?
H
Dte
\
e,y
1i
Max. Number
Samples
Ppssible
16
22
5
26
33
3
10
26
32
12
12
i
51
16
27
3
911
#Samples
Collected
16
19
5
26
33
3
10
26
31
12
12
Rl
16
27
3
885
Number of Samples Analyzed/Analysis
Total
10
12
5
16
31
0
7
21
22
7
9
51
16
27
3
688
N°X
10
11
4
15
30
0
7
20
21
7
9
24
"
463
CO
10
12
5
16
31
0
7
21
22
7
9
51
16
27
3
688
i ; -Y,
CH4
10
12
5
16
31
0
7
21
22
7
9
51
16
27
3
688
THC
10
12
5
16
31
0
7
21
22
7
9
51
16
27
3
688
S4iica
6
7
4
13
30
0
7
14
19
5
7
51
3
533
Squalane
4
6
1
11
0
7
2
6
3
50
Status of Sample Data .
foIWfffilc
10
12
5
16
31
0
7
21
22
7
9
51
16
688
, PunShto
8
7
4
16
24
0
7
20
15
7
9
24
13
564
bjtoredRKaDs
Data banK
-------
Concentration
Trap (glass
bead)
Dual Print-Out
Detector A
Dual Recorders
Electrometer Dual Channels A-B
Squalane Capillary
Column
Post Trap - Carbowax £OM "[PA
Backflush
Valve
Pretrap -
Air Sample
Bag
Helium
Gas
Constant
Volume
Cylinder
Vacuum Pump
Detecter B
Silica Gel
Column
Concentration
Trap (Carbowax
1540)
Air Sample
Bag
SAMPLE TRAPPING MODE
SAMPLE INJECTION MODE
FIGURE 1 - ATMOSPHERIC ORGANIC ANALYSIS SYSTEM - PE900
-------
3.1.2 C2 to Cc Hydrocarbon Analysis
The C2 - GS hydrocarbon analysis was established with a silica gel
column (3ft x 1/8 in. OD). Figure 2 contains a typical analysis of
an air sample from a road sample collected 18 August using the silica
gel column. In conjunction with this analysis, the PEP-1 integration
system was incorporated with average response factors and individual
components reported to the part per billion. The silica gel analysis
was conducted on atmospheric bag samples from 12 December through the
completion of the task order. The exception Was during!! April to 27
May when methane contamination in the hydrogen fuel caused erratic
conditions in the analysis and prevented quantisations of the C2 hydro-
carbons.
3.1.3 C^ to C-JQ Hydrocarbon Analysis
The C4 to CIO hydrocarbon analysis was to be conducted on a 200 foot
squalane SCOT capillary column. During W. Lonneman's visit in December,
it was recommended to condition the column above 100°C for a week to
minimize the column bleed and conduct the analyses to 80°. After the
conditioning period, the squalane column was found to have excess-ive
column bleed for use in the C4 to ClO hydrocarbon analysis. During the
period of 9 to 19 March, sampling at the RAMS sites was discontinued to
permit the investigation of a post column to collect the column bleed.
A packed column (10 x 1/16 inch) carbowax 20M-TPA (polyethylene glycol-
terephthalic acid ester) on Chromosorb W-AW was found acceptable with
limited loss of resolution on the squalane column. Because of the prob-
lems in the silica gel analysis, the squalane analysis was not pursued
until after W. Lonneman's visit on 5 June 1975. On his recommendation,
the squalane column was reduced to 100 feet in length and the analysis
limited to 75° with the post column incorporated. He also recommended
the use of a pretrap of potassium carbonate (K2C03) inserted prior to
the concentration trap to minimize the effect of water and polar com-
pounds with the squalane column. Figure 1 depicts the position of both
the pre and post traps in the squalane system. Figure 3 illustrates a
typical C2 to CIQ hydrocarbon analysis of an atmospheric bag sample
collected from RAMS site 121 in urban St. Louis.
3.1.4 Reproducibility Study of PE900 Chromatograph
To establish the reliability of the sampling system, a roadside sample
was analyzed six times over an eight hour period and the standard dev-
iation determined for the area response of seventeen hydrocarbons found
in the sample. Tabulated in Table 2 are the results of this investigation
illustrating seventeen hydrocarbons ranging from C2 to Cg carbon number.
67
-------
1.-- Mettiane
2. Ethane
3. . Ethylene
4._- Propane
5. "Acetylene
6.~7 Isobutane
7 7—N-Butane - •—
•8. — Propylene-
.9. —.Isopentane
10. N-Pentane
12
FIGURE 2 SILICA GEL COLUMN ANALYSIS
OF ATMOSPHERIC SAMPLE FOR C? - Cg HYDROCARBONS
68
-------
FIGURE 3
SQUALANE COLUMN ANALYSIS OF ATMOSPHERIC
SAMPLE FOR C2 - CIQ HYDROCARBONS
69
-------
TABLE 2
REPRODUCIBILITY STUDY OF PE900
CHROMATOGRAPH
Components
Ethane
Acetylene
Propyl ene
n-Propane
Isobutane
n -Butane
Isopentane
n- Pentane
2-Methyl Pentane
2,4-Cimethyl
Pentane
2, 3-Oi methyl
Pentane
Toluene
Ethyl Benzene
m & p Xylene
o -Xylene
1 , 3, 5-Tri methyl
Benzene
Analysis (Area Response)
1
4.80
2.74
1.10
2.71
1.94
6.36
7.06
5.28
2.74
1.01
2.52
8.31
4.88
16.75
3.48
0.76
2
4.73
2.65
1.09
2.70
1.93
6.39
6.96
5.44
1.99
0.36
2.66
8.15
4.31
15.81
3.78
0.43
3
4.60
2.67
1.13
2.68
1.95
6.38
6.96
4.83
1.89
0.37
2.69
8.05
4.30
15.90
3.55
0.44
4
4.60
2.70
1.13
2.69
2.00
6.43
7.04
4.90
1.89
0.57
2.85
7.80
5.03
18.43
4.68
0.52
5
4.80
2.65
1.16
2.73
2.00
6.42
7.03
4.86
1.91
1.19
2.97
8.49
5.19
19.37
4.53
0.47
6
5.18
2.85
1.16
2.88
2.04
6.80
7.46
4.84
1.91
0.64
2.48
8.62
5.08
18.12
4.05
0.44
T
4.79
2.71
1.13
2.73
1.98
6.46
7.09
5.03
2.06
.69
2.70
8.24
4.80
17.40
4.01
0.51
Sx
0.21
.08
.03
.07
.04
.17
.19
.27
.34
.34
.19
.30
.39
1.46
0.50
0.13
70
-------
3.1.5 Calibration for C2 to CIQ Hydrocarbon Analysis
Calibration was conducted with both column system used in the C
hydrocarbon analysis. Standard mixtures of hydrocarbons (minimum
purity of 99.0%) in hydrocarbon free air were used to determine
response factors incorporated in the analysis methods of the PEP-1
integration system. Table 3 lists those hydrocarbons investigated
with their respective response factors.
3.2 BECKMAN 6800 - AIR MONITORING CHROMATOGRAPH
Analyses of carbon monoxide (CO), methane (Cfy), and total hydrocarbons
(THC) were conducted on the Beckman 6800 chromatograph according to
the work plan in Appendix A. Throughout the task order period, it was
used primarily for atmospheric sample analyses and quality assurance
checks of standards used by EPA in the RAPS program. The C2 hydrocarbon
analysis was deleted on the 6800 chromatograph due to the lack of sensi-
tivity and peak broadening at low concentrations, resulting in inaccurate
results.
3.2.1 Reproducibility Study of Beckman 6800 Chromatograph
To determine the accuracy and precision of the 6800 chromatograph, ex-
periments were conducted to determine linearity, reproducibility and
effects on detector response by the sample. Accuracy of the 6800
chromatograph is assured with periodic five point calibrations of THC,
CH4, and CO analysis. Pictures 4 and 5 contain graphs of the calibrations
conducted in July. Linearity checks of the attentuator indicate an error
between the attenuation setting, therefore, all samples were analyzed
at the same attenuation as the daily standard calibration.
3.2.2 Determination of Precision of Beckman 6800 Chromatograph
Precision of the 6800 analysis was determined by repetitive analysis
of an atmospheric bag sample, collected over St. Louis 12 August by
the Battelle Research Aircraft. The results of this experiment are
tabulated in Table 4 as peak height response of THC, CO and CH4 found
in the sample.
3.2.3 Effect of Sample Characteristics on Flame lonization Detector
The flame ionization detector response was found to be effected by various
sample characteristics. Matrix effects of air vs nitrogen with the THC
analysis was substantiated with mixtures of a Scott gas standard (2 pmm
CH4 and 1 ppm Co hydrocarbons in air) with hydrocarbon free air and
nitrogen. Results of this test are shown in Figure 6 as THC response,
with a twenty percent difference in response between them. The matrix effect
was also investigated with the CO-CHa analysis and was not found to have any
effect in the analysis. Response differences/molecular weight for various
hydrocarbons was investigated with mixtures of each hydrocarbon (99% minimum
purity) in ultrapure air.
71
-------
TABLE 3
RESPONSE FACTOR DETERMINATIONS FOR PE9QO
CHROMATOGRAPH
Component
Ethane
N-Propane
N-Butane
N-Pentane
N-Hexane
2.4-DM,Pentane.
Toluene
m-Xylene
1,3,5-TM
Benzene
n-Butyl
Benzene
Concentra-
tion (ppb)
200
200
200
972.1
857.3
751.9
1053.9
916.2
805.2
717.8
Standard
1
33.78
49.78
67.81
409.2
443.01
420.33.
539.00
514.43
527.77
586.76
2
34.58
50.11
72.48
430.85
410.65
432.10
589.82
528.91
464.29
557.35
3
35.14
49.51
68.00
409.8
415.39
421.38
527.72
579.49
580.09
521.36
Average
Response
Factors
11.60
12.07
11.52
11.67
12.16
12.40
13.36
13.55
13.83
12.93
72
-------
160--
150-
140-
130-
120--
CO
O)
£ 1164
E
i 100-.
25 904
O
ex
to
80--
+J
JC
'S 704
(O
60--
50-
40-
30
20-
10-
, j , ,
1234
Concentration (ppm)
FIGURE 4
FIVE POINT CALIBRATION OF TOTAL HYDROCARBON ANALYSIS
73
-------
Q- Carbon Monoxide
O_ Methane
2 3 i
Concentration in PPM
FIGURE 5
FIVE POINT CALIBRATION OF CO AND CH, ANALYSIS
74
-------
TABLE 4
REPRODUCIBILITY STUDY OF BECKMAN 6800
CHROMATOGRAPH
RVN
1
2
3
4
5
6
7
8
9
10
X
Sx
Total
Hydrocarbon
Analysis
(mm-Peak Height)
116.1
116.9
116.3
115.7
116.3
115.3
115.3
115.7
116.3
115.9
115.98
0. 50
Methane
(mm-Peak Height)
62.7
62.3
62.9
62.2
62.1
62.1
62.2
62.6
62.0
62.0
62.31
0.31
Carbon
Monoxide
(mm-Peak Height)
22.3
21.9
21.4
21.3
21.1
22.0
21.3
21.3
21.1
21.2
21.49
0.42
75
-------
-t —-
80% Scot Blend
+
20% Hydrocarbon Free Air
80% Scot Blend
+
20%.Nitrogen
FIGURE 6
EFFECTS OF SAMPLE MATRIX ON
TOTAL HYDROCARBON ANALYSIS
76
-------
Table 5 contains the results of this experiment, indicating variations
in THC response of 7 to 51 percent lower than methane. Adjustment of
the flame detectors air and hydrogen mixture to minimize the differences
proved only to cause flame outs in sample injection.
3.2.4 Effects of Total Hydrocarbon Analysis by Tedlar Bag
Parallel to sample effects on flame response is the desorption problems
with Tedlar bags used in helicopter sampling. Distorted THC response
and secondary peaks were found in THC analysis of atmospheric samples
collected in Tedlar bags. During the February intensive period, THC
measurements were deleted from all helicopter samplings using Tedlar bags.
3.2.5 Effects on CO-CH4 Analysis By Contaminated Hydrogen Carrier Gas
The CH4-CQ analysis was also affected by problems of methane contamination
in the hydrogen carrier gas of the 6800 chromatograph. Negative responses
in the CH4-CO analysis occur when the purity of the sample is greater than
the hydrogen carrier. Control of this problem is achieved by changing the
molecular sieve 5A drier, but is short term as the methane will diffuse
through with time. A hydrogen generator is recommended to prevent this
problem and as an alternative to costly high purity hydrogen gas.
3.3 BENDIX TOTAL OXIDES OF NITROGEN (NO*) ANALYZER
The Bendix NOx Analyzer was operational 6 February and used continuously
throughout.the remaining Task Order period for total oxides of nitrogen
measurement. Nitric oxide (NO) was not analyzed in atmospheric bag sam-
ples due to the thermal degradation of NO during transfer of the sample
to the laboratory.
3.3.1 Improvements in Response and Accuracy
A few adjustments were made to improve the response of the NOx analyzer.
The response time was improved with the interchange of the inlet line
with the exhaust line to the reaction chamber. Oxygen (<10 ppm moisture)
was used for Ozone generation because of the zero offset that occurs when
insufficient moisture is present.
3.4 TRACOR 270 - SULFUR CHROMATOGRAPH
The sulfur chromatograph was not used throughout the Task Order period
due to the adsorption of sulfur compounds with Teflon and Tedlar material.
Graph of depletion of S02 in a Tedlar bag due to absorption is contained
in Figure 7. The sulfur chromatograph was maintained operational by the
performance of periodic calibration and maintenance.
77
-------
TABLE 5
TOTAL HYDROCARBON RESPONSE DIFFERENCES/MOLECULAR WEIGHT
Component
Methane
Ethane
Ethylene
Acetylene
Propane
Propylene
Isobutane
2-Methyl Pentane
Toluene
ffl-Xylene
Concentration
(ppm)
4.66
4.0
4.00
4.00
4.00
4.00
3.00
1.64
2.00
1.83
THC Response
(mmPeak Height)
130
154
117
236
232
170
230
138
272
238
Normalized
Response (1)
130
90
68
138
90
66
89
59
90
76
Percent
Difference
From
Methane
31
48
6
31
49
32
55
31
42
(1) Response normalized to methane in concentration and carbon number.
78
-------
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fo\—
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tifuj. •'•:
--- "* - •™
'
il
MT
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_, —t
urn
i i i
-H-
iTT
-IT.
i ' I-
!
^>**WW-
-r
j
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"r""<"U
i p
I I, h
- Trr
M.I
H
.I .
I 1-
I.
•r
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H-
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I'll.
1 TJ L
! ,-!
T i
j_J_:_i
Ti
11L
-ri L
in i i
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-f-
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*jp»».. • '
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T
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r
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FIGURE 7 - DEPLETION RATE/TIME OF S02 IN TEDLAR BAG
-------
3.5 VARIAN 460 CHROMATOGRAPH - ELECTRON CAPTURE DETECTOR
The Varian 460 chromatograph with an electron capture detector is in-
tended for the analysis of f1uorocarbons (Fluorocarbons 11 and 12 and SF5)
to the part per trillion level. Methods for the analysis :of the fluorocarbons
mentioned were established during the latter part of the Task Order but detec-
tion limits of 500 ppt for fluorocarbons and 20 ppt for ,SF6 was achieved. Figure
8 is a diagram of the sampling and column system used in the two analyses.
Note that the SFs analysis is conducted on the molecular sieve 5A analysis
column with a stripper used to remove heavy hydrocarbons and water. The
fluorocarbons 11 and 12 are separated with the silica gel column. Typical
chromatograms of the two analyses are shown in Figures 9 and 10.
3.6 BENDIX DYNAMIC CALIBRATION SYSTEM AND PURE AIR SYSTEM
Both systems were operative from February and used throughout the Task
Order period in calibration of the Bendix NOx analyzer and Tracer sulfur
chromatograph. Calibration is conducted with NBS certified S02 permeation
tubes and an Airco 100 ppm NO gas standard, standardized with an NBS
certified NO gas standard. Periodic checks of the dynamic calibration
system are conducted for linearity and flow rates of the capillary dilution
system. Figures 11 and 12 illustrate the linearity check conducted in July,
with graphic description of flow rates (cc/min) vs inlet pressure (1 Ib.)
to the capillaries.
3.7 EVALUATION OF SAMPLE BAG MATERIALS
Atmospheric samples are collected in Teflon and Tedlar bags for analysis
of various pollutants. Evaluation of the bag materials was conducted
to establish the hydrocarbon desorption in storage. The bags were purged
with helium gas (99.9999% purity) and filled with zero grade air (of
known purity). The bags were analyzed for total hydrocarbons (THC) on
the 6800 chromatograph, capped and stored. Re-evaluation of the THC is
conducted after a predetermined time.
3.7.1 Tedlar Material Evaluation
Tedlar material was proposed for use in atmospheric sampling because
of ease in sealing and repair of the bag seams. Evaluation of Tedlar
indicated a high THC build-up with distorted THC response and second-
ary peaks. Attempts were made to minimize the THC increase by heating
the Tedlar in an oven at 100° and evacuating, and to wash the inside
walls of the bag with an ionic detergent. Neither test was able to
correct the problem, and the Tedlar bags were limited to only CO and
CH4 analysis of helicopter sampling. Results of the investigations of
Tedlar for bag desorption time are contained in Table 6.
80
-------
Recorder
Recorder
Electron Capture
Detector
Analysis Column
Silica Gel
00
Stripper
Molsieve
5A
Nitrogen
In
Sample
In
Pump
Electron Capture
Detector
Nitrogen In
Sample Collection
Sample Loop
Stripper
Molsieve
5A
Nitrogen In
Sample Injection
FIGURE 8 - SFC ANALYSIS CONFIGURATION
D
-------
CO
Electron Capture
Detector
Electron Capture
Detector
Analysis Column
Silica Gel
Six
Port
Valve
Six
Port
Valve
Stripper
Molsieve
5A
Stripper
Molsieve
5A
Ten
Port
Valve
Ten
Port
Valve
Nitrogen In
Sample Collection
Sample Loop
Nitrogen In
Sample Injection
FIGURE 8A - FLUORO-HYDROCARBON ANALYSIS CONFIGURATION
-------
Attenuation - x4
Range
10"10 amps/
mv
FIGURE 9
CHROMATOGRAM OF SFC ANALYSIS
o
83
-------
Attenuation - x2
Range - l(HOamps/m
FIGURE 10 - CHROMATOGRAM OF FLUOROCARBONS 11 AND 12 ANALYSIS
84
-------
50
45 .
40
35 .
u
u
30
ra
cc.
25
20
10
INPUT A - LOW CALIBRATION
10 20 30 40 50 60 70
Pressure (Ibs)
80 90
100
FIGURE 11 - CALIBRATION OF BENDIX
DYNAMIC CALIBRATOR CAPILLARY SYSTEM
85
-------
600
550
500.
450.
400.
350.
,^300
•r-
e
u
u
250
ZOO-
ISO
TOO
50
INPUT A - HIGH CALIBRATION
VO 20 30
4d 0 5D fib 7b 80 90 TOO
Pressure (Ibs.)
FIGURE 12 - CALIBRATION OF BENDIX
DYNAMIC CALIBRATOR
86
-------
TABLE 6 RESULTS OF TEDLAR BAG DESORPTION/TIME
Material
Tested
Used Tedlar
Helicopter Bag
May 5-7
New Tedlar
Bag 1
Bag 2
Bag 3
May 7-11
Total Hydrocarbon (ppm) Increase/Time
Initial
0.096
0.053
0.059
0.057
24 Mrs
0.143
48 Hrs
0.226
72 Hrs
0.212
0.247
0.125
Increase In Total
Hydrocarbons
(ppm/Hr)
0.003
0,002
0.003
0.001
Remarks
Helium Purged-Filled Linde
Hydrocarbon Free Air
No Helium Purge-Filled With
Linde Hydrocarbon Free Air
00
-------
3.7.2 Teflon Material Evaluation
Teflon is presently used as the bag material in sampling at the RAMS
sites. Two mil thickness is used but forms seam leaks with extensive
sampling and handling. As an alternative, five mil Teflon bags were
investigated for material desorption/time and leakage. The tests were
conducted in a similar manner to the Tedlar evaluation, and the results
are tabulated in Table 7, comparing 2 mil Teflon to various 5 mil ma-
terial and manufacturers.
3.7.3 Bag Leak Test Modification
In the evaluation of the bag materials, a second criteria was determined,
leak rate/time. Initially the leak test procedure was per the one out-
lined in the Work Plan (Appendix A). Variations to this procedure were
incorporated because with applied weight and 100 liter volumes the pos-
sibility of seam flexing and leakage occurred. The new procedure entails
a 60 liter quantitative fill with no applied weight and a 10% leakage
allowable on quantitative evacuation. The number of 2 mil Teflon FEP-L
bags received and found acceptable were 232 and 122, respectively.
3.8 QUALITY CONTROL
Quality control procedures followed in the Gas Chromatography Laboratory
are outlined in the Work Plan. Quality control standards used daily in
the laboratory are certified periodically with NBS standards when available,
e.g., NOX and CO. Where NBS certification is not available, laboratory
standards are prepared of quantitative mixtures of pure hydrocarbons with
ultra pure air. Replicate standards are made up and their average re-
sponse factors taken to determine concentrations of the other quality
control standards.
3.8.1 Carbon Monoxide Depletion/Time in Quality Control Standards
Monthly checks of the CO concentration of the Quality Control standard
indicated a gradual decrease in the CO concentration. Because the CO
standard is made up in a steel cylinder, iron carbonyl (Peg-(C0)g) is
suspected to form and CO depleted. Figure 12 graphically shows the loss
of CO with time. Presently, CO standards in aluminum cylinders are used
in the laboratory, and their concentration monitored periodically.
88
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TABLE 7 RESULTS OF TEFLON BAG EVALUATION
Bag Material
And
Manufacturer
Teflon Type
1-2 Mil Xonics
Corp.
Teflon Type L
5 Mil
American
Durafilm Co.
Teflon Type L
5 Mil
Livingston
Coating Co.
Bag 1
2
3
Date
of
Test
6/3
To
6/6
5/16
To
5/20
5/23
To
5/26
5/28
To
6/2
Total Hydrocarbon (ppm) Increase/Time
Initial
0.16
0.02
1.06
0.16
0.16
0.16
24
Mrs
48 Hr
5.99
7.46
5.79
72 Hr
1.22
1.42
96 Hr
2.10
144 Hr
170 Hr
240 Hr
10.92
10.30
Increase
In THC
(ppm/Hr)
.015
.022
.004
0.045
0.042
Remarks
Helium Purqed-Filled
With Scott Marion Ultra
Pure Air
Initially Filled.With
Pure Air
Bag was heated @ 100° C
For 1 Hour Prior To
Refilled With Ultrapure
Air
Purged With Helium and
Filled With Scott Marion
Ultrapure Air
Bag 2 Sample Deplete On
Analysis At 240 Hours
00
-------
TABLE 7 (CONTINUED)
Bag Material
B „ J
And
Manufacturer
Tefzel Type A
5 Mil (Small
Bags)
Livingston Co.
Bag 1
Bag 2
Bag 3
Tefzel Type A
5 Mil
Teflon Type L
5 Mil
Tefzel Type A
5 Mil
Bag 1
Bag 2
Teflon Type A
5 Mil
American
Durafilm Co
Date
_ £
of
Test
5/28
To
6/2
6/11
To
6/11
To
6/13
8/8
To
8/12
Total Hydrocarbon (ppm) Increase/Time
Initial
0.16
0.16
0.16
0.21
0.21
0.21
0.21
0.10
24
Mrs
2.55
0.78
1.19
0.99
48 Hr
5.18
6.29
4.97
3.45
1.19
1.74
1.40
72 Hr
96 Hr
1.71
144 Hr
240 Hr
9.84
9.17
Increase
T M. Tl If*
In THC
(ppm/Hr)
0.040
0.038
0.068
0.020
0.032
0.025
0.017
Remarks
Purged With Helium And
Filled With Scott Marion
Ultrapure Air
Bag 2 Sample Depleted On
Analysis @ 240 Hours
Both. Bags Had Squared
Seams Helium Purged &
Filled With Scott Ultra
Pure Air
Both Bags Had Flat Seams
Helium Purged And Filled
With Scott Marion Ultra
Pure Air
Helium Purged Filled
With Linde Hydrocar-
bon Free Air
-------
25
75 TOO
Time - Days
125
150
FIGURE 13 - CARBON MONOXIDE LOSS/TIME
IN STEEL CYLINDER
-------
4.0 SUMMARY
The Gas Chromatography Laboratory is completely operational, with quan-
titative analysis established for C] to CIQ hydrocarbons, total oxides
of nitrogen, carbon monoxide, and total hydrocarbons. Sensitivity of
0.1 parts per billion for C] to CIQ hydrocarbons has been achieved with
carbon monoxide and total oxides of nitrogen determined to 10 and 5 parts
per billion, respectively. Halogenated organic compounds, SFs and fluoro-
carbons 11 and 12, were determined with an electron capture detector.
Sensitivity of 0.1 part per billion was obtained for SFs, but fluorocarbons 11
and 12 were detectable above 500 parts per billion.
92
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APPENDIX I
GAS CHROMATOGRAPHY LABORATORY
WORK PLAN
93
-------
TABLE OF CONTENTS
PAGE
1.0 INTRODUCTION 38
2.0 LABORATORY CAPABILITIES AND ANALYSIS PROCEDURES 38
3.0 DATA PROCESSING " 55
4.0 QUALITY ASSURANCE 58
5.0 LABORATORY OPERATING SCHEDULE 59
94
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RAPS GAS CHROMAT06RAPHY LABORATORY
WORK PLAN
1.0 INTRODUCTION
The St. Louis Regional Air Pollution Study is being conducted to develop,
evaluate and validate air-quality simulation models for both regional and local
scales covering urban and rural areas of stationary and mobile pollution sources.
In addition, a comprehensive, accurate and readily retrievable data base of pollu-
tants is being developed for RAPS and future simulation and effects of model test-
ing and validation. The RAPS:Gas Chromatography Laboratory is established to sup-
port a variety of studies under the program; e.g., A. Evaluation of the Regional
Air Monitoring Station (RAMS) sites; B. Validation of Automotive Emissions in-
ventory submodels; C. Defining the Composition of Emissions from significant
sources; D. Tracking Plumes; and E. Developing and Validating Photochemical
Sub-models.
The Gas Chromatography Laboratory collects and performs analysis of
atmospheric samples for a variety of pollutants, including hydrocarbons, carbon
monoxide, and atmospheric tracer gases. Supplemental analyses for sulfur com-
pounds and nitrogen-oxides are also conducted. The data produced from analysis
is validated for quality-assurance, recorded on magnetic tape and inputed to the
RAMS/RAPS Computer Data Bank, Research Triangle Park, North Carolina.
2.0 LABORATORY CAPABILITIES AND ANALYSIS PROCEDURES
The Gas Chromatography Laboratory is equipped and staffed to per-
form specific analyses of air samples as follows:
1. Hydrocarbon Analysis
The Co'^io hydrocarbon analyses are conducted on a Perkin-Elmer, model
900 gas chromatograph, using a glass bead concentration system with
separation of the hydrocarbons with a two column system. C, to C,
hydrocarbons are determined with a packed column, while the Cq. to CIQ
hydrocarbons analysis is achieved with a 200 foot capillary~column.
The procedure for operation, sample introduction and analysis follows:
A. Preparation of Chromatograph
1. Establish column flow rates of helium carrier gas using a bubble
flow meter:
a. Capillary column @ 12 ml/min.
b. Packed column @ 40 ml/min.
2. Turn on H2 and air source, 16 Ib. H« @ inlet gauge and 50 Ib. on
air regulator. Light flame ionizatfon detectors noting base
line shift on recorder when lite.
95
-------
3. Packed column is held at room temperature, while
capillary is set at 20 and held for six minutes,
then 16 /min. temperature program rate, for 5 minutes
to 100 C. Initiate pressure programming after 100 C
has been achieved.
4. Initiate cooling of the capillary column by turning on
liquid nitrogen at dewar.
5. Fill concentration traps with liquid oxygen.
6. Enter directives of identification, time of analysis,
and threshold values on teletype to the PEP-1 integrator.
7. Zero recorders with both electrometers, set on range 1,
xl for analysis.
B. Introduction of Sample into Concentration Traps
1. Assure the identity of the bag to be analyzed has been logged
in the PE 900 Operational Logbook as to the time, date, loca-
tion, and type (helicopter, site, etc.).
2. Connect quick disconnect fitting to the inlet of the sample
bag.
3. Connect appropriate vacuum line to the constant volume
cylinder attached to the vacuum pump (refer to Figure 1).
4. Connect bag sample to appropriate inlet line and open vacuum
source to draw a half liter of sample through the inlet lines
(allowing purging of the line of air from the previous sample),
5. Close the inlet valve to the constant volume cylinder and
evacuate to 10 mm Hg. with the vacuum pump.
6. Close the vacuum pump valve and open the inlet valve to draw
the air sample from the air bag sample through the sampling
system.
7. Switch the inlet valve to trapping mode and note starting posi
tion on vacuum gauge at the constant volume cylinder. Intro-
duce an accurately measured volume of sample (400 to 500 cc.)
through the concentration trap, and switch the valve back to
the backflush position.
8. Disconnect the bag and store.
C. Injection and Analysis of Bag Sample
96
-------
1. After the sample is trapped, switch the second valve to
injection mode and heat the trap with hot water (90 C).
2. Immediately, actuate ready light on PEP-1 interface, start
light to initiate temperature programming (capillary column
analysis only), and a start position on the recorders.
3. The second valve is returned to the backflush position once
ethylene has eluted from the column.
4. Continue the analysis for fifteen minutes with the packed column
analysis and for 60 minutes with the capillary analysis.
5. Maintain the capillary column at 100° while pressure program-
ing to 60 Ib. inlet pressure.
6. After elution of the C,n hydrocarbons, switch the backflush
valve until heavy hydrocarbons greater than C,Q molecular
weight have eluted from the column (note peaks on chromato-
gram).
7. Press the compute buttons on the interface modules to tabu-
late the area measurement concentration and identification of
the peaks found in the chromatogram.
8. Press the reset button on the front of the chromatograph to
cool the capillary column and refill the concentration traps
with liquid oxygen for resampling.
9. A single analysis of each bag sample will be performed with
a duplicate analysis at the end of the day of the first sample
analyzed from each set of samples to insure reproducibility
of the trapping system. The concentration of the hydrocarbon
components in the sample are determined to the nearest 0.2 ppb
carbon by direct comparison of area response with the standard
response factor for that component.
D. Calibrations
Daily calibrations and periodic calibrations are performed to assure
instrument performance and data accuracy. All calibration data is
logged in the operational Log Book and incorporated in the daily
analysis of air bag samples.
1. Daily Calibration
A quantitative calibration is performed daily before analysis of test
samples by:
a. Introducing into the chromatograph the quality control standard
gas mixture of fourteen hydrocarbons (C2 - C,Q) in air. Cali-
bration is performed with both column systems.
97
-------
b. Comparison and verification of retention times for each
component of the quality control standard will be conducted
and average response factors determined for each class of
hydrocarbon compound.
Periodic Calibration
a. Pressure gauges and rotameters on the chromatograph will be
functional checked every six months.
b. A linearity check of the Imv dual pen recorder will also
be conducted every six months.
Maintenance conducted will be logged in the Maintenance Log Book
under Section for the PE 900.
1. Once a month the charcoal scrubber on the helium carrier
cylinder is regenerated @ 200° for 24 hours.
2. Leak check of the chromatograph and pressure programmer.will
be conducted every three months.
3. System is serviced when duplicate analysis or response factors
exceed ten percent variation.
Hardware
1. The Perkin-Elmer PE900 Chromatograph is equipped with dual
flame ionization detectors, dual electrometers, and tempera-
ture programmer.
2. Utilized with the PE900 is the Perkin-Elmer PEP-1 computer
integrator with dual channels for interfacing with the dual
detector system.
3. The pressure programmer is an Analog Flogramer.
4. The analysis columns consist of a 200 ft. x 1/16 inch support
coated open tubular squalane capillary, and a packed column of
80/100 mesh acid washed silica gel, 5 ft. x 1/8 inch.
5. The inlet valve system indicated in Figure 1 (see page 9) is
a stainless steel body with Teflon diaphrams.
6. Gases used with the PE900 are:
a) Helium supplied by the Bureau of Mines and purified
with a charcoal drier.
b) Air, zero-grade of maximum 2ppm hydrocarbon and 3ppm
moisture.
c) Hydrogen, zero-grade of 99.99% purity with maximum hydro-
98
-------
carbon of Ippm.
7. All connecting lines and fittings are either Teflon or
. stainless steel."
2. Carbon Monoxide, Methane and Total Hydrocarbon Analysis
Analysis of carbon monoxide, (CO), methane, (Cfy), and total
hydrocarbons are conducted utilizing a Beckman Model 6800 process
gas chromatograph. Sampling of all bag samples is accomplished
through a pumping system which pulls the sample through the chroma-
tographic system, insuring no dilution or contamination of the sample
by the pump system. The procedure for operation and sample intro-
duction and analysis follows:
6800
A. Preparation of Chromatograph
1. Turn on the air cylinder (40# outlet pressure) and check
the hydrogen generator for proper water level and 40#
outlet pressure.
2. Light"flame ionization detector noting the flame out
Tight off and start light on, located on front control
panel.
3. Turn on the recorder, set on 10 mv range, and zero with
0 volt button depressed. Actuate auto zero toggle switch
on front control to zero electrometer of chromatograph.
4. Set Hp carrier pressure to give a 25 cc/min flow rate with
the-C-3 column.
5. Adjust the air carrier to 31-34 cc/min through the total
hydrocarbon capillary.
6. Set the detector air and hydrogen fuel to give the maxi-
mum total hydrocarbon response.
7. Attach air bag sample on inlet line at the rear of the
chromatograph and turn on the pumping system.
B. Analysis of Air Bag Sample
1. Enter all pertinent data of the air bag sample in the
6800 Log Book.
2. After five minutes of drawing the sample through the chro-
matograph, actuate valve B for twenty seconds to measure
the total hydrocarbons in the sample.
99
-------
3. The attenuation setting is normally set at x2 on range
of 10.
4. The methane and carbon monoxide are determined by
actuating valve A for forty-five seconds.
5. The attenuation setting will be from x2 to x8 on range
of 1.
6. The Cp's can be determined by actuating valve C until
completion of the analysis.
7. It is proposed that a C2 analysis of one of the air bag
samples per group of samples collected that day will be
analyzed and compared to the results obtained on the Per-
kin-Elmer 900 Chromatograph.
8. Air samples are analyzed once and the concentration to the
nearest 10 ppb carbon determined by comparison of the peak
height response of the sample to the standard for that day.
First sample of the day is run in duplicate at the end of
the day to insure reproducibility.
C. Calibrations
Calibrations performed are tabulated in the Operational Log Book
and incorporated daily in bag sample analysis.
1. Daily calibrations
a. A three-point calibration will be conducted daily using
zero air, a 5 and 15 ppm CO standard, and a 5 and 8 ppm
CH4 standard. The 5 ppm standard of CO and CH4 will be
a mixture in air and will allow a check of the separation
and condition of the C-3 analyses columns.
b. Both standard mixtures will be analyzed on the day of
sampling and response factors determined from an average
response of three analyses.
c. Once a month, a check of the standard cylinder mixtures
will be conducted with gas standards of CO and CH4 made
up in an air matrix of measured CO-CH4 impurity. This
will insure the concentration of the standard and de-
termination of loss due to adsorption on the walls of
the cylinder.
d. The standard mixture used in the 900 calibration will be
used for calibration for the Cp's on the day the C2
comparison analysis is conducted.
2. Periodic calibrations - Every six months will include:
100
-------
a. Linearity check of the 10 mv recorder
b Functional check of the pressure gauges
c. Five-point calibration
Maintenance
Maintenance conducted will be logged in the Maintenance Log Book
under the section for the 6800 Chromatograph.
1. Leak check once a month of the inlet gas lines, sampling
system, chromatograph valves and plumbing and establish proper
flowrates through the system.
2. Check the amplifier board once a month for auto zero and
range change linearity.
3. Change the sample inlet filter monthly.
4. Replace the deionizer resin in the hydrogen generator water
supply every two months.
5. Replace the moisture absorption columns in the hydrogen
generator and on the zero air cylinder.
Hardware
1. The Model 6800 Chromatograph is designed for monitoring of
six air pollutants, total hydrocarbons, methane, carbon monox-
ide, ethane, ethylene and acetylene. It is composed of a flame
ionization detector, pressure actuated valve introduction
system, and a three-column analysis system.
2. The three packed columns are a prestripper column of triton
350 combined with silica gel, molecular sieve 5A, and Porapak
N. The total hydrocarbon analysis is directly sampled from a
sample loop.
3. The fittings and plumbing are composed of 316 stainless steel,
with valves of Teflon slide type, stainless steel base.
4. The air source is of zero-grade (99.99% purity). Hydrogen
is generated from a hydrogen generator (99.9999% purity) and
dried with a molecular sieve 5A trap prior to entry to the
Chromatograph.
101
-------
3. Analysis of Sulfur Components
The determination of total sulfur, sulfur dioxide, hydrogen sulfide
and methyl mercaptan in air samples are conducted utilizing a Tracer, Model
270 Sulfur Chromatograph.
A. Preparation of Chromatograph
1. Plug in the analyzer and push the power "on" button on the
front of the analyzer.
2. Turn on the hydrogen source and establish 65 psi outlet
pressure.
3. Check the compressed air outlet pressure is 80 psi and a
50-60 milliliter flowrate on the flowmeter on the front
control panel.
4. Open the hydrogen control valve on the front panel and push
the ignition button to light the flame ionization detector.
Note the hydrogen pressure should be set to give a 55 cc/min
flow rate.
.5. Set the control knobs.on the front panel to ambient sampling
and automatic cycle.
6. Switch the range switch at the rear of the Chromatograph to
the appropriate range, 0-1 ppm or 0-200 ppb.
7. Attach the air sample bag to the ambient sample line and push
the manual zero and recycle buttons to inject a sample into
the Chromatograph.
B. Calibrations
Calibrations conducted are tabulated in the Operational Log Book
to be incorporated in the daily analysis of air bag samples.
1. Daily calibration
a. Calibration is conducted using a Bendix Dynamic Calibration
System, which consists of a NBS certified sulfur dioxide
permeation tube.
b. Total sulfur calibration is achieved using the sulfur dioxide
response on the total sulfur mode of the Chromatograph.
c. Calibration is initiated by connecting the standard sample
line to the permeation system and switching the sampling con-
trol knob to standard mode.
102
-------
d. Press the manual zero and the recycle button to inject a
sample from the permeation system.
e. The total sulfur response should appear in 7 seconds followed
by hydrogen sulfide, sulfur dioxide and methyl mercaptan
within the ten minute cycle period.
f. Calibration for hLS and ChLSH will be conducted at a later
date when permeation tubes or standard gas mixtures are ac-
quired.
2. Monthly Calibration
A monthly five-point calibration will be conducted to check
linearity.
3. Periodic Calibration
Periodic calibrations every six months will include:
a. Linearity check of the 1 mv recorder
b. Functional check of pressure gauges and rotameters
C. Sample Analysis
1. Enter all pertinent data of the air bag, sample in the Sulfur
Operational Log Book.
2. Bag sample analyses are conducted in duplicate with the first
sample repeated at the end of the day and the concentration
of the four components determined to the ppb level by com-
parison of peak height response of the sample to the daily
calibration curve.
D. Maintenance
Maintenance conducted will be logged in the Maintenance Log Book
under the section headed Sulfur Chromatograph.
1. Adjust the electrometer for zero and set the high and low
range chromatograph terminals to 1 mv every two weeks.
2. Set high and low linearizers at the same time as the electro-
meter adjustment.
3. Leak check the Chromatograph every three months or as needed.
4. Regenerate the molecular sieve moisture traps once a month.
103
-------
E. Hardware
1. The Tracer sulfur chromatograph consists of a dual mode
analysis of total sulfur and the three sulfur compounds SCL,
hLS, and HSCH-. Sulfur compounds are determined with a
flame-photometric detector utilizing a photo-multiplier and
hydrogen rich flame ionization detector.
2. Connecting lines and fittings are nylon or 316 stainless
steel.
3. Analysis columns are proprietary and are acquired directly
from Tracor.
4. The hydrogen and air supply are zero grade 99.99% purity
and are predried with molecular sieve driers.
4. Total Nitrogen Oxides Analysis
Total nitrogen oxides are determined utilizing a Bendix, Model
8101-B NOX analyzer.
A. Preparation of analyzer
1. Turn on oxygen source and set the pressure regulator at
30 psi outlet pressure.
2. Turn on power switch to pump and analyzer.
3. Set oxygen source for ozone generator to 20 psi by opening
valve on control panel.
4 Switch analysis mode knob to NOx only.
5. Switch analysis valve switch to N0-N02-N0 position; mode
switch to ambient; and the NO scale switch to 0.5 ppm.
/\
6. Turn on the chart recorder, 10 millivolt full-scale.
7. Check the chamber pressure, minimal value of 23 inches Hg.
8. Connect air bag sample to inlet port on rear of the analyzer
marked ambient air.
B. Calibrations
All calibrations are logged in the analysis book to be incorporated
into sample analyses for that day.
104
-------
1. Daily Calibration
Daily calibrations are conducted prior to sample analysis:
a. Connect the ambient air inlet line of the NO analyzer
to the Bendix Dynamic calibrator.
b. Allow pure air to enter the NO analyzer and set the
zero points for NO and NO using the appropriate zero
knobs on the front of the analyzer.
c. Connect the quality control standard of 100 ppm NO in
nitrogen gas to the inlet of the Bendix dilution system
and establish a 400 ppb NO concentration by switching
the appropriate dilution valves (consult the dilution
curves for each valve).
d. Adjust the NO and NOY span knobs to 80% of full scale.
A
e. Check the N02 converters efficiency by switching the
ozone generator, allowing part of the NO to be converted
to~N02, and checking to see if the NO value is the same
as the N0? is converted back to NO.
f. . Recheck the zero points with pure air for any deviation.
2. Periodic Calibration
Periodic calibrations are conducted monthly by:
a. Establishing a five-point calibration curve using the Dynamic
Calibrator with the NO quality control standard. This will
check the linearity, as well as, for leaks and errors in the
gas concentration from the Dynamic Calibrator.
b. Verification of the NO concentration of the quality control
standard by direct comparison to the NBS certified NO standard
on the NO analyzer.
/\
c. Establishing that sufficient moisture is in the zero air by
checking for a zero off-set. This can be prevented with the
use of oxygen, with 10 ppm moisture content, for ozone genera-
tion.
d. Determining the N02 content of the quality control standard
by running a standard NOx zero and span. Inside the analyzer
interchange the NO inret line to the control valves with the
NO line entering the control valve from the reduction catalyst,
allowing introduction of NO span gas with N02 impurity. If N02
105
-------
is present, the NOx span value will be lower than the previous
span value, and the difference is a measure of the N0£ present.
Instrument hardware checks will be made every six months, function-
ally checking the pressure gauges, valves, and Imv recorder.
C. Sample Analysis
To perform sample analysis, enter all pertinent data into the NO
Operational Log Book, then:
1. Connect the air sample bag to the ambient air inlet line of
the NO analyzer.
J\
2. Maintain the analyzer in the same concentration and operational
mode as it was calibrated.
3. Allow the pen on the recorder to stabilize and read ppm NO
directly by comparison to the span value set in calibration.
4. Nitric oxide will not be analyzed in the air sample bags due
to thermal degradation of the sample during transfer to the
laboratory.
5. First sample of the day is analyzed in duplicate at the end
of the day.
D. Maintenance
Maintenance is logged in the Maintenance Log Book under the section
for the NO analyzer.
/\
1. Monthly replace the charcoal in the ozone scrubber on the back
of the analyzer.
2. Conduct a leak check of the calibration system and NO analyzer
when deviations in the daily zero or span exceeds 1% of pre-
vious values.
E. Hardware
All materials used in the NO analyzer are either Teflon or 316
stainless steel, including tne connecting lines from the Bendix
Dynamic Calibration system.
1. Air source used in calibration with the Dynamic Calibration
system is discussed in the following sections.
2. The NO standard used in daily calibration is a nominal 100 ppm NO
in nitrogen gas, and traceable to NBS.
106
-------
3. The charcoal used in the ozone scrubber is activated cocoa-
nut charcoal .
5. Halogenated Compound Analysis
Halogenated compounds of SF5, fluorocarbon 11 and fluorocarbon 12 will be
determined using an electron capture detector, Varian Model 940 gas chromatograpl
A. Preparation of the chromatograph
1. Establish column flow rate at 30 ml/min nitrogen gas.
2. Check that column temperature is at ambient.
-8
3. Determine standing current is above 2 x 10 amps.
B. Calibrations are conducted daily and logged in the Operational
Log Book for the Varian Chromatograph.
1. Standards prepared in the laboratory are at the part per
.trillion concentration and are made from 99% purity fluorocarbon 11
and 12, SFs in hydrocarbon free air (+_ 10% accuracy).
C. Sample Analysis
1. Enter all pertinent data of the air bag sample in the Varian
Operational Log Book.
2. Air samples are analyzed in duplicate and concentration to the
nearest part per trillion determined for each compound.
3. The sample will be introduced with a valve system similar to
that previously described for the Perkin-Elmer 900 Gas Chroma-
tograph.
4. Concentration methods will be incorporated with samples where
necessary.
D. Maintenance
Maintenance conducted is logged in the Maintenance Log Book under
the section pertaining to the Varian Chromatograph.
1. Regeneration of the oxygen trap used with the nitrogen carrier.
2. Clean the radioactive foil every two months per instruction
manual .
3. Conduct a leak check of the chromatograph when the foil is
cleaned.
107
-------
E. Hardware
q
1. The electron capture is a Scandium Tritide Foil (Sc H) of
1000 millicure radioactivity strength.
2. Carrier gas is oxygen free nitrogen of 99.99% purity.
3. The analysis column is constructed of 316 stainless steel,
as well as the introduction valve system.
4. The oxygen trap is proprietary in nature and is purchased from
All tech Supplies.
6. Bendix Pure Air System
The Bendix Pure Air System is designed to supply pure, moisture-free
air to the Dynamic Calibration system. This is achieved by compress-
ing ambient air, converting NO impurity to N02 with an ultraviolet light
source, and subsequent adsorption of the N02 and other impurities on
charcoal. The free air is then dried by passing through a silica
gel trap and filtered prior to entering the Dynamic Calibration system.
A. Operational Procedure consists of plugging the power cord into
an electrical outlet and switching "ON" the ultraviolet light
source.
B. Maintenance performed will be logged in the Maintenance Log Book
under the section for Dynamic Calibration System.
1. Once a week the surge tank should be drained of excess water.
2. The charcoal and silica gel adsorbants should be changed
once a month if the system is connected to the laboratory
air system; otherwise, once a week when room air is used.
3. The ultraviolet light source is changed whenever NO is found
in the zero air used to zero the NO analyzer.
/\
C. Hardware is composed of activated cocoanut charcoal, 6 to 14 mesh;
indicating silica gel, grade 42, 6 to 16 mesh; and dust trap of
fine grade fiberglass wool.
7. Bendix Dynamic Calibration System
The Bendix Dynamic Calibration System is used in conjunction with the
NO Quality Control Standard and a NBS certified S02 permeation tube
to provide part per billion level calibration gases for the NOx and
sulfur analyzers. The calibration gases are established by the di-
lution of pure gas through a capillary system with pure air from a
Bendix Pure Air System.
108
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A. Preparation of the Calibration System.
1. Connect the Bendix Pure Air System to the inlets A and C
of the Dynamic Calibrator.
2. Attach the NO quality control standard to the inlet B of
the calibrator.
3. Attach the permeation tube vent line and the dilution
system vent line to the room air vent.
4. Connect the output of the calibration system to the
analyzer to be calibrated.
5. Turn the switches on the front panel for the particular
gas to be diluted, either NO or the SO^ permeation
system.
B. Calibration
1. Each of the seven flow regulating capillaries are cali-
brated every three months by plotting flow rate versus
pressure applied to a given capillary. The flow rates
are determined with a bubble flowmeter and are cross-
checked periodically with a mass flowmeter.
2. The constant temperature bath that houses the S02 permea-
tion tube, is checked for accuracy at the same time the
capillaries are calibrated.
3. Pressure gauges are functional checked every six months.
C. Operational Procedure
1. Once the calibration system has pure air flow, the desired
concentration is achieved by connecting the desired con-
centrated source of NO or SOp to the capillary network.
2. The NO span gas is obtained by adjusting the air pressure in
Section B and activation of the toggle valve to permit the NO
to flow to the capillary system.
3. The ppb NO span gas is achieved by switching the various
toggle valves to divert the NO gas through the individual
capillaries. Reference to the calibration curves for each
capillary will indicate what concentration to expect.
4. The S02 span gas is obtained in a similar manner by switching
the vent valve to connect Section A to the capillary section.
The flow rate is established by adjusting air pressure and
109
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switching the toggle switch for high or low flow rates.
5. The dilution gas desired is obtained, as before, with the
selection of which capillary to use.
6. Multipoint calibration can be achieved for either SO^ or NO
by choosing the proper combination of capillaries at a con-
stant pressure setting.
D. Maintenance
Maintenance is performed and logged in the Maintenance Log Book
under the section pertaining to the Dynamic Calibration System.
1. A leak check of the calibration system will be conducted
every three months.
E. Hardware
Material used in the Calibration System is either Teflon or 316
stainless steel.
1. The S02 permeation tube is NBS certified to 1.503 micro-
grams/mi n permeation rate at 25 C.
2. The NO standard cylinder is acquired from Airco Gas Co.
at nominal 100 ppm NO in nitrogen gas and certified with a
NBS NO standard.
8. General Procedures
A. RAMS Sample Bag Leak Checks
A leak check of Teflon bags used in sampling at the RAMS sites
is performed routinely before each use.
1. Initially, all new Teflon bags received are assigned a
serial number and filled with dry air for a leak test.
2. The bags are filled to 80% capacity and capped off.
3. A book (approx. 1/2 Ib.) is placed on the bag and left
over-night to check for leaks.
4. If the bag is leak-proof, it is purged with high-purity
helium repeatedly and stored for use in sampling.
5. If the bag is found to leak, it is filled with high-purity
hel ium and capped.
6. Using a Gow-Mac leak detector, which compares the thermo-
conductive of reference air to helium, the bag is leak
checked.
no
-------
7. If practical, identified leaks are sealed with a Weldron bag
sealer and leak check is initiated again with the bag filled
with air.
B. Laboratory Gas Standards
Calibration checks using gas standards made up in the laboratory
are prepared as follows:
1. The primary zero air standard consists of zero air with purity
of <0.1 ppm CH4, CO, and NOX, and-<0.01 ppm S02>
2. Standards are made up in the zero free air or of known purity
with pure gases of minimum purity of 99.0%.
3. Volume measurements of the a.ir is determined with a Precision
Scientific Wet Test Meter (- 0.5% volume) accuracy.
4. Volume measurements of pure gases are with precision gas tight
syringes (Hamilton, Precision Scientific, etc.)
C. Quality Control Standards
1. PE900 - laboratory prepared gas mixtures of pure hydrocarbons
in hydrocarbon free air, contained in a 22 liter steel cylinder
@ 200# pressure. Concentration is verified by repetitive
analysis with gas standards for each individual hydrocarbon.
2. Beckman 6800 - a mixture of 5ppm CO and CH. in air, and two
other gas standards of 8 ppm CH. in Air a.nd 15 ppm CO in
Nitrogen, will be used for calioration (- 1% accuracy), and
concentrations are verified by NBS certified gas standards.
3. Sulfur Chroma^ograph - NBS certified S02 permeation tube
(accuracy of - 1.0%).
4. Bendix NO Analyzer - use of an Airco NO gas standard in
nitrogen gas, which is certified with an NBS certified NO
in nitrogen gas standard (- 1.1% accuracy).
Ill
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3.0 DATA PROCESSING
Data generated by the RAPS Gas Chromatography Laboratory is processed
and entered into the RAPS Computer Data Bank, Research Triangle Park (RTP),
North Carolina. Data processing from analysis to final residence in the data
bank is performed as follows:
1. Data Tabulation
It is planned to perform approximately twenty analyses per week for
up to 126 components. When performing these analyses, as described in the
preceding section, the data is initially recorded in the form of strip chart
chromatograms, punch tape and/or teletype printouts. Next, the data is given
one of its first quality reviews by manually inspecting the data for general
chromatograph form factors and quantitative values for each gas component.
Following review and approval, the data is then tabulated on a special pre-
printed form for keypunching (inclusive as Figure 14).
2. Keypunching and Processing
At. the end of approximately a ten-day collection period, the data
forms are sent to Research Triangle Park for keypunching and keypunching
validation. The cards are then shipped to the RAMS Central Computer Facility,
St. Louis, for processing and further validation. Keypunching errors will
normally be corrected by computer operators at the RAMS Computer Facility,
provided they are not excessive. Should a significant quantity of keypunch
errors develop that the RAMS computer operators cannot process in their
normal schedule, the card decks and data sheets will be returned to RTP
for repunching.
Data processing entails checking the cards for index number consistency,
as provided for by the form, and then producing a triple copy printout of label-
ing information, and for each component the name, code number, concentration
(PPB), ratio relative to CO, and flags if the concentration or ratio is out-
side an upper and lower set of limits as provided by EPA. Four quantities, aggre-
gated by software, are treated as components in all respects: sum of non-methane
paraffins, olefins, aromatics, and non-methane hydrocarbons. Validation of the
data concludes upon successful visual inspection and comparison of the data
with the chromatogram and original tabulated data. Also, special attention will
be directed to flagged data for validity and proper annotation.
Upon completion of data validation, a 600 foot, 9 track, 800 BPI, odd-
parity magnetic data tape is prepared and sent to RTP, along with a copy of the
printout. One copy of the remaining two printouts is sent to the EPA Raps Task
Order Coordinator (St. Louis) and the third copy retained by the RAMS Central
Computer Facility.
112
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INDEX
NUMBER
SAMPLE SOURCE
SOURCE
/CODE
START STOP « - UTM START
UTM STOP
n,ff - -
:/ / TIME/ TIME/ E / N / E _ / N /
Illlllllllllllf II ..... MM 111(11 MINIM Illlll
22 28 32 36 44 51 59 66
TOTAL
n
78
-REMARKS-
INDEX
NUMBER
TS
001
HZS
002
S02
003
CH3SH
004
NO»N02
DOS
I 002 / 003 / 004 / 005 / 006 I' ' i i 111111111 n 1111 11111 n 11111 M 11
1 7 13 19 25 31 37 43
T2-C4H8 NUMBER C2-C4H8 3M1-C4HJ
019 / 020 / " B / 021 / 022 / 023
6019 / 020 J '""""" i 021 / 022 / 023 / 024 / 025 / 026 / 027 / 028 / 029 / 030 ~ Af
I II 111 M I I III I IN II I TNI I I I I III I I I irrTTTTTll I I I I I I I I IN I N M I I I I I II II iTfo
1 7 13 19 25 31 ' 37 43 49 55 61 67 73 79
7 13
3M1-C5H8
INDEX -
CY-CjHa 3M1-C5HJ* 4MC2 CjHg NUMBER CY-CsHjo 23DM-C4H84 ZMC^Hn 2M1-CsH9 3M-CsH||» T3-CgH]3 2M2 CjHgt 3MC2-C5H9 N-CgHi4 <£?
/ 031 / 032 / 033 / / 034 / 035 / 036 / 037 / 038 / 039 / 040 / 041 / 042 /
-------
4M1-C6H11* 3M2E1-C(jH6* CY-CgHK) 2M-C6H13* 230M-C5H10+ NUMBER
/ 055 / 056 / 057 / 058 / 059 / /
in iii (mi MM i ii (mi i in in in i ii (i
OGO 061
2E1-C5Hg»
062
224TM.C5Hgt C3-C7M,4 3MCK6H,,»
OH Og5 Q06
13
19 25
31
37 43
49 55
61
67
73
79
3E2-C5Hg N-C7Hi6 23DM2-CsHa* CUDM-CY-CsHg M-CY C6Hn* 4M-CY
067 / 068 / 069 / 070 / 071 / 072
NUMBFB 25DM CsH]2 E-CY-CsHg 24DM.C6H]7 223TM-CsHg CJ-TM-CY-CsH? TOLUENE «
m fl74 0?5 ^ on 07B
/ 067 / 068 / 069 / 070 / 071 / 072 / / 073 / 074 / 075 / 076 I 077 / 078 l^ttl
flllllllllllllllll llllllllllllllllllllllllllllllflllllllllllllllllllllllllllllf.1.1
1 7 13 19 25 31 37 43 49 55 61 67 '73 79
234TMCsHg 233TM CsHg 23DMC6H12< 2M-C7Hi5 4M-U7Hi5 JQDM 16^12' 3M-C7H16» UDCQ 225TMCjHip TKOM-CY-CeHlQli
/ 079 / 080 / 081 / 082 / 083 / 084 / 085 / NUMBtK / 08B / 087 /
11111111111 mnrrri 1111 (11 ITTTTTI 1111111 ITTTTI i (11111 (1111111
1 7 13 19 25 31 37 43 49 55 61
224TM.C6Hn
088 / 089
/ ' ° ° /$
I 1 I I I 1 l°l9
/
67
73 79
T120M-CY-C6HiQ» N-CsHi8 TISOM-CY-CgHifl 224TMC(-,H|| 235TMC(;Hii 22DM-C7H)4 24DM-C7H,/)t 2M4E CeH)2- niiiMBfH 26DM-C7H|4« N'PR-CY.CsHg E-CY-CjH])
/ 091 / 092 / 093 / 094 / 095 / 098 / 097 / 098 / NUMotH , 099 / 100 / 101 /
in iiifiiiiimi M iiiiiifiiiiifiiii! iniiiiiiii ifuiiifiiiiif iiiiiiiiiiif
1 7 13 19 25 31 37 43 49 55 61 57 7!
^
EC6H5 330MC7Hi4 233TM-C7H13 P XYL M XYL 4MC8H|7
43 49
3EC7H15
73 79
iVa °'XYL 224TM.C7H,3 225TM.C7H,3t
/ 103 / 104 / 105 / 106 / 107 / 108 / 109 / 110 / 111 / NUMBER 1)2 ])3 ,,„
/ / // / / / // / / / / A
r
Ml
i
i
i
i
i
i
i
i
i
i
i
i'
225TM.C7H13- N-CgH2fl NPRCoH5 2233TM-C6H10 1M2E-C6H/1 135TM.C6M3 TER BU CeH5 l24TMCsHn SEC BU CeH5« N.C10H22 MIIMRFII I23TM.CCH3« N-BU-CgHs <5>
/ 115 / 110 / 117 / 118 / 119 / 120 / 121 / 122 / 123 / 124 / ™uml>t" i 125 , \26 /Or*/
( MM i INI ii mi ii nun f mm fi in mil 11 (ii ii if miiiMinmiiiif.i.f
1 7 13 19 25 31 37 43 49 55 61 67 73 79
FIGURE 14 (CONTINUED) ~~~
GAS CHROMATOGRAPHY LABORATORY DATA SHEETS
-------
4.0 QUALITY ASSURANCE
Final application of data from the Gas Chromatography Laboratory
in the RAPS study and model development is highly dependent upon the quality
and validity of the data. Analysis methodologies and calibration procedures
must be established to insure that the highest quality data is compiled com-
mensurate with budgetary and technical constraints. In this light, a quality
assurance program has been established to provide meaningful data. .
1. Instrumentation System
The instrumentation selected and provided by the EPA for use in
the Gas Chromatography Laboratory was made to provide the latest, most ac-
curate, and dependable systems possible. Operational procedures have been de-
veloped for every instrument to insure its maximum performance. To insure
that high-quality data is generated by the laboratory, all instruments are
subjected to preventative maintenance and repair, both routinely and as re-
quired. A detailed description of all maintenance performed, both routine
and unscheduled, is entered in the laboratory, (also described in the pre-
vious instrument sections of this Work Plan).
Data accuracy is assured by performing both daily detailed and
monthly general instrument calibration with the quality control standards
discussed in the previous sections. The results of calibrations are entered
in the Operational Log Book for each instrument along with the sample analy-
sis for that day. To check repeatibility of the instrumentation, one of the
bag samples will be analyzed in duplicate before and after each set of samples,
This verification, along with daily calibration, will provide a check for var-
iations in instrument parameters (such as, temperature, pressure, flow rate,
etc.). A periodic cross-check between different instruments is frequently
made using the quality control gas standards. An independent auditing check
of the sample analysis is conducted weekly by the EPA Project Officer to
spot check the data reported.
115
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5.0 LABORATORY OPERATING SCHEDULE
For the laboratory to best serve the program objectives, it must be
flexible in its operation. Periods of heavy analysis must be accommodated as
well as days of light analysis. Also, the laboratory must be prepared and
staffed to accommodate other related functions; such as, equipment maintenance,
special testing, instrument modifications and calibrations. The laboratory
staff must also perform various administrative functions, such as, purchasing
and report writing. With this in mind, a laboratory capability has been estab-
lished based upon the equipment identified earlier and a full-time staff of two
and one-half personnel. With this staff the laboratory is designed to perform
an average of twenty analyses per week. This figure can vary, depending upon
the type of analysis to be run and how much analysis effort is required. To
estimate the laboratory normal capabilities, the following work schedule is
developed for each specific analysis and non-analysis work task. These time
estimates do not include sample pick-up at the various RAMS stations or other
sources.
116
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1. General Laboratory Requirements - Other than Sample Analysis:
Man-hours per
Man-hours Week — Total
A. Maintenance of Equipment 8
B. Leak test and cleaning of sample bags; 4
cleaning shall consist of two purgings
of the bag after each use; with a total
hydrocarbon check after four samplings
with the bag. 0.20 hr/bag x 2 bags/wk.
C. Report writing, seminars, etc. 7
Average of 30 hrs/month -.g
2. Labor Requirements for Chemical Analysis of
Air Samples:
A. Hydrocarbon analysis - C2to C,Q, using two
chromatographic columns Tor the total
analysis
1. A column for C, to C. hydrocarbons
2. A column for C- to C,0 hydrocarbons
3. Calibration - quantitative on those 3
days of sampling twice/week x 1.5 hrs.
4. Sample analysis - simultaneous analy- 20
sis of a sample on two columns, 1.0 hrs/
sample x 20 samples/week
5. Data reduction of analysis 0.25 hrs/ 5
sample x 20 samples/week
28
B. Hydrocarbon and carbon monoxide analysis
with 6800 Chromatograph
1. Calibration - quantitative with two 1
gas mixtures each of methane in air
and carbon monoxide in nitrogen.
Twice/week x 0.5 hrs./check
2. Sample analysis shall consist of a 10
replicate analysis of total hydro-
carbons and single analysis for
methane and carbon monoxide per
(cont'd.)
-------
Man-hours per
(Cont'd.) Man-hours Week -- Total
sample; including data reduction
0.5 hours/sample x 20 samples/wk.
C. Sulfur Component Analysis
1. Calibration-using permeating system 1
total sulfur and S02 on the day of
sampling 1 hr/day (ff total sulfur
S02, H2S, and CH-SH on the day of
sampling 2 hrs/day).
2. Sample analysis will consist of three 4.5
analysis per sample plus data reduction
240 samples over 40 weeks + 6 samples
per week - 0.45 hrs/sample x 6
5.5
D. NO Analysis
/\
1. Calibration-on the day of sampling 2
1 hr/day x twice/week
2. Sample analysis and Data reduction 5
consisting of only NO analysis 0.25
hrs/sample x 20 samples/week
7
E. Halogenated Compound Analysis
1. 'Calibration-made up daily and analyzed 2
1 hr/day x twice/week
2. Sample analysis and data reduction, com- 3
posed of analysis of Sf^, fluorocarbons
11 and 12 240 samples over 40 weeks = 6
samples/wk 0.5 hours/sample x 6 samples
5
F. Data Conversion to Magnetic Tape
Considered as the tabulation on one sheet of
all the analysis of a sample 1 hr/sheet x
20 samples 20
20
118
-------
Manrhours per
Man-hours Week -- Total
3. Estimate of Weekly Analysis Combinations:
A. Example 1
A week consisting of twenty samples
analyzed for:
1. Hydrocarbon analysis -C2 to C,Q 23
2. 6800 analysis 11
3. NOx analysis 7
4. Sulfur components analysis (6 samples 5.5
per/week)
5:.. Halogenated compounds analysis (6 sam- 5
pies per/week)
6. Data conversion to magnetic tapes 20
7. General labor requirements 19
90.5
B. Example 2
Assuming two analyses running simultan-
eously (e.g., 50% operator time on 900
analysis and 25% each on any two of the
other four analyzers).
1. Hydrocarbon analysis-Cp to C-jg 11.5
2. 6800 analysis 5.5
3. NOx analysis 3.5
4. Sulfur components analysis (6 sam- 5.5
pies per week).
5. Halogenated compounds analysis (6 sam- 5
pies per week).
6. Data conversion to magnetic tapes 20
7. General labor requirements 19
70
119
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/4-76-040
3. RECIPIENT'S ACCESSION-NO.
. TITLE AND SUBTITLE
REGIONAL AIR POLLUTION STUDY:
GAS CHROMATOGRAPHY LABORATORY OPERATIONS
5. REPORT DATE
July 1976
B. PERFORMING ORGANIZATION CODE
AUTHOR(S)
A.C. Jones
Raymond F. Mindrup, Jr.
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Air Monitoring Center
Rockwell International
11640 Administration Drive
Creve Coeur, MO 63141
10. PROGRAM ELEMENT NO.
1AA003 26AAI/413
11. CONTRACT/GRANT NO.
68-02-1081
Task Orders 3, 21, 53
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
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-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The Regional Air Pollution Study (RAPS) is collecting data on a regional
scale for the evaluation and further development of air quality simulation
models. A gas chromatography laboratory is operated to provide analyses for
. selected pollutants required to fully assess various submodels included in air
quality simulation models. Hydrocarbons and other components of the atmosphere
are analyzed in support of such studies as: 1) evaluation and development of
submodels concerned with photo-oxidation reactions and transformations in the
atmosphere; 2) evaluation of emissions inventory submodels; 3) tracking plumes;
and 4) relationship between grid area measurements and grid point measurements.
Specifically, atmospheric samples were analyzed for C -C hydrocarbons, CO,
NO + NO , and total hydrocarbons. Additionally, analytical procedures were
prepared and made operational for SO , SF , fluorocarbon -11, and fluorocarbon -
12. The report describes the preparations and operations of a gas chromatography
laboratory for analysis of atmospheric samples. The report includes a work
plan, chromatographic sampling and analysis schemes, quality assurance tests,
and air sample bag storage and contamination tests.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
*Air pollution
*Chemical analysis
*Gas chromatography
Chemical laboratories
operations
Regional Air
Pollution Study
St. Louis, Mo
13B
07D
14B
IS. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
123
20. SECURITY CLASS (This page)
UNCLAS SIFIED
22. PRICE
EPA Form 2220-1 (9-73)
120
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