EPA
600/4
84-002
N G IN
T U T E
RTI/2418/29
STATUS REPORT #5
STABILITY OF ORGANIC AUDIT MATERIALS
AND RESULTS OF SOURCE TEST ANALYSIS AUDITS
. K. M. Jayanty
W. F. Gutknecht
C. E. Decker
EJBD
ARCHIVE
EPA
600-
4-
84-
002
EPA Project Officers: Joseph E. Knoll
Darryl J. von Lehmden
EPA Contract No.
68-02-3431
Prepared for
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Quality Assurance Division
Research Triangle Park, North Carolina 27711
Environmental
Protection
DEC 1
LIBRARY
June 1983
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27709
-------
ETOO
$£*
(oOO-
^'
64;
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TABLE OF CONTENTS
SECTION NO. PAGE
1.0 INTRODUCTION
1.1 Objectives .................... 1
1.2 Audit Materials Contained in the Repository ... 1
2.0 EXPERIMENTAL PROCEDURES
2.1 Instrumentation ................. 6
2.2 Calibration . . . ................ 6
3.0 PERFORMANCE AUDITS .................. 9
4.0 STABILITY STUDIES ................... 22
5.0 SUMMARY AND CONCLUSIONS ................ 24
REFERENCES .......................... 25
ATTACHMENT 1 - STABILITY DATA AS OF JUNE 1983 ......... 26
ATTACHMENT 2 - SAMPLE CALCULATIONS OF PERCENT CHANGE/MONTH . . 75
US EPA
Headquarters and Chemical Libraries
EPA West Bldg Room 3340
Mailcode 3404T
1301 Constitution Ave NW
Washington DC 20004
202-566-0556
Repository Material
-------
SECTION 1.0
INTRODUCTION
1.1 OBJECTIVES
The need for reliable standards for source emission measurement of
hydrocarbons, halocarbons and sulfur compounds is well established.
The Research Triangle Institute (RTI) under contract to the U.S. Envi-
ronmental Protection Agency (USEPA) has responded to this need through
development of an extensive repository of qaseous compounds. The main
objectives of this ongoing project are (1) to provide qas mixtures to
EPA, state/local agencies, or their contractors as performance audits
to assess the relative accuracy of source emission measurements in cer-
tain organic chemical manufacturing industries, (2) to corroborate the
vendor's certified analysis of the aas mixtures by in-house analysis,
(3) to determine the stability of the qas mixtures with time by in-
house analysis, and (4) to explore the feasibility of new audit mater-
ials as reouested by EPA.
This report describes the present status of this project. Includ-
ed in the report are (1) a description of the experimental procedures
used for initial cylinder analyses and collection of stabilty data, (2)
a description of the audit procedure, (3) presently available audit re-
sults, and (4) presently available stability data. Full details of the
study with additional statistical analyses for ten (10) halocarbons and
eight (8) organics are presented in a journal publication (1,2). Sta-
tistical analysis for the remaining compounds will be presented in the
final report.
1.2 AUDIT MATERIALS CONTAINED IN THE REPOSITORY
The RTI repository currently contains 42 different compounds for
use in conducting performance audits during source testinq. The com-
pounds were selected based on the anticipated needs of the personnel of
the Emissions Measurements Branch, Office of Air Ouality Planning and
Standards, USEPA. Table 1 lists the compounds, the concentration
-------
ranges, the number of cylinders of each compound, and the cylinder
construction material. In Table 1, the audit materials fall into two
concentration ranges. The low concentration range between 5 and 20
parts per million (ppm) simulates possible emission standard levels.
The high concentration range between 50 and 700 ppm simulates expected
source emission levels. The balance gas for all gas mixtures is
nitrogen. In the case of some of the audit materials, a second
compound, which serves as an internal standard, was added to the oas
mixture.
-------
TABLE 1. AUDIT MATERIALS CURRENTLY HELD IN THE REPOSITORY
Hloh Concentration Range
Compound No. of
Cylinders
Benzene
Ethyl ene
P ropy lone
Methane/Ethane
Propane
Tol uane
Hydrogen Sulflde
Meta-Xy I ene
Methyl Acetate
Chloroform
Car bony I Sulflde
Methyl Mercaptan
Hexane
1 ,2-Olchloroetnane
Cyclohexane
Methyl Ethyl Ketone
Mathanol
1 , 2-0 I ch 1 oropropane
Trlchloroettiylene
14
4
4
-
4
2
4
2
2
2
2
4
2
4
-
1
1
2
2
W WII««0II 1 I V I • vii • "*
Concentration
Range (ppm)
8 -
5 -
5 -
5 -
5 -
5 -
5 -
5 -
5 -
5 -
3 -
20 -
5 -
30 -
30 -
5 -
5 -
13
20
20
20
20
20
20
20
20
20
to
BO
20
»«
80
80
20
20
Cylinder
Construction*
S
At
Al
-
Al
S
Al
S
S
S
S
Al
Al
Al
-
S
Al
Al
Al
No. of Concentration Cylinder
Cylinders Range (ppm) Construction*
17
4
6
4
4
4
2
2
2
2
2
2
2
4
1
-
-
2
2
60 -
300 -
3000 -
300 -
1000 -
200 -
300 -
300 -
300 -
300 -
300 -
300 -
100 -
1000 -
100 -
80 -
300 -
100 -
400
700
20.000
700
6000 (M),
700 (E)
700
700
700
700
700
700
300
3000
600
200
700
600
Al, S
Al
Al
Al
Al
Al
S
Al
LS
S
S
S
LS
Al
S
-
—
LS
Al
•Cylinder constructions: Al = Alunlnum, S = Steel, LS = Low-Pressure Steel
-------
Compound
TABLE I. AUDIT MATERIALS CURRENTLY HELD IN THE REPOSITORY (Continued)
Lox Concentration Range High Concentration Range
No. of Concentration Cylinder* No. of Concentration Cylinder*
Cylinders Range (ppm) Construction Cylinders Range (ppm) Construction
1,1-Dlchloro-
ethylene
1,2-Olbromo-
ethylene
Perchloro-
ethylene
Vinyl Chloride
1,3-Butadlene
Acrylonltrl le
"Aniline
Methyl Isobutyl Ketone 1
**Para-d Ichlorbenzene
**Ethylam1ne
••Formaldehyde
Methylene Chloride
Carbon Tetrachlorlde
Freon 113
Methyl Chloroform
Ethylene Oxide
Propylene Oxide
Allyl Chloride
5-20
5-20
5-20
Al
Al
9
1
3
1
1
2
2
1
1
1
1
1
1
1
5
5
5
5
5
5
5
5
5
5
5
5
5
5
- 30
- 30
- 20
- 20
- 20
- 20
- 20
- 20
- 20
- 20
- 20
- 20
- 20
- 20
S
S
LS, Al
Al
Al
S
Al
Al
Al
Al
Al
Al
Al
S
-
-
3
-
1
-
-
-
-
-
-
-
1
1
100 - 600
100 - 600
300 - 700
75
Al
Al
LS
300 - 700 LS, Al
Al
75 - 200 A I
75 - 200 S
-------
TABLE 1. AUDIT MATERIALS CURRENTLY HELD IN THE REPOSITORY (Continued)
Low Concentration Range High Concentration Range
Compound No. of Concentration
Cylinders Range (pptn)
Aero 1 el n 1 5-20
Chlorobenzene 1 5-20
Carbon Dlsulflde -
**Cyclohexanone 1 5-20
***EPA Method 25 Gas 3 100 - 200
Cy 1 1 nder*
Construction
Al
Al
Al
Al
Al
No. of Concentration Cylinder*
Cylinders Range (ppm) Construction
_________ —
1 75-200 Al
3 750 - 2000 Al
•Cylinder construction: Al = Aluminum, S = Steel, LS = Low Pressure Steel
"Cylinders are no longer available In the repository since the compounds are
found to be unstable In the cylinders.
•••The gas mixture contains an aliphatic, an aromatic and carbon dioxide
In nitrogen. Concentrations shown are reported In ppnC.
-------
SECTION 2.0
EXPERIMENTAL PROCEDURES
Analysis of the cylinder gases is required to corroborate the
concentrations reported by the company which prepared the gas mixtures
and also to measure concentration changes with time, that is, estimate
stability of the standards.
2.1 INSTRUMENTATION
Analyses are performed with (1) a Perkin-Elmer Model 3920B Gas
Chromatograph with flame ionization and flame photometric detectors,
and (2) a Tracer Model 560 Gas Chromatograph with a flame photometric
detector. The Tracer instrument has been used principally for
measurement of the sulfur-containing species. The gaseous samples are
injected onto the columns by means of gas sampling valves constructed-
of Hastalloy C (high nickel content and low adsorptive properties).
These valves are equipped with interchangeable sample loops to allow
the injection of variable but known volumes of gas. To further
facilitate the injection of varying sample sizes, a sample injection
system (Figure 1) is employed. The operation of the system is based
upon measurement of pressure differentials. Further details on the
system are published in the open literature (3).
The gas Chromatographic parameters used in the measurement of
individual compounds and problems that have arisen are listed in
Attachment 1.
2.2 CALIBRATION
Calibration of the gas chromatographs has involved measurement of
known concentrations of gases in air or nitrogen. The source or method
of preparation of calibration standards varies depending on the gas
involved.
National Bureau of Standards, Standard Reference Materials
(NBS-SRM's) of methane and propane are used for the calibration of the
GC for the measurement of methane and propane audit materials. These
-------
HELIUM
O
VALCO HASTALLOY-C _n _p .....
VALVE \ TO GC COLUMN
*t
\
O
SAMPLE
GAS
BOTTLE
TEFLON
VALVE
1
t
HEISE VACUUM
- PRESSURE GAUGE
NUPRO STAINLESS
•STEEL TOGGLE VALVES
Q
VACUUM PUMP
Figure 1. Sample Injection system.
-------
same gases are used to calibrate the chromatographic system for
measurement of ethylene and propylene, assuming the FID response per
carbon is constant from compound to compound.
A second method for the quantisation of gaseous compounds involves
the use of permeation tubes. Thus, the calibration gases for vinyl
chloride and ethylene oxide have been generated using permeation tubes.
The tube is placed in a temperature-controlled chamber and zero air is
passed over the tube at a known flow rate. The resultant gaseous
mixture is further diluted if necessary with additional zero air in a
glass dilution bulb. The final mixture is collected in a gas sampling
bulb or a Tedlar® bag and analyzed by 6C-FID. The permeation rates of
the tubes are determined periodically by weight loss.
A third method for developing a standard is the "glass bulb"
technique. A known volume of the compound, either gas or liquid, is
injected into an evacuated glass bulb of known volume. The bulb is
then returned to atmospheric pressure with a balance gas of choice. If
a pure liquid is injected, total vaporization is assumed and the
concentration is calculated by using the ideal gas law. Additional
dilutions are also made, if necessary, by utilizing additional bulbs or
by repeatedly pressurizing with a balance gas to a known pressure and
then partially evacuating to a known pressure.
With each of these approaches, multipoint calibration curves are
prepared each time a sample is analyzed. Certain quality control
procedures are followed, for example, equilibrating the permeation
system and the glass bulbs with the sample gas before taking an aliquot
for GC measurement. Also, an NBS standard cylinder of methane is used
to verify the constancy of the detector response. Blank measurements
are taken during the process of cylinder analysis and generally, blank
measurements have shown no signal above the baseline.
-------
SECTION 3.0
PERFORMANCE AUDITS
RTI supplies repository cylinders for audits upon reauest from
the EPA, state or local agencies or contractors. A contractor must be
performing source emission tests at the request of EPA or a state or
local agency in order to Qualify for the performance audit. When a re-
quest is received, the contents of the cylinders are analyzed, the tank
pressures are measured and the cylinders are shipped by overland carri-
er. Tank regulators are also provided when requested. A letter is in-
cluded with the cylinders which provides general instructions for per-
formance of the audit. The audit concentrations and cylinder pressures
are provided to the requesting agency audit coordinator.
To date, 106 individual audits have been initiated, and 102 are
complete. The audit results collected to date are presented in Table
2. Generally, the results of the audits show close agreement (+_ 10*)
with the actual cylinder concentrations measured prior to shipment.
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS
Audit
No.
1
2
3
4
5
6
7
8
9
10
11
12
Client Industry
A Ethylene oxide
production
A Ethylene oxide
production
A Ethylene oxide
production
A Acetone
production
A Malelc anhydride
production
A Ethylene oxide
p rod uct 1 on
B Malelc anhydride
production
C Malelc anhydride
production
D Ethyl benzene
styrene
manufacturer
E Gasoline bulk
terminal
F Gasoline transfer
terminal
F Gasol Ine transfer
terminal
Audit material
Ethylene In N2
Ethylene In NZ
Methane/ ethane In NZ
Methane/ethane In N^
Methane/ethane In NZ
Methane/ethane In N_
Benzene In N^
Benzene In NZ
Benzene In NZ
Ben zene 1 n N_
Ethylene In NZ
Ethylene In NZ
Benzene In N,
Benzene In NZ
Benzene In N^
Benzene In N^
Benzene In NZ
Benzene In N^
Benzene In N^
Benzene In NZ
Benzene In N_
Benzene In NZ
Benzene In N^
Benzene In N_
RTI audit
cone, (ppm)
3,239
21,226
1,710Me/220Et
8,130Me/597Et
1,021 Me/3 15Et
6,207Me/773Et
79.0
374.0
138
300
5,442
18,918
80.0
355
101
387
71.0
229
62.0
80.0
142
294
268
343
Client audit Status of
% bias (Avq. ) audit
-22.5 E
-20.0
+9/-20 E
+9/-1 .00
+21.5/-4.50 E
+23.5/-4.50
-19.0 E
-11.0
-9.40 E
+4.70
-27.0 E
-33.0
+2.30 E
+27.5
+12.9 E
+14.5
-2.80 E
-3.90
+3.80 E
+3.40
-3.50 E
+3.20
-11.8 E
-1.00
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TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
13
14
15
16
17a
17b
18
19
20
21
22
23
Client Industry
F Gasoline transfer
terminal
F Gasoline transfer
terminal
C Nitrobenzene
manufacturing
F Gasoline bulk
terminal
F Gasoline bulk
terminal
F Gasoline bulk
te rm 1 na 1
G Coke oven
F Gasoline bulk
terminal
F Gasoline bulk
terminal
F Linear al ky 1-
benzene manu-
facturing
F Gasoline bulk
terminal
F Gasol Ine bulk
tormina 1
Audit material
Benzene In NZ
Benzene In N^
Benzene In N2
Benzene In N^
Benzene In N^
Benzene In Nj
Benzene In N.
Benzene In N^
Benzene In N^
Benzene In N^
Benzene In N_
Hydrogen sulflde In N^
Hydrogen sulflde In N^
Benzene In Nj
Benzene In N.
Benzene In N.
Benzene In N?
Benzene In N^
Benzene In N.
Benzene In N_
Benzene In N,,
Benzene In N^
Benzene In N-
Benzene In N.,
RTI Audit
cone, (ppm)
129
318
10.7
9.73
269
8.20
140
9.50
127
9.50
127
7.05
9.73
12.0
218
7.65
396
98
294
331
9.85
81.0
10.15
61.0
Client Audit Status of
% bias (Avq. ) audit
+4.70 E
+8.70
+2.60 E
-4.60 E
-2.60
-2.30 E
-1.80
+10.4 E
-2.80
+12.5 E
-6.30
-24.8 E
-22.9
-0.80 E
+7.30
+ 16.3 E
+ 1.50
+5.70 E
+6.80
+4.50
-4.10 E
-6.80
+4.60 E
-9.50
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
ro
Audit
No.
24
25
26
27
28A
28B
28C
29
Client Industry
H Industrial
surface coating
process
C Acrylic acid and
ester Production
C Acrylic acid and
ester Production
E Malelc anhydride
A Carbon adsorber
A Carbon adsorber
A Carbon adsorber
EPA, QAD Instrument
check-out
Audit material
Toluene In N2
Propylene In N2
Propane In N2
Methane/ethane In N2
Propane In N2
Propane In N2
Propane In N2
Propane In N2
Benzene In N2
Benzene In N2
Toluene In N2
Toluene In N2
Toluene In N2
Toluene In N2
Toluene In N2
Toluene In N2
Ethylene In N2
Ethylene In N2
Ethylene In N2
Ethylene In N2
Ethylene In N2
RTI audit
cone, (ppm)
14.8
474
20.3
1.640Me/195et
10. 1
710
5.1
607
10.2
218
8.55
405
8.55
405
8.55
405
4.75
19.6
312
3021
20456
Client audit
% bias (Avq. )
-1.90
••0.20
-2.30
Status of
audit
E
-13.5 (as methane)
+8.60
+5.60
+17.6
-3.60
NA
MA
-6.40
-1.00
+4.10
NA
-8.80
NA
+4.00
+3.10
-0.80
+5.30
-8.60
E
E
F
E
E
E
E
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Ok)
Audit
No.
30
31
32
33
34
35a
35b
Client Industry
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
1 Vegetable ol 1
plant
1 Vegetable ol 1
plant
Audit material
Benzene In N_
Benzene In N^
Benzene In N_
Benzene In N^
Toluene In N^
Toluene In N^
Methyl acetate In N2
Methyl acetate In M2
Methyl acetate In «2
Methyl acetate In N2
Propylene In NZ
Propylene In N.
Propylene In N^
Propylene In N^
Propane In N.,
Propane In Nj
Propane In N^
Hexane In N2
Hexane In N2
Hexane In N2
Hexane In N2
RTI Audit
cone, (ppm)
8.20
78.0
133
348
405
579
6.80
17.2
326
455
4.90
19.7
300
685
14.6
303
439
82.2
1982
82.2
1982
Client Audit Status of
% bias (Avq. ) audit
+0.30 E
-0.90
-4.00
-0.90
+3.20 E
+ 1.00
-2.60 E
+1.70
-1.50
-1.30
-22.4 E
-7.80
+1.00
-1.80
-0.70 E
+7.60
+6.20
+8.10 E
+3.00
-1.20 E
-1.30
36
Carbon adsorber Toluene In N,
8.20
-2.40
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
37
38
39
40
41
42
43
44
45
46
Client Industry
B Coke oven
0 Ethyl benzene/
styrene
B Coke oven
Byproduct
D Coke oven
Byproduct
H Paint spray
H Tire
manufacturing
B Coke oven
D Ethyl benzene/
styrene
F Industrial
surface coating
EPA, QAO Tire
manufacturing
Audit material
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
m-Xylene In N2
Cyclohexane In N2
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Propane In N2
Propane In Air
Propane In Air
Propane In Air
Propane In Air
RTI audit
cone, (ppm)
12.1
105
9.90
77.9
345
8.20
85.4
10.9
147
10.8
16.4
93.4
7.54
225
8.20
74.5
10.6
316
450
15
316
Client audit Status of
% bias (Avq. ) audit
+0.80 E
+2.90
+5.70 E
+3.60
+1.50
-2.60 E
-8.70
+20.0
+6.80
NA F
NA
-11.1 D
+0.10 D
+0.40
-3.40 D
-0.20
-3.00
-3.20 E
-2.00
NA F
NA
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
en
Audit
No.
47
48
49
50
51
52
53
54
Client Industry
EPA, QAD Tire
manufacturing
0 Dimethyl
terephthalate
production
EPA, QAD Instrument
check-out
EPA, QAD Tire oven
manufacturing •
EPA, QAD Instrument
check-out
D Styrene
manufacturing
1 Veg. oil
manufacturing
M Research
Audit material
Propane In air
Propane In air
Meta-Xylene In air
Toluene In N2
Met ha no 1 In N2
Propane In air
Propane In air
Propane In air
Propane In al r
Propane In a!r
Benzene In N2
Benzene In N2
1.3-Butadlene In N2
Cyclohexane In N2
Chloroform In N2
Chloroform In N_
RTI audit
cone, (ppm)
20.6
453
487
61.5
55.2
4.9
613
718
20.8
316
106
358
20,9
99.0
16.51
5S1
Client audit Status of
% bias (Avq. )• audit**
-16.4 £
+ 13.4
-2. 10 E
NA F
NA
-48.8 E
+16.9
+ 16.8
+20.0 E
-9.20
-4.90 E
-3.70
+23.8
-3.50 E
NA F
NA
55
Ethylene In
300
+1.40
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No. Client Industry
56 K Reactivity of
vent activated
cha rcoa 1
57 EPA, QAD Instrument
check-out
58 C Coll coating
59 L
60 M
61 EPA (State of Conn.)
62 0
63 M
64 P
65 E Coke oven
Byproduct
Recovery
Audit material
Chloroform In N^
Hydrogen sulflde
In N2
Propane In N2
Propane In N2
Benzene In N_
Benzene In N_
Audit not Initiated
Benzene In N2
Meta-xylene In N2
Hexane In N2
Methy 1 mercaptan
In N2
Benzene In N^
Methyl ethyl ketone
In N2
Benzene In N^
Benzene In N^
RTI audit
cone, (ppm)
8.11
16.2
5.20
472
9.45
341
--
132.9
760
1986
4.44
13.4
44.5
7.93
132
Client audit Status of
$ bias (Avq.)* audit**
NA F
NA F
NA E
-8.40
NA F
NA
__
NA F
NA F
NA
NA F
NA F
NA
-2.90 E
+1.39
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
66
67
68
69
70
71
72
73
Client Industry
D Rubber
manufacturing
E Coke oven
Byproduct
Recovery
EPA, Reg Ion 1 1
EPA, QAD Instrument
Check-out
EPA, Region 1
E
Degrees Ing
vent
EPA, QAD Instrument
check-out
EPA, QAD Combustion
efficiency
test
Audit material
Benzene In N2
Benzene In N2
Benzene In N2
Benzene In N2
Hexane In N2
Hexane In N2
Propane In N2
Propane In N2
Benzene In N2
Benzene In N2
Vinyl chloride In N2
Vinyl chloride In N2
Propylene In N2
Propylene In N2
Vinyl chloride In NZ
Trlchloroethylene In N2
Trlchloroethy lene In N2
Hexane In N2
Hydrogen sulflde In N2
Methyl mercaptan In N2
RTI audit
cone, (ppm)
12.0
10.2
100.4
335
79.8
3076
9.97
314
8.29
75.7
5.74
28.3
328
725
7.5
14.9
566
3076
16.2
8.22
Client audit Status of
% bias (Avq. )» audit**
+14.2 E
0
+6.40
+6.00
+ 1.80
-7.50
-3.20
-10.8
-2.20 E
-2.50
NA F
NA
-7.00 E
-8.30
NA F
-0.40 E
-8.70
NA F
-7.50 E
-8.90
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
00
Audit
No.
74
75
76
77
78
79
80
81
82
83
Client Industry
E Vinyl chloride
manufacturing
N Coll coating
F Coll coating
D Maletc
anhydride
EPA. Region VII Instrument
checkout
0 Malelc
anhydride
F Plywood/ veneer
drying
P Ply wood/ veneer
drying
J Polypropylene
manufacturing
1 Coke oven
Audit material
1,2-Olchloroethane In N2
1,2-Olchloroethane In N2
Propane In air
Propane In air
Propane In air
Propane In air
Benzene In N2
Benzene In N2
Benzene In N2
Hexane In N2
Benzene In N2
Benzene In N2
Propylene In N2
Propylene In N2
Toluene In N2
Propylene In N2
Propylene In N2
Toluene In N2
Propylene In N2
Propane In N2
Propane In N2
Hydrogen sulflde In N2
Hydrogen sulftde In N2
Carbonyl sulflde
RTI audit
cone, (ppm)
9.30
462
10.01
309
10.01
309
9.46
66.9
120
30.2
9.46
127.60
14.8
328
430
20.3
479
487
9.63
19.70
296
428
647
101
Client audit
% bias (Avq.)*
+6.00
+3.70
NA
NA
NA
NA
-6.60
-11.7
NA
NA
-4.60
+12.5
-4.70
+4.40
-0.80
+18.2
-22.5.
+32.5
-0.35
+0.84
+0.45
+4.90
-16.5
+ 1.98
Status of
audit**
E
F
F
E
F
E
E
E
E
E
-------
SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
84
85
86
87
88
89
90
91
Client Industry
J Compliance
testing
1 Steel
manufacturing
1 Oil shale
Q Maletc Anhy-
dride Produc-
tion
R Refining
Air Quality Bureau, Refining
New Mexico
S Oil shale
F Compl lance
testing &
demonstration
Audit material
Benzene In N2
Hexane In N2
Toluene In N2
Methyl mercaptan In N2
Hydrogen sulflde In N2
Carbonyl sulflde In N2
Hydrogen sulflde In N2
Carbonyl sulflde In N2
Methyl mercaptan In N2
Benzene In N2
Hexane In N2
Hydrogen sulflde In N2
Hydrogen sulflde In N2
Hydrogen sulflde In N2
Carbonyl sulflde In N2
Methyl mercaptan In N2
Hydrogen sulflde In N2
Trlchlorethylene In N2
Propane In N2
Propane In N2
Propane In N2
RTI audit
cone, (ppm)
7.45
72.6
15.0
5.40
647
9.08
437
117
8.42
55.7
323.7
17.5
437
647
117.4
8.42
437
94.6
10.0
309
73.8
Client audit Status of
t bias (Ava.)* audit"
E
+3.70
E
E
+528.4 E
+20.5
21.1 E
22.0
NA F
-29. 1 E
-14.8
-3.65
NA E
NA
-54.0
8.7
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
ro
o
Audit
No. Client
92 EPA, Region 1
93 D
94 US EPA, Region 1
95 E
96 USEPA, Region 1
97 Tewksbury State
Hospital, MA
98 T
99 U
1 ndustry
Research Method
Development
Method
Validation
Research-
Method
Development
Acrylonltrlle
Production
Resource Re-
covery Garbage
Burning Emis-
sions
Research-
Method Develop-
ment
Plywood
Veneer
Hazardous
Materials
1 nctneratlon
RTI audit
Audit material cone, (ppm)
Toluene In N2
Hydrogen sulflde In N2
Vlnylchlorlde In N2
1,1-dlchlorethylene In N2
Trlchloroethylene In N2
Perch loroethylene In N2
Acrylonltrlle In N2
Acrylonltrlle In N2
Propane In N2
Propane In N2
Vinyl chloride
1 , 1 -d tch 1 oroethy 1 ene
T r 1 ch 1 oroethy 1 ene
Tetrach loroethylene
C02, propane, toluene
C02, propane, toluene
Trlchloroethylene In N2
Perch 1 oroethy 1 ene In N2
Chloroform In N2
347
8.32
8.39
14.2
13.46
7.94
413
10.8
10.0
296
8.39
U.2
13.5
7.94
102
1944
8.91
7.94
16.5
Client audit
% bias (Avq.)*
NA
NA
-20.2
+10.6
+55.6
+48.1
NA
6.94
-35.0
-17.2
+57
-9.9
-4.4
+48.6
NA
NA
NA
Status of
audit"
F
F
E
E
E
E
A
F
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No. Client Industry
100 USEPA, Region 1 Research Method
Development
101 U Hazardous
Materials
Incineration
102 Allegheny Source Testing
County
103 1 Hazardous
Waste Incin-
eration
104 1 Hazardous
Waste Incin-
eration
105 USEPA, Region VI Plastics
106 USEPA, Region VI Vinyl Chloride
Manufacturing
Audit material
Chlorobenzene
Ben zene
Hexane
M-xylene
Trlchloroethy lene In N2
Perchloroethylene In N2
To 1 uene
MEK
Acrylonltrlle
MIBK (n-pentane tracer)
Vinyl Id lene chloride In
Vinyl Id lene chloride In
Vlnylchlorlde
Vlnylchlorlde
RTI audit Client audit Status of
cone, (ppm) % bias (Avq.)* audit**
9.20 NA F
127.8 NA
30.2 NA
6.82 (cold bulb) NA
2.68 (warm bulb)
13.46 NA F
14.54 NA
8.51 A
38.69
11.60
9.49
N2 14.20 A
9.00 A
8.41 A
8.44 A
NA = Not analyzed
•Client % Bias
= 100 X
Client-Measured Concentration - RTI-Measured Concentration
RTI-Measured Concentration
••Status Codes:
A = Cylinder shipped; audit results not yet received;
B = Audit results received;
C = Audit report submitted to EPA;
D = Audit results received, audit report submitted to EPA, cylinder not yet returned by client;
E - Audit complete;
F = Audit completed without analysts of audit materials by client.
1977 - Audits 1-8
1978 - Audits 9-28
1979 - Audits 29-49
1980 - Audits 50-75
1981 - Audits 76-82
1982 - Audits 83-86
1983 - Audits 87-106
-------
SECTION 4.0
STABILITY STUDIES
An ideal calibration standard or audit material should be stable
over its total time of usage. Any change or instability should be less
than the measurement error tolerated during its use. The stabilities
of the compounds in the repository are being estimated through periodic
analysis of the cylinder contents. Improved estimates of stabilities
could be determined by increasing considerably the freciuency of the
analyses, however, this increase is beyond the scope and financial
limits of this project. The primary objective of this project is to
conduct performance audits during source testing to assess the relative
accuracy of the analytical results.
In this project, the gas mixtures in the repository are initially
analyzed upon receipt from the specialty gas vendor to corroborate the
vendor's analysis. If the RTI analysis differs from the vendor's value
by more than 10 percent, the cylinder is given to a third party for
analysis. The gas mixtures are again analyzed at 1 month, at 2 months,
and at one year following the initial analysis. These subsequent
analyses are made to determine the stability of the qas mixtures. In
some cases, analyses are not peformed on the dates specified above;
however, every attempt is made to acquire the data on this schedule.
Cylinder concentrations are also determined prior to each performance
audit, providing additional data for use in stability studies.
The estimates of stability have been calculated in terms of
percent change per month. These rates of change are calculated from a
linear regression analysis of the concentration/time data. Stability
estimates have been calculated only for cylinder contents analyzed
three or more times. Two standard deviations of percentage change oer
month have been calculated only for cylinder contents analyzed four or
more times. Attachment 1 shows the concentrations and time periods on
which the calculations are based and the percent change oer month for
each cylinder. Sample calculations for a 100 opm benzene cylinder are
given in Attachment 2 (See Page 76).
22
-------
As the number of analyses per cylinder increases, additional sta-
tistical analyses will be performed. These additional statistical
analyses will include testing models other than the linear regression
model. Such models are needed especially where the change is rapid at
first but later becomes slow or nonexistent. The results will be pre-
sented in a final report. Statistical analysis for ten (10) halocar-
hons and eiqht (8) organics were recently published in the open litera-
ture (1,2).
Absolute accuracies of the cylinder analyses have not been deter-
mined due to lack of NBS-SRM's as standards for most qas mixtures. Re-
cently NBS has issued SRM's for both benzene and for tetrachlorethvlene
and is in the process of preparing SRM's containing up to eight differ-
ent organic components. The available NBS-SRM's will he used in the
future to estimate the absolute accuracy. Absolute accuracy could also
be estimated by performing the analyses using several different ana-
lytical methods or by having a relatively large number of laboratories
perform anafyses on the same cylinders; both of these aporoaches are
beyond the financial limits of this project. An examination of the
data in Attachment 1 shows values for individual cylinder analyses usu-
ally have varied by less than 10 percent for 4-8 analyses over 2-3
years. This variation indicates either a real change in cylinder con-
tents (i.e., instability) and/or the orecision of the measurement pro-
cess. The possible sources of experimental error that could result in
apparent changes in concentrations include (1) the variability of the
analytical technique used for analysis, (2) stability of and/or accu-
racy of calibration standards, and (3) the ability to reproduce stan-
dards for which NBS-SRM's do not exist. Each of the above sources of
variability impacts to some extent on the resulting data oresented in
Attachment 1.
In some cases, the cylinder contents were lost after only a few
analyses. The possible reasons include leakage during storage or ship-
ping, misuse, multiple use in audits or initial low pressure in the
cylinder.
23
-------
SECTION 5.0
SUMMARY AND CONCLUSIONS
Cylinder qases of hydrocarbons, halocarbons, and sulfur containing
organic species have been used successfully as audit materials to
assess the relative accuracy of gas chromatographic systems used to
measure source emissions. Absolute accuracy has not been determined
because of lack of standard reference materials for most aas mixtures;
instead interlaboratory bias has been reported for the performance
audits conducted during source testing. The interlaboratory bias
determined has been generally within 10 percent for both low and high
concentration gases (Table 2).
Of the 42 gaseous compounds studied or currently under study, 37
have demonstrated sufficient stability in cylinders to be used further
as audit materials. Four compounds (ethylamine, paradichlorobenzene,
cyclohexanone, and aniline) are not recommended as audit materials for
various reasons as discussed in Attachment 1. One gaseous compound
(formaldehyde) was ordered but the speciality gas manufacturer indi-
cated that cylinder gases of this compound could not he prepared. As
stated previously, the percent change per month values reported in
Attachment 1 are only estimates of stability. Detailed statistical
analyses which would separate statistical deviations from true concen-
tration changes with time are in progress and will be presented in a
final report.
24
-------
REFERENCES
R. K. M. Jayanty, C. Parker, C. E. Decker, W. F. Gutknecht, J. E.
Knoll and D. J. VonLehmden, "Quality Assurance for Emissions
Analysis Systems," Environmental Science and Technology, 17. (6)»
257-263A (1983).
G. B. Howe, R. K. M. Jayanty, V. J. Rao, W. F. Gutknecht, C. E.
Decker and D. J. VonLehmden, "Evaluation of Selected Gaseous
Halocarbons for Use in Source Test Performance Audits," Accepted
for publication in J. of Air Pollution Control Association, (in
print).
S. K. Gangwal and D. E. Wagoner, "Response Correlation of Low
Molecular Weight Sulfur Compounds Using a Novel Flame Photometric
Detector," J. Chrom. Sci., 17. 196-201 (1979).
25
-------
ATTACHMENT 1
Stability Data
as of
June 1983
1.0 BENZENE STABILITY STUDY
2.0 ETHYLENE STABILITY STUDY
3.0 PROPYLENE STABILITY STUDY
4.0 METHANE/ETHANE STABILITY STUDY
5.0 PROPANE STABILITY STUDY
6.0 TOLUENE STABILITY STUDY
7.0 HYDROGEN SULFIDE STABILITY STUDY
8.0 META-XYLENE STABILITY STUDY
9.0 METHYL ACETATE STABILITY STUDY
10.0 CHLOROFORM STABILITY STUDY
11.0 CARBONYL SULFIDE STABILITY STUDY
12.0 METHYL MERCAPTAN STABILITY STUDY
13.0 HEXANE STABILITY STUDY
14.0 1,2-DICHLOROETHANE STABILITY STUDY
15.0 CYCLOHEXANE STABILITY STUDY
16.0 METHYL ETHYL KETONE STABILITY STUDY
17.0 METHANOL STABILITY STUDY
18.0 1,2-DICHLOROPROPANE STABILITY STUDY
19.0 TRICHLOROETHYLENE STABILITY STUDY
20.0 1,1-DICHLOROETHYLENE STABILITY STUDY
21.0 1,2-DIBROMOETHYLENE STABILITY STUDY
22.0 PERCHLOROETHYLENE STABILITY STUDY
26
-------
23.0 VINYL CHLORIDE STABILITY STUDY
24.0 1,3-BUTADIENE STABILITY STUDY
25.0 ACRYLONITRILE STABILITY STUDY
26.0 ANILINE STABILITY STUDY
27.0 METHYL ISOBUTYL KETONE STABILITY STUDY
28.0 CYCLOHEXANONE STABILITY STUDY
29.0 PARADICHLOROPENZENE STABILITY STUDY
30.0 ETHYLAMINE STABILITY STUDY
31.0 FORMALDEHYDE STABILITY STUDY
32.0 METHYLENE CHLORIDE STABILITY STUDY
33.0 CARBON TETRACHLORIDE STABILITY STUDY
34.0 FREON 113 STABILITY STUDY
35.0 METHYL CHLOROFORM STABILITY STUDY
36.0 ETHYLENE OXIDE STABILITY STUDY
37.0 PROPYLENE OXIDE STABILITY STUDY
38.0 ALLYL CHLORIDE STABILITY STUDY
39.0 ACROLEIN STABILITY STUDY
40.0 CHLOROBENZENE STABILITY STUDY
41.0 CARBON DISULFIDE STABILITY STUDY
42.0 METHOD 25 GAS MIXTURE
27
-------
t.O BENZENE STABILITY STUDY
Cylinder No. 1A IB 1C ID IE IF 1C
Cylinder Construction* Al Al Al Al S S S
Manufacturer
Concentration
pptn 65.4
324
200
117
61.0 71.0
80.0
Date 7/27/77 7/27/77 7/27/77 7/27/77 2/10/78 2/10/78 2/10/78
RTI
Concentration
ppm
(79.0) (374) (241) (138) (62.0) (71.0) (80.0)
Day 136
ppm
Day 156
ppm
Day 167
ppm
Day 630
ppm
136
247
29
78
232
78
(74.0) (337) (216) (144) (62.0) (73.0) (81.0)
156
252
157
216
385
216
(78.0) (350) (215) (134) (61.0) (75.0) (81.0)
167
381
252
385
586
385
(80.0) (355) (218) (129) (65.0) (74.5) (84.0)
402
(77.9) (331)
290 722 882 504
(127) (66.9) (75.7) (85.4)
Day
ppm
Day
ppm
Day
ppm
% Change/month
Two Std. Dev.
of % Change/month
*» 433 414 1337 1292 1292
(343) (127) (55.7) (65.7) (74.0)
969 1247 1858
(358) (132) (58.7)
1274
(348)
1491
(324)
2056
(305)
-0.01 -0.16 -0.87 -0.12 -0.13 -0.14 -0.17
0.42 0.12 0.66 0.27 0.19 0.29 0.25
Al = Aluminum; S = Steel; LS = Low-Pressure Steel.
CyIInder empty
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10jJ OV-101 on Chramosorb W-P column at 60'
CALIBRATION: Reagent-grade "Benzene" liquid Is used as a standard. Glass-bulb dilution
technique Is used for making the series of standards for calibration.
28
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cylinder No. 1H II U IK IL 1M IN
Cylinder Construction*** S S S S S S S
Manufacturer ppm 100
Concentration
139 232 265 296 326 344
RTI
Concentration
Date 2/8/78 2/9/78 2/9/78 2/9/78 2/9/78 2/9/78 2/9/78
ppm (101) (139) (229) (264) (295) (3|9) (332)
Day 65 49 233 49 49 49 49
ppm (102) (139) (237) (26|) (292) (316) (327)
Day 206 50 386 50 5| 5| 54
ppm (98.0) (142) (243) (268) (294) (318) (342)
Day 237 96 557 69 93 96 69
ppm (101) (139) (225) (254) (298) (323) (335)
Day 434 127
ppm (105) (140)
Day 773 205
ppm (106) (138)
Day 831 505
ppm (100) (147)
Day 1294 1293
ppm (92.0) (128)
84 205 433 809
(269) (294) (345) (342)
237 830 »»
(302) (335)
809 1294
(295) (320)
1294
(290)
1338
(128)
% Change/month
Two Std. Dev.
of % Change/month
-0.12 -0.16 -0.02 -0.04 -0.03 0.06 0.10
0.21 0.12 0.62 2.51 0.06 0.17 0.16
AI = Aluminum; S - Steel; LS = Low Pressure Steel.
Empty
29
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cyl Inder No. 10 IP 1
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cylinder No. W 1W IX 1Y |Z IAA 1AB
Cylinder Construction"* S S S S S S Al
Manufacturer ppm 12.2 8.09 11.0 11.2 8.09 9.14 270
Concentration
Date 4/25/78 5/19/78 5/4/78 5/4/78 5/4/78 5/4/78 7/27/77
ppm (12.7) (8.10) (11.2) (10.9) (8.20) (9.10) (300)
Day I 105 132 132 132 132 29
ppm (12.5) (7.70) (10.2) (9.90) (7.04) (7.80) (3|9)
RTI Day 2I 287 « 302 302 302 157
Concentration ppm (12.3) (8.10) (10.7) (7.70) (8.50) (3|2)
Day 109 488 393 473 1005 2056
ppm (12.0) (8.20) (10.8) (7.54) (8.17) (305)
Day 358 784 1209
ppm (12.1) (8.30) (8.42)
Day 755 1194
ppm (12.0) (7.45)
1218
(11.7)
% Change/month -0.14 -0.09 -2.04 0.11 -0.27 -0.08 -0.02
Two Std. Dev. 0.09 0.25 — 1.04 1.21 0.35 0.11
of % Change/month
**
Cy I Inder empty.
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
31
-------
2.0 ETHYLENE STABILITY STUDY
Cylinder No.
Cyl Inder Construct 1cn»*»
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
Day
ppm
Day
ppm
% Change/month
2A
Al
2920
2/23/78
(3066)
49
(3)15)
198
(2883)
809
(3203)
0.18
2B
Al
3000
2/23/78
(3127)
49
(3177)
198
(2942)
809
(3272)
0.19
2C
Al
4960
2/23/78
<52|4)
48
(5341)
201
(4662)
809
(5383)
0.14
2D
Al
4970
2/23/78
(5202)
48
(5284)
201
(49)3)
809
(5338)
0.10
2E
Al
19900
2/24/78
(20438)
48
(20780)
200
(20150)
808
(18906)
-0.31
2F
Al
19900
2/24/78
(20622)
48
(20822)
200
(203201
803
(18960)
-0.32
2G
Al
4.95
4/27/78
(4.70)
29
(4.
106
(4.
741
(4.
1180
(5.
+0.14
70)
85>
62)
12)
Two Std. Dev.
% of Change/month
0.44
0.44
0.72
0.39
0.10 0.07 0.22
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Plane lonlzatlon detector, Durapak n-octane on Pores 11 C column
at 30 degrees Celsius.
CALIBRATION: NBS-SRM Propane Is used for standard calibration.
32
-------
2.0 ETHYLENE STABILITY STUDY (Continued)
Cylinder No. 2H 21 2J 2K 2L 2M 2N
Cylinder Constructfon»*» Al Al Al Al Al Al Al
Manufacturer
Concentration
ppm 10.0
15.0 19.9
300 448
603
701
Date 4/27/78 4/28/78 4/28/78 4/28/78 4/28/78 4/28/78 4/28/78
RTI
Concentration
ppm
Day
PP«n
ppm
ppm
(9.7) (14.4) (|9.2) (306) (468) (629) (740)
29
(9.6)
Day 106
Day 740
28 28 33
(14.4) (|9.3) (319)
33
(493)
34
(646)
34
(749)
104
104
105
(9.9) (14.9) (20.3) (312)
104 104 104
(473) (636) (737)
739
739
728
740
740
740
(8.4) (18.0) <27.5) (300) (457) (606) (703)
Day 1180 1179 1179
ppm (10.0) (14.4) (18.9)
% Change/month
-0.07 40.18 +0.29 -0.17 -0.19 -0.20 -0.23
Two Std. Dev.
of % Change/month
0.44
0.66 1.14
0.22
0.27 0.14 0.08
Al = Aluminum; S » Steel; LS » Low Pressure Steel,
33
-------
3.0 PROPYLENE STAJILITY STUDY
Cylinder No. 3A
Cylinder Construction*** Al
Manufacturer ppm
Concentrat Ion
Date
ppm
Day
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
2 Change/month
Two Std. Dev.
of % Change/month
4.94
4/27/78
(4.86)
26
(4.94)
27
(4.78)
104
(4.98)
749
(4.93)
0.05
0.17
3B
Al
9.91
4/27/78
(9.83)
26
(9.85)
104
(10.3)
749
(9.76)
1250
(9.63)
-0.08
0.12
3C 3D
Al Al
14.8 20.0
4/27/78 4/27/78
(14.6) (19.8)
26 27
(14.5) (19.0)
104 104
(14.8) (20.0)
749 749
(14.8) (20.3)
0.06 0.16
0.09 0.25
3E
Al
298
4/27/78
(296)
27
(286)
104
(317)
750
(324)
820
(328)
0.38
0.29
3F
Al
446
4/27/78
(442)
27
(428)
105
(474)
750
(479)
0.33
0.47
36
Al
585
4/27/78
(577)
27
(560)
104
(629)
750
(620)
0.27
0.56
3H
Al
683
4/27/78
(672)
27
(655)
105
(729)
750
(721)
820
(725)
0.25
0.32
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Durapak n-octane on Porasll C column at 30 degrees
Celsius
CALIBRATION: NBS-SRM Propane Is used for standard calibration.
34
-------
4.0 METHANE/ETHANE STABILITY STUDY
Cylinder No. 4A
Cylinder Construction*** A|
Audit Material**** M E
Manufacturer ppm 6000 7|4
Concentration
Date 7/21/78 7/21/78
ppm (6207) (773)
Day 264 1 63
RTI ppm (5982) (7|5)
Concentration
Day 662 264
ppm (6584) (684)
Day 662
ppm (703)
Day
ppm
% Change/month 0.32 -0.34
4B
Al
M E
8130 597
7/21/78 7/21/78
(8130) (654)
35 35
(7551) (663)
264 163
(7824) (606)
662 264
(8592) (577)
662
(598)
0.43 -0.43
4C 4D
Al Al
M E M E
1000 295 1670 202
7/21/77 7/21/77 7/21/77 7/21/77
(1021) (315) (1710) (220)
264 163 35 29
(983) (292) (1563) (2|8)
1027 264 264 1 57
(1289) (283) (1640) (202)
1027 1027 258
(284) (1953) (195)
1027
(206)
0.90 -0.20 0.59 -0.13
Two Std. Dev.
of % Change/month
0.61
0.53
0.57
0.36
0.41
0.39
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
*««•
M = Methane; E = Ethane.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Dura pa k n-octane on Porasll C column at 30 degrees
Celsius.
CALIBRATION: NBS-SRM methane Is used for standard calibration.
35
-------
5.0 PROPANE STABILITY STUDY
Cylinder No. 5A
Cy 1 1 nder Construct lon»»» A I
Manufacturer ppm 5.01
Concentration
Date 4/25/78
ppm (4.90)
Day 24
ppm (4.90)
RTI Day 108
Concentration ppm (5.10)
Day 605
ppm (4.89)
Day 729
ppm (5.20)
Day
ppm
Day
ppm
Day
ppm
% Change/month 0. 1 1
Two Std. Dev. 0.26
of % Change/month
5B
Al
10.0
4/25/78
(9.70)
24
(9.80)
108
(10.1)
513
(10.6)
752
(10.0)
914
(10.0)
0.09
0.22
5C 50
Al A|
14.6 20.0
4/25/78 4/25/78
(14.3) (19.5)
25 25
(14.5) (19.8)
108 108
(14.9) (20.3)
582 582
(15.0) (20.8)
736 736
(14.7) (20.1)
1252
(19.7)
0.10 0.01
0.16 0.14
5E
Al
303
4/26/78
(304)
24
(301)
107
(305)
530
(316)
581
(316)
735
(313)
752
(314)
913
(309)
1251
(296)
0.01
0.12
5F
Al
439
4/26/78
(44|)
24
(436)
107
(440)
530
(450)
581
(453)
728
(472)
0.25
0.12
56 5H
Al Al
604 708
4/26/78 4/27/78
(615) (730)
27 26
(615) (723)
107 106
(607) (7|0)
604 603
(613) (718)
735 734
(628) (734)
0.08 0.3
0.10 0.13
Al = Aluminum; S = Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Durapak n-octane on Porasll C column at 30 degrees
Celsius.
CALIBRATION: NBS-SRM Propane Is used for standard calibration.
-------
5.0 PROPANE STABILITY STUDY (Continued)
Cylinder No. 51 5J
Cylinder Construct 1on»»» Al Al
Manufacturer ppm 1000 2000
Concentration
RTI Date 3/3/83 3/383
Concentration ppm 1270 2100
5K 5L
Al Al
10,000 20,000
3/3/83 3/3/83
11,760 20,073
% Change/month —~ — --
Two Std. Dev.
of % Change/month
Al = Aluminum; S • Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatton detector, Durapak n-octane on
Porasll C column at 30 degrees Celsius.
CALIBRATION: NBS-SRM Propane Is used for standard calibration.
37
-------
6.0 TOLUENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
% Change/month
6A
LS
408
12/6/78
(405)
3
(405)
86
(394)
too
(393)
»*
-0.29
6B
LS
606
12/6/78
(585)
3
(579)
86
(577)
358
(615)
982
(491)
985
(487)
-0.50
6C 6D 6E
S S S
16.2 9.11 9.00
10/3/78 10/3/78 3/29/83
(17.3) (9.62) (8.5)
48 64
(14.9) (8.50)
365 66
(15.0) (8.60)
1046 160
(8.91) (8.20)
•«
1373
(14.8)
-0.54 -2.67
Two Std. Dev.
of % Change/month
0.06
0.06
0.92
1.97
CylInder empty.
•«*
Al = Aluminum, S = Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 Chromosorb WHP column
at 60 degrees Celsius.
CALIBRATION: Reagent grade "Toluene" liquid Is used as a standard. "Glass bulb" technique Is
utilized for generation of series of standards for calibration.
ANALTYICAL PROBLEMS: All analyses of Cylinder No. 66 before Day 982 end of Cylinder No. 6C
before Day 1046 used glass calibration bulbs at room temperature rather than bulbs which were
heated to above toluene's boiling point. As a result, toluene may have condensed on the walls
of the room-temperature bulbs. This may explain why the earlier concentrations are greater than
those of the most recent analyses. However, actual degradation may have occurred In these
cylInders.
38
-------
7.0 HYDROGEN SUUFIOE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
7A
Al
399
10/1/78
(371)
38
(424)
111
(414)
Day 1030
ppm
Day
ppm
Day
ppm
% Change/month +0
Two Std. Dev. 0
of % Change/month
(437)
.28
.47
7B
Al
9.15
7/7/78
(9.73)
87
(6.72)
124
(7.11)
197
(6.36)
696
(6.23)
1116
(8.32)
-0.05
1.24
7C
Al
16.7
10/1/78
(16.1)
38
(16.5)
111
(15.7)
580
(16.2)
1030
(17.5)
•KJ.22
0.20
7D
Al
649
10/1/78
(641)
38
(655)
111
(690)
1030
(647 ) )
»*
-0.05
0.28
7E 7F 76
Al Al Al
6.95 6.45 6.71
10/1/78 10/1/78 3/2/83
(7.05) (4.94) (628)
87 38
(5.75) (5.14)
124 lit
(5.62) (4.81)
197 580
(5.23) (4.35)
696 1030
(5.14) (3.71)
1116
(5.38)
-0.43 -0.75
0.67 0.16
Cy Under empty.
»•»»
Al = Aluminum, S = Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10* OV-101 Chromosorb WHP column
at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Hydrogen sulflde" gas Is used as a standard. Dilutions are made
In a Tedlar bag for generation of series of standards for calibration.
ANALYTICAL PROBLEMS: Only a Teflon* column and Teflon* lines should be used. The air-to-hydrogen ratio Is
critical to the sensitivity of the FPD.
39
-------
8.0 M-XYLENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
8A
LS
405
10/5/78
(480)
63
(445)
158
(425)
412
(487)
606
(507)*
1040
(364)
0.35**
8B
LS
613
10/5/78
(720)
63
(676)
158
(656)
606
(760)*
1040
(534)
-1.65**
8C
S
17.3
10/5/78
(16.6)
63
(17.2)
166
(20.8)
302
(16.4)
948
1036
(19.0)
+0.24
8D
S
7.33
10/5/78
(6.20)
63
(6.81)
166
(6.82)
948
(4.36)*
1036
(5.66)
1596
(2.68)
-0.95
Two Std. Dev.
of f Change/month
0.74
0.77
0.84
0.52
Questionable value. Not Included In the calculation of % change/month.
«*
Calculated only through Day 412 because of change In analytical procedures as
described under analytical problems.
*»*
Al o Aluminum; S = Steel; LS = Low Pressure Steel.
CALIBRATION: Reagent grade "M-Xylene" liquid Is used. "Glass bulb" technique Is
used for generation of series of standards for calibration.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP
column at 60, 120 or 140 degrees Celsius.
ANALYTICAL PROBLEMS: All analyses before Day 948 used glass calibration bulbs at
room temperature rather than bulbs which were heated to above meta-xylene's boll-
Ing point. As a result, meta-xylene may have condensed on the walls of the room-
temperature bulbs. This may explain why the RTI concentration for cylinder Nos.
8A and BB before day 1040 are greater than those for the analysis on Day 1040.
40
-------
9.0 METHYL ACETATE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
9A
S
326
10/13/78
(271)
230
(340)
286
(324)
629
(348)
1.15
9B
S
455
10/13/78
(428)
230
(437)
286
(442)
629
(479)
0.60
9C
S
6.84
10/13/78
(5.29)
230
(4.86)
286
(5.02)
630
(5.88)
0.68
90
S
17.2
10/13/78
(12.9)
230
(12.5)
286
(11.8)
630
(12.5)
-0.13
Two Std. Dev.
of % Change/month
1.08
0.21
1.13
0.56
*«*
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-275 on Chromosorb WHP
column at 50 degrees Celsius.
CALIBRATION: Reagent grade 'Methyl acetate" liquid Is used as a standard.
"Glass bulb" technique Is utilized for generation of series of
standards for calibration.
41
-------
10.0 CHLOROFORM STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
% Change/month
IOA
S
520
10/17/78
(529)
161
(515)
256
(514)
553
(531)
0.06
IOB
S
348
10/17/78
(345)
161
(351)
256
(340)
975
(325)
-0.20
IOC
S
8.70
10/17/78
(8.08)
161
(7.39)
256
(7.50)
553
(8.11)
0.14
IOD
S
16.9
10/17/78
(17.6)
161
(16.5)
256
(16.2)
553
(16.5)
-0.29
Two Std. Dev.
of % Change/month
0.31
0.12
0.88
0.51
Al = Aluminum; S = Steel; LS = Low Pressure.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP
column at 50 or 100 degrees Celsius.
CALIBRATION: Reagent grade 'Chloroform" liquid Is used as a standard. "Glass
bulb" technique Is utilized for generation of series of standards for calibration
42
-------
11.0 CARBONYL SULFIOE STABILITY STUDY
Cylinder No. 11A
Cylinder Construction*** S
Manufacturer ppm 251
Concentration
Date 1 1/3/78
ppm (276)
RTI Day 78
Concentration ppm (281)
Day 185
ppm (275)
*
% Change/month -0.09
11B
S
100
11/3/78
(109)
78
(111)
185
(95)
*
-2.13
11C
S
9.96
11/3/78
(9.10)
78
(8.66)
185
(8.23)
*
-1.55
11D
S
7.03
1 1/3/78
(6.81)
78
(6.48)
185
(6.41)
«
-0.92
11E 11F
AL AL
9.54 101
9/18/81 9/18/81
(12.9) (111)
»» «»
Two Std. Dev.
of % Change/month
Cylinder empty.
**
Calculations for % change/month are only done when three or more analyses
are aval(able.
***
A| » Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame photometric detector, Carbopak B column at 50 degrees Celsius or
Chromosll 330 column at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Carbonyl Sulflde" gas Is used as a standard. Dilutions are made In
Teflon* bag for generation of series of standards for calibration.
ANALYTICAL PROBLEMS: Only a Teflon column and Teflon lines should be used. The al r-to-hydrogen
ratio Is critical to the sensitivity of the FPD.
43
-------
12.0 METHYL MERCAPTAN STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
% Change/month
Two Std. Dev.
of % Change/month
I2A
Al
8.03
1/24/79
(5.66)
104
(5.60)
139
(5.65)
985
(5.40)
-0.14
0.04
I2B
Al
10.0
1/24/79
(7.94)
104
(8.10)
139
(7.90)
985
(8.42)
0.18
0.10
I2C
Al
3.55
1/24/79
(3.65)
104
(3.50)
139
(3.56)
985
(3.64)
0.05
0.17
I2D
Al
4.22
1/24/79
(4.23)
104
(4.76)
139
(4.54)
*
2.04
***
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Empty
ANALYTICAL CONDITIONS: Flame photometric detector, Carbopak B column at
50 degrees Celsius or Chromosll 330 column at
60 degrees Celsius.
CALIBRATION: Reagent grade pure "Methyl mercaptan" gas Is used a standard.
Dilutions are made In a Teflon* bag for generation of series
of standards for calibration.
ANALYTICAL PROBLEMS: Only a Teflon column and Teflon lines should be used.
The air-to-hydrogen ratio Is a critical variable.
-------
13.0 HEXANE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI
Concentration Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
% Change/month
I3A
US
1975
2/6/79
(2170)
6
(1982)
337
(2069)
469
(1986)
-0.22
I3B
LS
2973
2/6/79
(3070)
6
(2855)
338
(2946)
469
(3076)
0.16
I3C
Al
30.6
2/6/79
(30.8)
296
(30.1)
337
(30.6)
469
(32.0)
523
(30.0)
835
(30.2)
-0.05
130 13E
Al Al
79.2 80.0
2/6/79 3/25/83
(82.2) (83.2)
296
(81.0)
337
(81.3)
469
(79.8)
835
(80.2)
12.47
(82.7)
-0.01
Two Std. Dev.
of % Change/month
0.69
0.60
0.26
0.09
A| o Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP
column at 60 or 100 degrees Celsius.
CALIBRATION: Reagent grade "Hexane" liquid Is used as a standard. "Glass bulb"
technique Is utilized for making series of standards for calibration.
45
-------
14.0 1,2 OICHLOROETHANE (ETHYLENE DICHLORIDE) STABILITY STUDY
Cyl Inder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
% Change/month
Two Std. Dev.
of % Change/month
I4A
Al
14.4
1/19/79
(14.1)
58
(15.2)
155
(14.9)
811
(14.2)
835
C13.5)
-0.22
0.28
148 I4C
Al Al
9.64 100
1/19/79 1/19/79
(9.20) (96.2)
58 58
(10.8) (103)
155 155
(10.0) (98.2)
811 501
(9.56) (87.3)
835 920
(9.19) (102)
-0.23 -0.01
0.50 0.58
14D
Al
526
1/19/79
(498)
58
(534)
155
(524)
501
(592)
920
(502)
+0.04
0.64
I4E
Al
6.92
4/5/79
(10.0)
30
(9.42)
69
(9.30)
586
(9.14)
811
(9.70)
835
(9.16)
-0.09
0.25
14F
Al
12.5
4/5/79
(15.2)
30
(14.7)
69
(14.3)
811
(14.5)
835
(13.8)
-0.16
0.21
|4G 14H
Al Al
97.9 439
4/5/79 4/5/79
(102) (463)
30 30
(105) (451)
69 69
(99.0) (462)
425 589
(87.3) (432)
844 697
(101) (451)
844
(453)
-0.18 -0.10
0.62 0.16
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame tonlzatlon detector, 10$ OV-101 on Chromosorb WHP column at 100 degrees
Celsius.
CALIBRATION: Reagent grade "1,2 Dlchloroethane" liquid Is used as a standard. "Glass bulb" technique
Is utilized for making series of standards for calibration.
46
-------
15.0 CYCLOHEXANE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
RTI ppm
Concentration
Day
ppm
Day
ppm
% Change/month
ISA
At
99.1
3/19/79
(106)
147
(93.4)
394
(99.0)
926
(102)
0.02
Two Std. Dev. 0.55
of % Change/month
»**
Al = Aluminum; S = Steel; LS = Low Pressure Steel,
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on
Chromosorb WHP column at 100 degrees Celsius.
CALIBRATION: Reagent grade "Cyelohexane" liquid Is used as a standard.
"Glass bulb" technique Is used for making series of standards for call
brat Ion.
47
-------
16.0 METHYL ETHYL KETONE STABILITY STUDY
Cylinder No.
Cylinder Construct 1on"*»
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
I6A
S
43.7
5/23/79
(42.3)
28
(40.0)
58
(39.9)
380
(44.5)
653
(38.7)
-0.08
Two Std. Dev. 0.67
of % Change/month
»**
A| = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Chromosorb 101
column at 180 degrees Celsius.
CALIBRATION: Reagent grade "Methyl ethyl ketone" liquid Is used as a
standard. "Glass bulb" technique Is utilized for making series of
standards for calibration.
48
-------
17.0 METHANOL STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
PMl
Day
ppm
Day
ppm
17A
Al
50.0
5/17/79
(58.8)
21
(52.3)
51
(51.1)
196
(55.2)
-1.03
Two Std. Dev. 3.01
of % Change/month
A| «« Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatton detector, Chromosorb 101 column
at 50 degrees Celsius or 0.2$ Carbowax 1500 plus 0.1$ SP-2100 on Carbowax C
at 60 degrees Celsius.
CALIBRATION: Reagent grade "Methanol" Is used as a standard. "Glass
bulb" dilution technique Is utilized for making series of standards for
calIbratlon.
49
-------
18.0 1,2-OICHLOROPROPANE (PROPYLENE DICHLORIDE) STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Two Std. Dev.
of % Change/month
18A
Al
7.07
7/10/79
(6.06)
28
(5.52)
48
(5.94)
497
(6.03)
749
(5.59)
-0.09
0.43
188
Al
14.6
7/10/79
(15.6)
28
(16.4)
48
(15.0)
749
(16.3)
+0.16
0.43
18C
Al
476
7/10/79
(496)
28
(455)
48
(480)
372
(497)
+0.33
0.89
18D
Al
664
7/10/79
(685)
28
(621)
48
(675)
372
(685)
+0.30
1.05
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP
column at 100 degrees Celsius.
CALIBRATION: Reagent grade "1,2-Olchloropropane" liquid Is used as a standard.
"Glass bulb" dilution technique Is utilized for making series of standards for
calI brat Ion.
50
-------
19.0 TRICHLOROETHYLENE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
% Change/month
19A
A|
9.23
5/24/79
(9.58)
77
(10.2)
92
(9.78)
683
(9.03)
820
(8.91)
-0.37
19B
Al
14.7
5/24/79
(14.3)
77
(15.1)
92
(14.9)
683
(13.6)
820
(13.5)
-0.33
19C
Al
100
5/24/79
(102)
77
(103)
92
(100)
810
(105)
820
(94.6)
-0.08
190
Al
505
5/24/79
(506)
77
(503)
92
(499)
810
(522)
820
(490)
0.02
Two Std. Dev.
of % Change/month
0.23
0.21
0.31
0.19
A) = Aluminum; S = Steel; LS = Low Pressure Steel,
ANALYTICAL CONDITIONS: Flame lontzatlon detector, 10? OV-101 on Chromosorb WHP
column at 100 degrees Celsius.
CALIBRATION: Reagent grade "Trlchloroethylene" liquid Is used as a standard.
"Glass bulb" technique Is used for making series of standards for calibration.
51
-------
20.0 1,1-OICHLOROETHYLENE (VINYLIDENE CHLORIDE) STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
% Change/month
Two Std. Dev.
of % Change/month
20A
Al
9.58
6/1/79
(10.3)
35
(9.90)
62
(10.1)
404
(11.5)
818
(9.0)
-0.25
0.81
208
Al
14.8
6/1/79
(15.6)
35
(15.1)
62
(15.5)
404
(17.1)
818
(14.2)
-0.17
0.63
20C
Al
96.8
6/1/79
(101)
35
(99)
62
(102)
817
(94)
+0.40
0.14
200
Al
490
6/1/79
(524)
35
(510)
62
(505)
404
(498)
-0.26
0.31
Al = Aluminum; S = Steel; LS = Low Pressure Steel,
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10* OV-101 on Chromosorb WHP
column at 100 degrees Celsius or 10* SP-2100 on Supelcoport column at 100 degrees
Celsius.
CALIBRATION: Reagent grade "1,t-Otchloroethylene" pure liquid Is used as a
standard. "Glass bulb" dilution technique Is utilized for making series of
standards for calibration.
52
-------
21.0 1,2-OIBROMOETHYLENE (ETHYLENE DIBROMIDE) STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
Two Std. Dev.
of % Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
2IA
LS
10.0
6/18/79
(7.90)
61
(7.80)
89
(7.40)
722
(7.72)
-1.90*
0.35
21B
LS
14.9
6/18/79
(12.2)
61
(12.0)
89
(11.6)
772
(8.02)
-1.53*
0.10
2 1C
LS
99.9
6/1/79
(110)
61
(107)
89
(105)
787
(99.2)
-1.52*
0.17
210
LS
301
6/18/79
(265)
61
(266)
89
(257)
643
(309)
-0.83*
0.29
% change/month Is calculated for only the first three analyses and are approximate
because of change In calculation procedure as described below In the analytical
problems.
*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame tonlzatlon detector, 10< OV-101 on Chromosorb WHP column
at 100 degrees Celsius.
CALIBRATION: Reagent grade "1,2-Olbrotnoethylene" pure liquid Is used as a standard.
"Glass bulb" dilution techniques Is utilized for making series of standards for calibra-
tion.
ANALYTICAL PROBLEMS: The gas mixtures and the calibration standards contain substantial
amounts of both the els and the trans Isomers of 1,2-0Ibromoethylene. The first three
sets of analyses are questionable because only one tsomer was measured during the cali-
brations and cylinder analyses.
53
-------
22.0 PERCHLOROETHYLENE STABILITY STUDY
Cylinder No. 22A 22B 22C
Cyl Inder Construction*** S S LS
Manufacturer ppm 7.98 13.0 487
Concentration
Date 7/6/79 7/6/79 7/6/79
ppm (8.40) (15.0) (419)
RTI Day 35 35 35
Concentration ppm (7.97) (14.9) (453)
Day 52 52 52
ppm (7.92) (14.7) (440)
Day 376 376 677
ppm (7.94) (14.5) (361)
713
(387)
% Change/month -0.22 -0.23 -0.63
22D
LS
629
7/6/79
(624)
35
(642)
52
(619)
677
(542)
713
(571)
-0.51
Two Std. Dev.
of I Change/month
0.61
0.17
0.37
0.22
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10* OV-I01 on Chromosorb WHP
column at 50 or 100 degrees Celsius.
CALIBRATION: Reagent grade "Perchloroethy lene" liquid Is used as a standard.
"Glass bulb" dilution technique Is utilized for making series of standards for
cal I brat Ion.
54
-------
23.0 VINYL CHLORIDE STABILITY STUDY
Cylinder No. 23A 23B 23C 23D 23E 23F 236 23H 231
Cylinder Construction*** S S S S SSSSS
Manufacturer ppm 5.94 8.00 8.03 8.52 20.0 20.1 30.0 30.3 7.98
Concentration
RTI Date 10/1/79 10/1/79 10/1/79 10/1/79 10/1/79 10/1/79 10/1/79 10/1/79 10/1/79
Concentration ppm (5.87) (7.71) (7.82) (7.85) (19.7) (20.1) (29.6) (29.8) (7.31)
18 19 18 18 18 18 18 18 18
(5.74) (7.50) (7.45) (7.61) (19.1) (19.3) (28.3) (28.7) (7.12)
700 700 700 700 700 700 700 700
(6.60) (8.44) (8.41) (20.7) (20.9) (20.4) (29.4) (8.39)
* Change/month 0.59 "* 0.45 0.38 0.29 0.25 0.21 0.01 0.71
Calculations for % change/month are only done when three or more analyses are available.
*•«
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame Ion 1 ration detector, 0.4$ Carbowax 1500 on Carbopak C at 50 degrees Celsius.
CALIBRATION: VJnyl chloride permeation tube purchased from Metronlcs Is used for calibration. Permeation
tube Is maintained at 30 °C.
55
-------
24.0 1,3 BUTADIENE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Date
ppm
Day
ppm
24A
S
22.6
3/21/80
(20.9)
95
(23.1)
480
(24.0)
"+0.73
*»«
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame Ion!ration detector, 0.1$ SP-IOOO on
Carbopak C column at 90 degrees Celsius or 10$ OV-101 on Chromosorb WHP
column at 60 degrees Celsius.
CALIBRATION: Reagent grade "1,3 Butadiene" liquid Is used as a stan-
dard. "Glass bulb" dilution technique Is utilized for making series of
standards for calibration.
5G
-------
25.0 ACRYLONITRILE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer ppm
Concentration
Date
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
% Change/month
25A
LS
20.1
7/24/79
(14.6)
185
(12.7)
349
(13.2)
841
(9.96)
-1.07
258
LS
348
7/24/79
(411)
165
(416)
349
(441)
641
(397)
-0.14
25C
LS
11.7
7/24/79
(6.38)
185
(3.35)
349
(2.87)
841
(4.05)
-1.12
250
LS
638
7/24/79
(678)
185
(699)
349
(703)
841
(667)
-0.10
25E 25F
AL AL
-
1 1/8/82 11/18/82
(413) (tO.8)
134 139
(410) (15.7)
Two Std. Oev.
of I Change/month
0.46 0.47 3.49 0.26
A| = Aluminum; S = Steel; LS= Low Pressure Steel
ANALYTICAL CONDITIONS: Flame tonlzatlon detector, 4J Carbowax 20M on Carbopak B at 50
or 150 degrees Celsius.
CALIBRATION: Aerylonltrl le permeation tube Is used for GC-FID calibration. Permeation
tube Is maintained at 30*^0.1°C.
ANALYTICAL PROBLEMS: The large changes noted at the low concentration levels are, at
least In part, a result of difficulty In making precise measurements at these levels.
57
-------
26.0 ANILINE STABILITY STUDY
Cylinder No. 26A 26B
Cylinder Construct1on»»« Al Al
Manufacturer ppm 11.3 18.4
RTI See Analytical Problems
Analysis
AI = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on
Chromosorb WHP column at 250 degrees Celsius.
CALIBRATION: Reagent grade "Aniline" pure liquid Is used as a
standard. "Glass bulb" dilution technique Is utilized for making
series of standards for calibration.
ANALYTICAL PROBLEMS: Because aniline has an extremely high boiling
point (186*0, special handling would be required to measure this
compound. A completely heated system for sampling In the vapor phase
and for preparing standards would be required. Temperature-dependent
condensation In the cylinder and the regulator causes the amount of
aniline which Is delivered by the cylinder to vary. 'As a result,
aniline Is not considered to be practical as an audit material.
58
-------
27.0 METHYL ISOBUTYL KETONE STABILITY STUDY
Cylinder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
27A
A|
9.51
12/18/80
(10.2)
27
(10.6)
83
(9.53)
202
(9.49)
-1.40
27C
Al
72.9
7/8/81
(75.4)
See Analytical
Problems
»»
Two Std. Dev.
of % Change/month
1.58
Calculations for % change/month are only done when three or more
analyses are available.
«**
Al - Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 0.1$ SP-1000 on
Carbopak C column at 180° degrees Celsius.
CALIBRATION: Reagent grade "Methyl Isobutyl ketone" liquid Is used
as a standard. "Glass bulb" technique Is utilized for making
series of standards for calibration.
ANALYTICAL PROBLEMS: Methyl Isobutyl ketone at high concentra-
t rat Ions Is not practical as an audit material because pressurlza-
tlon of the cylinder above approximately 200 psl results In conden-
sation of the analyte.
59
-------
28.0 CYCLOHEXANONE STABILITY STUDY
Cyl Inder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Analysis
ppm
Date
ppm
Day
ppm
28A
A|
10.1
12/11/80
(8.19)
85
(3.26)
288
Al
19.0
12/11/80
(25.5)
85
(17.1)
% Change/month
**
Calculations for % change/month are only done when three or more
analyses are available.
**•
Al = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10* SP-1000 on Supelco-
port column at 200 degrees Celsius.
CALIBRATION: Reagent grade "Cyclohexanone" liquid Is used as a standard.
"Glass bulb" technique Is used for making series of standards for
calibration.
ANALYTICAL PROBLEMS: The analysis of cyclohexanone gas Is dependent on
the temperatures of the cylinder and the regulator and on the length of the
sampling line between the regulator and the gas chromatograph. The concen-
tration In the cylinder decreases with time. Therefore, cyclohexanone Is
not practical as an audit material.
60
-------
29.0 PARADICHLOROBENZENE STABILITY STUDY
Cylinder No. 29A 293
Cylinder Construction*** S S
Manufacturer ppm 15.6 38.1
Concentration
RTI See Analytical Problems
Analysis
««*
A| • Aluminum; S = Steel; LS - Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ SP-I000 on
Supelcoport column at 200 degrees Celsius.
CALIBRATION: Reagent grade "Paradlchlorobenzene" Is used as a
standard. "Glass bulb" technique Is used for making series of
standards for cal I brat Ion.
ANALYTICAL PROBLEMS: The stability study for this compound was
terminated because of analytical difficulties and because the cylinder
pressure was less than 200 pslg. Paradlchlorobenzene Is a solid at
room temperature with a melting point of 54'C. Condensation In the
cylinder, regulator and sampling lines was extreme. Paradlchloro-
benzene Is not practical as an audit material.
61
-------
30.0 ETHYLAMINE STABILITY STUDY
Cylinder No. 30A 308
CyUnder Construction*** S S
Manufacturer ppm 10 20
Concentration
RTI
Analysis See Analytical Problems
***
Al = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame I on 1 ration detector, 10* OV-101
Chromosorb WHP column at 250 degrees Celsius.
CALIBRATION: Reagent grade "Ethylamlne" liquid Is used as a
standard. "Glass bulb" technique Is utilized for making series
of standards for calibration.
ANALYTICAL PROBLEMS: Because of vapor pressure considerations,
the cylinders could not be fully pressurized. The pressure In
the cylinder Is less than 200 psl. A completely heated system
for sampling In the vapor phase and for preparing standards would
be required. Temperature-dependent condensation In the cylinder
and the regulator causes the amount of ethylamtne which Is de-
livered by the cylinder to vary. As a result of these problems,
ethyl am Ine Is not considered to be practical as an audit mater-
ial.
62
-------
31.0 FORMALDEHYDE STABILITY STUDY
RTI
Requested ppm 10 20
Concentration
The speciality gas supplier Indicated that they could not
make gas mixtures containing formaldehyde.
63
-------
32.0 METHYLENE CHLORIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
32A
Al
10.2
3/5/82
(10.8)
31
(10.8)
70
(10.6)
96
(11.2)
124
(11.4)
160
(10.9)
277
(10.2)
278
(10.2)
278
(9.8)
381
(9.7)
-0.94
Two Std. Dev.
of % Change/Month 0.53
Al - Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame Ion 1 ration detector, 20 ft. x 1/8" SS column packed
with 10* SP-tOOO on 80/100 Supelcoport. 30 cnrVmtnute He carrier gas. Column
temp. = 100"C. Detector temp. = 175"C.
CALIBRATION: Reagent grade "Methylene chloride" liquid Is used as a standard.
"Glass bulb" technique Is utilized for making series of standards for
calIbratlon.
64
-------
33.0 CARBON TETRACHLORIDE STABILITY STUDY
Cy Under No.
Cylinder Construction*
Manufacturer ppm
Concentration
RTI Date
Concentration ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
% Change/Month
33A
AL
11.3
3/4/82
(12.7)
74
(11.7)
74
(10.2)
98
(11.1)
124
(10.6)
161
(10.2)
279
(9.3)
279
(9.4)
382
(10.5)
-1.57
Two Std. Dev. of
% Change/Month 1.21
*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lontzatlon detector, 20 ft. x 1/8" SS column packed
with 10$ SP-1000 on 80/1000 Supelcoport. 30 cm3/m1nute He carrier gas. Column
temp. = 100°C. Detector temp. = 175"C.
CALIBRATION: Reagent grade "Carbon tetrachlorlde" liquid Is used as a standard.
"Glass bulb" dilution technique Is utilized for making series of standards for
calibration.
65
-------
34.0 FREON 113 STABILITY STUDY
Cylinder No.
Cylinder Construct lon»
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
34A
Al
10.4
3/3/82
(10.8)
34
(10.1)
70
(10.0)
70
(9.6)
98
(10.0)
125
(10.0)
162
(10.3)
384
(9.8)
-0.37
Two Std. Dev. of
% Change/Month 0.66
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flams lonlzatlon detector, 20 ft. x 1/8" SS column
packed with 10? SP-1000 on 80/100 Supelcoport. 30 cnrVmlnute He carrier
gas. Column temp. = 100*C. Detector temp. - 175°C.
CALIBRATION: Reagent grade "Freon 113" liquid Is used as a standard.
"Glass bulb" dilution technique Is utilized for making series of standards
for calibration.
G6
-------
35.0 METHYL CHLOROFORM STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/Month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
35A
Al
10.2
3/2/82
(10.3)
70
(11.8)
99
(10.7)
136
(10.6)
161
(10.0)
381
(10.4)
-0.35
Two Std. Oev. of
% Change/Month 1.28
*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 20 ft. x
1/8" SS column packed with 102 SP-1000 on 80/100 Supeleoport.
30 cm /minute He carrier gas. Column temp. = 100*C.
Detector temp. = 175°C.
CALIBRATION: Reagent grade "Methyl chloroform" Is used as a
standard. "Glass bulb" dilution technique Is utilized for
making series of standards for calibration.
67
-------
36.0 ETHYLENE OXIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
36A
Al
10.0
3/12/82
(11.2)
73
(9.60)
88
(9.80)
157
(9.8)
122
(9.6)
-2.54
Two Std. Dev. of
% Change/Month 2.24
AI " Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 6 ft. x
1/8" SS column packed with 80/100 mesh Porapak OS. 30 cm3/
minute Helium carrier gas. Column temp. » 150"C. Detector
temp. = 175"C.
CALIBRATION: Ethylene oxide permeation tube purchased from
Metronlcs Is used for GC-FID calibration.
Permeation tube Is maintained at 30*C.
ANALYTICAL PROBLEMS: There appeared to be some loss of
ethylene oxide when a brass regulator was used on the cylinder.
68
-------
37.0 PROPYLENE OXIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/Month
ppm
Date
ppm
Date
ppm
Date
ppm
Date
ppm
37A 37B
Al Al
9.48 96.0
8/4/82 8/4/82
(12.3) (89.5)
55 55
(11.8) (86.9)
76 76
(10.6) (83.6)
121
(90.8)
0.09
Two Std. Dev.
of % Change/Month 3.06
*
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 6 ft. X
1/8" SS column packed with 80/100 mesh Porapak QS. 30
cmVmln Helium carrier gas. Column temp. » 150°C. Detector
temp. = 175°C.
CALIBRATION: Reagent grade "propylene oxide" Is used as a
standard. "Glass bulb" dilution technique Is utilized for
making series of standards for calibration.
69
-------
38.0 ALLYL CHLORIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/Month
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
38A
S
10.2
8/13/82**
(11.6)
75
(5.25)
110
(5.08)
167
(5.36)
40.92
368
S
99.5
8/13/82"
(124)
74
(87.2)
110
(87.7)
167
(83.4)
-1.45
Two Std. Dev. of
% Change/Month 3.10 1.58
AI « Aluminum; S =• Steel; LS = Low Pressure Steel.
««
Initial analysis was discarded.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector. 20 ft. X
1/8" SS column packed with 10 % SP-1000 Supelcoport. 30
cm3/m1nute Helium carrier gas. Column temp. = 100*C.
Detector temp. = 175*C,
CALIBRATION: Reagent grade "Ally! chloride" Is used as a
standard. "Glass bulb" dilution technique Is utilized for
making series of standards for calibration.
70
-------
39.0 ACROLEIN STABILITY STUDY
Cylinder No.
Cylinder Construction*
Requested ppm
Concentration
RTI Date
Concentration ppm
Day
ppm
Day
ppm
% Change/Month
39A
Al
10.2
8/18/82
(10.6)
28
(M.O)
69
(9.74)
-3.80
393
Al
107
8/18/82
(90.4)
28
(103)
69
(106)
6.94
Two Std. Dev. of
% Change/Month
6.82
6.70
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector. 20 ft. X 1/8"
SS column packed with 10 % SP-1000 on 80/100 Supelcoport. 30 cmVmln
Helium carrier gas. Column temp = 100'C. Detector temp. = 175°C.
CALIBRATION: Reagent grade "acroleln" Is used as a standard.
"Glass bulb" dilution technique Is utilized for making series
of standards for calibration.
71
-------
40.0 CHLOROBENZENE STABILITY STUDY
Cylinder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
% Change/Month
ppm
Date
ppm
Day
ppm
Day
ppm
40A
A|
9.66
8/6/82
(9.03)
39
(9.15)
75
(9.20)
0.76
Two Std. Dev. of
% Change/Month 0.32
*
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame Ion 1 ration detection, 20' X
1/8" stainless steel column packed with 102 SP-1000 on
80/100 mesh Supelcoport. 30 cc/mtn Helium carrier gas.
Column temp. = 150°C. Detector temp = 175°C.
CALIBRATION: Reagent grade chlorobenzene was used as a
standard. "Glass bulb" dilution technique Is utilized for
making a series of standards.
72
-------
41.0 CARBON DISULFIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
41A
Al
Manufacturer
Concentration
ppm
108
RTI
Concentration
Date
ppm
Day
ppm
Day
ppm
7/14/82
(100)
34
(114)
72
(116)
% Change/Month
6.42
Two Std. Oev. of
% Change/Month
6.06
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame photometric detector, 4.6' X 1/4"
Teflon* column packed with Carbopak BHT 100. 90 cc/mln Helium
carrier gas. Column temp. » 75*C. Detector temp. = 175°C.
CALIBRATION: Reagent grade carbon dlsulflde Is Injected Into a
Teflon* bag being filled with N2 at 5 L/mln. through a mass
flow controller. The Injection fitting Is heated slightly to
ensure volatilization.
ANALYTICAL PROBLEMS: There Is significant peak "tailing"
unless a very high flow rate Is used. 'Tailing" Is also caused
by "bleed" from the sample loop. Sample valve should be In the
Inject position for exactly 5 seconds and then switched back to
the sampling position to attenuate tailing.
All sample lines and regulators must be conditioned
extensively.
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42.0 EPA METHOD 25 GAS MIXTURE*
Cylinder No. 42A 42B 42C 420 42E 42F
Cylinder Construct Ion™ Al Al Al Al Al Al
Manufacturer ppm 100 100 200 750 1000 2000
Concentration
RTI Date 3/16/83 3/16/83 3/16/83 3/16/83 3/16/83 3/16/83
Concentration ppnC 102 107 205 775 1043 1944
Gas Mixture contains an aliphatic, an aromatic and carbon dioxide In
n1trogen.
*«
AI = Aluminum; S = Steel; LS = Low Pressure Steel
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ATTACHMENT 2
SAMPLE CALCULATIONS OF % CHANGE/MONTH
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ATTACHMENT 2
Sample Calculations of % Change/Month
Example: (Data shown for benzene cylinder.)
Data:
Date of Analysis
2/8/78
4/13/78
9/1/78
10/2/78
4/17/79
Concentration, ppm
101
102
98
101
105
1) Linear Regression, X and Y Data Points, Slope
X values correspond to the dates of analyses, with the first date
being day 1 (2/8/78). The second X value is equal to the number of
calendar days (i.e., 65) between the first analysis date and the
second analysis date (4/13/78) and so on. The Y values are the
concentrations (ppm) that were determined on the respective
analysis dates.
1
65
206
237
434
101
102
98
101
105
Perform the regression analysis and determine the slope of the line
utilizing commercially-available hand calculators or by the
following formula:
m =
0.0071
Standard deviation of slope
(N-2) E (X.-XT
1/2
0.0076
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m = slope of. regression line
X. = x-coordinate of an individual value
Y. = y-coordinate of an individual value
X" = average of all x.
? - average of all Yi
N = number of analyses
2) Percent change/month
% change/month = m (s^°Pe) x 100 x 30 days
where
Therefore,
b = y intercept - (Y - bX) - 100.06
% change/month = °'0071 x 100 x 30 = 0.21
100.06
3) Standard deviation of percent change/month
Standard deviation in units = Standard deviation of slope X 100 X 30 = 0.2270
of % change/month Intercept
95% Confidence interval = 0.21 + 2 X 0.2270 = (-0.255, 0.664)
for % change/month
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