& EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA-454/R-99-031
September 1999
Air
FTIR EMISSIONS TEST AT AN IRON
FOUNDRY
GM Powertrain Group, General Motors
Corporation
Saginaw Metal Casting Operations
Saginaw, Michigan
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11
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PREFACE
This draft report was prepared by Midwest Research Institute (MRI) for the U. S.
Environmental Protection Agency (EPA) under EPA Contract No. 68-D-98-027, Work
Assignment No. 2-13. Mr. Michael Ciolek is the EPA Work Assignment Manager (WAM).
Dr. Thomas Geyer is the MRI Work Assignment Leader (WAL). The field test was performed
under EPA Contract No. 68-D2-0165, Work Assignment No. 4-25 and a draft report was
submitted under EPA Contract No. 68-W6-0048, Work Assignment No. 2-08. Mr. Michael
Ciolek was the EPA WAM for the Emission Measurement Center (EMC) under Work
Assignment 4-25 and Mr. Michael Toney was the WAM under Work Assignment No. 2-08.
Mr. John Hosenfeld was the MRI WAL under Work Assignment 2-08 and Dr. Thomas Geyer
was the MRI task leader for Work Assignment 2-08, task 08.
This report presents the procedures, schedule, and test results for an emissions test
performed at GM Powertrain Group Saginaw Metal Casting Operations (GM/SMCO), a metal
casting facility in Saginaw, Michigan. The emissions test used Fourier transform infrared (FTIR)
sampling procedures to measure HAPs and other pollutants.
This report consists of one volume (381 pages) with seven sections and four appendices.
Midwest Research Institute
John Hosenfeld
Program Manager
Approved:
Jeff Shular
Director, Environmental Engineering Division
September 30, 1999
in
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IV
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TABLE OF CONTENTS
1.0 INTRODUCTION 1-1
1.1 BACKGROUND 1-1
1.2 PROJECT SUMMARY 1-1
1.3 PROJECT PERSONNEL 1-9
2.0 PROCESS AND CONTROL EQUIPMENT OPERATION 2-1
2.1 INTRODUCTION 2-1
2.2 PROCESS DESCRIPTION 2-1
2.2.1 Iron Melting in Cupolas 2-1
2.2.2 Pouring, Cooling and Shakeout 2-4
2.3 PROCESS AND CONTROL DEVICE MONITORING RESULTS 2-9
2.3.1 Cupola B 2-9
2.3.2 Mold Line 4 2-14
3.0 TEST LOCATIONS AND GAS COMPOSITION 3-1
3.1 VENTURI SCRUBBER OUTLET - STACK 3-1
3.2 VENTURI SCRUBBER INLET DUCT 3-1
3.3 MOLD POURING DUCT 3-1
3.4 MOLD COOLING LINE 3-1
3.5 MOLD SHAKE-OUT HOUSING 3-2
3.6 VOLUMETRIC FLOW 3-6
4.0 RESULTS 4-1
4.1 TEST SCHEDULE 4-1
4.2 FIELD TEST PROBLEMS AND CHANGES 4-1
4.3 FTIR RESULTS 4-2
4.3.1 Tedlar Bag Samples 4-2
4.3.2 Scrubber Inlet and Outlet 4-5
4.4 ANALYTE SPIKE RESULTS 4-5
5.0 TEST PROCEDURES 5-1
5.1 EXTRACTIVE SAMPLING SYSTEM 5-1
5.1.1 Sample System Components 5-1
5.1.2 Sample Gas Stream Flow 5-2
5.2 TEDLAR® GAS BAG SAMPLING 5-4
5.3 FTIR SAMPLING PROCEDURES 5-4
5.3.1 Batch Samples 5-4
5.3.2 Continuous Sampling 5-5
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TABLE OF CONTENTS (CONTINUED)
Page
5.4 ANALYTE SPIKING 5.5
5.4.1 Analyte Spiking Procedures 5-6
5.4.2 Analysis of Spiked Results 5-6
5.4.2.1 Determination of Formaldehyde Standard 5-6
5.4.2.2 Determination of Concentrations in Spike Mixtures 5-7
5.4.2.3 Determination of Percent Recovery 5-9
5.5 ANALYTICAL PROCEDURES 5-10
5.5.1 Program Input 5-11
5.5.2 EPA Reference Spectra 5-14
5.6 FTIR SYSTEM 5-14
6.0 SUMMARY OF QA/QC PROCEDURES 6-1
6.1 SAMPLING AND TEST CONDITIONS 6-1
6.2 FTIR SPECTRA 6-2
7.0 REFERENCES 7-1
APPENDIX A. FIELD DATA
APPENDIX B. FTIR DATA
APPENDIX C. CALIBRATION GAS CERTIFICATIONS
APPENDIX D. TEST METHODS
LIST OF FIGURES
Page
Figure 2-1. Schematic of the cupola gas handling system 2-3
Figure 2-2. Schematic of capture and control systems for Line 4 2-5
Figure 2-3. Hot blast temperature during each test run 2-12
Figure 2-4. Hot blast rate during the test runs 2-13
Figure 3-1. Schematic of GM Saginaw cupola gas handling system sampling
points A and B 3-3
Figure 3-2. Schematic of scrubber inlet and scrubber outlet; sampling points A and B 3-4
Figure 3-3. Pouring, cooling, and shake-out sampling points 3-5
Figure 4-1. Sample spectrum from the cooling process plotted with
a methanol reference spectrum 4-3
Figure 4-2. Sample spectrum from the cooling process plotted with a methanol reference
spectrum shown in a different frequency region 4-3
Figure 4-3. Sample spectrum from the cooling process plotted with toluene and hexane
reference spectra 4-3
Figure 5-1. Sampling system schematic 5-3
VI
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TABLE OF CONTENTS (CONTINUED)
LIST OF TABLES
TABLE 1-1. SUMMARY OF FTIR RESULTS FROM THE MOLD
POURING PROCESS 1-3
TABLE 1-2. SUMMARY OF FTIR RESULTS FROM THE MOLD
COOLING PROCESS 1-4
TABLE 1-3. SUMMARY OF FTIR RESULTS FROM THE SHAKEOUT HOUSING
PROCESS 1-6
TABLE 1-4. SUMMARY OF FTIR RESULTS (ppm) AT THE VENTURI
SCRUBBER INLET AND OUTLET 1-8
TABLE 1-5 PROJECT PERSONNEL 1-9
TABLE 2-1. TYPICAL CUPOLA CHARGE MATERIALS 2-2
TABLE 2-2. TYPICAL RESULTS FROM GREEN SAND ANALYSIS 2-5
TABLE 2-3. CHEMICALS USED IN CORE MAKING AND MOLD SPRAYING 2-8
TABLE 2-4. SUMMARY OF CUPOLA MONITORING RESULTS 2-10
TABLE 2-5. SUMMARY OF CUPOLA CHARGING DURING THE TEST DAYS 2-11
TABLE 2-6. SUMMARY OF NUMBER OF MOLDS POURED ON LINE 4 2-15
TABLE 2-7. SUMMARY OF METAL POURED AND DOWNTIME FOR LINE 4 2-16
TABLE 2-8. LINE 4 MOLD COUNTS DURING TESTING PERIODS 2-17
TABLE 2-9. MOLD LINE 4 PRODUCTION DURING TESTING PERIODS : 2-19
TABLE 3-1. CUPOLA GAS COMPOSITIONS AND FLOW SUMMARY 3-6
TABLE 3-2. MOLD POURING, COOLING, AND SHAKE-OUT HOUSING GAS
COMPOSITION AND FLOW SUMMARY 3-7
TABLE 4-1. TEST SCHEDULE AT GM POWERTRAIN,SAGINAW, MICHIGAN 4-1
TABLE 4-2. SUMMARY OF FORMALDEHYDE SPIKE RESULTS AT THE
SCRUBBER INLET 4-7
TABLE 4-3. SUMMARY OF TOLUENE SPIKE RESULTS AT THE
SCRUBBER INLET 4-8
TABLE 4-4. SUMMARY OF FORMALDEHYDE SPIKE RESULTS AT THE
SCRUBBER OUTLET 4-9
TABLE 4-5. SUMMARY OF TOLUENE SPIKE RESULTS AT THE
SCRUBBER OUTLET 4-10
TABLE 4-6. COMPARISON OF EPA TOLUENE REFERENCE SPECTRA
TO SPECTRA OF TOLUENE CYLINDER STANDARD 4-10
TABLE 5-1. DETERMINATION OF FORMALDEHYDE STANDARD
CONCENTRATION 5-7
TABLE 5-2. CALCULATED CONCENTRATIONS IN MIXTURES USED
FOR ANALYTE SPIKING AT THE SCRUBBER INLET 5-8
TABLE 5-3. CALCULATED CONCENTRATIONS IN MIXTURES USED FOR
ANALYTE SPIKING AT THE SCRUBBER OUTLET 5-8
TABLE 5-4. PROGRAM INPUT FOR ANALYSIS OF SAMPLE SPECTRA FROM
POURING AND COOLING AND SHAKE-OUT HOUSING 5-12
vii
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TABLE OF CONTENTS (CONTINUED)
TABLE 5-5. PROGRAM INPUT FOR ANALYSIS OF SAMPLE SPECTRA
FROM SCRUBBER INLET AND OUTLET 5-13
TABLE 5-6. PROGRAM INPUT FOR ANALYSIS OF CTS SPECTRA AND
PATH LENGTH DETERMINATION 5-13
TABLE 5-7. RESULTS OF PATH LENGTH DETERMINATION 5-14
vm
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FTIR EMISSIONS TEST AT AN IRON FOUNDRY
GM Powertrain Group, General Motors Corporation
Saginaw Metal Casting Operations
Saginaw, Michigan
Prepared for
Office of Air Quality Planning and Standards
Emissions, Monitoring and Analysis Division
Emission Measurement Center (MD-19)
Research Triangle Park, North Carolina 27711
Mr. Michael Ciolek
Work Assignment Manager
EPA Contract No. 68-D-98-027
Work Assignment 2-13
MRI Project No. 104951-1-013-04
September, 1999
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1.0 INTRODUCTION
1.1 BACKGROUND
The Emission Measurement Center (EMC) of the U. S. Environmental Protection Agency
(EPA) received a request from the Metals Group of the Emission Standards Division (BSD) and
Source Characterization Group of the Emission Monitoring and Analysis Division (EMAD), both
in the Office of Air Quality Planning and Standards (OAQPS), U. S. EPA, to perform emissions
testing at iron foundries, specifically on cupola emission control devices, and pouring, cooling,
and shake-out operations. The test program was performed in September, 1997 under EPA
Contract No. 68-D2-0165, Work Assignment 4-25. This draft report for testing conducted at the
GM Powertrain Group Saginaw Metal Casting Operations (GM/SMCO) facility was prepared
under EPA Contract No. 68-W6-0048, Work Assignment 2-08.
1.2 PROJECT SUMMARY
The cupola melting process is used to melt iron for casting into automotive parts. It is
potentially a significant source of hazardous air pollutant (HAP) emissions, including metal and
organic compounds. Emissions from the mold pouring, cooling, and shake-out are also potential
sources of HAP emissions.
The principal emission point at a cupola furnace is the exhaust from the furnace itself.
Emission controls for GM/SMCO include a coarse grain separator, afterburner, drop out
chamber, heat exchangers (recuperators), quench, venturi scrubber, and stack. Cupola emissions
testing was conducted at the stack (scrubber outlet) and the inlet to the scrubber to determine the
measurable emissions released during the melting process. Testing was also conducted at the
ducts drawing from the pouring, cooling, and shake-out lines to determine the measurable
emissions released during the pouring, cooling, and shake-out of the castings.
Three Fourier transform infrared (FTIR) test runs were conducted at the cupola inlet and
outlet locations over a three-day period simultaneously with manual method testing conducted by
Pacific Environmental Services (PES). Additionally, Midwest Research Institute (MRI)
collected Tedlar bag samples from pouring, cooling, and shake-out ducts. The Tedlar bag
samples were analyzed by FTIR. Summaries of the FTIR results are presented in Tables 1-1
to 1-4.
1-1
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The FTIR analyses followed EPA Method 3201, which employs an extractive sampling
procedure. A probe, pump, and heated line are used to transport samples from the source to a gas
manifold in a trailer that contains the FTIR equipment. A separate procedure for collecting and
analyzing the Tedlar bag samples was prepared by MRI and approved by EPA prior to the field
test. A preliminary analysis of the spectra was performed onsite. The analysis was reviewed and
revised after the FTIR data collection was completed. A compact disk containing all of the FTIR
data was provided with the draft report.
The results at the mold cooling, pouring and shakeout housing processes have been
revised since the draft report. The revised results are from analyses that included reference
spectra of additional aliphatic organic compounds. The additional reference spectra were
measured in the laboratory under work assignments 2-12 and 2-13. The revised analyses are
discussed in Section 4.3.1. Appendix B contains documentation of the reference spectra
prepared for the revised analysis.
1-2
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TABLE 1-1. SUMMARY OF FTIR RESULTS FROM THE MOLD POURING PROCESSa
Mold Pouring (ppm)
File name Date Time
POUR 101 9/23/97 11:07
POUR 102 9/23/97 11:25
Emission Rate
Average ppm
Ib/hr
kg/hr
Methanol Unc.
0.0 0.4
0.0 0.4
0.0 0.4
0.0
0.0
Toluene Unc.
0.0 0.9
2.3 0.6
1.2 0.8
0.89
0.41
Hexane Unc.
0.0 5.0
0.0 5.0
0.0 5.0
0.00
0.00
Ethylene Unc.
3.9 0.5
4.0 0.5
3.9 0.5
0.92
0.42
Methane Unc.
38.4 0.4
39.3 0.4
38.8 0.4
5.20
2.36
CO Unc.
87.1 12.8
86.3 12.6
86.7 12.7
20.3
9.2
a
Concentrations are in ppm. A zero concentration indicates a non-detect for that sample. "Unc" indicates an estimated uncertainty in each measurement.
TABLE 1-1. (CONTINUED)
Mold Pouring (p
File name Date Time
POUR101 9/23/97 n:07
POUR 102 9/23/97 ,,.25
Emission Rate
Average ppm
Ib/hr
kg/hr
Formalde-
hyde Unc.
1.0 0.4
1.4 0.4
1.2 0.4
0.30
0.14
pm)
Butane Unc.
3.70 0.24
0 5.49
1.85
0.90
0.41
1-Pentene Unc.
0 2.42
3.93 0.18
1.96
1.15
0.52
a
Concentrations are in ppm. A zero concentration indicates a non-detect for that sample.
"Unc" indicates an estimated uncertainty in each measurement.
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TABLE 1-2. SUMMARY OF FTIR RESULTS FROM THE MOLD COOLING PROCESS3
Mold Cooling (ppm)
Duct File name Date Time
Main COOLM101 9/25/97 14:09
COOLM102 14:13
Average -->
R COOLR101 11:09
COOLR102 11:13
Average — >
S COOLS101 9/24/97 15:32
COOLS102 15:37
Average -->
Emission Rate
Total ppm b
lb/hrc
kg/hrc
Methanol Unc.
1.8 0.7
1.8 0.7
1.8 0.7
2.5 0.8
2.5 0.8
2.5 0.8
4.5 0.7
4.5 0.7
4.5 0.7
8.8 0.7
1.48
0.67
Toluene Unc.
12.8 1.3
12.6 1.3
12.7 1.3
18.9 1.8
18.9 1.8
18.9 1.8
16.6 1.1
16.8 1.1
16.7 1.1
48.3 1.4
20.3
9.22
Hexane Unc.
2.1 0.5
2.2 0.5
2.2 0.5
2.2 0.8
2.2 0.8
2.2 0.8
5.2 0.5
5.1 0.5
5.1 0.5
9.5 0.6
4.47
2.03
Ethylene Unc.
10.2 0.8
10.2 0.8
10.2 0.8
16.8 1.0
16.8 1.0
16.8 1.0
8.2 0.8
8.3 0.8
8.3 0.8
35.2 0.9
4.01
1.82
Methane Unc.
139.7 0.8
139.0 0.8
139.4 0.8
195.0 1.1
195.2 1.1
195.1 1.1
118.3 0.8
119.4 0.8
118.8 0.8
453.2 0.9
30.92
14.04
CO Unc.
192.7 25.1
192.6 25.0
192.7 25.1
243.9 32.9
245.3 33.0
244.6 32.9
137.9 21.8
141.3 22.0
139.6 21.9
576.9 26.6
68.25
31.00
Formalde-
hyde Unc.
1.8 0.7
1.7 0.7
1.7 0.7
2.1 1.0
2.1 1.0
2.1 1.0
2.0 0.7
1.8 0.7
1.9 0.7
5.7 0.8
0.79 .
0.36
a Concentrations are in ppm. A zero concentration indicates a non-detect for that sample. "Unc" indicates an estimated uncertainty in each measurement.
° The total ppm concentration is the sum of the average concentrations in each duct.
c The emission rates for each duct were calculated separately using the flow rates in Table 3-2. The emission rates fo r the three ducts were summed to give the total emission rate.
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TABLE 1-2. (CONTINUED)
Mold Cooling (ppni)
Duct File name Date Time
Main COOLM101 9/25/97 14:09
COOLM102 14:13
Average -->
R COOLR101 11:09
COOLR102 11:13
Average — >
S COOLS101 9/24/97 15:32
COOLS102 15:37
Average — >
Emission Rate
Total ppm b
lb/hrc
kg/hrc
3-Methyl-
pentane Unc.
0.74 0.65
0.75 0.66
0.75 0.65
1.2 0.9
1.2 0.9
1.2 0.9
0 0.6
0 0.6
0 0.6
1.98
0.53
0.24
Butane Unc.
5.7 3.0
5.6 3.0
5.6 3.0
12.3 4.3
12.4 4.3
12.4 4.3
0 2.9
0 3.0
0 3.0
18.0
3.05
1.39
1-Pentene Unc.
7.5 1.8
7.4 1.8
7.5 1.8
8.9 2.6
8.8 2.6
8.9 2.6
13.4 1.1
13.5 1.1
13.5 1.1
29.8
10.59
4.81
Concentrations are in ppm. A zero concentration indicates a non-detect for that sample. "Unc" indicates an estimated uncertainty in each measurement.
The total ppm concentration is the sum of the average concentrations in each duct.
c The emission rates for each duct were calculated separately using the flow rates in Table 3-2. The emission rates for the three ducts were summed to give the total emission rate.
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TABLE 1-3. SUMMARY OF FTIR RESULTS FROM THE SHAKEOUT HOUSING PROCESS3
Shake-out Housing (ppm)
Stack Filename Date Time
3 SHK3J01 9/23/97 11:36
SHK3_201 9/24/97 13:22
SHK3_202 9/24/97 13:25
Average — >
4 SHK4_101 9/23/97 14:55
SHK4_102 9/23/97 15:00
Average — >
5 SHK5_101 9/24/97 13:29
Emission Rate
Total ppm b
lb/hrc
kg/hrc
Methanol Unc.
1.0 0.3
1.2 0.4
1.2 0.4
1.1 0.4
1.4 0.5
1.4 0.5
1.4 0.5
2.1 0.0
4.6 0.4
0.94
0.43
Toluene Unc.
7.0 0.4
4.4 0.5
4.1 0.6
5.2 0.5
9.6 0.5
8.9 0.6
9.3 0.5
4.8 0.0
19.2 0.4
11.5
5.2
Hexane Unc.
0.0 2.9
3.7 0.2
0.0 3.4
1.2 2.2
0.0 4.2
0.0 4.2
0.0 4.2
0.0 0.0
1.2 2.5
0.7
0.3
Ethylene Unc.
0.0 0.3
0.0 0.5
0.0 0.5
0.0 0.5
1.0 0.6
1.0 0.6
1.0 0.6
0.6 0.0
1.6 0.4
0.29
0.13
Methane Unc.
14.5 0.2
17.9 0.3
17.7 0.4
16.7 0.3
20.5 0.3
20.6 0.4
20.6 0.4
20.7 0.0
58.0 0.3
6.0
2.7
CO Unc.
32.9 5.4
61.8 9.4
62.1 9.4
52.3 8.1
66.1 9.3
66.5 9.4
66.3 9.3
75.2 0.0
193.8 7.2
34.8
15.8
Formalde-
hyde Unc.
1.1 0.2
0.8 0.3
1.0 0.3
0.9 0.3
1.6 0.3
1.3 0.3
1.4 0.3
1.2 0.0
3.6 0.2
0.7
0.3
ON a Concentrations are in ppm. A zero concentration indicates a non-detect for that sample. "Unc" indicates an estimated uncertainty in each measurement.
The total ppm concentration is the sum of the average concentrations in each duct.
c The emission rates for each duct were calculated separately using the flow rates in Table 3-2. The emission rates for the three ducts were summed to give the total emission rate.
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TABLE 1-3. (CONTINUED)
Shakeout Housing (ppm)
Stack File name Date Time
3 SHK3_101 9/23/97 11:36
SHK3_201 9/24/97 13:22
SHK3_202 9/24/97 13:25
Average — >
4 SHK4_101 9/23/97 14:55
SHK4_102 9/23/97 15:00
Average -->
5 SHK5_101 9/24/97 13:29
Emission Rate
Total ppm b
lb/hrc
kg/hrc
3-Methyl-
pentane Unc.
0 0.6
0 0.3
0.44 0.3
0.15 0.4
0 0.9
0 0.9
0 0.9
0 0.2
0.15 1.5
0.084
0.038
Butane Unc.
0 0.8
0 0.9
0 1.2
0 1.0
0 1.1
0 1.1
0 1.1
1.7 0.9
1.7 2.9
0.59
0.27
2-Methyl-
1-Pentene Unc.
0 0.8
0.8 0.3
5.4 0.6
2.1 0.6
0 0.9
4.2 0.3
2.1 0.6
1.7 0.5
5.8 1.7
3.17
1.44
n-
Heptane Unc.
2.2 O.I
0 1.4
0 1.5
0.7 1.0
3.2 0.1
2.9 0.2
3.1 0.2
3.3 0.1
7.0 1.3
4.48
2.03
1-Pentene Unc.
4.2 0.3
0 1.6
0 1.7
1.4 1.2
5.5 0.4
0 2.0
2.8 1.2
0 1.6
4.2 4.0
1.93
0.88
2-Methyl-
2-butene Unc.
0.40 0.3
1.01 0.3
2.78 0.3
1.40 0.3
0 1.2
1.25 0.3
0.624 0.8
1.77 0.3
3.79 1.3
1.72
0.782
J, Concentrations are in ppm. A zero concentration indicates a non-detect for that sample. "Unc" indicates an estimated uncertainty in each measurement.
The total ppm concentration is the sum of the average concentrations in each duct.
c The emission rates for each duct were calculated separately using the flow rates in Table 3-2. The emission rates for the three ducts were summed to give the total emission rate.
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TABLE 1-4. SUMMARY OF FTIR RESULTS (ppm) AT THE VENTURI SCRUBBER INLET AND OUTLET
Compound
Methane
Carbon Monoxide
Units
ppm
Ib/hr
kg/hr
ppm
Ib/hr
kg/hr
Run 1
Inlet
52.7
9.9
91.1
29.9
Unc.a
4.6
68.4
Outlet
18.5
3.5
1.6
76.8
25.4
11.5
Unc.
3.7
64.9
Run 2
Inlet
27.0
5.6
2.6
ND
Unc.
7.1
101.8
Outlet
20.5
4.0
1.8
ND
Unc.
5.3
82.08
Run 3
Inlet
25.4
5.0
2.2
ND
Unc.
7.1
103.3
Outlet
11.2
2.0
0.89
0.20
0.06
0.03
Unc.
3.1
61.08
aUnc is the estimated uncertainty (ppm) in the calculated analyte concentration.
oo
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1.3 PROJECT PERSONNEL
The EPA test program was administered by EMC. The Test Request was initiated by the
Metals Group of the BSD and the Source Characterization Group of the EMAD, both in OAQPS.
Some key project personnel are listed in Table 1-5.
TABLE 1-5 PROJECT PERSONNEL
Organization and Title
Coordinator Environmental & Energy
GM Powertrain Group
General Motors Corporation
Saginaw Metal Casting Operations
77 W. Center Street
P.O. Box 5073
Saginaw, MI 48605-5073
Environmental Auditor
GM Powertrain Group
General Motors Corporation
Saginaw Metal Casting Operations
Mail Code 486-629-0 16
1629 N. Washington Avenue
Saginaw, MI 48605
U. S. EPA, EMC
Work Assignment Manager
Work Assignment 4-25
U. S. EPA, EMC
Work Assignment Manager
Work Assignment 2-08
MRI
Work Assignment Leader
Work Assignment 4-25
Work Assignment 2-13
MRI
Program Manager
Work Assignment Leader
Work Assignment 2-08
Name
Steven M. Tomaszewski
David F. Genske
Michael K. Ciolek
Michael L. Toney
Thomas J. Geyer
John Hosenfeld
Phone No.
(5 17) 757-0920 Tel
(5 17) 757-0899 Fax
(5 17) 757-1455 Tel
(517) 757-1652 Fax
(919) 541-4921 '
(919) 541-5247
(919) 851-8181, ext 3120
(8 16) 753-7600, ext 1336
1-9
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2.0 PROCESS AND CONTROL EQUIPMENT OPERATION
The information in Section 2 was prepared by Research Triangle Institute and provided to
MRI by the EMC. It was included in the report without MRI review.
2.1 INTRODUCTION
The GM Powertrain Group, part of the General Motors Corporation, operates a foundry in
Saginaw, Michigan named Saginaw Metal Casting Operations (SMCO), which casts grey iron
and aluminum. This foundry was constructed by GM in 1918 and is currently operating three
cupolas and two green sand lines for casting iron along with a melting furnace and one casting
line for aluminum to produce engine blocks for use in GM automobiles. The plant has about
2,000 employees. This section of the test report provides a description of the cupola operation
for iron melting and the casting operation, including pouring, cooling, and shakeout.
2.2 PROCESS DESCRIPTION
2.2.1 Iron Melting in Cupolas
There are three cupolas in operation ("B", "C", and "D"). Cupolas B and C are very
similar and are configured with an afterburner followed by a venturi scrubber (i.e., they bum
"dirty" gas). Cupola D bums the gas after removal of paniculate matter by the scrubber. Plant
personnel indicated that Cupolas B and C were more representative of the industry and pointed
out that cupolas configured like D are no longer constructed. Consequently, Cupola B was
chosen for testing, primarily because it had more modern and complete controls and
instrumentation.
Cupola B has a diameter of 114 inches (in.) and melts at a rate of about 55 tons per hour
(tph) with a blast rate of 21,000 to 23,000 cfm, which makes it among the larger cupolas in use in
the U.S. The blast is enriched with oxygen at a rate of about 4 percent. Figure 2-1 is a simplified
schematic of the cupola gas handling system and emission control equipment.
The cupola is charged with metal scrap, briquettes made from metal shavings, coke, and
limestone at a point that is above the gas take-off. The composition of a typical charge is given
in Table 2-1 and includes 6 tons of iron. Very few emissions occur from charging because of the
below-charge gas take-off and the maintenance of negative pressure on the cupola. The off gas
from the cupola is removed at about 400° to 500 °F and contains 12 to 14 percent carbon
monoxide (CO). This gas enters a large combustion chamber where the CO is burned at about
2-1
-------
1500° to 1600°F. Some heavy and larger size particles settle out in the combustion chamber and
are removed at that point. The hot exhaust gases from the combustion chamber pass through two
recuperators that are used to pre-heat the cupola's blast air to about 1100°F. There is also a
cooler available for additional temperature control as necessary.
TABLE 2-1. TYPICAL CUPOLA CHARGE MATERIALS
Material
Remelt from foundry
Steel scrap
Gray iron bricks^' c
Silicon bricks
Blend bricks (Si, Mn, Cr)
Silicon carbide
Coke
Limestone
Typical range (lbs/charge)a
4,000 to 6,000
3,000 to 4,000
3,000
70 to 105
260 to 300
300
1,400 to 1,500
500
a Typical range observed during the test days.
k Remelt, steel scrap, and gray iron bricks are the sources of iron and total 12,000 Ibs (6 tons) per charge.
c Gray iron bricks are a pressed material made from borings, shavings, etc.
2-2
-------
Quencher
K)
Off gas
Recuperator
Wet cap
Heated
blast air
Exhaust stack
Solids
removed
•---»
i
Recuperator
Blast air
Cooled gas
Scrubber water
Venturi
scrubber
CUPOLA
..- _ ,
S Combustion CuP°la
' chamber blower
Cleaned
\
O
Solids removed
Scrubber water Exhaustfan
to wastewater treatment
Figure 2-1. Schematic of the cupola gas handling system.
-------
From the recuperators, the gas passes through a quencher, which cools the gas and also
removes some of the entrained particulate matter. The gas then enters a venturi scrubber
(manufactured by Air Pollution Industries) that is operated at a pressure drop of about 40 in. of
water and a water flow rate of about 625 gallons per minute (gal/min). A vacuum is maintained
on the system and the gas is moved by a 1200 horsepower (hp) exhaust fan following the
scrubber. The cleaned gas is exhausted through a stack. The wastewater from the scrubber is
sent to a wastewater treatment recycle system where polymers are added to assist in settling fine
particles, and 99 percent of the water is recycled to the scrubber (with a one percent blowdown to
the city's wastewater treatment facility). Particulate matter emissions from the scrubber are
limited to 0.15 pounds (Ib) per 1,000 Ib of gas by the State.
The plant has instrumentation available to monitor several parameters associated with the
emission control system, including the pressure drop across the scrubber, the water flow rate,
electric current to the fan, and gas temperature. Temperature and blast rate for the cupola are
monitored routinely. In addition, an accurate measure of the melting rate (e.g., for use in
normalizing mass emission rates by production rate) can be obtained from the charging data
sheets.
The plant buys scrap from other GM plants and controls the quality because scrap quality
directly affects the quality of the castings. However, plant personnel pointed out that it would be
difficult to have a parameter to measure scrap quality that could be used to make valid
comparisons among different foundries.
2.2.2 Pouring, Cooling and Shakeout
The two iron pouring lines are labeled Lines 3 and 4. Plant personnel indicated that Line
4 was the best candidate for testing because it is newer and the layout is more amendable to
sampling. A simplified schematic of the capture and control equipment for Line 4 is given in
Figure 2-2. The line has a capacity of 270 molds per hour with two engine blocks per mold.
Each horizontal mold contains 3,300 Ibs of green sand (lake sand, sea coal, and bentonite). The
typical properties that are measured and the range during the test days are given in Table 2-2.
2-4
-------
TABLE 2-2. TYPICAL RESULTS FROM GREEN SAND ANALYSIS3
Property
Moisture (%)
Clay (%)
Compactability (%)
Green strength (psi)
Permeability (AFS units)
Loss on ignition (%)
Range
2.8 to 3.3
6.8 to 7.4
3.6 to 4.8
164 to 221
114 to 130
3. 8 to 5.0
From analyses during the first shift of the test days.
2-5
-------
To atmosphere
(50,000 cf m)
OS
Circular side
draft hood....
From mold
and core —
preparation
To atmosphere
(50,000 cfm)
i A A
Pre-coate
cartridge..
filters--"'
To atmosphere
(150,000 cfm total)
A A A
A A k
Spray
scrubbers
Shakeout
40 x 60 ft enclosure
To finishing
Figure 2-2. Schematic of capture and control systems for Line 4.
-------
The cores used in the molds include both hot box and cold box systems with phenol-
formaldehyde. For the 4-cylinder engine, 15.7 Ibs of hot box cores and 74.5 Ibs of cold box cores
are used for a total core weight of 90.2 Ibs per block or 180.4 Ibs per mold. For the 6-cylinder
engine, 17.9 Ibs of hot box cores and 95.2 Ibs of cold box cores are used for a total core weight of
113 Ibs per block or 226 Ibs per mold. The chemicals used to make the cores are summarized in
Table 2-3. The materials used for core dipping are primarily minerals, such as crystalline silica
(quartz), mica, aluminum silicate, along with graphite, clay and water.
The pouring station for Line 4 is automated and uses 6 ladles in a circular configuration.
A large, circular side draft hood evacuates the entire pouring area at a rate of about 50,000 cfm.
During the testing, no significant visible emissions were observed escaping capture from the
pouring operation. The captured emissions are ducted overhead through the roof to the
atmosphere. During the test days, both 4- and 6-cylinder engine blocks were poured on Line 4.
The pouring weight of iron for the 4-cylinder block is 202.8 Ibs to produce a casting of 116.2 Ibs.
For the 6-cylinder block, the pouring weight is 250.4 Ibs and the casting weight is 149.2 Ibs.
The cooling line is enclosed and has a series of hoods throughout the line that evacuate
the enclosures at a rate of about 50,000 cfm and send the emissions to a bank of pre-coated
cartridge filters to remove paniculate matter. The cooling line is evacuated through three main
ducts that send the cooling emissions to three separate sets of cartridge filters. The residence
time of the cooling line is about 25 minutes (min).
The shakeout operation is totally enclosed in a small, evacuated building (roughly 40 by
60 feet [ft]). The room is evacuated at about 150,000 cfm, and the captured emissions are sent to
three spray scrubbers that have 2 to 3 stages for cleaning.
The plant monitors the pressure drop across the cartridge filters used for the cooling
emissions and also the pressure drop across the shakeout scrubbers. No other parameters
associated with the control equipment are monitored.
2-7
-------
TABLE 2-3. CHEMICALS USED IN CORE MAKING AND MOLD SPRAYING3
Product
Acme45MRlBS®
Acme 745LF®
Acme-flow 2012®
Acme-flow 2052A®
Tribonol®
Function
Hot box catalyst
Phenolic resin for hot box
cores
Phenolic resin for cold box
cores
Isocyanate resin for cold box
Part 2
Mold spray
Chemical
Urea
Ammonium hydroxide
Ammonium nitrate
Water
Ammonium chloride
Siloxanes and silicones
Formaldehyde
Phenol
Formaldehyde
Phenol
Ethyl 3-ethoxypropionate
Heavy aromatic solvent naphtha
Diphenylmethane4,4'-Diisocyanate
Kerosine
Polymeric Diphenylmethane
Diisocyanate
Isocyanic acid, methylenediphenylene
ester
Heavy aromatic solvent naphtha
Zircon
Diethylene glycol polymer with 1-chloro-
2,3-epoxypropane
Percent
30 to 35
0.1 to 1
10 to 15
45 to 50
0.1 to 1
Ito5
Ito5
5 to 10
0.1 to 1
Ito5
5 to 10
10 to 30
10 to 30
5 to 10
30 to 50
Ito5
10 to 30
90
10
a From the manufacturer's material safety data sheets (MSDS).
2-8
-------
2.3 PROCESS AND CONTROL DEVICE MONITORING RESULTS
2.3.1 Cupola B
During each test run, several parameters associated with the operation of the cupola and
the Venturi scrubber were monitored and recorded. For the cupola, these parameters included the
blast air flow rate, the relief stack flow rate, the hot blast temperature, oxygen feed pressure, and
the combustion chamber temperature. In addition, information was obtained on each time the
cupola was charged and the charge composition. Each time period that the blast was stopped
(and the emission testing was also stopped) was also recorded.
The plant had instrumentation installed to monitor several parameters associated with the
Venturi scrubber, including the water flow rate to the scrubber, flow rate of makeup water, inlet
temperature, inlet pressure, pressure drop, and the pressure (vacuum) at the induced draft fan.
These parameters, with the exceptions noted below, were monitored and recorded during the test.
Before the sampling runs were begun, the process observers worked with the plant personnel to
determine if the instruments indicating venturi pressure drop and water flow rate to the scrubber
were showing correct readings. Calibration of the pressure drop instrumentation, completed
early on September 24, consisted of a direct manometer reading at the venturi followed by
adjustment of the pressure drop reading in the control room. Calibration of the water flow rate
reading could not be confirmed during the sampling campaign. After the testing was completed,
plant personnel confirmed that the instrument had been calibrated and that the water flow rate
was 625 gal/min.
Table 2-4 summarizes the major monitoring results for the cupola during each test run,
and Table 2-5 provides the cupola charging data for about 12 hours (hr) during each test day.
The blast air temperature and flow rate are plotted for the four test runs in Figures 2-3 and 2-4.
The blast air rate showed very little variability during the test; however, there were significant
differences in the temperature of the hot air blast, which averaged 464° to 488 °F during Runs 1
and 2 and 364° to 366 °F during Runs 3 and 4.
The pressure drop across the Venturi scrubber increased during each run. At the request
of EPA personnel, adjustments were made after the first test run to increase the scrubber pressure
and to maintain a range closer to the original design specifications. The pressure drop averaged
33,35, 38, and 42 in. of water for Runs 1, 2, 3, and 4 respectively.
2-9
-------
TABLE 2-4. SUMMARY OF CUPOLA MONITORING RESULTS
Parameter
Blast flow rate (cfm)
Hot blast temperature (°F)
Oxygen (psig)
Combustion chamber
temperature (°F)
Melting rate (tons/hr)a
Time blast stopped (min)
Scrubber Ap (in. water)
Run
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
Average
21,400
22,100
21,900
21,800
488
464
366
364
30
49
50
59
Range
21,000-22,200
21,800-22,500
21,700-22,800
21,000-22,400
443 - 539
448 - 488
336-385
327 - 409
30
43-61
40-65
54-65
not available
1,557
1,518
1,608
38.8
41.7
45.4
43.5
156
6
29
15
33.4
35
38
42
1,401 - 1,669
1,276- 1,633
1,495 - 1,670
-
-
-
-
-
-
-
-
33-35
32-37
36-40
40-42
a Adjusted for the downtime when the blast was stopped (i.e., the downtime was subtracted from the operating time
when determining the melting rate).
2-10
-------
TABLE 2-5. SUMMARY OF CUPOLA CHARGING DURING THE TEST DAYS
9/23/97*
Time period
-
-
-
-
--
-
-
--
-
13:58-14:49
15:51-16:19
18:20-19:12
Average rate
(tons/hr)
Tons charged
-
-
-
-
- .
-
-
-
-
48
30
24
38.8
9/24/97
Time period
6:00-7:05
7:13-8:02
8:25-9:14
9:19-10:09
10:14-11:05
11:14-12:05
12:10-13:02
13:20-14:03
14:08-15:12
15:17-16:08
16:21-17:10
17:17-18:18
Average rate
(tons/hr)
Tons charged
54
42
30
42
36
42
42
42
54
42
36
36
40.5
9/25/97
Time period
7:11-8:05
8:11-9:01
9:10-10:07
10:12-11:06
11:10-12:02
12:12-13:03
13:12-14:07
14:18-15:10
15:27-16:02
16:11-17:03
17:12-17:59
18:07-19:10
Average rate
(tons/hr)
Tons charged
42
36
42
42
36
42
42
48
30
42
42
42
40.6
* Run 1 on this day was a short test with 110 min of sampling between 14:10and 18:41.
2-11
-------
to
I
h—*
to
300
0:00
1:00
2:00 3:00
RUN TIME
4:00
5:00
RUN1
RUN 2
RUNS
RUN 4
Figure 2-3. Hot blast temperature during each test run.
-------
23.0
22.5-
22.0
21.5
21.0
20.5
20.0
0:00
1:00
2:00
3:00
4:00
5:00
6:00
RUN TIME
Figure 2-4. Hot blast rate during the test runs
-------
2.3.2 Mold Line 4
During the testing of Line 4, a record was kept of the rate at which the line moved (e.g.,
molds per hour) and pouring was observed to identify when broken molds were not poured and
the temperature of the molten iron when poured. Several observations were made of the time to
"light off after pouring, when the vapors escaping from the mold self-ignited. The first hole
ignited on average about 6 to 8 seconds (sec) after pouring, and all holes were lit 11 to 18 sec
after pouring. During the testing of the scrubbers used on the shakeout operation, the pressure
drop across the scrubbers was recorded and ranged from 13.9 to 16.5 in. of water.
Table 2-6 provides a summary of the number and types of molds that were processed
during each test day from plant records, and Table 2-7 provides a summary of the quantity of iron
poured and the amount of downtime during each hour of the testing days. Table 2-8 contains the
mold counts made by the process observers when testing was being performed. Table 2-9
provides an estimate of the tons of iron poured per hour and the number of molds poured per
hour during the testing periods on Line 4.
During the testing days, the pouring temperature of the iron was maintained within a
narrow range of 2,743° to 2,818 °F. A typical analysis of the iron (from 9/25/97) showed
3.11 percent carbon, 0.13 percent sulfur, and 2.28 percent silicon.
2-14
-------
TABLE 2-6. SUMMARY OF NUMBER OF MOLDS POURED ON LINE 4
Hour
(first
shift)
1
2
3
4
5
6
7
8
9b
Number of molds poured3
9/22/97
4-cyl.
223
' 64
--
-
56
237
37
-
-
.
6-cyl.
-
126
220
185
36
-
46
217
106
-
9/23/97
4-cyl.
224
16
-
~
-
225
205
70
-
-
6-cyl.
-
165
214
208
217
-
-
76
108
-
9/24/97
4-cyl.
152
194
59
0
171
114
-
-
83
104
6-cyl.
~
-
-
-
--
98
195
227
109
-
9/25/97
4-cyl.
180
235
155
-
-
48
202
176
-
-
6-cyl.
-
-
48
208
245
126
-
18
108
-
1 Does not include broken molds that were not poured.
' The line usually shut down around 3 p.m.
2-15
-------
TABLE 2-7. SUMMARY OF METAL POURED AND DOWNTIME FOR LINE 4
Hour
(first
shift)
1
2
3
4
5
6
7
8
9
Tons of metal poured3
9/22/97
45.2
44.5
55.1
46.3
20.4
48.1
19.0
54.3
26.5
-
9/23/97
45.4
44.6
53.6
52.1
54.3
45.6
41.6
33.2
27.0
-
9/24/97
30.8
39.3
12.0
0.0
34.7
47.7
48.8
56.8
44.1
21.1
9/25/97
36.5
47.7
43.5
52.1
61.3
41.3
41,0
40.2
27.0
--
Downtime (minutes)
9/22/97
8
17
11
15
40
7
42
12
0
--
9/23/97
10
20
12
14
12
10
14
26
0
-
9/24/97
26
17
47
60
22
13
17
10
17
1
9/25/97
20
8
15
14
6
21
15
. 17
0
-
a Based on 202.8 Ibs per 4-cylinder engine block (405.6 Ibs per mold) and 250.4 Ibs per 6-cylinder engine block
(500.8 Ibs per mold).
2-16
-------
TABLE 2-8. LINE 4 MOLD COUNTS DURING TESTING PERIODS
Date: 09/22/97
Time
1:41 pm
1:42 pm
1:45 pm
1:50 pm
2:00 pm
2:15 pm
2:20 pm
2:25 pm
2:30 pm
2:40 pm
2:45 pm
2:50 pm
2:53 pm
2:55 pm
3:00pm
Number of
moldsa
0
5
14
21
40
57
21
21
22
28 .
22
21
17
3
16
Molds/hrb
0
300
280
252
240
228
252
252
264
168
264
252
340
90
192
Cumulative molds/hrc
0
300
285
267
253
242
243
244
246
233
235
237
241
237
234
Comments
6-cylinder engine blocks; 8 broken molds
were not poured between 1:30 and 3:00
Date: 9/23/97
Time
8:39 am
8:40 am
8:43 am
8:57 am
9:23 am
9:41 am
10:00 am
10:18 am
10:30 am
10:42 am
10:54 am
11:02 am
ll:10am
11:42 am
12:01 om
Number of
molds3
0
5
14
54
93
69
64
73
32
49
44
35
34
109
78
Molds/hrb
0
300
280
231
215
230
202
243
160
245
220
263
255
204
246
Cumulative molds/hrc
0
300
285
243
226
227
221
225
218
221
221
223
225
221
224
Comments
6-cylinder engine blocks; 26 6-cylinder
molds not poured between 8:00 and 12:00
Switched to 4-cylinder blocks at 1 1 :45;
3 4-cylinder molds not poured
2-17
-------
TABLE 2-8. (continued)
Date: 9/24/97
Time
11:03 am
11:06 am
11:08 am
ll:10am
11:35 am
11:51 am
12:04 pm
Number of
moldsa
0
12
9
9
94
68
44
Molds/hrb
0
240
270
270
226
255
203
Cumulative molds/hrc
0
240
252
257
233
240
232
Comments
4-cylinder engine blocks; 5 molds not
poured
Date: 9/25/97
Time
8:57 am
9:17 am
9:30 am
9:48 am
9:58 am
10:15 am
10:26 am
10:41 am
10:57 am
11:25 am
11:32 am
Number of
molds3
0
68
41
72
42
52
38
59
64
118
29
Molds/hrb
0
204
189
240
252
184
207
236
240
253
249
Cumulative molds/hrc
0
204
198
213
219
212
211
215
218
225
226
Comments
4-cylinder engine blocks; 3 molds not
poured
Switched to 6-cylinder at 9:30; 14 molds not
poured
a Number of molds counted for the incremental time period.
Rate based on the incremental time period.
c Cumulative rate based on number of molds from the start time; this is the most accurate measure of the rate over
the time period (i.e., the last bolded number in this column).
2-18
-------
TABLE 2-9. MOLD LINE 4 PRODUCTION DURING TESTING PERIODS
Date
9/22/97
9/23/97
9/24/97
9/25/97
Time Period
1:41- 3:00 pm
8:39 - 12:01 pm
11:03- 12:04 pm
8:57 -11:32 am
No. of molds poured
4-cylinder
-
75
231
106
6-cylinder
300
652
-
460
Molds/hr
poured
227
216
226
219
Tons/hr
poured3
56.9
53.0
45.8
53.0
a Based on 405.6 Ibs for 4-cylinder molds and 500.8 Ibs for 6-cylinder molds.
2-19
-------
3.0 TEST LOCATIONS AND GAS COMPOSITION
Figure 3-1 is an overview of the cupola gas handling system and the locations of the
sample points. Figure 3-2 is a more detailed schematic of the scrubber inlet and scrubber outlet
(exhaust stack). The cupola inlet and outlet were sampled concurrently.
Figure 3-3 is a schematic showing detailed views of the sampling points for the pouring,
cooling, and shake-out. One pouring duct was sampled, three cooling ducts (Main, R, S) were
sampled, and three shake-out stacks (3,4, 5) were sampled.
3.1 VENTURI SCRUBBER OUTLET - STACK
The test ports on the stack (Location B) are located on the roof at about 140 ft above
ground level and 50 ft north of the venturi scrubber inlet duct. Access to the stack ports is by
stairways in the interior of the cupola building, a short exterior catwalk, and stairs. Sufficient
ports were installed to allow simultaneous FTIR and manual method sampling.
3.2 VENTURI SCRUBBER INLET DUCT
The test ports were installed on the inlet duct (Location A) and located on the roof about
140 ft above ground level. Access to the inlet location on the roof was the same route as to the
stack. Testing was run in a 66-in. interior-diameter duct.
3.3 MOLD POURING DUCT
The duct is inside the main facility, with the ports at a height of approximately 25 ft
above the shop floor. The sampling location was identified as location "E" by GM Powertrain
personnel. Access to the ports is available from a little-used stair platform, although access to
one port required the use of scissors-type platform. The ports were used by MRI for obtaining
volumetric flow, diluent, moisture, and FTIR data across the 51.75-in. interior diameter duct.
Previous testing indicated a particulate loading range of 0.0171 to 0.0312 grains per dry standard
cubic foot (gr/dscf). Gas temperatures in this duct ranged from 80° to 101 °F. Flow data are
reported in Table 3-1.
3.4 MOLD COOLING LINE
Testing at the mold cooling line occurred at three separate ducts, identified in this report
as Main, R, and S. Titles used to identify the ducts are the same as those used by GM Powertrain
personnel. The Main duct is circular with ports accessed approximately 10 ft above the facility
3-1
-------
first floor level. Ducts R and S are both rectangular with dimensions 34 by 68 in. Ducts R and S
were accessed at two different locations in the facility upper level.
Previous testing on the Main duct reported paniculate loading that ranged from
0.00132 to 0.00206 gr/dscf. Temperatures in the three ducts ranged from 94° to 115°F. MRI
collected volumetric flow rates, moisture content, and diluent gas information for this location.
3.5 MOLD SHAKE-OUT HOUSING
The mold shake-out housing and its ducting system are located inside the main facility.
Each duct leads to a scrubber, then is vented through stacks to atmosphere on the roof. Sampling
of three shake-out housing stacks (Nos. 3, 4, and 5) on the roof level was performed. Four-in. test
ports following the scrubbers were utilized on the stacks at a height of approximately 3 ft above
the roof. MRI collected volumetric flow, diluent, moisture, and h'l'lR data across the diameter of
the duct interiors.
3-2
-------
Wet cap
Recuperator
Quencher
U) I
JCoolerl T
Recuperator x Solids
removed
I Heated
I blast air /
Combustion
chamber
Blast air
Cooled gas
A
Scrubber water
Venturi
scrubber
tit
Cupola blower
Exhaust
stack
B
Cleaned gas
Solids
removed
Scrubber water blow-down
to wastewater treatment
\
Cupola
Figure 3-1. Schematic of GM Saginaw cupola gas handling system sampling points A and B.
Exhaust fan
9/061/1
-------
u>
11
1
3 ft.
F
1
4 °n ft »
* '** £\J 11. *
A
Roof
•
•
i
![
Exhi
Pnrtd F
A 1 Ul lO [_
] Ports ~|fL
I i
aust st
A
ack
Roof
i
From quencher To venturi
Sample Point A
Scrubber inlet
From venturi
Sample Point B
Exhaust stack
960114-2
Figure 3-2. Schematic of scrubber inlet and scrubber outlet; sampling points A and B.
-------
OJ
Roof
- 51" I.D. 0
Exhaust stack
Ports [
O ft Pouring Ports Location
~ 25' above shop floor
Platform
~4ft.
Roof
Duct for Pouring Emissions
51" I.D. 0'
From Scrubber
Stacks 3,4,5 for Shake-out Emissions
Duct "R"
34"x68"
oooo
A
I
Main Cooling Duct
Ports
O
Ports
-0-51" I.D.
facility 1st floor
Duct "S"
34" x 68"
Ports
o
O
o
Figure 3-3. Pouring, cooling, and shake-out sampling points.
-------
3.6 VOLUMETRIC FLOW
Table 3-1 summarizes the gas composition and flow data provided by PES for the cupola
test locations. PES provided volumetric flow rates, moisture content, gas molecular weight, etc.
as part of their manual testing; therefore, MRI did not conduct these tests.
Table 3-2 summarizes the gas composition and flow data for the sampling conducted at
the pouring, cooling, and shake-out housing. Measurements for velocity, flow, and oxygen (O2)
and carbon dioxide (CO2) concentrations were conducted and calculated following EPA Test
Methods 1, 2, and 3B referenced in 40 CFR Part 60, Appendix A. Moisture content of the stack
gas was calculated using wet bulb/dry bulb measurements. Records of volumetric flow data are
located in Appendix A.
TABLE 3-1. CUPOLA GAS COMPOSITIONS AND FLOW SUMMARY
Cupola Test Data a
Run No.
Date
1
23-Sep-97
2
24-Sep-97
3
25-Sep-97
4
25-Sep-97
Scrubber Inlet - Location A
Oxygen, %
Carbon dioxide, %
Moisture content, %
Volumetric flow rate, dscfm
Volumetric flow rate, dscmm
12.3
8.9
20.0
60,183
1,704
12.7
9.4
30.0
58,682
1,662
12.2
10.0
28.9
56,090
1,588
11.9
11.0
30.3
54,702
1,549
Scrubber Outlet - Location B (Exhaust Stack)
Oxygen, %
Carbon dioxide, %
Moisture content, %
Volumetric flow rate, dscfm
Volumetric flow rate, dscmm
16.7
4.0
12.6
66,304
1,878
11.8
10.6
16.4
64,783
1,834
12.5
9.7
9.1
63,143
1,788
12.4
10.3
9.1
64,748
1,833
aThe data were collected by PES with their Method 29 manual sampling trains. Two manual runs were
performed on 9/25 from 8:38 to 11:49, and from 15:12 to 18:45. The FTIR measurements were performed semi-
continuously from about 8:00 to about 17:00.
3-6
-------
TABLE 3-2. MOLD POURING, COOLING, AND SHAKE-OUT HOUSING GAS
COMPOSITION AND FLOW SUMMARY
Mold Pouring
Sample location
Date
Carbon dioxide, %
Oxygen, %
Moisture content, %
Gas stream velocity, fps
Volumetric flow rate, dscfm
Volumetric flow rate, dscmm
E
23-Sept-97
0.2
20.7
1.7
65.8
52,824
1,495
-
-
-
-
-
-
-
-
-
—
Mold Cooling
Sample location
Date
Carbon dioxide, %
Oxygen, %
Moisture content, %
Gas stream velocity, fps
Volumetric flow rate, dscfm
Volumetric flow rate, dscmm
Main Duct
25-Sept-97
0.3
20.2
1.9
40.6
30,674
868
RDuct
24-Sept-97
0.3
19.8
1.7
15.0
13,118
371
SDuct
24-Sept-97
0.2
20.4
1.7
51.7
45,393
1,285
Average
0.3
20.1
1.8
• 35.7
29,645
838.9
Shake-out housing"
Sample location
Date
Carbon dioxide, %
Oxygen, %
Moisture content, %
Gas Stream velocity, fps
Volumetric flow rate, dscfm
Volumetric flow rate, dscmm
Stack3
22-Sept-97
0.2
20.4
3.3
52.2
41,046
1,162
Stack 4
22-Sept-97
0.2
20.1
3.8
51.5
40,679
1,151
StackS
22-Sept-97
0.2
20.3
3.3
47.9
37,751
1,068
Average
0.2
20.3
3.5
50.5
39,825
1132.4
The velocity traverses were performed and stack temperatures were measured on 9/22/97. The Tedlar bags were
collected and the Orsat analyses were performed on 9/23 and 9/24/97.
3-7
-------
4.0 RESULTS
4.1 TEST SCHEDULE
The testing at GM Powertrain, Saginaw, Michigan was performed from September 21 to
September 26,1997. Table 4-1 summarizes the sampling schedule. A complete record of all
FTIR sampling is in Appendix B. The FTIR sampling at the cupola locations was coordinated
with the manual sampling conducted by PES. The FTIR sampling at the mold cooling line and
the mold shake-out housing were conducted independently.
TABLE 4-1. TEST SCHEDULE AT GM POWERTRAIN,
SAGINAW, MICHIGAN
Date
9/21/97
9/22/97
9/23/97
9/24/97
9/25/97
9/26/97
Task
Arrive on site and started set-up at cupola.
Complete cupola set-up;
Obtain shake-out flow data.
Test Shake-out #3 and #4
Test Pouring "E"
Cupola Test Run 1 w/ FTIR 14:43 - 18:45
Test Shake-out #3 and #5
Test Cooling "S"
Cupola Test Run 2 w/ FTIR 8:41 - 13:04
Test Cooling "R" and "Main"
Collected Background Sample in facility
Cupola Test Run 3 w/ FTIR 8:54 - 13:50
Packed equipment and departed site
Location3
•Cupola
•Cupola
••Shake-out Stacks
••Shake-out Stacks
••Pouring Duct
••Cupola
••Shake-out Stacks
••Cooling Ducts
•Cupola
•Cooling Ducts
•Facility 1st Level
• •Cupola
a Location descriptions are in Section 3.
4.2 FIELD TEST PROBLEMS AND CHANGES
The cupola gas at GM Powertrain contained high concentrations of both water vapor and
CO2 with respect to other compounds. Analyte spiking for quality assurance was conducted
using toluene and formaldehyde vapor. The CO2 spectrum interfered with the strongest toluene
infrared band near 730 cm"1 so the weaker toluene absorbance, in the analytical region 2,850 to
3,100 cm"1 range, was used for the analysis. The presence of other hydrocarbon species
contributed to the total infrared absorbance in the 2,850 to 3,100 cm"1 region.
Moisture collected in the pitot tubes used to monitor pressure drop in the ducts. The pitot
lines were cleaned regularly by back-blowing pitot lines with compressed nitrogen gas.
4-1
-------
4.3 FTIR RESULTS
The FTIR results from the mold cooling and pouring and shake-out housing ducts are
presented in Tables 1-1 to 1-3. A summary of the FTIR results from the cupola scrubber inlet
and outlet locations is presented in Table 1-4. Detailed FTIR results from the cupola scrubber
inlet and outlet are presented in Appendix B in Tables B-l and B-2.
4.3.1 Tedlar Bag Samples
Tables 1-1 to 1-3 present the FTIR results and the mass emissions rates for the Tedlar bag
samples. The emissions rates for the pouring process were determined using the average concen-
trations in the two bag samples taken from a single duct.
Three ducts were sampled at the cooling process and at the shake-out housing. The
emissions rates were calculated for each duct, and then summed to obtain the total emissions
from the process. For example, the methanol concentrations were 1.8, 2.5, and 4.5 ppm at the
main, R, and S cooling ducts, respectively. The methanol mass emissions were calculated using
the flow data in Table 3-2 to be 0.28,0.17, and 1.03 Ib/hr in the main, R, and S cooling ducts,
respectively. The total methanol emission rate was the sum of the emissions in each duct, or
1.48 Ib/hr. Only the total emission rates are shown in Tables 1-1 to 1-3.
The moisture content was lower at the mold process locations so the calculated
uncertainties in the results were also relatively small compared to the uncertainties for the
scrubber inlet and outlet results. None of the bag samples were spiked.
Emissions from the mold cooling and shakeout housing included CO, methane, methanol
and ethylene. The emissions also contained a mixture of heavier aliphatic hydrocarbon
compounds. In the draft report the mixture of heavier hydrocarbons was represented by "hexane"
because hexane and isooctane are the only aliphatic hydrocarbons in the EPA library of HAP
reference spectra. There are many hydrocarbon compounds that are structurally similar to hexane
and have similar spectral features. Since the draft report was submitted, EPA directed MRI to
measure quantitative spectra of some additional compounds. MRI selected some candidate
compounds that were likely components of the sample mixture and measured spectra of butane,
n-heptane, pentane, 1-pentene, 2-methyl-l-pentene, 2-methyl-2butene, 2-methyl-2-pentene, and
3-methylpentane. MRI also measured new high-temperature spectra of the HAPs hexane and
isooctane. The new spectra were used in revised analyses that gave the results presented in
4-2
-------
Tables 1-1 to 1-3. The new spectra made it possible to better represent the sample mixture
spectrum and the reported hexane concentrations are lower compared to the draft results. The
revised toluene results are similar to the draft toluene results because the addition of the new
spectra did not significantly affect the analysis of the aromatic compounds in the mixture.
Samples collected at the pouring process also contained methane, ethylene, and CO, but
at lower concentrations. Heavier hydrocarbons, such as methanol, toluene and hexane were not
detected at the pouring process.
Figure 4-1 is a plot of a spectrum of a sample taken from a cooling duct. Reference
spectra of water and methane have been scaled and subtracted from the original sample spectrum
to give the spectrum plotted in Figure 4-1. This figure also shows a reference spectrum of
methanol plotted underneath the sample spectrum. The presence of methanol and ethylene are
clearly indicated in Figure 4-1. Figure 4-2 shows the same two spectra as Figure 4-1 plotted in
the region near 3,000 cm-1. It is clear from Figure 4-2 that most of the infrared absorbance near
2,900 cm"1 cannot be attributed to the methanol. Figure 4-3 shows the same sample spectrum as
in the previous two figures, but it is plotted with reference spectra of hexane and toluene. The
.05-
u
I
.0
<
1100
1000 900
Wavenumbers
800
Top trace, Sample from the cooling line, "cools!02"; bottom trace, methanol reference
spectrum 104a4ase offset by -.025
Figure 4-1. Sample spectrum from the cooling process plotted with
a methanol reference spectrum.
4-3
-------
.1-
.05-
o-
3100
3000 2900
Wavenumbers
2800
Top trace, Same sample from cooling line "cools!02"; bottom trace, methanol reference
spectrum 104a4ase offset by -.025
Figure 4-2. Sample spectrum from the cooling process plotted with a methanol reference
spectrum shown in a different frequency region.
.4-
.3-
.1-
o-
Wavenumbers
3100
3000
2900
2800
Top trace, "cools 102" after water and methane have been subtracted. Middle, toluene reference spectrum, 153a4arc, which has been
scaled by a factor of 0.483. Bottom, hexane reference spectrum, 095a4asd, which has been scaled by a factor of 0.285. All
three spectra are plotted from-0.05 to + 0.1 absorbance units. Calculation of seating factors is in section 5.5.
Figure 4-3. Sample spectrum from the cooling process plotted with toluene and hexane
reference spectra.
4-4
-------
reference spectra have each been multiplied by a scaling factor determined from the reported
concentrations of 19.4 parts per million (ppm) for toluene and 11.1 ppm for hexane (Table 1-2,
spectrum "cools!02"). The scaling factors are derived from equations 5 and 6 in Section 4.5.
In Figure 4-2, it is the region between 3,000 and 2,800 cm"1 that was represented by
"hexane" in the draft results and is now better represented by including spectra of additional
hydrocarbon compounds in the revised results.
4.3.2 Scrubber Inlet and Outlet
The spectra were analyzed for a number of HAP's which were not detected. The analysis
was then refined to analyze for the spiked compounds and a smaller number of selected
compounds. The hydrocarbon emissions consisted primarily of methane. Formaldehyde and
toluene were not detected in the unspiked samples. The uncertainties for carbon monoxide were
relatively high. In runs 2 and 3 the calculated CO uncertainties were greater than the reported
concentrations.
4.4 ANALYTE SPIKE RESULTS
A toluene gas standard and a formaldehyde permeation tube were used for analyte spiking
experiments for quality assurance. The analyte spike results are presented in Tables 4-2 to 4-5.
Table 4-6 compares measured band areas of the EPA toluene reference spectra
(deresolved to 2.0 cm"1) and a spectrum of a sample taken directly from the 196.6 ppm toluene
cylinder standard. The cylinder standard spectrum was measured at the Saginaw test site. The
band area comparison is different from the comparison of the concentrations, corrected for path
length and temperature: for a given concentration (ppm-m/K) the infrared absorbance in the
cylinder standard spectra is about 45 percent greater than the absorbance in the EPA library
spectra. Therefore, the library spectra calculate a toluene concentration that is 45 percent lower
than that calculated using the cylinder standard spectra. Tables 4-3 and 4-4 present the toluene
spike recoveries using both the library spectra and the cylinder standard spectra.
A similar disagreement was observed in other field tests using another toluene gas
standard. One possibility is that there was a systematic error in the original toluene library
reference spectra. This could be evaluated by purchasing several toluene gas standards from
different sources and doing a comparison similar to that shown in Table 4-6.
4-5
-------
The disagreement is compound specific, and the information in Table 4-6 does not apply
to the measurements of other analytes. Deresolved calibration transfer standard (CTS) (ethylene
calibration) spectra give a path length result that is consistent with the observed number of laser
passes and the instrument resolution. But ethylene is a relatively stable compound, which is why
it can serve as a CTS. The disagreement is also not related to the deresolution of the toluene
spectra because the band areas in the original 0.25 cm~1 toluene spectra are nearly equal to the
band areas in the deresolved 2.0 cm"1 versions of these spectra.
4-6
-------
TABLE 4-2. SUMMARY OF FORMALDEHYDE SPIKE RESULTS AT THE SCRUBBER INLET
Spiked samples
INLSP102
INLSP201
INLSP202
INLSP203
INLSP301
INLSP302
INLSP304
Formaldehyde concentration
Date
9/23/97
9/24/97
9/25/97
Spike Unspike Calc
0.0 0.5 -0.5
0.0 0.0 0.0
9.8 0.0 9.8
17.7 0.0 17.7
22.0 0.0 22.0
14.6 0.0 14.6
0.0 0.0 0.0
SF/r concentration
Spike Unspike Calc
0.424 0.018 0.406
0.924 0.000 0.924
0.875 0.000 0.875
0.909 0.000 0.909
0.921 0.000 0.921
0.729 0.000 0.729
0.483 0.000 0.483
DF Cexp A % Recovery
9.8 6.0 -6.5 ND
3.1 10.3 -10.3 ND
3.3 9.7 0.03 100.3
3.0 21.2 -3.6 83.3
3.0 21.5 0.4 102.0
3.8 170 -2.5 85.5
4.6 10.9 - 10.9 ND
Average recovery = 91.7
•{*• Spike and unspike are equal to the measured analyte concentrations in spiked and unspiked samples. Calc is equal to the difference, spike - unspike. DF, the
dilution factor, is given in Equation 2 in Section 5.4.2.3. Cexp is equivalent to the calculated 100 % recovery (Equation 3 in Section 5.4.2.3). A is equal to Calc
- Cexp. % Recovery is equal to (Calc/Cexp) * 100 (Equation 4 in Section 5.4.2.3). ND indicates that formaldehyde was not detected in these samples.
-------
TABLE 4-3. SUMMARY OF TOLUENE SPIKE RESULTS AT THE SCRUBBER INLET
Spiked samples
INLSP102
INLSP202
INLSP203
ENLSP301
INLSP302
INLSP304
Toluene concentration
Date
9/23/97
9/24/97
9/25/97
Spike Unspike Calc
34.8 0.0 34.8
32.5 0.0 32.5
28.9 0.0 28.9
29.4 0.0 29.4
22.5 0.0 22.5
35.5 0.0 35.5
SFg concentration
Spike Unspike Calc
0.424 0.018 0.406
0.875 0.000 0.875
0.909 0.000 0.909
0.921 0.000 0.921
0.729 0.000 0.729
0.483 0.000 0.483
DF Cexp A
9.8 12.7 22.1
3.3 23.3 9.2
3.0 24.0 4.9
3.0 24.3 5.1
3.8 19.2 3.3
4.6 26.9 8.6
% Recovery
EPA Ref Cylinder
273.5 150.0
139.7 76.6
120.6 66.1
121.0 66.3
117.0 64.2
131.9 72.4
Average recovery = 153.2 82.6
Spike and unspike are equal to the measured analyte concentrations in spiked and unspiked samples. Calc is equal to the difference, spike - unspike. DF, the
dilution factor, is given in Equation 2 in Section 5.4.2.3. Cexp is equal to the calculated 100 % recovery (Equation 3 in Section 5.4.2.3). A is equal to Calc -
Cexp. % Recovery is equal to (Calc/Cexp) * 100 (Equation 4 in Section 5.4.2.3). "EPA Ref indicates the EPA toluene reference spectra were used in the
analysis. "Cylinder" indicates that a spectrum of the toluene cylinder standard was used in the analysis.
oo
-------
TABLE 4-4. SUMMARY OF FORMALDEHYDE SPIKE RESULTS AT THE SCRUBBER OUTLET
Spiked samples
OUTSP104
OUTSP105
OUTSP201
OUTSP203
OUTSP205
OUTSP301
OUTSP305
Formaldehyde concentration
Date
9/23/97
9/24/97
9/25/97
Spike Unspike Calc
16.7 0.0 16.7
15.5 0.0 15.5
9.0 0.0 9.0
13.6 0.0 13.6
20.2 0.0 20.2
30.7 0.0 30.7
13.3 0.0 13.3
SFg concentration
Spike Unspike Calc
0.914 0.000 0.914
0.866 0.000 0.866
1.071 0.000 1.071
1.247 0.000 1.247
0.942 0.000 0.942
1.221 0.000 1.221
0.563 0.000 0.563
DF Cexp A % Recovery
3.2 10.2 6.5 163.8
3.4 9.7 5.8 160.6
2.7 11.9 -2.9 75.7
2.3 13.9 -0.3 97.6
2.9 22.0 -1.9 91.6
2.3 28.6 2.2 107.7
3.9 12.7 0.6 105.1
Average recovery = 1 14.6
Spike and unspike are equal to the measured analyte concentrations in spiked and unspiked samples. Calc is equal to the difference, spike - unspike. DF, the
. dilution factor, is given in Equation 2 in Section 5.4.2.3. Cexp is equal to the calculated 100 % recovery (Equation 3 in Section 5.4.2.3). A is equal to Calc -
Jo Cexp. % Recovery is equal to (Calc/Cexp) * 100 (Equation 4 in Section 5.4.2.3).
-------
TABLE 4-5. SUMMARY OF TOLUENE SPIKE RESULTS AT THE SCRUBBER OUTLET
Spiked samples
OUTSP104
OUTSP105
OUTSP203
OUTSP205
OUTSP301
OUTSP305
Toluene concentration
Date
9/23/97
9/24/97
9/25/97
Spike Unspike Calc
32.6 0.0 32.6
31.2 0.0 31.2
40.6 0.0 40.6
26.2 0.0 26.2
35.7 0.0 35.7
36.1 0.0 36.1
SFg concentration
Spike Unspike Calc
0.914 0.000 0.914
0.866 0.000 0.866
1.247 0.000 1.247
0.942 0.000 0.942
1.221 0.000 1.221
0.563 0.000 0.563
DF Cexp A
3.2 24.3 8.3
3.4 23.0 8.2
2.3 33.2 7.4
2.9 24.8 1.4
2.3 32.2 3.4
3.9 31.3 4.7
% Recovery
EPA Ref Cylinder
134.2 73.6
135.4 74.3
122.4 67.1
105.5 57.9
110.6 60.7
115.1 63.1
Average recovery = 120.5 66.1
Spike and unspike are equal to the measured analyte concentrations in spiked and unspiked samples. Calc is equal to the difference, spike - unspike. DF, the
dilution factor, is given in Equation 2 in Section 5.4.2.3. Cexp is equal to the calculated 100 % recovery (Equation 3 in Section 5.4.2.3). A is equal to Calc -
Cexp. % Recovery is equal to (Calc/Cexp) * 100 (Equation 4 in Section 5.4.2.3). "EPA Ref indicates the EPA toluene reference spectra were used in the
analysis. "Cylinder" indicates that a spectrum of the toluene cylinder standard was used in the analysis.
TABLE 4-6. COMPARISON OF EPA TOLUENE REFERENCE SPECTRA TO SPECTRA OF TOLUENE
CYLINDER STANDARD
1
Toluene spectra
153a4ara(2cm-l)
153a4arc (2cm- 1)
to!0923a1
Source
EPA library
EPA library
GM
Band area
23.4
4.3
38.1
Region, cm
3160.8-2650.1
Spectra comparison:
based on band areas
Ratio (Ra)2
5.4
1.0
8.8
Spectra comparison:
based on standard concentrations
(ppm-m)/K
4.94
1.04
5.02
Ratio (Re)3
4.8
1.0
4.8
Rc/Ra, %
88
100
55
When the spectrum of the cylinder standard, "tolo923a" is compared to the reference spectrum, "153a4arc," the ratio of the concentration is 35 percent less
than the comparison of the band areas.
2 For example 5.4 = 23.4/4.3
3 For example 4.8 = 4.94/1.04
-------
5.0 TEST PROCEDURES
The procedures followed in this field test are described in the EPA Method 320 for using
FTIR spectroscopy to measure HAP's and the EPA Protocol for extractive FTIR testing at
industrial point sources.2 The objectives of the field test were to use the FTIR method to
measure emissions from the processes, screen for HAP's in the EPA FTIR reference spectrum
library, and analyze the spectra for compounds not in the EPA library. Concentrations are
reported for compounds that could be measured with FTIR reference spectra. Additionally,
manual measurements of gas temperature, gas velocities, moisture, CO2, and O2 were used to
calculate the mass emissions rates. MRI collected such data for the mold cooling and the shake-
out housing ducts, and PES collected the data at the scrubber inlet and outlet.
An extractive sampling system was utilized for the cupola sampling points and gas bags
were collected at the pouring, cooling, and shake-out locations. Extractive sampling is generally
the preferable approach, however, access restrictions at GM Powertrain prevented extractive
sampling at the pouring, cooling, and shake-out locations. Gas samples were collected in
Tedlar® bags at these locations and analyzed by FTIR.
5.1 EXTRACTIVE SAMPLING SYSTEM
A schematic of the extractive sampling and spiking system is shown in Figure 5-1.
5.1.1 Sample System Components
The sampling system consists of three separate components:
1. Two sample probe assemblies;
2. Two sample lines and pumps; and
3. A gas distribution manifold cart.
All wetted surfaces of the system are made of unreactive materials, Teflon®, stainless
steel, or glass and are maintained at temperatures at or above 300°F to prevent condensation.
The sample probe assembly consists of the sample probe, a pre-filter, a primary
particulate filter, and an electronically actuated spike valve. The sample probe is a standard
heated probe assembly with a pitot tube and thermocouple. The pre-filter is a threaded piece of
tubing loaded with glass wool attached to the end of sample probe. The primary filter is a
Balston particulate filter with a 99 percent removal efficience at 0.1,um. The actuated spike
5-1
-------
valve is controlled by a radio transmitter connected to a switch on the sample manifold cart. All
sample probe assembly components are attached to or enclosed in an insulated metal box.
The sample lines are standard heated sample lines with three 3/8-in. Teflon tubes in 10,
25, 50, and 100 ft lengths. The pumps are heated, single-headed diaphragm pumps manufactured
by either KNF Neuberger or Air Dimensions. These pumps can sample at rates up to 20 liters
per minute (L/min) depending on the pressure drop created by the components installed
upstream.
The gas distribution manifold was constructed for FTIR sampling by MRI. It is built onto
a cart that can be operated inside the MRI mobile lab or in an alternate location, if necessary.
The manifold consists of a secondary particulate filter, control valves, rotameters, back pressure
regulators and gauges, and a mass flow controller. The manifold can control two sample gas
stream inputs, eight calibration gases, and has three individual outputs for analyzers. The cart
also contains a computer work station and controls for the spike valves and mass flow controller.
5.1.2 Sample Gas Stream Flow
Exhaust gas was withdrawn through the sample probe and transported to the gas
distribution manifold. The mold cooling and shake-out processes were each sampled alternately
with the two gas handling systems during a single run. The scrubber inlet and outlet were
sampled alternately over three runs. Inside the manifold the gas passed through separate
secondary particulate filters. Downstream of the secondary filters, a portion of either gas stream
could be directed to the FTIR gas cell. The remainder of each gas stream was exhausted through
a manifold vent. The scrubber inlet and outlet were sampled alternately (i.e., inlet sample was
analyzed for an interval while the outlet sample was exhausted, then outlet sample was analyzed
while the inlet sample was vented). A location was selected for analysis using the 4-way gas
selection valve on the manifold outlet to the instrument. Gas flow to the instrument was
regulated with a needle valve on a rotameter at the manifold outlet.
5-2
-------
Data Storage & Analysis FTIR Spectrometer Heated Cell
Vent
Vent
L/l
U)
Heated Probe #1
Heated Probe #2
Vent
V)
Flow Meter
Flow Meter
Flow Meter
Calibration Gas /
Spike Line
Secondary PM Fitter
Heated Manifold Box
20 ft. of heated line
Calibration Standards
Heated Probe Box #1
3-Way Valve
ialston® Filter
Bundles are 50-300+ ft. long.
Sample Line
Calibration Gas / Spike Line
20 ft. of heated line
Heated Probe Box #2
3-Way Valve
Balston® Filter
Sample Transfer Line (Heated Bundle) #1
Bundles are 50-300+ ft. long.
Heated
Pump #1
Sample Line
Calibration Gas / Spike Line
Unheated line
Heated Pump #2
MFM - Mass Flow Meter
Sample Transfer Line (Heated Bundle) #2
Figure 5-1. Sampling system schematic.
-------
5.2 TEDLAR® GAS BAG SAMPLING
The Tedlar gas bag sampling approach was derived from EPA Method 18. MRI extracted
the sample from ports in the designated process ducts using a Teflon sampling line connected to
a sampling pump with Teflon-coated heads and exhausting into a Tedlar bag. Prior to connecting
the bag to the pump, the sampling pump was operated for one minute in order to purge the
sampling system with process gas. The bag was then connected and the pump operated at a flow
of about 250 milliliter (ml)/min for a period of approximately 1 hr. Data recording sheets are
presented in Appendix A. Periodically during the sample collection, the flow meter was checked
for a constant flow rate. At the completion of the sampling period, the bag was sealed and taken
to the onsite FllK instrument for analysis.
5.3 FTIR SAMPLING PROCEDURES
For each run, two locations were sampled using two separate sample systems that were
both connected to the main manifold (Figure 5-1). In the first run, the mold cooling and shake-
out housing were sampled together and for three runs the scrubber inlet and scrubber outlet were
sampled together. A single FTIR instrument was used to analyze samples from both locations
during a test run. The manifold's four-way valves allowed the sample from either of two
locations to be directed alternately to the FTIR cell. Sample flow was controlled by a needle
valve and measured with a rotameter.
FTIR sampling was conducted using either the batch or the continuous sampling
procedures described below. All data were collected according to the Method 320 sampling
procedure, which is described below.
5.3.1 Batch Samples
In this procedure, the four-way valve on the manifold outlet was turned to divert a portion
of the sample flow to the FTIR cell. A positive flow to the main manifold outlet vent was
maintained as the cell was filled to just above ambient pressure. The cell inlet valve was then
closed to isolate the sample, the cell outlet valve was open to vent the cell to ambient pressure,
the spectrum of the static sample was recorded, and then the cell was evacuated for the next
sample. This procedure was repeated to collect a desired number of discreet samples.
Batch sampling has the advantage that every sample is independent from the other
samples. The time resolution of the measurements is limited by the interval required to evacuate
5-4
-------
a sample, pressurize the cell, and record a spectrum. All of the calibration transfer standards, and
spiked samples were collected using this procedure. Several spectra in each run were also
collected in this manner.
5.3.2 Continuous Sampling
The cell was filled as in the batch sampling procedure, but the cell inlet and outlet valves
were kept open to allow gas to continuously flow through the cell. The inlet and outlet flows
were regulated to keep the sample in the cell at ambient pressure. The flow through the cell was
maintained at about 5 L/min. The cell volume was about 7 liters (L).
The FTIR instrument was automated to record spectra of the flowing sample about every
2 min, and the quantitative analysis was automated to measure pollutant concentrations as each
spectrum was recorded. The analytical program was revised after the test was completed and all
of the spectra were reanalyzed.
This procedure with automated data collection was used during each of the test runs.
Because spectra were collected continuously as the sample flowed through the cell, there was
mixing between consecutive samples. The interval between independent measurements (and the
time resolution) depends on the sample flow rate (through the cell), and the cell volume.
The Time Constant (TC) defined by Performance Specification 15 for FTIR Continuous
Emission Monitoring Systems (CEMS), is the period for one cell volume to flow through the
cell. The TC determines the minimum interval for complete removal of an analyte from the cell
volume. It depends on the sampling rate (Rs in L/min), the cell volume (Vcell in L) and the
analyte's chemical and physical properties. Performance Specification 15 defines 5 * TC as the
minimum interval between independent samples.
TC = ^ (1)
A stainless steel tube ran from the cell inlet connection point to the front interior of the
cell. The outlet vent was at the back of the cell so that the flowing sample passed through the
greatest portion of the cell volume and minimized the likelihood of a short-circuiting flow.
5.4 ANALYTE SPIKING
There was little information available about HAP emissions from this source, so there
was no plan for validating specific HAP's during this test. MRI conducted spiking for quality
5-5
-------
assurance (QA) purposes using a toluene in nitrogen standard and a vapor-generated
formaldehyde standard.
5.4.1 Analyte Spiking Procedures
The infrared spectrum is ideally suited for analyzing and evaluating spiked samples
because many compounds have distinct infrared spectra.
The reason for analyte spiking is to provide a QA check that the sampling system can
transport the spiked analytes to the instrument and that the quantitative analysis program can
measure the analyte in the sample gas matrix. If at least 12 (independent) spiked and
12 (independent) unspiked samples are measured, then this procedure can be used to perform a
Method 301 validation.3
The spike procedure follows Sections 9.2 and 13 of EPA Method 320 in Appendix D. In
this procedure a gas standard is measured directly in the cell.. This direct measurement is then
compared to measurements of the analyte in spiked samples. Ideally, the spike will comprise
about 1/10 or less of the spiked sample. The expected concentration of the spiked component is
determined using a tracer gas, SF6. The SF6 concentration in the direct sample divided by the
SF6 concentration in the spiked sample(s) is used as the spike dilution factor (DF). The analyte
standard concentration divided by DF gives the expected value of the spiked analyte
concentration.
5.4.2 Analysis of Spiked Results
The statistical procedures in Section 6.3 of EPA Method 301 were followed to analyze
the spiked and unspiked results. The application of these procedures to FTIR test data is
described in Section 13 of EPA Method 320. This involved evaluating the measurement
precision, determining any systematic bias in the results, and calculating a correction factor that
can be applied to the results when the validated method is used.
5.4.2.1 Determination of Formaldehyde Standard
Formaldehyde vapor was produced by heating a permeation tube filled with solid
paraformaldehyde. The tube was placed in a vapor generation oven (Kintek) equipped with a
temperature controller and mass flow meter to regulate the carrier gas. The oven was raised to
100° or 110°C and the vapor of the formaldehyde monomer was purged with a continuous flow
of a carrier gas. For spiking, the carrier gas was from the SF6 cylinder standard (4.01 ppm in
5-6
-------
nitrogen at ±2 percent, Scott Specialty Gases). When spiking was not performed, the
formaldehyde vapor was continuously vented using a low flow of nitrogen as the carrier gas.
With this device it was practical to generate a very stable concentration output of formaldehyde.
The concentration of this formaldehyde standard was determined with respect to formaldehyde
reference spectra in the EPA FTIR spectral library (Table 5-1).
TABLE 5-1. DETERMINATION OF FORMALDEHYDE STANDARD
CONCENTRATION
Date
9/23/97
9/23/97
File name of
direct measurement
FOR0923A
FOR0923B
Average
Formaldehyde,
ppma
74.8
81.7
78.3
Uncertainty
1.1
1.2
aMeasured between 3160.8 and 2650.1 cm"1 using EPA reference spectrum
087b4anb, deresolved to 2.0 cm"1. The vapor generation oven was kept at 100°C and
the carrier gas flow rate was 1.00 L/min. Nitrogen was the carrier gas for the direct-to-
cell measurements of formaldehyde.
5.4.2.2 Determination of Concentrations in Spike Mixtures
Frequently the output formaldehyde from the vapor generation oven was mixed
quantitatively with the toluene standard so that sample stream could be spiked with toluene, SF6
and formaldehyde simultaneously. Mixing the two spike streams together introduced another
dilution factor that had to be accounted for. The concentration of each component in the spike
mixtures was determined independently by preparing a separate analytical computer program.
The input for the computer program consisted of reference spectra of each analyte in the
mixtures. For SF6 and toluene spectra the program used spectra of samples taken directly from
the cylinder standards and measured in the FTIR cell. For formaldehyde the program used a
spectrum from the EPA library. The program was used to analyze spectra of each of the spike
mixtures, which were measured directly in the FTIR gas cell. Tables 5-2 and 5-3 present the
results from this analysis and show the mass flow meter readings used to prepare the spike
mixtures, the files names for the direct-to-cell measurements of each mixture, and the file names
of the samples that were spiked with each mixture.
5-7
-------
TABLE 5-2. CALCULATED CONCENTRATIONS IN MIXTURES USED
FOR ANALYTE SPIKING AT THE SCRUBBER INLET
Spectra
INLSP102
INLSP201
INLSP202
INLSP203
INLSP301
INLSP302
INLSP304 .
Spike mixture concentrations, ppm
Formaldehyde
59.2
32.4
32.4
64.8
64.8
64.8
49.8
SF6
3.97
2.91
2.91
2.77
2.77
2.77
2.21
Toluene
124.5
0.0
77.3
73.1
73.1
73.1
122.9
Spike flow, L/min
spy
form flow1
1.0
2.0
2.0
2.0
2.0
2.0
1.0
Toluene flow
1.00
X
1.00
1.00
1.00
1.00
1.00
Kintek
oven temp.,
°C
100
100
100
110
110
110
100
Mixture
mix0923 a
mix0924a
mix0924a
mix0925a
mix0925a
mix0925a
mrx0925B
'Combined flow of formaldehyde vapor with SF6 carrier gas.
TABLE 5-3. CALCULATED CONCENTRATIONS IN MIXTURES USED
ANALYTE SPIKING AT THE SCRUBBER OUTLET
FOR
Spectra
OUTSP104
OUTSP105
OUTSP201
OUTSP203
OUTSP205
OUTSP301
OUTSP305
Spike mixture concentrations, ppm
Formaldehyde
32.4
32.4
32.4
32.4
64.8
64.8
49.8
SF6
2.91
2.91
2.91
2.91
2.77
2.77
2.21
Toluene
77.3
77.3
0.0
77.3
73.1
73.1
122.9
Spike flow, L/min
spy
form flow1
2.0
2.0
2.0
2.0
2.0
2.0
1.0
Toluene
flow
1.00
1.00
1.00
1.00
1.00
1.00
1.00
Kintek
oven temp.,
°C
100
100
100
100
110
110
100
Mixture
mix0924 a
mix0924 a
mix0924a
mix0924a
mix0925a
mix0925a
mix0925B
'Combined flow of formaldehyde vapor with SF6 carrier gas.
5-8
-------
The measured concentrations in Tables 5-2 and 5-3 were used to determine the percent
recoveries in Tables 4-2 to 4-5: the SF6 concentrations were used to determine the dilution
factor (DF) and the toluene and formaldehyde concentrations were combined with DF to
determine the C and the percent recoveries for those analytes.
5.4.2.3 Determination of Percent Recovery
The expected concentration of the spiked component was determined using the tracer gas,
SF6. In the following discussion the "direct" measurement refers to the measured concentration
in the spike mixture before it was added to the sample stream (i.e., the concentrations presented
in Tables 5-2 and 5-3).
The DF was determined by the ratio of the measured SF6 concentration in the direct
measurement of the spike mixture, SF6/directx, to the measured SF6 concentration in the spiked
samples, SF6(spike).
cp
DF = — 3*5* (2)
cp ^'
Or6(spike)
The direct measurement of the analyte concentration in the spike mixture divided by DF gives
the expected concentration for a 100 percent recovery of the analyte spike, Ce .
Analyte(dtel)
(-3)
where:
Analyte/direct) = The concentration of either toluene or formaldehyde from the direct
measurement of the spiked mixture (from Tables 5-2 and 5-3).
The actual spike recovery in Tables 4-2 to 4-5 is the percent difference between the measured
analyte concentrations in the spiked samples and Cexp.
% Recovery = -- x 100 (4)
Cexp v '
where "Calc" is equal to the difference between the measured analyte concentration in spiked
samples minus the measured analyte concentration in the unspiked samples.
5-9
-------
5.5 ANALYTICAL PROCEDURES
Analytical procedures in the EPA FTIR Protocol 2 were followed for this test. A
computer program was prepared with reference spectra shown in Tables 5-4 and 5-5. The
computer program used techniques based on a K-matrix analysis4"6.
Initially, the spectra were reviewed to determined appropriate input for the computer
program. Next an analysis was run on all of the sample spectra using a large data set of reference
spectra. Finally, undetected compounds were removed from the analysis, and the spectra were
analyzed again using a smaller reference spectra data set. The results from this second analytical
run are summarized in Tables 1-1 and 1-2 and reported in Appendix B.
The same program used for the analysis also calculated the residual spectra (the
difference between the observed and least squares fit absorbance values). Three residuals, one
for each of the three analytical regions, were calculated for each sample spectrum. All of the
residuals were stored electronically and are included with the electronic copy of the sample data
provided with this report. Finally the computer program calculated the standard Isigma
uncertainty for each analytical result, but the reported uncertainties are equal to 4*sigma.
Calculated concentrations in sample spectra were corrected for differences in absorption
path length and temperature between the reference and sample spectra by
C
con
L
r
L
s
X
s
r
Ccalc (5)
where:
Ccorr = Concentration, corrected for path length and temperature.
Ccajc = Calculated analyte concentration based on the best fit of the spectra without
accounting for the path lengths and temperatures.
L,. = Reference spectrum path length.
Ls = Sample spectrum path length.
Ts = Absolute temperature of the sample gas, K.
Tr = Absolute gas temperature of reference spectrum sample, K.
The values of L,., Ls, Ts, and Tr are included in the computer program input for each
spectrum. The program output gives Ccorr directly for each detected component of the mixture.
5-10
-------
The scaling factors in Figure 4-3 were determined by using the output of the computer program,
Ccorr , and solving equation 5 for Ccalc.
C ,
Scaling factor = ^— (6)
Ref ppm
Then where "Ref ppm" is the ppm concentration (ASC in Appendix A of the FTIR
Protocol) associated with the reference spectrum to be scaled. The scaling factors were
multiplied by the toluene and hexane reference spectra. The scaled reference spectra are plotted
in Figure 4-3.
The sample path length was estimated by measuring the number of laser passes through
the infrared gas cell. These measurements were recorded in the data records. The actual sample
path length, LS, was calculated by comparing the sample CTS spectra to CTS (reference) spectra
in the EPA FTIR reference spectrum library. The reference CTS spectra were recorded at the
same time as the toluene reference spectra and are included in the EPA library. The reference
CTS spectra were used as input for a K-matrix analysis of the CTS spectra collected at the
Saginaw field test.
5.5.1 Program Input
Tables 5-4 and 5-5 summarize the reference spectra input for the computer program used
to analyze the sample spectra. Table 5-6 summarizes the program input used to analyze the CTS
spectra recorded at the field test. The CTS spectra were analyzed as an independent determina-
tion of the cell path length. To analyze the CTS spectra, MRI used 0.25 cm"1 spectra "cts0814b"
and "cts0814c." These reference CTS spectra were recorded on the same dates as the toluene
reference spectra used in the analysis. These spectra were deresolved to 2.0 cm in the same
way as the toluene reference spectra using Section K.2.2 of the EPA FTIR protocol. The
program analyzed the main two ethylene bands centered near 2,989 and 949 cm . Table 5-7
summarizes the results of the CTS analysis. The cell path length from this analysis was used as
Lg in equation 5.
5-11
-------
TABLE 5-4. PROGRAM INPUT FOR ANALYSIS OF SAMPLE SPECTRA FROM
POURING AND COOLING AND SHAKE-OUT HOUSING
Compound name
Water
Carbon monoxide
Carbon dioxide
Formaldehyde
Methanol
Methane
Toluene
Ethylene
Hexane
butane
n-heptane
pentane
1-pentene
2-methyl- 1 -pentene
2-methyl-2butene
2-methyl-2-pentene
Isooctane
3-methylpentane
File name
194a2sub
co20829a
193b4a_g
087b4anb
104a4ase
1962bsft
153a4arc
cts0923c
0950709a
but0715a
hep0716a
pen0715a
Ipe0712a
2mlp716a
2m2b716a
2m2p713a
16507 15a
3mp0713a
Region No.
1,2,3
1
1,2,3
3
2
3
3
2
3
3
3
3
3
3
3
3
3
3
ISCa
100a
167.1
415a
100.0
20.0
80.1
103.0
20.1
46.9
100.0
49.97
49.99
50.1
50.08
50.04
51.4
50.3
50.0
Reference
Meters
22
22
11.25
3.0
22
3
10.4
10.3
11.25
10.3
10.3
10.3
10.3
10.3
10.3
10.3
10.3
T (K)
394
394
373
298
394
298
408
399
397.8
398.3
397.9
399
398.2
398.2
398.6
398.3
398.5
Region No.
1
2
3
Upper cm
2,142.0
1,275.0
3,160.8
Lower cm
2,035.6
789.3
2,650.1
Indicates an arbitrary concentration was used for the interferant.
5-12
-------
TABLE 5-5. PROGRAM INPUT FOR ANALYSIS OF SAMPLE
FROM SCRUBBER INLET AND OUTLET
SPECTRA
Compound name
Water
Carbon monoxide
Carbon dioxide
Formaldehyde
HC1
Methane
Toluene
Hexane
SF6
File name
194h2sub
co20829a
193b4a_a
087b4anb
097b4asd
196clbsd
153a4arc
095a4asd
Sf60923a
Region No.
1,2,3
1
1,2,3
3
3
3
3
3
2
ISCa
100a
167.1
415a
100.0
72.2
16.1
103.0
101.6
4.01
Reference
Meters
22
22
11.25
2.25
22
3
3
10.4
T (K)
394
394
373
373
394
298
298
408
Region No.
1
2
3
Upper cm"1
2,142.0
1,275.0
3,160.8
Lower cm
2,035.6
789.3
2,650.1
alndicates an arbitrary concentration was used for the interferant.
TABLE 5-6. PROGRAM INPUT FOR ANALYSIS OF CTS SPECTRA AND
PATH LENGTH DETERMINATION
Compound name
Ethylenea
Ethylene
File name
cts0814b.spc
cts0814c.spc
ASC
1.007
1.007
ISC
1.014
0.999
% Difference
0.7349
0.7350
aThis spectrum was used in the analysis of the GM Powertrain CTS spectra.
5-13
-------
TABLE 5-7. RESULTS OF PATH LENGTH DETERMINATION
CIS spectra
100 ppm ethylene
CTS0921A
CTS0921B
CTS0923A
CTS0923B
CTS0923C
CTS0924A
CTS0924B
CTS0925A
CTS0925B
CTS0925C
Average path length (M)
Standard deviation
Meters
10.49
10.45
10.43
10.43
10.40
10.49
10.48
10.29
10.29
10.37
10.41
0.074
Aa
0.08
0.04
0.02
0.02
-0.01
0.08
0.06
-0.12
-0.12
-0.04
%A
0.7%
0.4%
0.2%
0.2%
-0.1%
0.8%
0.6%
-1.2%
-1.1%
-0.4%
aThe difference between the calculated and average values.
5.5.2 EPA Reference Spectra
The formaldehyde, hexane, methanol, HC1, and toluene spectra used in the MRI analysis
were taken from the EPA reference spectrum library (http://www.epa.gov/ttn/emc/ftir.html). The
original sample and background interferograms were truncated to the first 8,192 data points. The
new interferograms were then Fourier transformed using Norton-Beer medium apodization and
no zero filling. The transformation parameters agreed with those used to collect the sample
spectra. The deresolved 2.0 cm single beam spectra were combined with their deresolved
single beam background spectra and converted to absorbance. This same procedure was used to
prepare spectral standards for the HAP's and other compounds included in the preliminary
analysis.
5.6 FTIR SYSTEM
The FTIR system used in this field test was a KVB/Analect Diamond-20 interferometer.
The gas cell is a heated variable path (D-22H) gas cell from Infrared Analysis, Inc. The path
length of 20 laser passes was used for measurement at both locations. The inside of the cell
walls have been treated with a Teflon coating to minimize potential analyte losses. A
5-14
-------
mercury/cadmium/ telluride (MCT) liquid nitrogen detector was used. Spectra were collected at
2.0 cm"1, the highest resolution of the Diamond-20 system.
The optical path length was measured by shining a He/Ne laser into the cell and adjusting
the mirror tilt until the desired number of passes was obtained. The number of passes was
recorded on the field data sheets in Appendix B-l. The path length in meters was determined by
comparing calibration transfer standard (CTS, ethylene in nitrogen) spectra measured in the field
to CTS spectra in the EPA reference spectrum library.
5-15
-------
6.0 SUMMARY OF QA/QC PROCEDURES
6.1 SAMPLING AND TEST CONDITIONS
Before the test, sample lines were checked for leaks and cleaned by purging with moist
air (250°F). Following this, the lines were checked for contamination using dry nitrogen. This is
done by heating the sampling lines to 250°F and purging with dry nitrogen. The FTIR cell was
filled with some of the purging nitrogen and the spectrum of this sample was collected. This
single beam spectrum was converted to absorbance using a spectral background of pure nitrogen
(99.9 percent) taken directly from a cylinder. The lines were checked again on site before
sampling, after each change of location, and after spiking.
During sampling at the scrubber inlet and outlet an effort was made to measure at least
five different samples from each location.
Each spectrum was assigned a unique file name and written to the hard disk and a backup
disk under that file name. Each interferogram was also saved under a file name that identifies it
with its corresponding absorbance spectrum. All background spectra and calibration spectra
were also stored on disks with their corresponding interferograms.
Notes on each calibration and sample spectrum were recorded on hard copy data sheets.
Below are listed some sampling and instrument parameters that were documented in these
records.
Sampling Conditions
• Line temperature
• Process conditions
• Sample flow rate
• Ambient pressure
• Time of sample collection
Instrument Configuration
• Cell volume (for continuous measurements)
• Cell temperature
• Cell path length
• Instrument resolution
• Number of scans co-added
6-1
-------
• Length of time to measure spectrum
• Time spectrum was collected
• Time and conditions of recorded background spectrum
• Time and conditions of relevant CTS spectra
• Apodization
Hard copy records were also kept at the mold cooling and shake-out housing line of all
flue gas measurements, such as sample flow, temperature, moisture and diluent data. Flow data
at the cupola scrubber inlet and outlet were obtained by PES.
Effluent was allowed to flow through the entire sampling system for at least 5 min before
a sampling run started or after changing to a different test location. FTIR spectra were
continuously monitored to ensure that there was no deviation in the spectral baseline greater than
±5 percent (-0.02 < absorbance <, +0.02). When this occurred, sampling was interrupted and a
new background spectrum was collected. The run was then resumed until completed or until it
was necessary to collect another background spectrum.
6.2 FTIR SPECTRA
For a detailed description of QA/QC procedures relating to data collection and analysis,
refer to the "Protocol For Applying FTIR Spectrometry in Emission Testing".2
A spectrum of the CTS was recorded at the beginning and end of each test day. A leak
check of the FTIR cell was also performed according to the procedures in references 1 and 2.
The CTS gas was 20.1 ppm ethylene in nitrogen. The CTS spectrum provided a check on the
operating conditions of the FTIR instrumentation, e.g. spectral resolution and cell path length.
Ambient pressure was recorded whenever a CTS spectrum was collected. The CTS spectra were
compared to CTS spectra in the EPA library. This comparison is used to quantify differences
between the library spectra and the field spectra so library spectra of HAP's can be used in the
quantitative analysis.
Two copies of all interferograms, processed backgrounds, sample spectra, and the CTS
were stored on separate computer disks. Additional copies of sample and CTS absorbance
spectra were also be stored for data analysis. Sample absorbance spectra can be regenerated from
the raw interferograms, if necessary. A copy of the data was provided with the draft report.
6-2
-------
To measure HAP's detected in the gas stream, MRI used spectra from the EPA library,
when available.
6-3
-------
7.0 REFERENCES
1. Test Method 320 (Draft) "Measurement of Vapor Phase Organic and Inorganic Emissions by
Extractive Fourier Transform Infrared (FTIR) Spectroscopy," 40 CFR Pan 63, Appendix A.
2. "Protocol for the Use of FTIR Spectrometry to Perform Extractive Emissions Testing at
Industrial Sources," Revised, EPA Contract No. 68-D2-0165, Work Assignment 3-12,
September, 1996.
3. "Method 301 - Field Validation of Pollutant Measurement Methods from Various Waste
Media," 40 CFR Part 63, Appendix A.
4. "Computer-Assisted Quantitative Infrared Spectroscopy," Gregory L. McClure (ed.), ASTM
Special Publication 934 (ASTM), 1987.
5. "Multivariate Least-Squares Methods Applied to the Quantitative Spectral Analysis of*
Multicomponent Mixtures," Applied Spectroscopy, 39(10), 73-84,1985.
6. "An Examination of a Least Squares Fit FTIR Spectral Analysis Method," G. M. Plummer
and W. K. Reagen, Air and Waste Management Association. Paper Number 96-WA65.03,
1996.
7-1
-------
APPENDIX A
FIELD DATA
-------
A-l VOLUMETRIC FLOW
CUPOLA SCRUBBER
-------
The flue gas data and flow calculation results from the cupola scrubber inlet and outlet were
provided to MRI by Pacific Environmental Services (PES). In the draft report the inlet flow
results were incorrect. The corrected inlet flow results were provided by PES for the revised test
report. The corrected inlet flow results are also present in summary Table 3-2 and the corrected
inlet flows have been incorporated into the mass emission results.
-------
InM29
PARTICULATE/METALS EMISSIONS SAMPLING AND FLUE GAS PARAMETERS
CUPOLA INLET
GM POWERTRAIN - SAGINAW, MICHIGAN
Run No.
Date
Total Sampling Time, min
Average Sampling Rate, dscfin a
Sample Volume:
dscfb
dscmc
Average Flue Gas Temp., °F
O2 Concentration, % by Volume
C02 Concentration, % by Volume
Moisture, % by Volume
Flue Gas Volumetric Flow Rate:
acfmd
dscfin a
dscmme
Isokinetic Sampling Ratio, %
I-M29-1
9/23/97
115
0.517
59.458
1.684
125
12.3
8.9
20.0
81,999
60,183
1,704
102.3
I-M29-2
9/24/97
237.3
0.515
122.140
3.459
128
12.7
9.4
30.0
81,108
58,682
1,662
104.5
I-M29-3
9/25/97
120
0.897
107.586
3.046
133
12.2
10.0
28.6
82,857
56,090
1,588
103.8
I-M29-4
9/25/97
120
0.858
103.008
2.917
137
11.9
11.0
30.3
83,329
54,702
1,549
105.1
Average
0.643
96.394
2.730
129
12.4
9.4
26.2
57,280
40,743
1,154
103.5
a Dry standard cubic feet per minute at 68° F (20° C) and 1 atm.
b Dry standard cubic feet at 68° F (20° C) and 1 atm.
c Dry standard cubic meters at 68° F (20° C) and 1 atm.
d Actual cubic feet per minute at exhaust gas conditions.
e Dry standard cubic meters per minute at 68° F (20° C) and 1 atm.
-------
OutMM5
SVOHAPs EMISSIONS SAMPLING AND FLUE GAS PARAMETERS
CUPOLA OUTLET
GM POWERTRAIN - SAGINAW, MICHIGAN
Run No.
Date
Total Sampling Time, min
Average Sampling Rate, dscfin a
Sample Volume:
dscf
dscmc
Average Flue Gas Temp., °F
O2 Concentration, % by Volume
CO2 Concentration, % by Volume
Moisture, % by Volume
Flue Gas Volumetric Flow Rate:
acfind
dscfin3
dscmm*
Isokinetic Sampling Ratio, %
BO-0010-1
9/23/97
110
0.640
70.444
1.995
125
16.7
4.0
12.7
74,589
58,567
1,658
98.4
BO-0010-2
9/24/97
240
0.636
152.632
4.322
135
11.8
10.6
16.6
76,444
56,562
1,602
101.2
BO-0010-3
9/25/97
240
0.882
211.667
5.994
111
12.5
9.7
9.3
64,403
52,693
1,492
101.2
BO-0010-4
9/25/97
240
0.895
214.771
6.082
111
12.4
10.3
9.2
65,580
53,676
1,520
100.8
Average
0.763
162.378
4.598
121
13.4
8.7
11.9
70,254
55,375
1,568
100.4
-------
OutM29
PARTICULATE/METALS EMISSIONS SAMPLING AND EXHAUST GAS
PARAMETERS
CUPOLA BAGHOUSE OUTLET
GM POWERTRAIN - SAGINAW, MICHIGAN
Run No.
Date
Total Sampling Time, min
Average Sampling Rate, dscfm a
Sample Volume:
dscfb
dscrn0
Average Exhaust Gas Temp., °F
O2 Concentration, % by Volume
C02 Concentration, % by Volume
Moisture, % by Volume
Exhaust Gas Volumetric Flow Rate:
acfmd
dscfm a
dscmme
Isokinetic Sampling Ratio, %
O-M29-1
9/23/97
110
0.692
76.163
2.157
125
16.7
4.00
13.0
80,243
62,768
1,777
95.4
O-M29-2
9/24/97
240
0.633
151.911
4.302
133
11.80
10.60
16.4
74,042
55,151
1,562
99.3
O-M29-3
9/25/97
120
0.946
113.491
3.214
109
12.5
9.70
9.2
68,668
56,641
1,604
97.8
O-M29-4
9/25/97
120
0.939
112.649
3.190
109
12.4
10.30
9.6
69,760
57,542
1,629
95.5
Average
0.757
113.855
3.224
122.3
13.67
8.10
12.9
74,318
58,187
1,648
97.5
-------
OutM23
PCDDs/PCDFs EMISSIONS SAMPLING AND FLUE GAS PARAMETERS
CUPOLA OUTLET
GM POWERTRAIN - SAGINAW MICfflGAN
Run No.
Date
Total Sampling Time, min
Average Sampling Rate, dscfin "
Sample Volume:
dscf
dscrn0
Average Flue Gas Temp., °F
O2 Concentration, % by Volume
CO2 Concentration, % by Volume
Moisture, % by Volume
Flue Gas Volumetric Flow Rate:
acfmd
dscfm*
dscmme
Isokinetic Sampling Ratio, %
BO-23-1
9/23/97
110
0.499
54.895
1.554
125
16.7
4.0
12.2
98,273
77,577
2,197
93.0
BO-23-2
9/24/97
240
0.629
151.041
4.277
133
11.8
10.6
16.2
110,810
82,637
2,340
102
BO-23-3
9/25/97
240
0.904
217.061
6.146
110
12.5
9.7
8.7 '
97,171
80,094
2,268
103.4
BO-23-4
9/25/97
240
0.925
221.977
6.286
108
12.4
10.3
8.5
100,082
83,025
2,351
102.0
Average
0.739
161.244
4.566
119
13.4
8.7
11.409
101,584
80,833
2,289
99.993
-------
A-l VOLUMETRIC FLOW
Shakeout Housing
-------
A-2 GAS BAG COLLECTION DATA
-------
ii 5bfeb v t_-.5 ktJ:3_.
9
<\
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location:
Date:
Sampling personnel:
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. 1^=^
T^r-tiT-
7^__
0,£
Z—alt &»,0-2-
/D^I.'MS'
/<>,• 37
Sample No.
Sample No.
Sample No.
Time Flowmeter Reading
\o '$ 3
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location:
Date: 9 -3-1 -I
Sampling personnel:
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. -*f- J
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location:
Date:
Sampling personnel: /<^. /<:/yUf*-\ A
r
Pump ID "Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. \W &f~
5kJsi*j d 3
5. $.
0- ^
•
•
Sample No. • "&,< t*C?
y ._
Jflt~/&!?-^ ^
T*{/.
.
£>,£""
• • •
Sample No.
Time
Flowmeter Reading
Sample No.
Time
•
Flowmeter Reading
//ef
ft>
f"00
-------
lVg\£ aV ^.-VI\NN<'\S
^O
x* _cNA\
iry-lvv
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location: ^
Date: */Z,'yh~
Sampling personnel:
*
^
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. i
^Itfis,*!
c.'S
0&
\
/o:o? 'oo
/>,'«*'. '09 •
Sample No.
Sample No.
Sample No.
Time Flowmeter Reading
Time Flowmeter Reading
EPA/EMC/Iron/GMsamp.doc
-------
J
y
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location: f^, fc^. "p^-A- $
Date:
Sampling personnel:
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time y
Finish Time
Sample No. J3a.* if- 1
j
s.s
o.^
v 30 C_
y- 1*< *-> ?*elj
y^',07 .'_?o ,,*,
/f'.«T%^
Sample No.
3*1
Sample No.
Time
Flowmeter Reading
EPA/EMQ'Iron/GMsamp.doc
,>'
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location: Afb>'
Date: 9-/5-V7
u C
oo
Sampling personnel:
.:/*.}
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. *jp
$.*.
/. **;,;
A*,l.-<«-4- &**!***
r/y-t
//S6>
Sample No.
Sample No.
Sample No.
Time
t( ?(,
Flowmeter Reading
Time
Flowmeter Reading
t/3/
/.
tiff
EPA/EMC/Iron/GMsamp.doc
-------
Field Sample Data Sheet - Tedlar Bag Collection Method
GM/SMOC
MRI Project No. 3804.25
Sampling Location: ^U(^J^(iM^^> ^v ^A:^ c*>lt~
Date:
Sampling personnel:
7
\Jte\v\
Sample No.
Time Flowmeter Reading
Pump ID Number
Source Temperature (deg. C)
Barometric Pressure (mm Hg)
Ambient Temperature (deg. C)
Sample Flow Rate (L/min)
Sample Volume (L)
Sample Number
Start Time
Finish Time
Sample No. &,£.")
- j
5-$'
oJ
G-iP*L '£"
0703:00
/0&3 /0*
Sample No. &/ta ""/> £M/,-s*
/o?l\e* /
//3 1 ' * e>
x^^
-------
APPENDIX B
FTIRDATA
-------
B-l CUPOLA FTIR RESULTS TABLES
-------
TABLE B-1. FT1R RESULTS FROM THE SCRUBBER INLET
Dale
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/9.7
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
Time
10:59
12:2
12:11
13:17
13:23
13:53
14:32
15:7
15:44
15:46
15:49
15:51
15:53
15:55
15:57
15:59
16:25
16:27
16:29
16:32
16:36
16:38
- 16:40
17:8
17:10
17:12
Filename
INLSP1M
INLSFM2
INLN2103
INLUN104
INLUNIOS
INLUNI06
INLUN107
INLUNI08
19230014
19230015
19230016
19230017
19230018
19230019
19230020
19230021
19230033
19230034
19230035
19230036
19230037
19230038
19230039
19230052
19230053
19230054
Hydrogen chloride
ppra
•JM
tM
O.M
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
1.7
21.«
0.4
16.9
17.4
180
11.4
18.3
12.0
11.9
11.7
11.5
11.4
II. 1
10.9
10.8
10.3
10.4
10.2
10.2
10.3
10.4
104
10.2
10.3
10.3
Toluene
ppm
25.3
34.8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
Uncertainly
1.1
14.1
0.3
116
12.0
12.4
7.8
12.6
8.3
8.2
80
7.9
7.8
77
7.5
7.5
7.1
7.1
7.0
7.0
7.1
7.1
7.2
7.0
7.1
7.1
Hexane
ppm
•.«
•••
0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
00
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Uncertainly
12
1.9
0.0
16
16
1.7
I.I
1.7
I.I
I.I
I.I
II
I.I
10
1.0
1.0
1.0
1.0
0.9
0.9
1.0
1.0
1.0
0.9
1.0
1.0
Methane
ppm
*.2
3*2
0.8
25.3
25.9
26.8
19.4
26.7
20.4
20.0
19.8
19.7
20.0
19.8
19.4
18*8
19.1
18.8
18.4
18.3
18.0
18.6
19.6
19.7
19.7
19.8
Uncertainly
•.«
7.4
O.I
5.9
61
6.3
4.0
6.4
42
4.2
4.1
4.0
4.0
3.9
3.8
3.8
3.6
3.6
3.6
3.6
3.6
3.6
3.7
3.6
3.6
36
Carbon monoxide
ppm
•.•
».•
22.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1115
113.6
118.7
122.8
129.2
131.3
1342
144.6
146.2
150.2
Uncertainly
12.9
114.7
5.2
85.8
88.7
87.2
57.0
94.9
613
62.4
62.4
627
635
62.4
621
62.9
62.0
62.3
61.8
62.2
63.3
63.8
643
64.9
654
657
Formaldehyde
ppm
14.9
IM
2.8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
0.7
•.9
0.17
7.2
7.4
7.6
4.8
7.7
5.1
50
5.0
4.9
4.8
4.7
46
4.6
4.4
4.4
4.3
43
4.4
4.4
4.4
4.3
43
43
Bold lexl indicates that Ihis is spiked data nol used in average.
-------
TABLE B-l. (continued)
Dale
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
Avenge — >
Time
17:15
17:17
17:19
17:21
17:23
17.25
18:36
File MTOC
19230055
19230056
19230057
19230058
19230059
19230060
INAIRI09
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
Uncertainly
10.2
II. 1
62.0
15.3
15.0
16.2
15
13.1
Toluene
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
7.0
7.6
41.5
10.6
10.3
II. 1
1.0
9.0
Hexanc
ppm
0.0
2.2
0.0
0.0
0.0
0.0
0.0
O.I
Uncertainly
0.9
1.0
5.8
1.4
1.4
15
01
1.2
Methane
ppm
19.8
78.7
848.6
138.9
43.3
26.8
6.3
52.7
Uncertainly
3.6
3.9
21.8
5.4
5.3
5.7
0.54
4.6
Caibon monoxide
ppm
148.6
312.2
737.6
300.9
0.00
0.00
0.00
91.1
Uncertainly
65.3
81.3
134.8
99.8
87.1
86.1
105
68.4
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.09
Uncertainly
4.3
4.7
26.3
6.5
6.3
6.8
06
5.6
CO
i
N)
Bold lext indicates that this is spiked data nut used in average.
-------
TABLE B-l. (continued)
Dale
9/24/97
9124191
9/24/97
9/24/97
9/24/97
9/24/97
9/24»7
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
Time
8:47
9:32
9:58
10:0
10:2
10:4
10:6
10:9
10:11
10:45
10:47
10:49
10:52
10:54
10:56
10:58
11:51
11:54
11:56
11:58
12:0
12:2
12:4
12:6
12:9
File name
INLSmi
INLSmt
19240001
19240002
19240003
19240004
19240005
19240006
19240007
19240022
19240023
19240024
19240025
19240026
19240027
19240028
19240051
19240052
19240053
19240054
19240055
19240056
19240057
19240058
19240059
Hydrogen chloride
ppm
Mt
Mt
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
17.4
8.4
18.8
I9.S
19.4
19.1
19.1
18.9
18.8
20.0
19.9
19.6
19.4
19.4
196
19.8
22.3
22.6
22.3
22.0
21.9
21.9
21.8
21.7
21.4
Toluene
ppm
0.0*
32.5
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainty
12.9
5.*
12.9
13.4
13.3
13.2
13.1
13.0
13.0
13.8
13.7
13.5
13.4
13.4
13.5
J3.7
15.4
15.5
15.4
15.2
15.1
151
15.0
14.9
147
Hexane
ppm
•A
9.9
0.0
0.0
0.0
0.0
00
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Uncertainly
l.t
0.8
1.7
1.8
18
1.8
1.8
1.8
1.7
1.9
1.9
1.8
1.8
1.8
18
18
2.1
2.1
2.1
2.0
2.0
2.0
2.0
2.0
2.0
Methane
ppm
22.2
133
25.6
26.1
25.9
25.4
25.4
25.2
24.9
26.3
26.5
25.9
25.6
25.6
25.8
261
29.4
29.8
29.8
29.4
29.2
29.3
29.2
29.0 .
28.6
Uncertainly
4.1
3.0
6.6
6.8
6.8
6.7
6.7
6.7
6.6
7.0
7.0
6.9
6.8
6.8
6.9
7.0
7.9
7.9
7.8
7.7
7.7
7.7
7.7
7.6
7.5
CaitKMi monoxide
ppm
9M
9.99
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
87.1
49.9
94.7
98.6
98.1
968
962
95.6
95.5
100.6
100. 1
98.9
97.7
97.5
98.3
99.8
112.6
113 1
II 1.7
110.6
110 1
109.8
109.0
108.9
1078
Formaldehyde
ppm
9.09
9*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
7.4
34
8.0
8.2
8.2
8.1
8.1
8.0
8.0
8.5
8.4
8.3
8.2
8.2
8.3
8.4
9.5
9.6
9.5
9.3
9.3
93
9.2
9.2
9.1
CO
Bold text indicates thai this is spiked data nut used in average.
-------
TABLE B-l. (continued)
Date
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
Average — >
Time
12:41
12:43
1245
12:47
12:49
12:51
12.54
12:56
12:58
13:0
13:2
13:54
13:56
13:58
14:0
14:2
14:5
14:7
14:9
14:23
14:58
filename
19240074
19240075
19240076
19240077
19240078
19240079
19240080
19240081
19240082
19240083
19240084
192401 10
192401 II
192401 12
192401 13
192401 14
192401 IS
19240116
192401 17
INLSP203
INLN2204
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.2
0.03
Uncertainly
10.8
20.8
20.8
20.7
21 1
215
21.9
22.2
22.6
22.9
22.6
21.5
22.0
22.0
21.8
21.7
22.0
22.2
21.8
14.5
0.6
20.3
Toluene
ppm
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
28.9
0.00
0.00
Uncertainly
7.4
14.4
14.3
14.3
14.5
14.8
15.1
15.3
15.6
15.8
15.6
14.8
15.1
15.1
15.0
15.0
15.1
15.3
15.0
9.7
0.42
140
Hexane
ppm
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Uncertainly
1.0
1.9
1.9
1.9
2.0
2.0
2.0
2.1
2.1
2.1
2.1
2.0
2.0
2.0
2.0
2.0
2.0
21
2.0
1.3
O.I
1.9
Methane
ppm
16.6
28.0
28.0
27.9
28.2
28.7
29.2
294
29.8
302
30.1
28.3
288
291
28.9
28.7
28.7
29.0
28.6
18.8
0.5
27.0
Uncertainly
3.8
7.3
7.3
7.3
7.4
7.6
7.7
7.8
8.0
8.1
8.0
7.6
7.7
7.7
7.7
7.6
7.7
7.8
7.7
5.1
0.2
7.1
Carbon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
Uncertainly
51.0
104.9
104.5
104.5
106.3
107.5
1094
110.9
112.9
1138
II 2.5
107.6
II 0.0
109.6
108.8
108.5
109.9
110.4
108.4
73.4
50
101.8
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
17.7
0.00
0.00
Uncertainly
46
8.8
8.8
8.8
8.9
9.1
93
9.4
96
9.7
96
9.1
9.3
93
9.2
9.2
9.3
9.4
9.2
6.1
03
8.6
00
Bold text indicates lhat (his is spiked data nut used in average.
-------
TABLE B-l. (continued)
Dale
9/25/97
9125191
905191
9125191
9125191
9125191
905191
9I25J91
9125191
9125191
9125191
9/25/97
9/25/97
9/25/91
9125191
9/25/97
9/25/97
9125191
9/25/97
9125191
9125191
9/25/97
9/25/97
9125m
9/25/97
Time
8:15
8:25
8.32
9:18
9:20
9:22
9:24
9:26
9:28
9:31
10:8
10:10
10:12
10.15
10:17
10:19
10:21
10:23
10:25
11:20
11:22
11:24
11:26
11:28
11:31
Filename
1NLST3M
INLSnU
INLN2303
19250011
19250012
19250013
19250014
19250015
19250016
19250017
19250030
19250031
19250032
19250033
19250034
19250035
19250036
19250037
19250038
19250050
1925005 1
19250052
19250053
19250054
19250055
Hydrogen chloride
ppm
•M
•M
1.2
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
133
15.3
0.52
21.6
21.8
21.5
21.1
20.6
20.4
20.3
21.8
21.9
22.3
22.0
22.1
220
21.8
22.0
22.1
20.2
19.6
15.6
14.3
13.4
15.9
Toluene
ppm
29.4
22.5
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
9.1
19.3
0.27
14.9
150
14.8
14.5
14.2
14.1
14.0
15.0
15.1
15.4
15.2
15.2
15.2
15.0
15.1
15.2
13.9
13.5
10.8
9.9
9.3
110
Hexane
ppm
«.«
to
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Uncertainly
1.3
1.4
0.0
2.0
2.0
2.0
2.0
1.9
1.9
1.9
2.0
2.0
2.1
2.0
2.1
2.1
2.0
2.0
2.1
1.9
1.8
1.5
1.3
1.2
1.5
Methane
ppm
153
17.7
0.00
26.3
26.5
26.2
25.7
25.0
24.9
24.8
26.4
26.4
27.0
26.5
26.6
26.6
26.5
26.5
26.8
24.5
29.9
33.5
20.6
18.4
20.0
Uncertainly
4.8
5.4
0.14
7.6
7.7
7.6
7.4
7.2
7.2
7.1
7.7
7.7
7.9
7.7
7.8
7.8
7.7
7.7
7.8
7.1
6.9
5.5
5.0
4.7
56
Carbon monoxide
ppm
O.M
•.M
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
469.7
232.8
246.0
000
Uncertainly
48.8
77.6
2.4
107.3
108.3
106.9
104.5
102.4
101.7
101.7
109.6
109.7
II 1.8
110.6
110.7
110.4
109.2
110.5
110.9
100.5
100.2
113.6
88.5
85.5
858
Formaldehyde
ppm
22*
144
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
5.7
6.4
0.16
9.1
9.2
9.1
8.9
8.7
8.6
8.6
9.2
93
9.5
9.3
9.4
9.3
9.3
9.3
9.4
8.6
83
6.6
6.1
5.7
68
DO
«!*»
Bold text indicates thai this is spiked data not used in average.
-------
TABLE B-l. (continued)
Dale
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
Time
11:33
11.35
11:37
11:39
11:41
11:43
12.11
12:14
12:16
12:18
12:20
12:22
12:24
12:27
12:57
12:59
13:1
13:3
13:5
13:7
13:10
14:32
14:39
15:35
15:37
Filename
19250056
19230057
19250058
19250059
19250060
19250061
19250074
19250075
19250076
19250077
19250078
19250079
19250080
19250081
19250095
19250096
19250097
19250098
19250099
19250100
19250101
1NLSF304
1NLN2305
19250122
19250123
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.39
0.00
0.00
Uncertainly
19.5
20.6
20.1
19.9
20.0
19.9
21.3
21.6
21.7
21.7
21.7
21.8
22.3
22.0
22.6
22.7
23.2
23.6
23.7
23.5
23.1
20.8
0.2
IS 1
147
Toluene
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
35.S
000
0.00
000
Uncertainly
13.4
14.2
13.8
13.7
13.7
13.7
14.6
14.9
14.9
15.0
15.0
15.0
15.4
15.2
15.5
157
16.0
16.3
16.4
162
15.9
13.9
O.I
10.4
10 1
Hexane
ppm
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
00
Uncertainly
1.8
1.9
1.9
1.8
1.9
1.8
2.0
2.0
2.0
2.0
2.0
2.0
2.1
2.0
2.1
2.1
2.2
2.2
2.2
2.2
2.1
1.9
0.0
1.4
14
Methane
ppm
23.7
24.9
24.3
24.2
24.5
24.1
25.4
25.9
26.0
26.0
26.0
25.9
26.2
26.0
26.3
26.4
26.8
27.2
27.4
27.4
26.5
23.7
0.2
36.7
23.0
Uncertainly
6.9
7.2
7.1
7.0
7.0
7.0
7.5
7.6
7.6
7.6
76
7.7
7.8
7.8
7.9
8.0
8.2
8.3
8.4
83
8.1
7.3
O.I
5.3
51
Caibon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
493.3
200.0
Uncertainly
97.7
101.7
99.7
98.5
99.0
98.3
105.5
106.6
107.0
107.5
107.4
107.8
109.8
108.1
II 1.0
II 1.4
114.0
1155
1161
114.7
112.7
107.0
1.9
110.2
87 1
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
000
0.00
0.00
000
000
Uncertainty
8.3
8.7
8.5
8.4
8.5
8.4
90
9.2
9.2
9.2
9.2
9.2
9.4
9.3
9.6
96
9.8
10.0
10. 1
9.9
9.8
8.8
O.I
64
62
CO
Bold text indicates that (his is spiked data not used in average.
-------
TABLES 1. (continued)
Dale
9/25/97
9/25/97
9/25191
9/25/97
905191
9/25191
9/25/97
9125191
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/2V97
Average — >
Time
15:40
15:42
15:44
15:46
15:48
15:50
15:52
15:55
15:57
16:23
16:25
16:27
16:29
16:32
16:34
16:36
17:0
Filename
19250124
19250123
19250126
19250127
19250128
19250129
19250130
19250131
19250132
19250144
19250145
19250146
19250147
19250148
19250149
19250150
19250160
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
0.03
Uncertainty
16.6
20.0
20.8
21.1
21.2
21.4
21.9
21.8
16.7
22.4
22.7
22.9
230
226
226
22.8
25.7
203
Toluene
Ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
000
000
0.00
0.00
0.00
Uncertainty
11.5
13.8
14.3
14.6
14.6
14.7
15.1
IS.O
11.5
15.4
15.6
158
158
15.5
15.5
15.7
17.7
14.0
Hexane
ppm
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Uncertainly
1.5
1.9
1.9
2.0
2.0
2.0
2.0
2.0
1.6
2.1
2.1
2.1
2.1
21
2.1
21
2.4
1.9
Methane
ppm
21.6
24.1
24.7
24.8
24.7
25.1
25.8
29.5
43.9
25.9
26.2
26.5
26.6
25.9
25.9
262
28.2
254
Uncertainty
5.8
7.0
7.3
7.4
7.4
7.5
7.7
7.7
5.8
7.9
8.0
8.0
8.1
7.9
7.9
8.0
9.0
71
Carbon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
578.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
34.7
Uncertainly
88.4
100.5
102.7
103.8
104.5
105.6
107.4
108.0
129.8
110.8
112.0
112.3
II 2.5
110.8
III 1
1120
124.1
1033
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
7.1
8.5
8.8
9.0
9.0
9.1
9.3
93
7.1
9.5
9.6
9.7
9.7
9.6
96
9.7
109
8.6
CD
Bold text indicates thai this is spiked data nut used in average.
-------
03
oo
TABLE B-2. FTIR RESULTS FROM THE SCRUBBER OUTLET
Dale
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
Time
12:30
12:53
13:30
13:38
13:46
15:16
15:19
15:21
15:23
15:25
15:27
15:29
15:31
15:34
15:36
15:38
16:6
16:8
16:10
16:12
16:14
16:17
16:19
" ' 16:47
16:49
16:51
16:53
16:55
Hie name
oirrsFioi
OUTONOJ
OUTST1M
OUTST1M
OUTSP1M
19230001
19230002
19230003
19230004
19230005
19230006
19230007
19230008
19230009
19230010
192300 II
19230024
19230025
19230026
19230027
19230028
19230029
19230030
19230042
19230043
19230044
19230045
19230046
Hydrogen chloride
ppm
•.00
0.00
MO
•JO
•40
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
000
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainty
15.1
13.4
1.7
9.2
14.0
135
13.9
13.6
137
13.6
13.6
13.7
13.5
13.8
11.9
10.5
7.3
7.3
7.3
7.2
7.1
7.1
7.1
6.8
69
6.9
69
69
Hexane
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
0.00
000
Uncertainly
1.4
1.2
•••
•.9
IJ
1.3
1.3
1.3
1.3
13
1.3
1.3
1.3
1.3
II
0.98
0.68
0.68
0.67
0.67
0.66
0.66
0.66
0.64
0.64
0.64
0.64
0.64
Methane
ppm
23.5
20.7
14.2
14.9
21.2
20.5
20.6
20.3
20.6
20.9
20.6
20.9
20.8
231
363
20.4
15.8
16.0
16.0
15.9
15.9
161
153
152
14.7
14.6
14.8
14.4
Uncertainty
5.3
4.7
3.1
3.2
4.9
4.8
4.9
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.2
37
2.6
2.6
2.5
2.5
2.5
2.5
2.5
2.4
2.4
2.4
2.4
2.4
Carbon monoxide
ppn>
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
544.3
102.1
139.3
126.5
127.4
129.6
143.5
153.0
153.8
163.7
1656
163.9
166.0
1656
Uncertainly
•23
75.0
50.2
52.4
7*.*
77.0
78.9
78.0
78.6
76.8
78.0
77.8
77.1
79.0
115.8
650
51.8
508
50.6
505
513
522
52.3
51.8
52.2
52.1
524
52.4
Formaldehyde
ppm
•M
0.00
14.7
153
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
4.4
5.7
3.4
3J
5.9
5.7
5.9
58
58
58
5.8
5.8
5.7
5.8
5.1
4.5
3.1
3.1
3.1
3.0
3.0
3.0
3.0
2.9
29
29
2.9
2.9 J
Bold text indicates thai this is spiked daia not used in average.
-------
TABLE B-2. (continued)
Due
9/23/97
9/23/97
9/23/97
903191
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
9/23/97
Average— >
Time
16:57
17:32
17:34
17:36
17:38
17:40
17:43
17:45
17:47
17:49
18:50
Filename
19230047
19230063
19230064
19230065
19230066
19230067
19230068
19230069
19230070
19230071
OUTARI07
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
6.9
13.1
13.7
14.0
14.3
14.6
14.3
12.3
II. 1
10.3
1.4
10.5
Hexane
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
0.64
1.2
1.3
1.3
1.3
1.4
1.3
I.I
1.03
0.9S
0.13
0.97
Methane
ppm
14.9
19.7
20.3
20.8
21.2
21.4
21.2
19.7
18.4
17.1
4.6
18.5
Uncertainly
2.4
4.6
4.8
4.9
S.O
5.1
5.0
4.3
3.9
3.6
0.49
37
Caibon monoxide
ppm
166.1
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
76.8
Uncertainly
52.4
76.0
78.5
79.0
80.1
81.0
77.4
61.8
55.5
52.4
9.7
64.9
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
2.9
5.6
5.8
5.9
6.0
6.2
6.1
5.2
4.7
4.4
0.59
4.4
CO
MD
Bold text indicates that this is spiked data not used in average.
-------
TABLE B-2. (continued)
Dale
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
Tune
8:34
9:8
9:41
9:50
10:17
10.21
10:24
10:26
10:28
10:30
10:32
10:34
10:37
11:9
11:11
11:13
11:15
11:17
11:20
11:22
II 24
11:26
12:15
12:17
12:19
12:21
12:24
File nune
OUTSTM1
OUTUN202
OU1SPM3
OU1UN2M
19240010
1924001 1
19240012
19240013
19240014
19240015
19240016
19240017
19240018
19240032
19240033
19240034
19240035
19240036
19240037
19240038
19240039
19240040
19240062
19240063
19240064
19240065
19240066
Hydrogen chloride
ppm
tM
0.00
•M
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
000
Uncertainly
12.1
14.5
8.2
13.5
13.9
13.9
14.0
14.1
14.2
14.1
14.3
14.4
14.4
15.2
15 1
15.3
15.2
15.2
15.1
15.4
157
15.7
154
15.3
15.3
15.1
15.0
Hexane
ppm
0.00
0.00
•.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
000
0.00
Uncertainly
1.1
1.3
0.8
1.3
1.3
1.3
1.3
1.3
13
1.3
1.3
1.3
1.3
1.4
1.4
1.4
1.4
1.4
1.4
1.4
15
1.5
1.4
1.4
1.4
1.4
14
Methane
ppm
15.8
30.1
11.8
18.7
18.8
18.8
19.1
19.1
19.1
18.9
19.4
19.4
19.3
20.7
20.6
20.9
20.6
20.4
20.3
20.5
21.0
21.0
21.5
21.4
21.2
21.0
20.8
Uncertainly
4.3
S.I
2.9
4.8
4.9
4.9
4.9
5.0
5.0
4.9
5.0
5.1
5.0
5.3
5.3
54
5.4
5.3
5.3
5.4
55
5.5
5.4
5.4
5.4
5.3
5.3
Carbon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
000
Uncertainly
68.5
82.4
47.1
75.0
77.4
77.2
77.6
78.1
78.5
78.5
79.3
79.8
79.7
83.9
83.6
84.1
83.9
83.7
84.0
85.4
86.5
86.8
84.5
83.7
838
H27
82.5
Formaldehyde
ppm
>.o
0.00
13.*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
000
0.00
000
Uncertainly
5.1
6.1
3.5
5.7
5.9
5.9
5.9
6.0
60
6.0
6.1
6.1
61
64
64
6.5
6.5
6.4
6.4
6.5 1
67 I
6.7
6.5
65
65
6.4
64 J
CO
I
o
Bold text indicates thai this is spiked dula not used in average.
-------
TABLE B-2. (continued)
Date
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
9/24/97
Average— >
Time
12:26
12:28
12:30
12:32
12:34
13.35
13:37
13:39
13:41
13:43
13:45
13:47
14:35
14:49
15:5
Hie Mine
19240067
19240061
19240069
19240070
19240071
19240101
19240102
19240103
19240104
19240105
19240106
19240107
OUTSP205
OUTN2206
OUTUN207
Hydrogen chloride
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.2
000
0.03
Uncertainly
IS.I
15.4
15.4
15.2
IS.I
18.7
18.4
18.1
17.0
165
16.6
164
11.3
0.7
142
149
Hexane
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
1.4
1.4
1.4
1.4
1.4
1.7
17
1.7
1.6
1.5
1.5
15
1.1
0.06
1.3
1.4
Methane
ppm
20.7
21.1
21.1
21.0
20.9
24.6
24.2
24.1
22.7
22.4
22.3
22.2
14.9
0.66
19.7
20.5
Uncertainly
5.3
5.4
5.4
5.3
5.3
6.6
6.5
6.4
6.0
5.8
5.8
5.8
4.0
0.24
5.0
5.3
Carbon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
. 0.00
0.00
000
Uncertainly
83.0
84.0
83.8
83.0
83.1
104.1
99.0
96.6
91.2
89.2
89.4
88.8
«!.«
5.7
77.5
82.1
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
20.2
0.00
0.00
0.00
Uncertainly
6.4
6.5
6.5
6.4
6.4
79
7.8
7.7
7.2
7.0
7.0
7.0
4.8
0.28
60
63
DO
Bold text indicates thai this is spiked data not used in average.
-------
TABLE B 2. (continued)
Dale
9fUI91
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
Time
•:1
8:8
8:56
8:58
9:1
9:3
9:5
9:7
9:9
9.11
9:42
9:45
9:47
9:49
9:51
9:53
9:55
9:57
10:0
10:32
10:34
10:36
10:38
10:41
10:43
10:45
10:47
Filename
oursrtti
OUTN2302
19250001
19250002
19250003
19250004
19250005
19250006
19250007
19250008
19250018
19250019
19250020
19250021
19250022
19250023
19250024
19250025
19250026
19250041
19250042
19250043
19250044
19250045
19250046
19250047
19250048
Hydrogen chloride
ppm
0.00
0.88
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
000
Uncertainly
4.2
0.34
9.4
9.5
9.7
9.6
9.6
9.6
9.6
9.6
9.0
9.1
9.1
91
9.1
9.1
9.1
9.1
9.2
9.4
9.4
9.4
9.4
9.4
9.4
92
9.2
Hexane
ppm
•.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
0.57
0.03
0.87
0.89
0.90
0.90
0.89
0.89
0.89
0.89
0.84
085
0.85
0.85
0.85
0.84
0.84
0.85
0.86
0.87
0.87
0.88
0.88
0.88
087
0.86
085
Methane
ppm
7.7
0.00
11.7
11.7
11.8
11.8
11.7
11.8
11.8
11.8
H2
114
11.4
11.3
11.3
113
113
11.2
11.4
115
11.6
11.6
11.8
11.7
11.6
11.5
115
Uncertainly
2.2
0.10
3.3
3.4
34
3.4
3.4
3.4
3.4
3.4
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.3
3.3
3.3
3.3
3.3
3.3
3.2
3.2
Caiton monoxide
ppm
0.00
70
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainty '
40.0
2.6
64.2
65.0
65.4
65.0
64.5
64.2
64.2
64.0
60.8
61.4
614
61.1
61.1
607
61.1
61.5
62.2
61.9
62.2
62.5
62.2
620
614
60.6
604
Fbfmaldehyde
ppm
30.7
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
2.4
0.1
4.0
4.0
4.1
4.1
41
4.1
4.1
41
38
3.9
3.9
3.9
3.9
3.8
3.8
3.9
3.9
40
4.0
40
4.0
40
40
39
39
CD
Ki
Bold lexl indicates thai this is spiked data not used in average.
-------
TABLE B 2. (continued)
[tele
9/25/97
905191
9/25/97
9/25/97
9/2V97
9/25/97
9/2$/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/2S/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
Time
10:49
11:50
11:52
11.54
11:56
11:59
12:1
12:3
12:5
12:33
12:35
12:37
12:40
12:42
12:44
12:46
12.48
12:50
13:16
13:18
13:20
13:23
13:25
13:27
13:29
13:46
13:54
Filename
19230049
19250064
19250065
19250066
19250067
19250068
19250069
19250070
19250071
19250084
19250085
19250086
19250087
19250088
19250089
19250090
19250091
19250092
19250104
19250105
19250106
19250107
19250108
19250109
19250110
OUTDI303
OUTDI304
Hydrogen chloride
pfMD
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Uncertainly
9.1
9.0
9.1
9.2
9.2
9.2
9.2
9.2
9.2
9.2
9.3
9.4
9.4
9.4
9.4
9.4
9.4
9.4
9.7
9.8
9.9
9.9
9.9
9.9
9.8
5.3
52
Hexane
ppm
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
0.85
0.84
0.85
0.85
0.86
0.86
0.86
0.86
0.85
0.86
0.86
0.87
0.87
0.87
0.87
0.87
0.87
0.87
0.90
0.91
0.92
0.92
0.92
0.92
0.92
0.49
049
Methane
ppm
11.4
11.4
11.8
11.7
11.6
11.6
11.8
11.7
11.5
11.7
11.8
11.8
11.7
11.7
11.6
11.7
11.9
121
12.0
12.0
12.2
12.1
12.0
12.0
11.9
6.2
61
Uncertainly
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.3
3.3
3.3
3.3
33
3.3
3.3
3.3
3.4
3.4
3.5
3.5
3.5
3.5
3..S
1.9
1.8
Carbon monoxide
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
60.2
63.2
63.2
62.9
63.1
62.9
62.6
62.7
62.6
63.1
63.5
63.8
63.8
63.9
63.9
63.7
63.0
62.7
65.5
66.0
66.2
66.3
66.4
66.2
66.4
34.7
36.3
Formaldehyde
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
Uncertainly
39
3.8
3.9
3.9
3.9
3.9
3.9
3.9
3.9
3.9
3.9
4.0
4.0
4.0 I
40
4.0
4.0
4.0
4.1
4.2
4.2
4.2
4.2
4.2
4.2
22
2.2
CO
Bold text indicates that this is spiked data not used in average.
X
-------
TABLE B-2. (continued)
Dale
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
9/25/97
Average — >
Time
14:4*
14:54
15:14
15:16
15:18
15:20
15:22
15:24
15:27
16.5
16:8
16:10
16:12
16:14
16:16
16:44
16:47
16:49
16:51
16:53
Hie name
OUT8TM5
OUTN2306
19250112
192501 13
192501 14
192501 15
192501 16
192501 17
192501 18
19250136
19250137
19250138
19250139
19250140
19250 141
19250154
19250155
19250156
19250157
19250158
Hydrogen chloride
ppm
fcM
0.40
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
Uncertainly
8.0
0.17
9.7
9.6
9.6
9.5
9.5
9.5
9.4
8.3
8.4
8.5
8.7
8.7
88
9.3
9.3
9.2
9.2
9.2
8.9
Hexane
ppm
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
000
Uncertainly
•.74
0.02
0.90
0.90
0.89
0.88
0.88
0.88
0.87
0.77
0.78
0.79
0.81
081
0.81
0.87
0.86
0.86
0.85
0.85
083
Methane
ppm
»J
0.00
12.4
12.1
12.0
11.9
12.1
12.3
12.1
113
11.4
11.6
11.5
11.7
116
12.0
11.9
12.1
11.8
11.8
112
Uncertainly
2.1
0.06
3.4
3.4
3.4
3.3
3.3
3.3
3.3
2.9
2.9
3.0
3.0
3.1
3.1
3.3
33
3.2
3.2
3.2
3.1
Canton monoxide
ppm
0.00
7.2
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.20
Uncertainly
*1.1
2.0
75.3
68.1
66.6
65.7
65.2
65.0
64.5
59.5
60.1
60.5
61.6
61.6
61.6
65.9
65.8
65.6
65.7
653
61 1
Fbnnaldehyde
ppm
13J
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
Uncertainly
3.4
0.1
4.1
4.1
4.1
4.0
4.0
40
40
3.5
3.6
3.6
3.7
37
3.7
4.0
3.9
3.9
3.9
39
38
00
Bold lext indicates (hat (his is spiked data not used in average.
-------
B-2 FTIR FIELD DATA RECORDS
-------
PROJECT NO. 4701-OI-M
PLANT: GMPowertrain
FTIR FIELD DATA FORM
(F1W Sampling D»l»)
DATE:
9/23/91
BAROMETRIC: 749 mm Hj
OPERATOR: LMH
SAMH.E
TIME
11:55
*
12:04
12:14
12:21
12:33
12:58
13:07
13:27
13:50
14:00
14:14
14:19
14:27
14:35
FILE
NAME
INLSP101
POUR101
BKG0923b
POUR102
SHK3.101
INLSP102
INI.N2103
OUTSP101
BADSPKE
OUTN2102
BAOSPDCE
OUTSPI03
BADSPKE
BKG0923C
INL.UNI04
INLUN105
OUTSPI04
OUTSP105
fATM
Inlet air w/Spikegat
1.0 hM tolncae 196 ppm
1 .0 Ipin SP6 4 ppm tad formaldehyde @ 100C
flow —Cell » 4.0 |pm, veal » 2.0 Ipm
BAGfl-pourmglnc
sampled IftOO am to 1 1 :32 am
Background. N2
BAG #1- pouring line
BAG#2-Shakeout-3
NUMBEI
SCANS
250
250
500
250
250
* Sucked out bag wkh pump before realized value was incorrect
Slack #3. shakeoui line «4
Inlei - In slack w/ spike gas
1 .0 Ipm toluene 196pfm
1 .0 jpoi SF6 4 ppm and formaldehyde @ 100C
flow —Cell = 4.0 Ipm. venl = 2.0 Ipm
N2 flooding spike line
Outlet - in slack, spike SF6, 4 ppm@ l.Olpm
w/fonn»ldehyde@ 100 C. toluene . 1% ppm.
a 1 .0 Ipm, flow - cell = 4.0 Ipm. venl - 2.0 Ipm
N2 flooding spike line
••didn't work**
SF6
-------
FTIR FIELD DATA FORM
PROJECT NO. 4701-M-Ot
PLANT: CM Powtrtrain
DATE:
BAROMETRIC: 74» mm Hg
OPERATOR: LMH
SAMPLE
TIME
14:43
14:49
14:50
15:29
15:45
15:52
15:56
16:05
16:12
16:38
16:40
16:41
16:58
17:02
17:17
17:21
17:39
17:43
17:51
18:05
.FILE
NAME
OUTSP106
1NLUN106
INLUNI07
BKG0923d
SHK4JOI
S11K4 102
INLUN108
1923001
1023011
1923014
1923021
1923024
1923030
1923033
1923039
1923042
1923047 '
1923052
PATH
OUTLET- NO SPIKEIII
INLET
Yoceu went down - inlet flaw dropped
Uowenoff
NLET
Background. N2
BAG*3--Shakeoul4
JAG»3 ShakeouU
NLET
*rocess software
Outlet
Slop
1923012 and 1923013 purge and fill cell
Vice is down
INLET
Slop
1923022 and 1923023 purge and fill cell
Outlet
Stop
Process software
INLET
Stop
40 and 4 1 purge and fill cell
Outlet
Pound probe and probe box unplugged
Probe <3> 125C. Box @ 188C
only effects dm outlet run
Slop
INLET
NUMBER
SCANS
250
250
250
500
250
250
250
250
250
250
250
250
RES
(ۥ-1)
2
2
2
2
2
2
2
2
2
2
2
2 .
CELL
TEMP(F)
275
275
275
275
275
275
275
277
275
275
275
275
SPIKED/
UNSPIKED
UN
UN
UN
UN
UN
UN
UN
UN
SAMPLE
CONO.
dynamic
dynamic
dynamic
static
suite
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
SAMPLE
FLOW
5.01pm
5.01pm
501pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
CELL PRES.
758
757
758
748
748
755
755
757
758
759
759
•KG
0923c
0923c
0923d
0923d
0923d
0923d
0923d
0923d
0923d
0923d
-------
PROJECT NO. 4701-0«.M
PLANT: CM Powertr«ln
FTIR FIELD DATA FORM
(FT1R StmpUng Otto)
DATE:
9/13/97
BAROMETRIC: 74»mmHg
OPERATOR: LM»
SAMPLE
TIME
18:20
18:24
18:29
18:45
18.48
19:01
19:10
19:20
19:24
19:33
19.46
FILE
NAME
1923060
1923063
1923071
N20923c
MDC09236
CTS0923c
BKG0923e
1NAIR109
OUTAR107
PATH
Proceu rcilaited
Slop
61 and 62purie and fill cell
Owl*
Proceii went down
Stop
N2onJy
Toluene flow off, SF64ppro,<5> 2.01pm
w/fomuldehyde@ IOOC
Elhylcne 200m
N2onjy
Air from roof - Intel
Air from roof- Outlet
NUMBER
SCANS
250
250
250
250
250
250
250
250
RES
<«•-!)
2
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
275
275
276
276
SPIKED/
UNSPIKED
UN
UN
UN
UN
SAMPLE
COND.
dynamic
dynamic
dynamic
dynamic
Malic
static
.
SAMPLE
FLOW
5.01pm
5.01pm
5.01pm
3.01pm
5.01pm
5.01pm
CELL PBES.
759
759
759
755
754
754
757
757
BKG
0923d
0923d
0923d
0923d
0923d
092 3e
0923e
-------
PROJECT NO. 47>1-0«-M
PLANT: CM Powertrain
FTIR FIELD DATA FORM
(FJIRStmpUngI**)
DATE:
»/24/»7
BAROMETRIC: 7S2 mm Hg
OPERATOR: LMH
SAMPLE
TIME
7:46
8:29
8:41
8:51
9:06
9:08
9:16
9:30
9:35
9:39
9:48
9:55
10:11
10:17
10:36
10:43
10:58
11:05
11:18-11:45
11:26
FILE
NAME
N20924*
OUTSP20I
1NLSP201
OUTUN202
BKG0924b
INLSP202
OUTSP203
OUTUN204
19240001
19240007
19240010
19240018
19240022
19240028
19240032
19240040
PATH
20m
N2 only direct lo cell
Owlet Spike
SP6, 4ppm @ 2.0 Ipm w/formaldehyde <2> IOOC
Toluene v«hre off
Ceil flow = 4.0 Ipm, vent flow = 2.0 Ipm
Inlet - Spike unte conditions as above
Manual sampling suited
Outlet
hroceudown
Background
Inlet spike wAoluene
SF6 4 ppm @ 2.0 Ipm w/fonnaldehyde @ IOOC
and toluene 1% ppm
2
2
2
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
275
276
275
276
276
276
SPIKED/
UNSPUED
SP
SP
UN
UN
SP
UN
UN
UN
UN
SAMPLE
COND.
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
SAMPLE
FLOW
5.01pm
4.01pm
4.01pm
3.01pm
5.01pm
4.01pm
3.01pm
5.01pm
5.01pm
5.01pm
CELL PRES.
758
758
759
760
760
758
759
756
759
•KG
0923e
0924a
0924*
0924a
0924b
0924a
0924b
0924b
0924b
0924b
-------
PROJECT NO. 4701-08-M
PLANT: CM Powertrain
FTIR FIELD DATA FORM
(FTia StmpUng D*tt)
DATE:
BAROMETRIC: 752 mm Hg
OPERATOR: LMH
SAMPLE
TIME
11:31
11:49
12:09
12:13 .
12:35
12:41
13.04
13:15
13:20
13:23
13.27
13:33
13:49
13:52
14:09
14.21
14:33
14.46
14:56
15:03
15:16
15:23
15:30
15:35
FILE
NAME
BKG0924c
19240001
19240009
19240012
19240021
19240024
19240034
N20924b
SHK3.201
SHK3_202
SHK5J01
19240001
19240007
19240010
19240017
INSP203
OUTSP205
OUTN2206
INLN2204
OUTUN207
N20924c
BKG0924d
COOLS101
COOLS 102
PATH
Background
leilait process software
Inlet (rename lo 0051)
Stop (rename 10 0059)
Owlet (rename lo 0062)
Slop (rename to 0071)
Inlet (resume lo 0074)
Stop (rename lo 0084)
N2 direct lo cell, only
NO BAG #4 TESTED
Shakeout#3-BAG»S
Shakeoui «3 - BAG #5
Shakeoul #5 BAG «6
Outlet (rename lo 0101)
Slop (rename lo 0107)
Inlet (rename lo 01 10)
Slop (rename lo 01 17)
Inlet spike
SF6 (S> 2.0 Ipm w/formaldehyde @ 1 IOC
toluene @ 1.0 Ipm
Cell How = 4.0 Ipm, Vent = 10 Ipn
Outlet - Spike
Nitrogen in Mack line - OuUel
Nitrogen in Hack - inlel
Outlet
N2 direct lo cell
Background
BAG #7- Cooling Mack
BAG #7- Cooling Mack
NUMtEB
SCANS
500
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
500
250
250
RES
-------
FTIR FIELD DATA FORM
PROJECT NO. 4701-Og-M,
PLANT: CM Powertmin
DATE: 9J2SO2
BAROMETRIC: 73S rooi Hg
OPERATOR: LMH
SAMPLE
TIME
7.59
8:06
8:13
8:23
8:31
8:34
8.54
9:12
9:16
9:31
9:40
9:41
10:00
10:08
10.26
10:30
10:49
11:01
11:07
11.11
11:17
11.25
11:32
11:44
FILE
NAME
OUTSP301
OUTN2302
INLSP301
INLSP302
1NLN2303
19250001
19250008
19250011
19250017
19250018
19250026
19250030
19250038
19250041
19250049
N2BAG101
COOLR101
COOLRI02
19250050
19250061
PATH
Outlet spike
SP6 4 ppm @ 2.0 Ipm w/lbrmaldehyde @ 1 10 C
and toluene 196 ppm@ 1.0 Ipm
ccU flow = 4.0 Ipm, vent flow = 2.0 Ipm
Outlet - Nitrogen only in line
Inlet -Spike
Intet- Spike
Spike levels time as above
cell flow = 5.0 Ipm, vent flow = 4.0 Ipm
nlet - Nitrogen only in sample line
tlanual nni Muted
Vocess software
Outlet
Stop
Inlet
Slop
Slopped program
Moved inlet ports
Outlet - Continuous software restarted
Stop
Intel
Stop
Outlet
Slop
N2 only in bag - Nitrogen blank
Bag #9 - Cooling Hack "R"
Bag #9 - Cooling suck "R"
Inlet
Process down
Process up and running
Stop
NUMBER
SCANS
250
250
250
250
250
250
250
250
250
250
250
250
250
250
RES
(CM-1)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
275
276
276
276
276
276
276
275
275
276
SPIKED/
UNSPIKED
SP
N2
SP
SP
N2
UN
UN
UN
UN
UN
N2
UN
SAMPLE
COND.
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
static
italic
static
dynamic
SAMPLE
FLOW
4.01pm
401pm
4.01pm
5.01pm
4.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
CELL PRES.
742
742
742
742
743
743
743
742
745
736
733
733
747
•KG
0925.
0925a
0925a
0925a
0925b
0925b
0925b
0925b
0925b
0925c
0925c
0925c
0925c
-------
FTIR FIELD DATA FORM
PROJECT NO. 47>1.>«-M
PLANT: CM Powertr.in
DATE:
BAROMETRIC: 74? mm Hg
OPERATOR: LMH
SAMPLE
TIME '
11:48
12:05
12:10
12:26
12:31
12:50
12:55
13:10
13:14
13:29
13:44
13:50
13:58
14:00
14:07
14:11
14:17
14:20
14:30
14:37
14:46
14.53
FILE
NAME
19250064
19250071
19250074
19250081
19250084
19250092
19250095
19250101
19250104
19250110
Ouidi303
uuidi304
N20925c
Bkg6925d
COOLM101
COOL1RI02
BACKlOl
BACK102
INLSP304
INLN2305
OUTSP305
OUTN2306
PATH
Outlet
Stop
Inlet
Slop
Outlet
Slop
Into
Stop
Outlet
Stop
Diluted outlet - outlet sample
diluted with N2 it manifold
sample = 2.5 Ipm
N2 = 2.5 Ipm
Diluted outlet - ume is above
N2 to cell
Background
BAG 410 - cooling main Mack
BAG #10 - cooling main suck
BAG *8 - Background bag
sampled inside facility on 1st floor
near the cooling main suck
Same as above
Inlet spike SF6 4 ppm @ 1.0 Ipm w/foimaldehyde
@ 100C and toluene I96ppm@ 1.0 Ipm
cell flow = 5.0 Ipm, vent = 2.0 Ipm
Inlet zero - N2 only in sample line
Outlet spike (same as above)
Outlet - zero - N2 in sample line
NUMBER
SCANS
250
250
250
250
250
250
500
250
250
250
250
250
250
250
250
EES
<«•-!)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CELL
TEMP(F)
276
276
275
275
275
275
275
275
275
275
276
276
276
276
SPIKED/
UNSPIKED
UN
UN
UN
UN
UN
diluted @
manifold
SP
N2
SP
N2
SAMPLE
COND.
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
static
static
static
static
dynamic
dynamic
dynamic
dynamic
SAMPLE
FLOW
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
501pm
5.01pm
CELL PRES.
747
747
746
744
745
745
738
738
733
733
746
745
745
745
BUG
0925c
0925c
0925c
0925c
0925c
0925c
0925d
0925d
0925d
0925d
0925d
0925d
0925d
0925d
-------
PROJECT NO. 47H-08-M
PLANT: CM Powertrain
FTIR FIELD DATA FORM
(FTIft Stmpllng D»t»)
DATE:
§/25/»7
BAROMETRIC: 749 mm Hg
OPERATOR: LMH
SAMPLE
TIME
15:11
15:27
15:33
15:35
15:43
15:55
16:01
16:03
16:16
16:21
16:37
16:46
16:54
16:56
16:58
17:08
FILE
NAME
19250112
19250118
19250122
19250132
19250136
19250141
19250144
19250150
19250154
19250158
19250160
N20925d
PATH
Outlet
Slop
Inlet
•roceudown
Vooeuup
Voces* down
Slop
Vocesi up
Oullel
Slop
Inlet
Slop
Outlet
Slop
Inlet
Slop
N2 direct lu cell
NUMBER
SCANS
250
250
250
250
250
250
250
RES
<ۥ-!)
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
276
276
275
SPIKED/
UNSPIKEU
UN
UN
UN
UN
UN
UN
SAMPLE
CONO.
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
dynamic
SAMPLE
FLOW
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
5.01pm
CELL PRES.
745
745
747
746
744
747
•KG
0925d
0925d
0925J
0925d
0925d
0925d
^0925d
-------
PROJECT NO. 4701-0|-0«-
PLANT: CM Powertraln
FTIR FIELD DATA FORM
(Bmdcground and calibration tpoctn.)
DATE: 9/23/97
BAROMETRIC:
OPERATOR:
749 nun HE
T. Cwr
SAMPLE
TIME
9:00
9:21
9:28
9:37
9:43
9:50
9:57
10:10
10:38
10:47
11:07
11:42
FILE
NAME
N20923a
BKG0923a
CTS0923a
CTS0923b
SF60923a
TOL0923a
FOR0923a
FOR09236
A«0923a
AK0923b
MDC0923b
PATH
N2only
Cell leak check T=0 2.3 loir, T=87s 3.3loir
Background, N2 only
Elhylene, 20 ppm in nitrogen
Elhylene, 20 ppm in nitrogen
SF6 direct to cell - 4.01 ppm
Toluene direct to cell 196.9 ppm in air
Formaldehyde perm lube
1 000 1pm of N2 @ 100 C 94,087 nano L/min
direct lo cell
Formaldehyde - same as above
Inlet - Air only
Outlet -air only
Toluene 196.9 ppm @ 1 1pm
Kiniek = SF6 - 4ppm @ 1 .0 Ipm and form @ 100C
direct to cell
NUMBER
SCANS
250
500
250
250
250
250
250
250
250
250
250
RES
(c«-l)
2
2
2
2
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
275
275
275
275
275
275
275
PRESSURE
760
756
752
752
752
752
752
752
752
752
752
•KG
0922a
0923a
0923a
0923a
0923a
0923a
0923a
0923a
0923a
0923a
APOD
gain = 4
NOTES
flowing - 51pm
Malic
static
slalic
static
slalic
dynamic - 1 Ipm
dynamic - 5 Ipm
dynamic - 5 Ipm
dynamic - 5 Ipm
-------
PROJECT NO. 4701-08-08
PLANT: CM Powcrtrain
FTIR FIELD DATA FORM
(Background and calibration tpoctra.)
DATE: 9/24/97
BAROMETRIC:
OPERATOR:
7S2 mm Hg
T. Gever
SAMPLE
TIME
7:50
8:14
8:57
9:00
9:16
11:31
15:23
15:47
FILE
NAME
BKG0924a
CTS0924a
MLX0924a
BKG0924b
BKG0924c
BKG0924d
CTS0924b
PATH
Background, N2 only
20 ppm Elhylenc in nitrogen
SF6, 4 ppm <§> 2.0 1pm wilh formaldehyde @ 100 C
94,000 nanoL/min and toluene 196 ppm @ 1 .0 Ipm
Leak check cell T=0 3.7. T=60sec 4.3
0.6 mm Hg/60 sec
N2, Background
N2. Background
N2, Background
20 ppm Eihylene
NUMBER
SCANS
500
250
250
500
500
500
250
RES
(e»l)
2
2
2
2
2
2
2
CELL
TEMP (F)
275
275
275
275
275
275
275
PRESSURE
758
757
757
760
758
. 755
BUG
0924a
0924a
0924d
APOD
NOTES
5 1pm flow
-------
PROJECT NO. 4701-08-08
PLANT: CM Powertrain
FTIR FIELD DATA FORM
(Background and calibration apactra.)
DATE: 9/25/97
BAROMETRIC:
OPERATOR:
73SmmHf
T. Gevtr
SAMPLE
TIME
7:29
7:32
7:42
7:47
8:39
8.43
8:48
10:54
13:58
14:00
15:04
17:12
17:20
FILE
NAME
N20925a
BKG0925a
CTS0925a
CTS0925b
MIX0925a
N20925b
BKG0925b
BKG0925c
N20925c
BKG0925d
MLX0925b
BKG0925e
CTS0925C
PATH
*42 only direct to cell
Background
Elhylene 20ppm in Nitrogen
Elhylenc 20ppm in Nitrogen
SF6 4ppm @ 2.0 1pm with formaldehyde @ 1 10 C
NUMBER
SCANS
250
500
250
250
250
(202.000 nanoL/min) and toluene 196 ppm @ 1 .0 1pm
direct to cell
M2 only, direct to cell
Background, N2 only
Background, N2 only
M2 only, direct to cell
Background, N2 only
SF6 4ppm @ 1 .0 Ipm w/ fomaldehyde (ffi 100C
(94,000 nanoL/min) and toluene 196 ppm @ 1 .0 Ipm
direct 10 cell
Background, N2 only
Ethylene, 20 ppm
250
500
500
250
500
250
500
RES
(«-!)
2
2
2
2
2
2
2
2
2
CELL
TEMP(F)
275
275
275
275
276
276
276
276
276
276
276
PRESSURE
742
742
742
739
747
746
745
745
741
BKG
0924a
0925a
0925a
0925a
0925a
0925c
0925d
0925e
APOD
NOTES
5 Ipm
3.0 Ipm
5.0 Ipm
5.0 Ipm
-------
PROJECT NO.
PLANT;
OPERATOR:
FTIR FIELD DATA FORM
Sampling Data
DATE:
BAROMETRIC:.
LEAK CHECK-START:
LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
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09-15-97
-------
FTIR FIELD DATA FORM
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DATE:
BAROMETRIC:
LEAK CHECK-START:
LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
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SCANS
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FTIR FIELD DATA FORM
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LEAK CHECK-END:
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TIME
FILE
NAME
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NAME
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BAROMETRIC: W
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TIME
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MIDWEST RESEARCH INSTITUTE
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09-15-97
-------
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PROJECT NO.
PLANT;
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-------
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-------
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Sampling Data
OPERATOR:
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LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION / NOTES
NUMBER
SCANS
RES
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CELL
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-------
PROJECT NO.
PLANT:
FTIR FIELD DATA FORM
Sampling Data
OPERATOR:
DATE:
BAROMETRIC:
LEAK CHECK-START:.
LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
NUMBER
SCANS
RES
CELL
TEMP(f)
SPIKED/
UNSPIKEO
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FLOW
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My Documcnu/FTr ">RM/FieldalO XI-S
09 15 97
-------
' CjJopoV
FTIR FIELD DATA FORM
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PROJECT NO.
PLANT; 6M\>if*>V-%«!.
SAMrLE
TIME
FILE
NAME
PATH
LOCATION/ NOTES
NUMBER
SCANS
CELL
TEMP(F)
SPIKED/
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09-15-97
-------
PROJECT NO.
PLANT;
OPERATOR;
FTIR FIELD DATA FORM
Sampling Data
DATE: __1J!£JY7_
BAROMETRIC: 73$
LEAK CHECK-START:_
LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
NUMBER
SCANS
RES
(0.1)
CELL
TEMP(F)
SPIKED/
UNSPIKED
SAMPLE
COND.
SAMPLE
FLOW
CELL
PRESS.
BKC
-------
PROJECT NO.
PLANT: kftv
FTIR FIELD DATA FORM
Sampling Data
OPERATOR;
DATE:
BAROMETRIC:
LEAK CHECK-START:
LEAK CHECK-END:
SAMPLE
TIME
FILE
NAME
fATH
LOCATION /NOTES
NUMBER
SCANS
RES
(CM-1)
CELL
TEMP(F)
SPIKED/
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00 15-97
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PROJECT NO.
PLANT; (>m
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Sampling Data
BAROMETRIC: '? 3 5/v~- \
DATE:
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LEAK CHECK-END:
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SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
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SCANS
RES
CELL
TEMr(F)
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FLOW
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09-15-97
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PROJECT NO..
PLANT; ftn\ &*•*»<
FTIR FIELD DATA FORM
Sampling Data
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DATE:
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09-15-97
-------
PROJECT NO.
PLANT:
FTIR FIELD DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
NUMBER
SCANS
RES
CELL
TEMP(F)
PRESSURE
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09-15-97
-------
PROJECT NO.
PLANT;
FTIR FIELD DATA FORM
Background and Calibration Spectra
BAROMETRIC:
OPERATOR:
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500
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My UocumenlVFTIPpORM/Field«u2 XtS
09-15 97
-------
PROJECT NO.
PLANT:
FTIR FIELD DATA FORM
Background and Calibration Spectra
DATE:
BAROMETRIC
OPERATOR:
SAMPLE
TIME
FILE
NAME
PATH
LOCATION /NOTES
NUMBER
SCANS
RES
CELL
TEMP(F)
PRESSURE
BKG
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-------
B-3 FTIR FLOW AND TEMPERATURE READINGS
-------
FTIR FIELD DATA FORM
PROJECT NO. 5 tt* I" c
PLANT: 61
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08-27-97
-------
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08-27-97
-------
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MIDWEST RESEARCH INSTITUTE
My Documents/FTIRFORM/Field»Ul XLS
08-27-97
-------
B-4 HYDROCARBON REFERENCE SPECTRA
-------
Reference Spectra of Hydrocarbon Compounds
The purpose of measuring reference spectra of some hydrocarbon compounds was to aid the
analyses of FTIR sample spectra from iron and steel foundries and from integrated iron and steel
plants. Four facilities were tested at these sources. At each facility hydrocarbon compounds were
detected in the emissions. Because the EPA library of FTIR reference spectra contains only
spectra of hazardous air pollutant (HAP) compounds, only quantitative reference spectra of
hexane and isooctane were available to analyze the sample hydrocarbon emissions. As a result the
hydrocarbon emissions were represented primarily by "hexane" in the draft report results. Many
hydrocarbon compounds have infrared spectra which are similar to that of hexane in the spectral
region near 2900 cm"1. MRI selected nine candidate hydrocarbon compounds and measured their
reference spectra in the laboratory. In addition MRI measured new high-temperature reference
spectra of hexane and isooctane. The new reference spectra of these 11 compounds were
included in revised analyses of the sample spectra. The FTIR results presented in the revised test
reports show the measured concentrations of the detected hydrocarbons and also show revised
concentrations of hexane and toluene. The hexane concentrations, in particular, are generally
lower because the infrared absorbance from the hydrocarbon emissions is partly measured by the
new reference spectra. As an example, figure B-l illustrates the similarities among a sample
spectrum and reference spectra of hexane and n-heptane.
MRI prepared a laboratory plan specifying the procedures for measuring the reference spectra.
The EPA-approved laboratory plan is included in this appendix. The data sheets, check lists and
other documentation are also included. During the measurements some minor changes were made
to the laboratory plan procedures. These changes don't affect the data quality, but did allow the
measurements to be completed in less time. This was necessary because the plan review process
was more length than anticipated.
The following changes were to the procedures. The spectra were measured at 1.0 cm"1 resolution,
which was the highest resolution of the sample spectra. It was unnecessary to use a heated line
connection between the mass flow meter and the gas cell because the gas temperature in the cell
was maintained without the heated line. Leak checks were conducted at positive pressure only
because all of the laboratory measurements were conducted at ambient pressure. The reference
spectra, CTS spectra, and background spectra will be provided on a disk with a separate reference
spectrum report.
-------
3000
2950 2900
Wavenumbers (cm'1)
2850
Figure B-l. Top trace, example sample spectrum; middle trace, n-heptane reference spectrum; bottom trace, n-hexane reference
Spectrum.
-------
LABORATORY PLAN FOR
REFERENCE SPECTRUM MEASUREMENTS
DRAFT
Prepared for
Office of Air Quality Planning and Standards
Emissions, Monitoring and Analysis Division
Emission Measurement Center (MD-19)
Research Triangle Park, North Carolina 27711
Mr. Michael Ciolek
Work Assignment Manager
EPA Contract No. 68-D-98-027
Work Assignment 2-12 and 2-13
MRI Project No. 4951-12 and 4951-13
June 14,1999
MIDWEST RESEARCH INSTITUTE 5520 Dillard Road, Suite 100, Gary, NC 27511-9232 • (919) 851-8181
-------
TABLE OF CONTENTS
1.0 INTRODUCTION !
1.1 Objective 1
1.2 Background 2
2.0 TECHNICAL APPROACH 2
2.1 Measurement System 2
2.2 Procedure 3
3.0 QUALITY ASSURANCE AND QUALITY CONTROL 5
3.1 Spectra Archiving .. .• 5
3.2 CTS Spectra 6
3.3 Sample Pressure 6
3.4 Sample Temperature 6
3.5 Spectra 6
3.6 Cell Path Length 6
3.7 Reporting 6
3.8 Documentation 7
FIGURE AND TABLE LIST
Figure 1. Measurement system configuration 4
TABLE 1. ORGANIC COMPOUNDS SELECTED FOR THE LABORATORY STUDY .... 3
in
-------
Laboratory Plan For Reference Spectrum Measurements
EPA Contract No. 68-D-98-027, Work Assignments 2-12 and 2-13
MRI Work Assignments 4951-12 and 4951-13
1.0 INTRODUCTION
In 1997 Midwest Research Institute (MRI) completed FTIR field tests at two iron and
steel sintering facilities and at two iron and steel foundries. The tests were completed under EPA
Contract No. 68-D2-0165, work assignments 4-20 and 4-25 for the sintering plants and
foundries, respectively. The draft test reports were completed in 1998 under EPA Contract
No. 68-W6-0048, work assignment 2-08, tasks 11 and 08 for the sintering plants and foundries,
respectively.
Results from the data analyses indicated that the emissions from some locations included
a mixture of hydrocarbon compounds, one of which was hexane. The EPA spectral library of
FTIR reference spectra is comprised primarily of hazardous air pollutants (HAPs) identified in
Title HI of the 1990 Clean Air Act Amendments and, therefore, contains a limited number of
aliphatic hydrocarbon compounds. MRI will measure reference spectra of some additional
organic compounds that may have been part of the sample mixtures. The new reference spectra
will be used in revised analyses of the sample spectra. The revised analyses will provide a better
measure of the non-hexane sample components and, therefore, more accurate hexane
measurements.
A Quality Assurance Project Plan (QAPP) was submitted for each source under EPA
Contract No. 68-D2-0165, work assignments 4-20 and 4-25. When the QAPPs were prepared it
was not anticipated that laboratory measurements would be required. This document describes
the laboratory procedures and is an addition to the QAPPs.
This document outlines the technical approach and specifies the laboratory procedures
that will be followed to measure the FTIR reference spectra. Electronic copies of the new
reference spectra will be submitted to EPA with corresponding documentation. The laboratory
procedures are consistent with EPA's Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry for the Analyses of Gaseous Emissions From Stationary Sources,
revised 1996.
1.1 Objective
The objective is to obtain accurate hexane measurements from FTIR spectra recorded at
field tests at iron and steel sintering plants and at steel foundry plants. The approach is to
measure reference spectra of some organic compounds that are not included in the EPA reference
spectrum library and then use these new reference spectra in revised analyses of the field test
spectra. The revised analyses will provide better discrimination of the hexane component from
the absorbance bands of the organic mixture.
Laboratory Reference Spectrum Plan EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-13
Draft June 14, 1999 Pa8e 1
-------
1.2 Background
Spectra of samples measured at the field test sites contained infrared absorbance features
that may be due to a mixture of non-aromatic organic compounds. The samples were measured
using quantitative reference spectra in the EPA library and the hexane reference spectra provided
the best model for the observed absorbance features. The EPA library contains a limited number
of reference spectra, primarily HAPs, listed in Title ffl of the 1990 Clean Air Act Amendments,
which includes hexane. To obtain accurate measurements of target components it is helpful to
use reference spectra of all compounds in the sample gas mixture. In this case it was decided to
measure reference spectra of some additional organic compounds, which are similar in structure
and have spectral features similar to hexane. The revised analyses will measure the sample
absorbance in the 2900 cm"1 region using a combination of the hexane and new reference
spectra. The revised analyses should provide more accurate hexane measurements, by measuring
the non-hexane sample components more accurately.
•
2.0 TECHNICAL APPROACH
The analytical region used to measure hexane lies near 2900 cm"1. Other aliphatic
hydrocarbons with structures similar to hexane exhibit similar absorbance band shapes in this
region. MRI viewed spectra of aliphatic organic compounds to identify some likely components
of the sample spectra. Table 1 identifies the compounds that were selected for reference
spectrum measurements. Cylinder standards of the selected compounds will be purchased from a
commercial gas supplier. The standards will be about SO ppm of the analyte in a balance of
nitrogen. The cylinders will contain gravimetric standards (analytical accuracy of ±1 percent) in
a balance of nitrogen.
2.1 Measurement System
A controlled, measured flow of the gas standard will be directed from the cylinder to the
infrared gas cell. The gas cell is a CIC Photonics Pathfinder. This is a variable path White cell
with an adjustable path length from 0.4 to 10 meters. The path lengths have been verified by
measurements of ethylene spectra compared to ethylene spectra in the EPA FTIR spectral library.
The inner cell surface is nickel coated alloy to minimize reactions of corrosive compounds with
the cell surfaces. The cell windows are ZnSe. The cell is heat-wrapped and insulated.
Temperature controllers and digital readout are used to control and monitor the cell temperature
in two heating zones. The gas temperature inside the cell will be recorded using a T-type
thermocouple temperature probe inserted through a 1/4 in. Swagelok fitting. The gas
temperature will be maintained at about 120°C. Documentation of the temperature probe and
thermometer calibration will be provided with the report.
Laboratory Reference Spectrum Plan EPA Contract No. 68-D-98-027; MRI Work Assignments 2-12 and 2-13
Draft June 14.1999 FaSe 2
-------
TABLE 1. ORGANIC COMPOUNDS SELECTED FOR THE LABORATORY STUDY
Compound Name
n-hexanea
n-heptane
Pentane
isooctanea
1-pentene
2-methyl,l-pentene
2-methyl,2-butene
2-methyl,2-pentene
3-methylpentane
Butane
Boiling Point (°C)
69
98.4
36.1
99.2
30
60.7
38.6
67.3
63.3
-0.5
a Hexane and isooctane are HAPs. Their reference spectra will be re-measured because the reference
spectra in the EPA library were measured at ambient temperature.
The instrument is an Analect Instruments (Orbital Sciences) RFX-65 optical bench
equipped with a mercury-cadmium-telluride (MCT) detector. The RFX-65 instrument is capable
of measuring spectra at 0.125 cm"1 resolution. The reference spectra will be measured at
0.25 cm"1 or 0.50 cm"1 resolution. Gas pressure in the sample cell will be measured using an
Edwards barocell pressure sensor equipped with an Edwards model 1570 digital readout. A
record of the pressure sensor calibration will be provided with the report.
A continuous flow of the gas standard will be maintained through the cell as the spectra
are recorded. A mass flow meter will be used to monitor the gas flow (Sierra Instruments, Inc.,
model No. 822S-L-2-OK1-PV1-V1-A1,0 to 5 liters per minute).
The instrument system will be configured to measure 0.25 cm"1 or 0.50 cm"1 resolution
spectra. The measurement configuration is shown in Figure 1. Calibration transfer standards
(CTS) will be measured each day before any reference spectra are measured and after reference
spectra measurements are completed for the day.
2.2 Procedure
Information will be recorded in a laboratory notebook. Additionally, the instrument
operator will use check lists to document that all procedures are completed. There will be three
checklists for: (1) daily startup prior to any reference measurements, (2) reference spectrum
measurements, and (3) daily shut down after reference measurements are completed. Example
checklists are at the end of this document.
The information recorded in the laboratory notebook includes; the cell temperature,
ambient pressure, background, CTS and spectrum file names, sample temperatures and pressures
for each measurement, cell path length settings, number of background and sample scans,
instrument
Laboratory Reference Spectrum Plan '• EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-13
Draft June 14,1999 8
-------
Cylinder gas inlets
Calibration
manifold
Vent
Figure 1. Measurement system configuration.
PG = pressure gauge; TP = temperature probe; MFM = mass flow meter.
resolution, gas standard concentration, sample cylinder identification, and sample flow rates for
each measurement. Certificates of Analysis for all gas standards used in the project will be
provided with the report.
The MCT detector will be cooled with liquid nitrogen and allowed to stabilize before
measurements begin.
The cell will be filled with dry nitrogen and vented to ambient pressure. The pressure, in
torr, will be recorded from the digital barocell readout. The cell will then be evacuated and leak
checked under vacuum to verify that the vacuum pressure leak, or out-gassing, is no greater than
4 percent of the cell volume within a 1-minute period. The cell will then be filled with nitrogen
and a background will be recorded as the cell is continuously purged with dry nitrogen. After the
background spectrum is completed the cell will be evacuated and filled with the CTS gas. The
CTS spectrum will be recorded as the cell is continuously purged with the CTS gas standard.
The purge flow rates will be 0.5 to 1.0 LPM (liters per minute) as measured by the mass flow
meter.
Laboratory Reference Spectrum Plan
Draft June 14,1999
EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-13
Page 4
-------
After the background and CTS measurements are completed the cell will be filled with a
reference gas sample. The reference spectra will be recorded as the cell is continuously purged at
0.5 to 1.0 LPM with gas standard. The gas flow will be monitored with a mass flow meter before
the gas enters a heated line, and with a rotameter after the gas exits the cell. The mass flow
meter is calibrated for nitrogen in the range 0 to 5 LPM. The purpose of the heated line
connection is to help maintain the gas temperature inside the cell. This may only require placing
a heat wrap on the line where the gas enters the cell.
The gas temperature of each nitrogen background, CTS, and reference gas will be
recorded as its spectrum is collected.
Several preliminary spectra will be recorded to verify that the in-cell gas concentration
has stabilized. Stabilization usually occurs within 5 minutes after the gas is first introduced into
the cell with the measurement system that will be used for this project. Duplicate (or more)
reference spectra will be collected for each flowing sample. The second reference spectrum will
be recorded at least 5 minutes after the first spectrum is completed while the continuous gas flow
is maintained.
At least 100 scans will be co-added for all background, CTS , and reference
interferograms.
A new background single beam spectrum will be recorded for each new compound or
more frequently if the absorbance base line deviates by more than ±0.02 absorbance units from
zero absorbance in the analytical region.
After reference spectrum measurements are completed each day, the background and CTS
measurements will be repeated.
The CTS gas will be an ethylene gas standard, either 30 or lOOppm in nitrogen
(±1 percent) or methane (about 50 ppm in nitrogen, ±1 percent). The methane CTS may be
particularly suitable for the analytical region near 2900 cm"1.
3.0 QUALITY ASSURANCE AND QUALITY CONTROL
The following procedures will be followed to assure data quality.
3.1 Spectra Archiving
Two copies of all recorded spectra will be stored, one copy on the computer hard drive
and a second copy on an external storage medium. The raw interferograms will be stored in
addition to the absorbance spectra. After the data are collected, the absorbance spectra will be
converted to Grams (Galactic Industries) spectral format. The spectra will be reviewed by a
second analyst and all of the spectra, including the Grams versions will be provided with a report
and documentation of the reference spectra.
Laboratory Reference Spectrum Plan EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-13
Draft June 14, 1999 Page 5
-------
3.2 CTS Spectra
The CTS spectra will provide a record of the instrument stability over the entire project.
The precision of the CTS absorbance response will be analyzed and reported. All of the CTS
spectra will be archived with the background and reference spectra.
3.3 Sample Pressure^
The barocell gauge calibration will be NIST traceable and will be documented in the
reference spectrum report. The ambient pressure will be recorded daily and all of the samples
will be maintained near ambient pressure within the IR gas cell.
3.4 Sample Temperature
The IR gas cell is equipped with a heating jacket and temperature controllers. The
temperature controller readings will be recorded whenever spectra are recorded. Additionally,
the temperature of each gas sample will be measured as its spectrum is collected using a
calibrated temperature probe and digital thermometer. The calibration record will be provided
with the reference spectrum report. The gas sample will be preheated before entering the cell by
passing through a heated 20 ft. Teflon line. The Teflon line temperature will be maintained at
about 120°C. The line temperature controllers will be adjusted to keep the gas sample
temperature near 120°C.
3.5 Spectra
MRI will record parameters used to collect each interferogram and to generate each
absorbance spectrum. These parameters include: spectral resolution, number of background and
sample scans, cell path length, and apodization. The documentation will be sufficient to allow an
independent analyst to reproduce the reference absorbance spectra from the raw interferograms.
3.6 Cell Path Length
The cell path length for various settings is provided by the manufacturer's documentation.
The path length will be verified by comparing ethylene CTS spectra to ethylene CTS spectra in
the EPA spectral library.
3.7 Reporting
A report will be prepared that describes the reference spectrum procedures. The report
will include documentation of the laboratory activities, copies of data sheets and check lists, and
an electronic copy of all spectra and interferograms.
Laboratory Reference Spectrum Plan EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-13
Draft June 14,1999 Pa8e6
-------
3.8 Documentation
Laboratory analysts will use three check lists to document data recording activities. The
check lists are appended to this plan. The checklists: (1) record start up activities such as
instrument settings, background and CTS spectra, (2) record reference spectra activities, and
(3) record daily shut down procedures, including post-reference spectra background and CTS
measurements.
In addition to the check lists the operator will record notations in a laboratory notebook.
Copies of the check lists and note book pages will be provided with the reference spectrum
report.
A draft of the reference spectrum report will be provided with the revised test reports.
The reference spectrum report will then be finalized and submitted separately.
Laboratory Reference Spectrum Plan EPA Contract No. 68-D-98-027, MRI Work Assignments 2-12 and 2-J3
Draft June 14, 1999
-------
Project No. MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE: OPERATOR: .
Initials
Check cell temperature
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure in cell, (PJ
Vacuum Leak Check Procedure:
Evacuate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure
Leave cell isolated for one minute Time
Record time and cell pressure (?„,„)
Calculate "leak rate" for 1 minute Time P,
ram
Calculate "leak rate" as percentage of total pressure
%VL = (AP/Pb)*100
|%VL|shouldbe<4
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (4QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectrum
Record Cell path length setting
Evacuate Cell
Fill Cell with CTS gas
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet.
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
Reviewed by: Date: •
-------
Project No. _ MIDWEST RESEARCH INSTITUTE
h'l'lR Reference Spectrum Checklist
DATE: OPERATOR:
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: Date:.
-------
Project No. MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE: OPERATOR:
Initials
Purge sample from cell using ambient air or nitrogen
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectrum
Evacuate Cell
Fill Cell with CTS gas
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet.
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
Close cylinders
Evacuate or Purge CTS from cell using nitrogen
Leave cell under low nitrogen purge or under vacuum
Fill MCT detector dewar
Reviewed by: Date:.
-------
D TRANSFER
D EXCHANGE
\
TO AVv£u*ist
5S2.0
SHIPPING ORDER
MIDWEST RESEARCH INSTITUTE
425 Volkar Boulevard, Kansas City, Missouri 64110
D RETURN FOR CREDIT
D RETURN FOR REPAIR
DATE
144099
REFER TO THIS NO. IN
ALL CORRESPONDENCE
/oo
VIA
a A.M.
n P.M.
D PREPAID
D COLLECT
INSURE: D YES Q NO
AMOUNT
REQUESTED BY
Charge NO. _
or
Bill Recipient Acct No.
REFERENCE
QUANTITY
DESCRIPTION OF MATERIAL
PRESENT LOCATIOl
ff/f
/?
SIGNED
V
PACKING SLIP
MRI11 (Rev. 8/92)
-------
Code: MRI-0701
Revision: 3
Effective: 10/23/98
Page: 12 of 12
Attachment 1
Instrument Found Out of Tolerance
Instrument: /S"?Q
'
Manufacturer:
MRI Number: ~W V-^7^ * /-4rl3
i
^37
Serial Number:
Acceptance Criteria:
Date of calibration or test that revealed the out of tolerance condition:
Date of previous calibration:
Responsible person: j otn *ejsof (Must receive a copy of this report)
Tested/Calibratedbyr^a-^e- Ufvl^ Date:
Reviewed by: 3^&^S&_^!Z^ _ Date:
J f' •_ TL -_lf ^ ' ^-C'_r-l" ^~ —
16
I hereby certify that I have received a copy of this report and will notify the appropriate
people and take the appropriate actions necessary to determine what data may have been
corrupted and what corrective actions are indicated.
Signed: C^/^'^^H^-^^ (Responsible person)
Date: W/V/^
MRI-QA\MRI-070I.DOC
-------
Code: VtRJ-0722
Revision: 0
Effective: 03/22/99
Page: 6 of 6
f£
MRINo.
Report NoT^
Noun aVeCt.
Attachment 1
Pressure Gauge Calibration Data Sheet
No. / Type /r?o
Serial No. <-(227
fJtttCgyW Ambient Temperature "73*F Ambient Humidity $1 10
Applied Pressure
Initial Check
Final Check
Tolerance ±
Pass
Fail
5-07.? 7*1
&0>*
1.4
-7S-7.7
7^.7
1.7
Trig.
2.1
Cumulative uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMRI-0701 and ISO 10012-1.
Standards Used: MRI No
Notes/ Adjustments/Repairs/Modifications:
fafJ aeairae *peuf,'ca*>
-------
Code: MRI-0721
Revision: 0
Effective: 01/29/99
Page: 9 of 9
MRINo.:
Attachment
Calibration Data Sheet
Model No/Type: TT^-IBc-12. Serial No.: TO° Cal Interval: f J*&r
A ' ^ Date: _£l2z21____
-------
Code: MRI-0721
Revision: 0
Effective: 01/29/99
Page: 9 of 9
Attachment
Calibration Data Sheet
MR! No.: j'&'dj Model No/Type: H HZ\ Serial No.: T'&bKl Report No.: •-—
"Tbs/Hgfl4sf*S
Applied temperature
** " t Or*
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T" o'c
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Ambient Tempera
Initial check
—fjOO.^'c.
-/00-3'c,
-0.2
.—
~-
*—
Fail
Cumulative uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMRI-070landISOlOOl2-l.
Standards used: MRI No
Notes/Adjustments/Repairs/Modifications:
Limitations for use:
q.O
Date Calibrated: r-?-
Date Due Recalibration:
Calibration Performed bv
Reviewed by:
vy— -£<
Cal Interval: /
Date:
-------
PAGE 33
Scott Specialty Gases
.pped 6141 EASTON ROAD, BLDG 1 PO BOX 310
From: PLUMSTEADVILLE PA 18949-0310
Phone: 215-766-8861 Fax: 215-766-2070
CERTIFICATE OP ANALYSIS
MIDWEST RESEARCH
SCOTT KLAMM
425 VOLKER BLVD
KANSAS CITY
MO 64110
PROJECT #: 01-01788-006
P0#: 033452
ITEM #: 01021951 5AL
DATE: 3/31/98
CYLINDER #: ALM025384
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +/-5%
BLEND TYPE
COMPONENT
ETHYLENE
NITROGEN
CERTIFIED WORKING STD
REQUESTED GAS
CONC MOLES
20.
PPM
BALANCE
ANALYSIS
(MOLES)
20.0
PPM
BALANCE
ANALYST:
-------
Scott Specialty Gases
Dped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
Fax: 919-220-0808
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
CARY NC
27511
PROJECT #: 12-34162-005
P0#: 038546
ITEM #: 12022751 1AL
DATE: 5/26/99
CYLINDER #: ALM046483
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE
COMPONENT
METHANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
50.
PPM
BALANCE
52.6
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
B.M > BECTON
-------
Scott Specialty Gases
sped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
CERTIFICATE OF
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
CARY NC 27511
PROJECT #: 12-34162-004
P0#: 038546
ITEM #: 12022232 1AL
DATE: 5/25/99
CYLINDER #: ALM045092
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/25/2000
BLEND TYPE
COMPONENT
N-HEXANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
50.
PPM
BALANCE
ANALYSIS
(MOLES)
49.6
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L. BAYLOR
-------
Scott Specialty Gases
Tpped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE OP
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC 27511
PROJECT #: 12-34167-006
P0#: 038545
ITEM #: 1202M2034951AL
DATE: 5/27/99
CYLINDER #: ALM037409
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/27/2000
BLEND TYPE : GRAVIMETRIC MASTER GAS
REQUESTED GAS
COMPONENT CONG MOLES
3-METHYLPENTANE
NITROGEN
50.
PPM
BALANCE
ANALYSIS
(MOLES)
50.0
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
TAYLOR
-------
Scott Specialty Gases
Dped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
Fax: 919-220-0808
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC
27511
PROJECT #: 12-34162-006
P0#: 038546
ITEM #: 1202P2000801AL
DATE: 5/27/99
CYLINDER #: ALM041358
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/27/2000
BLEND TYPE
COMPONENT
N-PENTANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
50.
PPM
BALANCE
49.99
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
-------
Scott Specialty Gases
Shipped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE OF
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC
PROJECT #: 12-34167-005
P0#: 038545
ITEM #: 1202M2034941AL
DATE: 5/26/99
27511
CYLINDER #: ALM054078
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE : GRAVIMETRIC MASTER GAS
REQUESTED GAS
COMPONENT CONG MOLES
2-METHYL-2-PENTENE 50. PPM
NITROGEN ' BALANCE
ANALYSIS
(MOLES)
51.4 PPM
BALANCE
NIST TRACEABLE 'BY WEIGHT
-------
Scott Specialty Gases
Tpped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
Fax: 919-220-0808
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH
CROSSROADS 'CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC
27511
PROJECT #: 12-34167-004
P0#: 038545
ITEM #: 1202M2034961AL
DATE: 5/26/99
CYLINDER #: ALMO05876
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE
COMPONENT
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
2-METHYL 2-BUTENE
NITROGEN
50.
PPM
BALANCE
50.04
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L.
-------
Scott Specialty Gases
'pped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: ,919-220-0803
NC 27704
Fax: 919-220-0808
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY . NC 27511
PROJECT #: 12-34167-003
P0#: 038545
ITEM #: 1202M2034971AL
DATE: 5/26/99
CYLINDER #: ALM017936
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE : GRAVIMETRIC MASTER GAS
REQUESTED GAS
'COMPONENT CONG MOLES
ANALYSIS
(MOLES)
2 -METHYL-1-PENTENE
NITROGEN
50.
PPM
BALANCE
50.08
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L. TAYLOR
-------
Scott Specialty Gases
Dped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
CERTIFICATE OF
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC
27511
PROJECT #: 12-34162-003
P0#: 038546
ITEM #: 1202N2007311AL
DATE: 5/26/99
CYLINDER #: AAL21337
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE
COMPONENT
N-HEPTANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
50.
PPM
BALANCE
49.97
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L. TAYLOR
-------
Scott Specialty Gases
ipped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
CERTIFICATE OF
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC
27511
PROJECT #: 12-34167-002
P0#: 038545
ITEM #: 1202P2019421AL
DATE: 5/27/99
CYLINDER #: ALM041929
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/27/2000
BLEND TYPE
COMPONENT
1-PENTENE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
50.
PPM
BALANCE
ANALYSIS
(MOLES)
50.1
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
B.M. BECTON
-------
Scott Specialty Gases
)ped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE OF
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
GARY NC 27511
PROJECT #: 12-34162-001
P0#: 038546
ITEM #: 12021152 1AL
DATE: 5/25/99
CYLINDER #: ALM020217
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/25/2000
BLEND TYPE
COMPONENT
N-BUTANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
50 .
PPM
BALANCE
51.3
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST
= &.W--
B.M. BECTON
-------
Project No. _LIZill±_^_l_ MIDWEST RESEARCH [NSTTTUTE
DAILY CHECKLIST
Start up Procedure
nm_Zil1 OPERATOR:
Check cell temperatan
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure ia ceO, (PJ
i Leek Cheek Procedure: £ f.^^ (Vr ,|U(hJ )
Evacuate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (P^
Leave cell isolated for one minute
Record time and cell pressure (?„,)
Calculate "leak rate" for 1 minute Time
Calculate "leak rate" as percentage of total pressure ^j>
%VL.(AP/Pb)*lOO
|%VL|shouldbe<4 % V,
Record NHrofea Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record t^iS Spectevii , *
Record Cell path length setting
£yacaM»CeU
Fill Cell with CTSp»
Open cell oudet and purge cell wim. CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration fcTk^Wtu Ui
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect r.
Verify that spectrum and interferogram wen copied to directories.
Record CTS Spectrum File Name
Reviewed by: ^ Datec Wl/H
-------
No —-;; MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
'• jf • &P+ l
Check cefl tempenton
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure ta cefl, (PJ
i Leak Check Procedure:
Evacuate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (P^)
Leave cell isolated for one minute Time
Record time and ceil pressure (1^)
Calculate "leak rate" for 1 minute
Calculate "leak rate" as percentage of total pressure
%VL«(AP/Pb)MOO
% VL| shouldbe<4 %VL
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background IAQBK) under continuous flow and ambient pressure
Record information in data book,
Copy Background to C-drive and backup using batch file. _ & K bol^l A
Record CTS Spectra*
Record Cell path length setting
Fill Cell withCTS fe»
Opm<^owie« and pwjeceUwim CIS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file. ~r
Record Barytron pressure during collect • -y^2-p jiTTnt.i nmi nililiiallrriii" I l>nt ' «jfr
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Nam*
-------
Project No. .Wj- \1 ^ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
OPERATOR; 7~
Check cell tenpentar*
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient preuurt in eel, (PJ
I Leak Check Procedure:
Eyao2& ceU to \*t%£&pressure.
Isolate cell (close cell inlet and ceil outlet)
Record time and baseline pressure (
Leave cell isolated for one minute Time
Record time and cell pressure (P^J lO'tf
Calculate "leak rate" for 1 minute Time
fOL Cell with CTS gu
Open cell oudet and purge cell wim CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS ga* cylinder identity and concentration
Record and copy spectrum and interferognm to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet
Verify that spectrum and interferognm were copied to directories.
Record CTS Spectrum File Nam*
Date:
:ft\
Calculate "leak rate" as percentage of total pressure ^ HF r
%Vt-(£P/Pb)MOO /fotf -$f-
|%VIt|shouldbe<4 ^ % VL
I I . * _£
Reconl Nttrotea BMkgroond
Purge cell wim dry nitrogen ^y^
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book. ^^
Copy Background to C-drive and backup using batch file.
Record CTS Spectra*
Record Cell peth length setting
-------
PrcJ6^ No ~ ! MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
OPERATOR;
<&
Check airtenperetore
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressore to cefl, (PJ
uU Bv&cuateceU to* baseline pressure.
^bolatecell (close cell inlet and cell outlet)
Record time and baseline pressure
Leave cell isolated for one minute
Record time and cell pressure (P^
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book,
Copy Background to C-drive and backup using batch file.
Record CTS Spectrae*
Record Cell path length setting
Fill Cell with CTS ge»
Open cell oodet and purge cell with CTS at sampling rate (1 to 5 LPM)
Record cytinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum Pile Name
Reviewed by: o/lk/y*^ Datec
Calculate "leak rate" for 1 minute Time Pom
Calculate "leak rate" as percentage of total pressure ^p
|%Vt|shouldbe<4 * %Vt
I I
-------
Project No.
' >*•
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE
OPERATOR:
Check ceB temperate*
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambkat pressure a cefl, (PJ
i Procedure:
*?'. S2."l *
Isolate ceil (close cell inlet and cell outlet)
Record time and baseline pressure (P^)
Leave ceil isolated for one minute
Record time and cell pressure (Pg,,)
Calculate 'leak rate" for 1 minute
Time
Calculate 'leak rate* as percentage of total pressure
%Vt»(AP/Pb)*100
|%Vt|shouldbe<4
Record Nitrogen Beckgroaad
Purge cell with dry nitrogen
Verify ceil is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (A.QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
m*
0.10
AP
. % V,
#/
y&
4L
Record CTS S|
Reoxd Cell path length setting
-Evarttfle Celt
Fill Cell with CTS ga»
Open cefl oudet and purge cell with CTS at sampling rate (1 toSLPM)
Record cy under ID Nbniber
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferognm to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
K0#5*
Reviewed by:.
Date:
-------
Project No.
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE:
OPERATOR: T.
Check ceO temperajon
Verify temperature using thermocouple probe and hand-held readout
Purge ceil with dry nitrogen and vent to ambient pressure
Record ambient pressure hi ceB, (PJ
*
i Leak Check Procedure; ^tftf^fp-ftsi***,*
? cttf^Evacuate'cell to baseline pressure.
Isolate cell (close ceil inlet and ceil outlet)
Record time and baseline pressure (P^J
Leave cell isolated for one minute
Record time and cell pressure (P^J
Calculate "leak rate" for 1 minute
Time
Time
AP
1.1
Calculate "leak rate" as percentage of total pressure
%V1.»(AP/Pk)«100
j%VL| sfaouldbe<4
Record Nitrogen Background *
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (&QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectroam
Record Cell path length setting
Evacuate Cell
Fill Cell with CTS ft*
Open cell outlet and purge cell with CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record HTV* gnpy tpectmm and inierferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet
Verifythat spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
_^ Datec
Reviewed by: / ft— Ifi,
V "™y
Ilili*
-------
Project No.
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE
OPERATOR:
Check cefl temperatve
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure in ceo, (Pj
Vacuum Leak Check Procedure v
Q^ Evactfate cell to baseline pressurei '*'"''
Isolate cell (close cell inlet and cell outlet)
Record time and baseline 01
Leave cell isolated for one minute
Record time and cell pressure (POM)
Calculate "leak rate" for 1 minute
Time
Time
Calculate 'leak rate* as percentage of total pressure
• %VL.(AP/Pb)*100
I%VL| shouldbe<4
Record Nitrogen Background '*
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (4QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Speetnam
Record Cell path length setting
Fill Cell with CTS gM
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barvtron pressure during collect
Record information on "Background and Calibrations" data sheet.
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
77V-Y
P*
77 V. 8
P—
-------
Project No. T^H^ P_ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE -7/rf,/11 nDBn
OPERATOR:
Check ceOtempentgre
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure in cefl, (PJ
Vacuum Lea Check Procedan:
fWffyjuwete cell to baeefine pressure.
Isolate cell (close cell inlet and cell outlet)
Record tune and baseline pressure (P^J «j5*.'¥p 775, f
Leave ceil isolated for one minute Time pnfc
Record time and cell pressure OU) fiS/.'VO T7f. 2 Ji/
Calculate "leak rate" for 1 minute Time p^ T~~
0.1
Calculate "leak rate" as percentage of total pressure
%Vt»(AP/Pk)*100
|%VL| shouidbe<4
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (&QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to Cdrive and backup using batch file.
RCCOffQ
Record Cell path length settine;
Fill CeU with CTS ga«
Open cefl outlet and purge ceil with CTS at sampling rate (1 to 5 LPM)
Record cylinder ID Manbat
RecordCI^ gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file. ' A*
Record Barytron pressure during collect
Record information on "Background and Calibrations" datasheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum Pile Name
Reviewed bv M^^V' D**:-
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
DATE:
BAROMETRIC:.
OPERATOR: -
TIME
FILE
NAME
(Dtal)
PATH
NOTES
NUMBER
SCANS
Roolutlon
(CD-I)
Gw
TEMP(F)
Gat
PRESSURE
•KG
APOD
d.f
757.*"
u
101 f
12: <>
•70-7I1
•i
(.0
emcjMckNfy
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR: /. £
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
Roolulloo
(cm-1)
GM
GM
PRESSURE
•KG
APOD
(.0
to.***
f *«*• 0 0.
fCO
'.O
fee
1.0
TVf . 7
1.0
tl
cmc_b»dc\fy9SM95l\17>«fs'^Cird»l» sheets for references.xls
07-07-99
Reviewed by _
Dale
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC: 7ff>
DATE:
; 7/J/fl
OPERATOR:
TIME
FILE
NAME
(Dbl)
PATH
NOTES
NUMBER
SCANS
RtMlullon
(cn-I)
CM
TEMP(F)
GM
PRESSURE
•KG
APOD
0. f *
f.t>
'.0
. 3
to.* 3
*'•< •
''"'
1.0
t.O
/ot
5*°
0*0
'151.'*
It,
:0'*
b
A).
10.
(.0
/.to
&
cmc bickNfy99v«95l\12Vefs\flirdau sheeu for references.xli
07-07-99
Reviewed by
D«le
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
PTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC; ?S*
DATE:
OPERATOR: 77
TIME
FILE
NAME
(DW)
PATH
NOTES
NUMBER
SCANS
RcMlulloa
(cm-1)
Gw
TEMf(F)
CM
PRESSURE
•KG
APOD
It* •)
1.0
. 3
Sf 1. Obi. ?M
l/ilo
/. 0
12 ',10
It.O
/•O
75^' T
7/i-
<*
f XCr
Q
TK*
tmc_b»ckSfyS>5M951\lZ\refs\flird»u iheeu for references xli
07-07-99
Reviewed by
4'y^~
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR: /'
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
RcMlUllOD
(cm-1)
Gas
TEMP(F)
Gas
PRESSURE
•KG
APOD
U
/•O
/ar.
-rsf.f
fte-1
ff.tl
1-0
-7SS-0
(i
<*rwiJi«u«* ^
f.o
{00
/. o
75V. *
(i
*•"*
So*
l.o
inc.
r**
(?*.*
70C-
emc_b»d(Nfy9SM95l\l7yefjVlir d»U iheeu for referenceulj
07-07-99
Reviewed by.
Date.
-------
PROJECT NO. 4»5MlMdl3
SITE: NCOI
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE;
OPERATOR:
T.
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
GM
TEMPO))
Gm
PRESSURE
•KG
APOD
'. 0
. ;
£•0
1. O
•757.0
lo.o
£**
i.C?
f
$<*
f.o
emc_b«lNy9
-------
PROJECT NO. 4»SM2mdl3
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE;
OPERATOR: T
TIME
FILE
NAME
.(DM)
FATH
NOTES
NCMIEU
SCANS
GM
Qm
PRESStlllE
•KG
AfOD
II '. 7- f
Q *'l* Lfa
1.0
.0
1.0
7*7. 0
7/A/f
Lot
5°°
7/U
t as.*
emc_b««*My99V«95I\l7«fWtir
-------
Project No "»' ~tL ,«, MIDWEST RESEARCH INSTITUTE
rTIK Reference Spectrum Checklist
DATE 1'1*1
-------
Project No. /?> / -I* , >^_ MIDWEST RESEARCH rNSTTTUTE
FTIR Reference Spectrum Checklist
DATE 7-Vy/> OPERATOR: f
Reference Spectrum Sample
Start Tune /$'«"*<*
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LFM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in ceil
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogrmm to backup directories
EndTime
|2<*.( *<-
Reviewed by: 4/\(t ^-^^ . Date:.
-------
ProiectNo.
MIDWEST RESEARCH INSTITUTE
FITR Reference Spectrum Checklist
DATE
OPERATOR;
Reference Spectrum Sample
Start Tim*
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LFM Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Initi«|f
Reviewed by:
Datec
-------
Project No. !T=>ITA ^ MIDWEST RESEARCH INSTITUTE
FTTR Reference Spectrum Checklist
DATE 7U/^ OPERATOR: T. 6«^r
Reference Spectrum Sample
Stan Tim*
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Initials
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate (. a •)<.//*
Allow to equilibrate for 5 minutes L*&*+M) L**. fie 4(t
Record sample pressure in cell 7f?>
Record sample flow rate through cell _
Start spectrum collect program _
Record information in data book _
Copy Spectrum and Interferogram to backup directories _
End Tune
Reviewed by: * (/• ~ls*^ Date:
-------
Project No. _nZili±J— MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE i- i* i-1 OPERATOR:
— Initials
Reference Spectrum Sample
Stan Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration H<\.vi jf~
Record Spectrum File Nam*
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minutes £
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviawad hy Of \(/*Y*-^ Date:
-------
Project No ll^l "'^ j i> MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE •?//*.( If OPERATOR: T<
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum Hie Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gu from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minute* (^3i»—*tf fa** A
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: 7\(j^^^ Date:
-------
Project No. W^rZ-jl7? MIDWEST RESEARCH INSTITUTE
MIR Reference Spectrum Checklist
DATE 'I""' OPERATOR:
Initials
Reference Spectrum Sample
Start Tim*
Record Cell path length setting ' 0 • o ^
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minute* LsJ9<*4i*9 £v" *
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by:
-------
Project No. ^Itl'l* ,/?>_ MIDWEST RESEARCH INSTITUTE
MIR Reference Spectrum Checklist
DATE
OPERATOR:
Tniriak
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample, flow rale through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
EndTime \<4'<10
Reviewed by: r /(/^^ Datec
-------
Project No. l2ill tL MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE: 1\&\
-------
Project No.
, I?
MIDWEST RESEARCH INSTITUTE
FITR Reference Spectrum Checklist
DATE
OPERATOR:
Reference Spectrum Sample
Start Tun* i
Record Cell path length setting
Record Background Spectrum File Name
RecordCTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill ceil to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in ceil
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by:.
Date:.
-------
Project No.
1** I -'
MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE
OPERATOR;
, 6
-------
Project No. " f MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE imm OPERATOR:
Reviewed by: _^ Datee
Reference Spectrum Sample A-
Start Time ~^7
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Nam* Cf^T/Sfl ,» fit, ol ii ft, &
Record Compound Nam*
Record Cylinder Identification Number •
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate Sj\(* [ .01 uf ^
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell j, o*
Start spectrum collect program St
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
-------
Proj*61 No. IT>/- [*• ^ MIDWEST RESEARCH INSTITUTE
FTTR Reference Spectrum Checklist
DATE:
OPERATOR:
Initial.?
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
. Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and mterferogram to backup directories
End Time
Reviewed by:
-------
Project No. ">('( jl MIDWEST RESEARCH INSTITUTE
FITR Reference Spectrum Checklist
DATE MI *.7/ OPERATOR:
Initial*
Reference Spectrum Sample
Stan Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample Sow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rale through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferognm to backup directories
End Time
Reviewed by {pf * T^ Date: 1
-------
froj*" NO- —HT>''' (' . MIDWEST RESEARCH INSTITUTE
Fi'iK Reference Spectrum Checklist
DATE '/(fr/Y* OPERATOR: T<
— Initials
Reference Spectrum Sample
Stan Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name 2*2 9 71C, (\
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through ceil to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in ceil
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories fl/e
End Time 1 V.'fr
Reviewed by: ^_^L^f^L Date:. "-HI
-------
ProJW No. _!_! 1 MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE 'f>"|VT OPERATOR: r. 6«y«<-
Reference Spectrum Sample ^ o ./miotil,[ -.* -1»/»«-*
Start Time *'
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minuiee
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and rnterferogram to backup directories
End Time
P»v,«^hv \llli Y*""^ . Date:
-------
No- . MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectnim Checklist
DATE OPERATOR:
Initials
Reference Spectnim Sample
Start Time
Record Cell path length setting
Record Background Spectrum Hie Nam*
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Cepy Spectnim and Interferogram to backup directories
End Time
Reviewed by: ^_________-____________ Date:.
-------
Project No. M'Pr^,^ MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE /i-win OPERATOR:
Tnitialf
Reference Spectrum Sample
Sun Tim*
1*44
Record Cell paih length setting
Record Background Spectrum File Name
RecordCTS Spectrum File Name .
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate
Allow to equilibrate for 5 minute*
Record sample pressure in cell
Record sample flow rate through cell
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: ^____^__^____________ ' Date:.
-------
Project No. ^I'l"*, & MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE' '• ' ' ' OPERATOR:
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
RecordCTS Spectrum Rle Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve ^
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rate g/fc»
Allow to equilibrate for 5 minutes ' jfc
Record sample pressure in cell *
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interierogram to backup directories
End Tune
Reviewed by: Date:.
-------
Project No.
MIDWEST RESEARCH INSTITUTE
FDR Reference Spectrum Checklist
OPERATOR: T.
Reference Spectrum Sample
Stan Time
Record Cell path length setting
Record Background Spectrum File Name
RecordCTS Spectrum File Name .
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through cell to 0.5 to 1LPM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rale through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Initials
-r/u
j.
,.<» ^ ^
g.1*7
TtL.l
0
Reviewed by:
Date: .
-------
Project No. fl MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
OPERATOR. T6
Reference Spectrum Sample
Start Tune
Record Cell path length setting
Record Background Spectrum File Na
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fill cell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve
Adjust sample flow through ceil to 0.5 to 1 LFM. Record flow rate
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book ^
Copy Spectrum and Interferognun to backup directories j)lt
End Time \
Reviewed by: • Date:.
-------
PROJECT NO. 4951-12 and 13
FTIR DATA FORM
Sampling Data
BAROMETRIC; 757. «/
SITE: NCO Laboratory DATE:
Time
,<-.«<
,5,V
cmc b»ckN
07-07-99
FHe
Name
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1
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(DM)
Path
,..0
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NOTES
^ W ^d 2.
lu;^M^f^^x
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Scau
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. (cm-l)
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Flow
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-------
PROJECT NO. 4951-12 and 13
FTIR DATA FORM
Sampling Data
BAROMETRIC;
SITE: NCO Laboratory DATE:
Tine
IT.,1
a-.»
11 :«
,i.i.
File
,*«*.
\ fto"fi*^
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NOTES
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07-07-99
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l f f
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTDt DATA FORM
Sampling Data
DATE:
BAROMETRIC:.
OPERATOR: '
Time
FUe
Nam
(DW)
NOTES
Scans
RenlulloB
GM
Flow
Rate
Gw
PreMirt
•KG
*<*>
f*
cmc_b>dMy99vt951\12Vefi>llirdaUiheeli for referaicei xlj
07-07-99
Reviewed by
D«ie
-------
FTIR DATA FORM
Sampling Data
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
DATE:
BAROMETRIC:
OPERATOR:
Time
Fife
Nine
(DM)
fttk
NOTES
Scani
RMOlUllOB
. (cm-1)
CM
TempCQ
Ftow
Rile
Gat
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0
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5"!.
(.0
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emc_bacWy99vt95IMZ\refiViir
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Sampling Data
DATE:
BAROMETRIC: "7 5^
OPERATOR:
Time
File
Name
(DM)
Path
NOTES
SCMM
(cm-I)
CM
Te«pCC)
Flow
Rate
GM -
P tenure
•KG
A 91* A
-3 - £%*
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1.0
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?*>
1-0
l.o
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emc_bKkNfy9
-------
Project No. ^f I'11 , **_ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE OPERATOR.-
Purge sample from cell using ambient air or nitrogen
Record Nttrofm Background
Purge cell with dry nitrogen vV,
Verify cell is a* dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (4QBK) under continuous flow and ambient pressure
Record information in data boot
Copy Background to C-drive and backup using batch file.
Record CTS Spectra
Evacuate Cell
Fill Cell withCTS gas
Open cell outlet and purge cell withCTS at sampling rate (1 to 5 LPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration _____
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytroo pressure during collect ________
Record information on "Background and Calibrations" data sheet ________
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum Pita Nam* C.T>*7»")
Close cylinder*
Evacuate or Porn CTS from call using nitrogen
Leave cell undv low nitrogen purge or under vacuum
Fill MCT detect* deww
Reviewed by: t* \^\~^ DatK
-------
Project No. Wl ' I2-, '** MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE T«|
-------
Project No. >— MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE I\VM OPERATOR:
Initials
Purge sample bom cell using ambient air or nitrogen
Record NUrofea Backcnxmd
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge *jy'q t f
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.-
Record CTS Spectrua
Fill Cell with CTS gas
Open cell outlet and purge cell with CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration ;K* /UJft** -V
Record and copy spectrum and interferognm to C-drive and back up using CTS batch file.
Record Barytroa pressure during collect
Record information on "Background and Calibrations" data sheet
Verify that spectrum and interferognm were copied to directories.
Record CTS Spectrum File Name
Close cylinders
Evacuate or Purg* CTS from cell using nitrogen
Leave cell undet low nitrogen purge or under vacuum
Fill MCTdetMtarcbwiK
Reviewed by: ffl.*** \fa ~_*-~~ ' Date:
-------
Project No. PX'^/X MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
OPERATOR: T.
Initials
Purge sample from cell using ambient air or nitrogen
Record Nitrofra Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rale (about sampling flow rate)
Collect Background (4QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectra
Fill Cell with CTS g» f ^
Open cell outlet and purge cell withCTS at sampling rate (1 to 5 LPM) I,(Q L-fa
Record cylinder ID Number 4/u^ ^S">gH
Record CTS gas cylinder identity and concentration %o oil?/**. 4Tt*(t~«
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet &}C,
Verify that spectrum, and interferogram were copied to directories.
Record CTS Spectrum File Name
Close cylinders
Evacuate or Purg* CTS from cell using nitrogen
Leave <^under km nitrogen purge or under vacuum
Fill MCT defector dwwr
Reviewed by: ij\\**~^ Date:
-------
Project No. " ( \ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE OPERATOR:
Tnitj«|g
Purge sample from cell using ambient air or nitrogen
Record NHroffn Backfrond
Purge ceil with dry nitrogen
Verify ceil is as dry as previous background
Record ambient pressure using ceil BaroceU gauge • 0 ..A
jjf i»T
Record nitrogen flow rate (about sampling flow rate) of*
Collect Background (A.QBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectra
reyacuate Cell
Fill Cell with CTS gas
Op« cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM) jlf j>LA»
Record cylinder DD Number ^
Record CTS gas cylinder identity and concentration ^ .,
-------
Project No. W 1 - ^ trt MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATS f||»|H OPERATOR: <
Initialf
Purge sample from cell using ambient air or nitrogen
Record NHrofea Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record-ambient pressure using cell Barocell gauge \*
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectra
>%w6uate Cell
Fill Cell with CTS gu
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM) *
Record cylinder ID Number A I*'
f
Record CTS gas cylinder identity and concentration Iff
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect 3I&
Record information on "Background and Calibrations" data sheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum F51* Na
Qose cylinders
Evacuate or Purge CTS ftom cell using nitrogen
Leave cell under tow nitrogen purge or under vacuum
FdlMCT detector dewac
Reviewed by: VjV^^ Date:
-------
Project No. 1V'''T-;>* MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE: -7 h« U^ OPERATOR: ?..
Purge sample from cell using ambient air or nitrogen
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background ^tf
Record ambient pressure using cell Barocell gauge » j^
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectra
Fill Cell with CTS gas
Open cell outlet and purge cell with CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on "Background and Calibrations" data sheet
Verify that spectrum and intecferogram were copied to directories.
Record CTS Spectrum FU0 Na
Close cylinder*
Evacuate or Port* CTS from cell using nitrogen
Leave cell under tow nitrogen purge or under vacuum
Fill MCT detector dtwv
Reviewed by: M^V D«t«
Initials
-------
APPENDIX C
CALIBRATION GAS CERTIFICATIONS
-------
01/05/98 16:56 ®215 766 0320 SCOTT
Scott Specialty Gases
6141 BASTON ROAD PO BOX 310
From*: PLUMSTBADVXLLB PA 18949-0310
Phone: 215-766-8861 Fax: 215-766-2070
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH PROJECT #: 01-88514-001
TOM GEYER P0#: 029257
425 VOLKER BLVD ITEM #: 01021951 1AL
DATE: 3/25/97
KANSAS CITY MO 64110
W_.^MM«MM»MW«M«»«» — •••— ™-»«*»«««*»»«»«i«»*»«»»«»««»**»^^*««»««w«««»w«i«p» — — — ™ — « — «•• — — —. — «i»&4»A«iAw«
CYLINDER #: ALM023940 ANALYTICAL ACCURACY: +-1%
FILL PRESSURE: 2000 PSIG
BLEND TYPE : GRAVIMETRIC MASTER GAS
REQUESTED GAS ANALYSIS
COMPONENT gQMC MQLBS
BTHYLENB 20. . PPM 20.01 PPM
NITROGEN BALANCE BALANCE
V.
ANALYST:
U9 <•
GKNYA
. . LDNOMWfT.CO CH(C*OO.ll
OUWMM.N6 SOUTH PUUNBSLD.MJ CMMM. OMTAWO »tUMSTtWWUX W PMMWIA.TX
-------
12/19/1997 16:46 9192208888
SCOTT SPECIALTY ISC
PAGE 02
^m?i
Scott Specialty Gases
pped
From:
1750 EAST CLUB BLVD
DURHAM
Phone: 919-220-0803
NC 27704
CERTIFICATE
O F
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
PO # 031064
425 VOLKER BLVD
KANSAS CITY
MO 64110
PROJECT #: 12-24558-001
PO#: 031064
ITEM #: 12023912 4AL
DATE: 8/14/97
CYLINDER #: ALM060523
FILL PRESSURE: 600 PSIG
ANALYTICAL ACCURACY: +/- 2%
BLEND TYPE :. CERTIFIED MASTER GAS
COMPONENT
TOLUENE
AI*
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES)
200.
PPM
BALANCE
196.6
PPM
BALANCE
ANALYST:
B.M. BECTON
-------
Scott Specialty Oases
jped 1290 COMBERMERJE STREET
35 « 48083
Phone: 248-589
C E R T I P I
"295° Fax: 248-589-2134
GATE OP ANALYSIS
MIDWEST RESEARCH ' ..... ..... ---------------
MELISSA TUCKER; # 026075 S5JECT #: 05-97268-002
425 VOLKER BLVD P0#: °26075
ITEM #: 05023822 4A
KANSAS CITY M0 64110 DATE' */03/9S
CYLINDER #: A7853 ANALYTIC^
Pit* PRESSURE: 2000 PSI HttSSg
BLEND TYPE : CERTIFIED WASTER GAS
REQUESTED GAS ANALYSIS
BALANCE BALANCE
CERTIFIED MASTER GAS
ANALYST:
-------
APPENDIX D
TEST METHODS
-------
D-l EPA METHOD 320
-------
1
Appendix A of part 63 is amended by adding, in numerical
order, Methods 320 and 321 to read as follows:
Appendix A to Part 63-Test Methods
*****
TEST METHOD 320
MEASUREMENT OF VAP01 PHASE ORGANIC AND INORGANIC EMISSIONS
•Y EXTRACTIVE FOURIER TRANSFORM INFRARED (FTIR) SPECTROSCOPY
1.0 Introduction.
Persons unfamiliar with basic elements of FTIR
spectroscopy should not attempt to use this method. This
method describes sampling and analytical procedures for
extractive emission measurements using Fourier transform
infrared (FTIR) spectroscopy. Detailed analytical
procedures for interpreting infrared spectra are described
in the "Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous
Emissions from Stationary Sources," hereafter referred to as
the "Protocol." Definitions not' given in this method are
given in appendix A of the Protocol. References to specific
sections in the Protocol are made throughout this Method.
For additional information refer to references 1 and 2, and
other EPA reports, which describe the use of FTIR
spectrometry in specific field measurement applications and
validation tests. The sampling procedure described here is
-------
2
extractive. Flue gas is extracted through a heated gas
transport and handling system. For some sources, sample
conditioning systems may be applicable. Some examples are
given in this method. Note: sample conditioning systems
may be used providing the method validation requirements in
Sections 9.2 and 13.0 of this method are met.
1.1 Scope and Applicability.
1.1.1 Analytes. Analytes include hazardous air pollutants
(HAPs) for which EPA reference spectra have been developed.
Other compounds can also be measured with this method if
reference spectra are prepared according to section 4.6 of
the protocol.
1.1.2 Applicability. This method applies to the analysis
of vapor phase organic or inorganic compounds which absorb
energy in the mid-infrared spectral region, about 400 to
4000 cm"1 (25 to 2.5 um) . This method is used to determine
compound-specific concentrations in a multi-component vapor
phase sample, which is contained in a closed-path gas cell.
Spectra of samples are collected using double beam infrared
absorption spectroscopy. A computer program is used to
analyze spectra and report compound concentrations.
1.2 Method Range and Sensitivity. Analytical range and
sensitivity depend on the frequency-dependent analyte
absorptivity, instrument configuration, data collection
parameters, and gas stream composition. Instrument factors
-------
3
include: (a) spectral resolution, (b) interferometer signal
averaging time, (c) detector sensitivity and response, and
(d) absorption path length.
1.2.1 For any optical configuration the analytical range is
between the absorbance values of about .01 (infrared
transmittance relative to the background = 0.98) and 1.0 (T
= 0.1). (For absorbance > 1.0 the relation between
absorbance and concentration may not be linear.)
1.2.2 The concentrations associated with this absorbance
range depend primarily on the cell path length and the
sample temperature. An analyte absorbance greater than 1.0,
can be lowered by decreasing the optical path length.
Analyte absorbance increases with a longer path length.
Analyte detection also depends on the presence of other
species exhibiting absorbance in the same analytical region.
Additionally, the estimated lower absorbance (A) limit (A =
0.01) depends on the root mean square deviation (RMSD) noise
in the analytical region.
1.2.3 The concentration range of this method is determined
by the choice of optical configuration.
1.2.3.1 The absorbance for a given concentration can be
decreased by decreasing the path length or by diluting the
sample. There is no practical upper limit to the
measurement range.
1.2.3.2 The analyte absorbance for a given concentration
-------
4
may be increased by increasing the cell path length or (to
some extent) using a higher resolution. Both modifications
also cause a corresponding increased absorbance for all
compounds in the sample, and a decrease in the signal
throughput. For this reason the practical lower detection
range (quantitation limit) usually depends on sample
characteristics such as moisture content of the gas, the
presence of other interferants, and losses in the sampling
system.
1.3 Sensitivity. The limit of sensitivity for an optical
configuration and integration time is determined using
appendix D of the Protocol: Minimum Analyte Uncertainty,
(MAU). The MAU depends on the RMSD noise in an analytical
region, and on the absorptivity of the analyte in the same
region.
1.4 Data Quality. Data quality shall be determined by
executing Protocol pre-test procedures in appendices B to H
of the protocol and post-test procedures in appendices I and
J of the protocol.
1.4.1 Measurement objectives shall be established by the
chpice of detection limit (DLJ and analytical uncertainty
(AUt) for each analyte.
1.4.2 An instrumental configuration shall be selected. An
estimate of gas composition shall be made based on previous
test data, data from a similar source or information
-------
5
gathered in a pre-test site survey. Spectral interferants
shall be identified using the selected DI^ and AUi and band
areas from reference spectra and interferant spectra. The
baseline noise of the system shall be measured in each
analytical region to determine the MAU of the instrument
configuration for each analyte and interferant (MIUJ .
1.4.3 Data quality for the application shall be determined,
in part, by measuring the RMS (root mean square) noise level
in each analytical spectral region (appendix C of the
Protocol). The RMS noise is defined as the RMSD of the
absorbance values in an analytical region from the mean
absorbance value in the region.
1.4.4 The MAU is the minimum analyte concentration for
which the AUt can be maintained; if the measured analyte
concentration is less than MAUj, then data quality are
unacceptable.
2.0 Summary of Method.
2.1 Principle. References 4 through 7 provide background
material on infrared spectroscopy and quantitative analysis.
A summary is given in this section.
2.1.1 Infrared absorption spectroscopy is performed by
directing an infrared beam through a sample to a detector.
The frequency-dependent infrared absorbance of the sample is
measured by comparing this detector signal (single beam
spectrum) to a signal obtained without a sample in the beam
-------
6
path (background).
2.1.2 Most molecules absorb infrared radiation and the
absorbance occurs in a characteristic and reproducible
pattern. The infrared spectrum measures fundamental
molecular properties and a compound can be identified from
its infrared spectrum alone.
2.1.3 Within constraints, there is a linear relationship
between infrared absorption and compound concentration.. If
this frequency dependent relationship (absorptivity) is
known (measured), it can be used to determine compound
concentration in a sample mixture.
2.1.4 Absorptivity is measured by preparing, in the
laboratory, standard samples of compounds at known
concentrations and measuring the FTIR "reference spectra" of
these standard samples. These "reference spectra" are then
used in sample analysis: (1) compounds are detected by
matching sample absorbance bands with bands in reference
spectra, and (2) concentrations are measured by comparing
sample band intensities with reference band intensities.
2.1.5 This method is self-validating provided that the
results meet the performance requirement of the QA spike in
sections 8.6.2 and 9.0 of this method, and results from a
previous method validation study support the use of this
method in the application.
2.2 Sampling and Analysis. In extractive sampling a probe
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7
assembly and pump are used to extract gas from the exhaust
of the affected source and transport the sample to the FTIR
gas cell. Typically, the sampling apparatus is similar to
that used for single-component continuous emission monitor
(CEM) measurements.
2.2.1 The digitized infrared spectrum of the sample in the
FTIR gas cell is measured and stored on a computer.
Absorbance band intensities in the spectrum are related to
sample concentrations by what is commonly referred to as
Beer's Law.
Ai = aib ci (1)
where:
At = absorbance at a given frequency of the ith sample
component.
at = absorption coefficient (absorptivity) of the ith
sample component.
b = path length of the cell.
G! = concentration of the ith sample component.
2.2.2 Analyte spiking is used for quality assurance (QA).
In this procedure (section 8.6.2 of this method) an analyte
is spiked into the gas stream at the back end of the sample
probe. Analyte concentrations in the spiked samples are
compared to analyte concentrations in unspiked samples.
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Since the concentration of the spike is known, this
procedure can be used to determine if the sampling system is
removing the spiked analyte(s) from the sample stream.
2.3 Reference Spectra Availability. Reference spectra of
over 100 HAPs are available in the EPA FTIR spectral library
on the EMTIC (Emission Measurement Technical Information
Center) computer bulletin board service and at internet
address http://info.arnold.af.mil/epa/welcome.htm.
Reference spectra for HAPs, or other analytes, may also be
prepared according to section 4.6 of the Protocol.
2.4 Operator Requirements. The FTIR analyst shall be
trained in setting up the instrumentation, verifying the
instrument is functioning properly, and performing routine
maintenance. The analyst must evaluate the initial sample
spectra to determine if the sample matrix is consistent with
pre-test assumptions and if the instrument configuration is
suitable. The analyst must be able to modify the instrument
configuration, if necessary.
2.4.1 The spectral analysis shall be supervised by someone
familiar with EPA FTIR Protocol procedures.
2.4.2 A technician trained in instrumental test methods is
qualified to install and operate the sampling system. This
includes installing the probe and heated line assembly,
operating the analyte. spike system, and performing moisture
and flow measurements.
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3.0 Definitions.
See appendix A of the Protocol for definitions relating
to infrared spectroscopy. Additional definitions are given
in sections 3.1 through 3.29.
3.1 Analyte. A compound that this method is used to
measure. The term "target analyte" is also used. This
method is multi-component and a number of analytes can be
targeted for a test.
3.2 Reference Spectrum. Infrared spectrum of an analyte
prepared under controlled, documented, and reproducible
laboratory conditions according to procedures in section 4.6
of the Protocol. A library of reference spectra is used to
measure analytes in gas samples.
3.3 Standard Spectrum. A spectrum that has been prepared
from a reference spectrum through a (documented)
mathematical operation. A common example is de-resolving of
reference spectra to lower-resolution standard spectra
(Protocol, appendix K to the addendum of this method).
Standard spectra, prepared by approved, and documented,
procedures can be used as reference spectra for analysis.
3.4 Concentration. In this method concentration is
expressed as a molar concentration, in ppm-meters, or in
(ppm-meters)/K, where K is the absolute temperature
(Kelvin). The latter units allow the direct comparison of
concentrations from systems using different optical
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10
configurations or sampling temperatures.
3.5 Interferant. A compound in the sample matrix whose
infrared spectrum overlaps with part of an analyte spectrum.
The most accurate analyte measurements are achieved when
reference spectra of interferants are used in the
quantitative analysis with the analyte reference spectra.
The presence of an interferant can increase the analytical
uncertainty in the measured analyte concentration.
3.6 Gas Cell. A gas containment cell that can be
evacuated. It is equipped with the optical components to
pass the infrared beam through the sample to the detector.
Important cell features include: path length (or range if
variable), temperature range, materials of construction, and
total gas volume.
3.7 Sampling System. Equipment used to extract the sample
from the test location and transport the sample gas to the
FTIR analyzer. This includes sample conditioning systems.
3.8 Sample Analysis. The process of interpreting the
infrared spectra to obtain sample analyte concentrations.
This process is usually automated using a software routine
employing a classical least squares (els), partial least
squares (pis), or K- or P- matrix method.
3.9 One hundred percent line. A double beam transmittance
spectrum obtained by combining two background single beam
spectra. Ideally, this line is equal to 100 percent
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transmittance (or zero absorbance) at every frequency in the
spectrum. Practically, a zero absorbance line is used to
measure the baseline noise in the spectrum.
3.10 Background Deviation. A deviation from 100 percent
transmittance in any region of the 100 percent line.
Deviations greater than ± 5 percent in an analytical region
are unacceptable (absorbance of 0.021 to -0.022). Such
deviations indicate a change in the instrument throughput
relative to the background single beam.
3.11 Batch Sampling. A procedure where spectra of
discreet, static samples are collected. The gas cell is
filled with sample and the cell is isolated. The spectrum
is collected. Finally, the cell is evacuated to prepare for
the next sample.
3.12 Continuous Sampling. A procedure where spectra are
collected while sample gas is flowing through the cell at a
measured rate.
3.13 Sampling resolution. The spectral resolution used to
collect sample spectra.
3.14 Truncation. Limiting the number of interferogram data
points by deleting points farthest from the center burst
(zero path difference, ZPD).
3.15 Zero filling. The addition of points to the
interferogram. The position of each added point is
interpolated from neighboring real data points. Zero
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filling adds no information to the interferogram, but
affects line shapes in the absorbance spectrum (and possibly
analytical results).
3.16 Reference CTS. Calibration Transfer Standard spectra
that were collected with reference spectra.
3.17 CTS Standard. CTS spectrum produced by applying a de-
resolution procedure to a reference CTS.
3.18 Test CTS. CTS spectra collected at the sampling
resolution using the same optical configuration as for
sample spectra. Test spectra help verify the resolution,
temperature and path length of the FTIR system.
3.19 RMSD. Root Mean Square Difference, defined in EPA
FTIR Protocol, appendix A.
3.20 Sensitivity. The noise-limited compound-dependent
detection limit for the FTIR system configuration. This is
estimated by the MAU. It depends on the RMSD in an
analytical region of a zero absorbance line.
3.21 Quantitation Limit. The lower limit of detection for
the FTIR system configuration in the sample spectra. This
is estimated by mathematically subtracting scaled reference
spectra of analytes and interferences from sample spectra,
then measuring the RMSD in an analytical region of the
subtracted spectrum. Since the noise in subtracted sample
spectra may be much greater than in a zero absorbance
spectrum, the quantitation limit is generally much higher
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than the sensitivity. Removing spectral interferences from
the sample or improving the spectral subtraction can lower
the quantitation limit toward (but not below) the
sensitivity.
3.22 Independent Sample. A unique volume of sample gas;
there is no mixing of gas between two consecutive
independent samples. In continuous sampling two independent
samples are separated by at least 5 cell volumes. The
interval between independent measurements depends on the
cell volume and the sample flow rate (through the cell).
3.23 Measurement. A single spectrum of flue gas contained
in the FTIR cell.
3.24 Run. A run consists of a series of measurements. At
a minimum a run includes 8 independent measurements spaced
over 1 hour.
3.25 Validation. Validation of FTIR measurements is
described in sections 13.0 through 13.4 of this method.
Validation is used to verify the test procedures for
measuring specific analytes at a source. Validation
provides proof that the method works under certain test
conditions.
3.26 Validation Run. A validation run consists of at least
24 measurements of independent samples. Half of the samples
are spiked and half are not spiked. The length of the run
is determined by the interval between independent samples.
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3.27 Screening. Screening is used when there is little or
no available information about a source. The purpose of
screening is to determine what analytes are emitted and to
obtain information about important sample characteristics
such as moisture, temperature, and interferences. Screening
results are semi-quantitative (estimated concentrations) or
qualitative (identification only). Various optical and
sampling configurations may be used. Sample conditioning
systems may be evaluated for their effectiveness in removing
interferences. It is unnecessary to perform a complete run
under any set of sampling conditions. Spiking is not
necessary, but spiking can be a useful screening tool for
evaluating the sampling system, especially if a reactive or
soluble analyte is used for the spike.
3.28 Emissions Test. An ETIR emissions test is performed
according specific sampling and analytical procedures.
These procedures, for the target analytes and the source,
are based on previous screening and validation results.
Emission results are quantitative. A QA spike (sections
8.6.2 and 9.2 of this method) is performed under each set of
sampling conditions using a representative analyte. Flow,
gas temperature and diluent data are recorded concurrently
with the FTIR measurements to provide mass emission rates
for detected compounds.
3.29 Surrogate. A surrogate is a. compound that is used in
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a QA spike procedure (section 8.6.2 of this method) to
represent other compounds. The chemical and physical
properties of a surrogate shall be similar to the compounds
it is chosen to represent. Under given sampling conditions,
usually a single sampling factor is of primary concern for
measuring the target analytes: for example, the surrogate
spike results can be representative for analytes that are
more reactive, more soluble, have a lower absorptivity, or
have a lower vapor pressure than the surrogate itself.
4.0 Interferences.
Interferences are divided into two classifications:
analytical and sampling.
4.1 Analytical Interferences. An analytical interference
is a spectral feature that complicates (in extreme cases may
prevent) the analysis of an analyte. Analytical
interferences are classified as background or spectral
interference.
4.1.1 Background Interference. This results from a change
in throughput relative to the single beam background. It is
corrected by collecting a new background and proceeding with
the test. In severe instances the cause must be identified
and corrected. Potential causes include: (1) deposits on
reflective surfaces or transmitting windows, (2) changes in
detector sensitivity, (3) a change in the infrared source
output, or (4) failure in the instrument electronics. In
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routine sampling throughput may degrade over several hours.
Periodically a new background must be collected, but no
other corrective action will be required.
4.1.2 Spectral Interference. This results from the
presence of interfering compound(s) (interferant) in the
sample. Interferant spectral features overlap analyte
spectral features. Any compound with an infrared spectrum,
including analytes, can potentially be an interferant. . The
Protocol measures absorbance band overlap in each analytical
region to determine if potential interferants shall be
classified as known interferants (FTIR Protocol, section 4.9
and appendix B). Water vapor and C02 are common spectral
interferants. Both of these compounds have strong infrared
spectra and are present in many sample matrices at high
concentrations relative to analytes. The extent of
interference depends on the (1) interferant concentration,
(2) analyte concentration, and (3) the degree of band
overlap. Choosing an alternate analytical region can
minimize or avoid the spectral interference. For example,
C02 interferes with the analysis of the 670 cm"1 benzene
band. However, benzene can also be measured near 3000 cm'1
(with less sensitivity).
4.2 Sampling System Interferences. These prevent analytes
from reaching the instrument. The analyte spike procedure
is designed to measure sampling system interference, if any.
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4.2.1 Temperature. A temperature that is too low causes
condensation of analytes or water vapor. The materials of
the sampling system and the FTIR gas cell usually set the
upper limit of temperature.
4.2.2 Reactive Species. Anything that reacts with
analytes. Some analytes/ like formaldehyde, polymerize at
lower temperatures.
4.2.3 Materials. Poor choice of material for probe, or
sampling line may remove some analytes. For example, HF
reacts with glass components.
4.2.4 Moisture. In addition to being a spectral
interferant, condensed moisture removes soluble compounds.
5.0 Safety.
The hazards of performing this method are those
associated with any stack sampling method and the same
precautions shall be followed. Many HAPs are suspected
carcinogens or present other serious health risks. Exposure
to these compounds should be avoided in all circumstances.
For instructions on the safe handling of any particular
compound, refer to its material safety data sheet. When
using analyte standards, always ensure that gases are
properly vented and that the gas handling system is leak
free. (Always perform a leak check with the system under
maximum vacuum and, again, with the system at greater than
ambient pressure.) Refer to section 8.2 of this method for
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18
leak check procedures. This method does not address all of
the potential safety risks associated with its use. Anyone
performing this method must follow safety and health
practices consistent with applicable legal requirements and
with prudent practice for each application.
6.0 Equipment and Supplies.
Note: Mention of trade names or specific products does
not constitute endorsement by the Environmental
Protection Agency.
The equipment and supplies are based on the schematic
of a sampling system shown in Figure 1. Either the batch or
continuous sampling procedures may be used with this
sampling system. Alternative sampling configurations may
also be used, provided that the data quality objectives are
met as determined in the post-analysis evaluation. Other
equipment or supplies may be necessary, depending on the
design of the sampling system or the specific target
analytes.
6.1 Sampling Probe. Glass, stainless steel, or other
appropriate material of sufficient length and physical
integrity to sustain heating, prevent adsorption of
analytes, and to transport analytes to the infrared gas
cell. Special materials or configurations may be required
in some applications. For instance, high stack sample
temperatures may require special steel or cooling the probe.
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For very high moisture sources it may be desirable to use a
dilution probe.
6.2 Particulate Filters. A glass wool plug (optional)
inserted at the probe tip (for large particulate removal)
and a filter (required) rated for 99 percent removal
efficiency at 1-micron (e.g., Balston") connected at the
outlet of the heated probe.
6.3 Sampling Line/Heating System. Heated (sufficient.to
prevent condensation) stainless steel,
polytetrafluoroethane, or other material inert to the
analytes.
6.4 Gas Distribution Manifold. A heated manifold allowing
the operator to control flows of gas standards and samples
directly to the FTIR system or through sample conditioning
systems. Usually includes heated flow meter, heated valve
for selecting and sending sample to the analyzer, and a by-
pass vent. This is typically constructed of stainless steel
tubing and fittings, and high-temperature valves.
6.5 Stainless Steel Tubing. Type 316, appropriate diameter
(e.g., 3/8 in.) and length for heated connections. Higher
grade stainless may be desirable in some applications.
6.6 Calibration/Analyte Spike Assembly. A three way valve
assembly (or equivalent) to introduce analyte or surrogate
spikes into the sampling system at the outlet of the probe
upstream of the out-of-stack particulate filter and the FTIR
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analytical system.
6.7 Mass Flow Meter (MFM). These are used for measuring
analyte spike flow. The MFM shall be calibrated in the range
of 0 to 5 L/min and be accurate to ± 2 percent (or better)
of the flow meter span.
6.8 Gas Regulators. Appropriate for individual gas
standards.
6.9 Polytetrafluoroethane Tubing. Diameter (e.g., 3/8 in.)
and length suitable to connect cylinder regulators to gas
standard manifold.
6.10 Sample Pump. A leak-free pump (e.g., KNF") , with by-
pass valve, capable of producing a sample flow rate of at
least 10 L/min through 100 ft of sample line. If the pump
is positioned upstream of the distribution manifold and FTIR
system, use a heated pump that is constructed from materials
non-reactive to the analytes. If the pump is located
downstream of the FTIR system, the gas cell sample pressure
will be lower than ambient pressure and it must be recorded
at regular intervals.
6.11 Gas Sample Manifold. Secondary manifold to control
sample flow at the inlet to the FTIR manifold. This is
optional, but includes a by-pass vent and heated rotameter.
6.12 Rotameter. A 0 to 20 L/min rotameter. This meter
need not be calibrated.
6.13 FTIR Analytical System. Spectrometer and detector,
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capable of measuring the analytes to the chosen detection
limit. The system shall include a personal computer with
compatible software allowing automated collection of
spectra.
6.14 FTIR Cell Pump. Required for the batch sampling
technique, capable of evacuating the FTIR cell volume within
2 minutes. The pumping speed shall allow the operator to
obtain 8 sample spectra in 1 hour.
6.15 Absolute Pressure Gauge. Capable of measuring
pressure from 0 to 1000 mmHg to within ± 2.5 mmHg (e.g.,
Baratron") .
6.16 Temperature Gauge. Capable of measuring the cell
temperature to within ± 2°C.
6.17 Sample Conditioning. One option is a condenser
system, which is used for moisture removal. This can be
helpful in the measurement of some analytes. Other sample
conditioning procedures may be devised for the removal of
moisture or other interfering species.
6.17.1 The analyte spike procedure of section 9.2 of this
method, the QA spike procedure of section 8.6.2 of this
method, and the validation procedure of section 13 of this
method demonstrate whether the sample conditioning affects
analyte concentrations. Alternatively, measurements can be
made with two parallel FTIR systems; one measuring
conditioned sample, the other measuring unconditioned
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sample.
6.17.2 Another option is sample dilution. The dilution
factor measurement must be documented and accounted for in
the reported concentrations. An alternative to dilution is
to lower the sensitivity of the FTIR system by decreasing
the cell path length, or to use a short-path cell in
conjunction with a long path cell to measure more than one
concentration range.
7.0 Reagents and Standards.
7.1 Analyte(s) and Tracer Gas. Obtain a certified gas
cylinder mixture containing all of the analyte(s) at
concentrations within ± 2 percent of the emission source
levels (expressed in ppm-meter/K). If practical, the
analyte standard cylinder shall also contain the tracer gas
at a concentration which gives a measurable absorbance at a
dilution factor of at least 10:1. Two ppm SFS is sufficient
for a path length of 22 meters at 250 °F.
7.2 Calibration Transfer Standard(s). Select the
calibration transfer standards (CTS) according to section
4.5 of the FTIR Protocol. Obtain a National Institute of
Standards and Technology (NIST) traceable gravimetric
standard of the CTS (± 2 percent).
7.3 Reference Spectra. Obtain reference spectra for each
analyte, interferant, surrogate, CTS, and tracer. If EPA
reference spectra are not available, use reference spectra
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prepared according to procedures in section 4.6 of the EPA
FTIR Protocol. '
8.0 Sampling and Analysis Procedure.
Three types of testing can be performed: (1) screening,
(2) emissions test, and (3) validation. Each is defined in
section 3 of this method. Determine the purpose(s) of the
FTIR test. Test requirements include: (a) AUj, DLt, overall
fractional uncertainty, OFUi, maximum expected concentration
(CMAXt) , and t^, for each, (b) potential interferants, (c)
sampling system factors, e.g., minimum absolute cell
pressure, (Pmin) , FTIR cell volume (Vss) , estimated sample
absorption pathlength, Lg', estimated sample pressure, Ps',
Tsf, signal integration time (tss) , minimum instrumental
linewidth, MIL, fractional error, and (d) analytical
regions, e.g., m = 1 to M, lower wavenumber position, FLm,
center wavenumber position, FCm, and upper wavenumber
position, FUm, plus interferants, upper wavenumber position
of the CTS absorption band, FFU,,,, lower wavenumber position
of the CTS absorption band, FFLm, wavenumber range FNU to
FNL. If necessary, sample and acquire an initial spectrum.
From analysis of this preliminary spectrum determine a
suitable operational path length. Set up the sampling train
as shown in Figure 1 or use an appropriate alternative
configuration. Sections 8.1 through 8.11 of this method
provide guidance on pre-test calculations in the EPA
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protocol, sampling and analytical procedures, and post-test
protocol calculations.
8.1 Pretest Preparations and Evaluations. Using the
procedure in section 4.0 of the FTIR Protocol, determine the
optimum sampling system configuration for measuring the
target analytes. Use available information to make
reasonable assumptions about moisture content and other
interferences.
8.1.1 Analytes. Select the required detection limit (DLJ
and the maximum permissible analytical uncertainty (AUJ for
each analyte (labeled from 1 to i). Estimate, if possible,
the maximum expected concentration for each analyte, CMAXt.
The expected measurement range is fixed by DLt and CMAXi for
each analyte (i).
8.1.2 Potential Interferants. List the potential
interferants. This usually includes water vapor and C02,
but may also include some analytes and other compounds.
8.1.3. Optical Configuration. Choose an optical
configuration that can measure all of the analytes within
the absorbance range of .01 to 1.0 (this may require more
than one path length). Use Protocol sections 4.3 to 4.8 for
guidance in choosing a configuration and measuring CTS.
8.1.4. Fractional Reproducibility Uncertainty (FRUt) . The
FRU is determined for each analyte by comparing CTS spectra
taken before and after the reference spectra were measured.
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The EPA para-xylene reference spectra were collected on
10/31/91 and 11/01/91 with corresponding CTS spectra
"cts!031a," and "ctsllOlb." The CTS spectra are used to
estimate the reproducibility (FRU) in the system that was
used to collect the references. The FRU must be < AU.
Appendix E of the protocol is used to calculate the FRU from
CTS spectra. Figure 2 plots results for 0.25 cm'1 CTS
spectra in EPA reference library: S3 (ctsllOlb - cts!031a),
and S4 [(ctsllOlb + cts!031a)/2]. The RMSD (SRMS) is
calculated in the subtracted baseline, S3, in the
corresponding CTS region from 850 to 1065 cm'1. The area
(BAV) is calculated in the same region of the averaged CTS
spectrum, S4.
8.1.5 Known Interferants. Use appendix B of the EPA FTIR
Protocol.
8.1.6 Calculate the Minimum Analyte Uncertainty, MAU
(section 1.3 of this method discusses MAU and protocol
appendix D gives the MAU procedure). The MAU for each
analyte, i, and each analytical region, m, depends on the
RMS noise.
8.1.7 Analytical Program. See FTIR Protocol, section 4.10.
Prepare computer program based on the chosen analytical
technique. Use as input reference spectra of all target
analytes and expected interferants. Reference spectra of
additional compounds shall also be included in the program
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if their presence (even if transient) in the samples is
considered possible. The program output shall be in ppm (or
ppb) and .shall be corrected for differences between the
reference path length, LR/ temperature, TR, and pressure, PR,
and the conditions used for collecting the sample spectra.
If sampling is performed at ambient pressure, then any
pressure correction is usually small relative to corrections
for path length and temperature, and may be neglected. •
8.2 Leak-check.
8.2.1 Sampling System. A typical ETIR extractive sampling
train is shown in Figure 1. Leak check from the probe tip
to pump outlet as follows: Connect a 0- to 250-mL/min rate
meter (rotameter or bubble meter) to the outlet of the pump.
Close off the inlet to the probe, and record the leak rate.
The leak rate shall be * 200 mL/min.
8.2.2 Analytical System Leak check. Leak check the FTIR
cell under vacuum and under pressure (greater than ambient).
Leak check connecting tubing and inlet manifold under
pressure.
8.2.2.1 For the evacuated sample technique, close the valve
to the FTIR cell, and evacuate the absorption cell to the
minimum absolute pressure Pmin. Close the valve to the pump,
and determine the change in pressure APV after 2 minutes.
8.2.2.2 For both the evacuated sample and purging
techniques, pressurize the system to about 100 mmHg above
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27
atmospheric pressure. Isolate the pump and determine the
change in pressure APP after 2 minutes.
8.2.2.3 Measure the barometric pressure, Pb in mmHg.
8.2.2.4 Determine the percent leak volume %VL for the
signal integration time tss and for APmax, i.e., the larger of
APV or APP, as follows:
ss
where 50 = 100% divided by the leak-check time of 2 minutes.
8.2.2.5 Leak volumes in excess of 4 percent of the FTIR
system volume Vss are unacceptable.
8.3 Detector Linearity. Once an optical configuration is
chosen, use one of the procedures of sections 8.3.1 through
8.3.3 to verify that the detector response is linear. If
the detector response is not linear, decrease the aperture,
or attenuate the infrared beam. After a change in the
instrument configuration perform a linearity check until it
is demonstrated that the detector response is linear.
8.3.1 Vary the power incident on the detector by modifying
the aperture setting. Measure the background and CTS at
three instrument aperture settings: (1) at the aperture
setting to be used in the testing, (2) at one half this
aperture and (3) at twice the proposed testing aperture.
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Compare the three CTS spectra. GTS band areas shall agree
to within the uncertainty of the cylinder standard and the
RMSD noise in the system. If test aperture is the maximum
aperture,, collect CTS spectrum at maximum aperture, then
close the aperture to reduce the IR throughput by half.
Collect a second background and CTS at the smaller aperture
setting and compare the spectra again.
8.3.2 Use neutral density filters to attenuate the infrared
beam. Set up the ETIR system as it will be used in the test
measurements. Collect a CTS spectrum. Use a neutral
density filter to attenuate the infrared beam (either
immediately after the source or the interferometer) to
approximately 1/2 its original intensity. Collect a second
CTS spectrum. Use another filter to attenuate the infrared
beam to approximately 1/4 its original intensity. Collect a
third background and CTS spectrum. Compare the CTS spectra.
CTS band areas shall agree to within the uncertainty of the
cylinder standard and the RMSD noise in the system.
8.3.3 Observe the single beam instrument response in a
frequency region where the detector response is known to be
zero. Verify that the detector response is "flat" and equal
to zero in these regions.
8.4 Data Storage Requirements. All field test spectra
shall be stored on a computer disk and a second backup copy
must stored on a separate disk. The stored information
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includes sample interferograms, processed absorbance
spectra, background interferograms, CTS sample
interferograms and CTS absorbance spectra. Additionally,
documentation of all sample conditions, instrument settings,
and test records must be recorded on hard copy or on
computer medium. Table 1 gives a sample presentation of
documentation.
8.5 Background Spectrum. Evacuate the gas cell to z 5
mmHg, and fill with dry nitrogen gas to ambient pressure (or
purge the cell with 10 volumes of dry nitrogen). Verify
that no significant amounts of absorbing species (for
example water vapor and C02) are present. Collect a
background spectrum, using a signal averaging period equal
to or greater than the averaging period for the sample
spectra. Assign a unique file name to the background
spectrum. Store two copies of the background interferogram
and processed single-beam spectrum on separate computer
disks (one copy is the back-up).
8.5.1 Interference Spectra. If possible, collect spectra
of known and suspected major interferences using the same
optical system that will be used in the field measurements.
This can be done on-site or earlier. A number of gases,
e.g. C02, S02, CO, NH3, are readily available from cylinder
gas suppliers.
8.5.2 Water vapor spectra can be prepared by the following
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procedure. Fill a sample tube with distilled water.
Evacuate above the sample and remove dissolved gasses by
alternately freezing and thawing the water while evacuating.
Allow water vapor into the FTIR cell, then dilute to
atmospheric pressure with nitrogen or dry air. If
quantitative water spectra are required, follow the
reference spectrum procedure for neat samples (protocol,
section 4.6). Often, interference spectra need not be
quantitative, but for best results the absorbance must be
comparable to the interference absorbance in the sample
spectra.
8.6 Pre-Test Calibrations
8.6.1 Calibration Transfer Standard. Evacuate the gas cell
to s 5 mmHg absolute pressure, and fill the FTIR cell to
atmospheric pressure with the CTS gas. Alternatively, purge
the cell with 10 cell volumes of CTS gas. (If purge is
used, verify that the CTS concentration in the cell is
stable by collecting two spectra 2 minutes apart as the CTS
gas continues to flow. If the absorbance in the second
spectrum is no greater than in the first, within the
uncertainty of the gas standard, then this can be used as
the CTS spectrum.) Record the spectrum.
8.6.2 QA Spike. This procedure assumes that the method has
been validated for at least some of the target analytes at
the source. For emissions testing perform a QA spike. Use
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31
a certified standard, if possible, of an analyte, which has
been validated at the source. One analyte standard can
serve as a QA surrogate for other analytes which are less
reactive or less soluble than the standard. Perform the
spike procedure of section 9.2 of this method. Record
spectra of at least three independent (section 3.22 of this
method)'spiked samples. Calculate the spiked component of
the analyte concentration. If the average spiked
concentration is within 0.7 to 1.3 times the expected
concentration, then proceed with the testing. If
applicable, apply the correction factor from the Method 301
of this appendix validation test (not the result from the QA
spike).
8.7 Sampling. If analyte concentrations vary rapidly with
time, continuous sampling is preferable using the smallest
cell volume, fastest sampling rate and fastest spectra
collection rate possible. Continuous sampling requires the
least operator intervention even without an automated
sampling system. For continuous monitoring at one location
over long periods, Continuous sampling is preferred. Batch
sampling and continuous static sampling are used for
screening and performing test runs of finite duration.
Either technique is preferred for sampling several locations
in a matter of days. Batch sampling gives reasonably good
time resolution and ensures that each spectrum measures a
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32
discreet (and unique) sample volume. Continuous static (and
continuous) sampling provide a very stable background over
long periods. Like batch sampling, continuous static
sampling also ensures that each spectrum measures a unique
sample volume. It is essential that the leak check
procedure under vacuum (section 8.2 of this method) is
passed if the batch sampling procedure is used. It is
essential that the leak check procedure under positive
pressure is passed if the continuous static or continuous
sampling procedures are used. The sampling techniques are
described in sections 8.7.1 through 8.7.2 of this method.
8.7.1 Batch Sampling. Evacuate the absorbance cell to
z 5 mmHg absolute pressure. Fill the cell with exhaust gas
to ambient pressure, isolate the cell, and record the
spectrum. Before taking the next sample, evacuate the cell
until no spectral evidence of sample absorption remains.
Repeat this procedure to collect eight spectra of separate
samples in 1 hour.
8.7.2 Continuous Static Sampling. Purge the FTIR cell with
10 cell volumes of sample gas. Isolate the cell, collect
the spectrum of the static sample and record the pressure.
Before measuring the next sample, purge the cell with 10
more cell volumes of sample gas.
8.8 Sampling QA and Reporting.
8.8.1 Sample integration times shall be sufficient to
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33
achieve the required signal-to-noise ratio. Obtain an
absorbance spectrum by filling the cell with N2. Measure
the RMSE) in each analytical region in this absorbance
spectrum. Verify that the number of scans used is
sufficient to achieve the target MAU.
8.8.2 Assign a unique file name to each spectrum.
8.8.3 Store two copies of sample interferograms and
processed spectra on separate computer disks.
8.8.4 For each sample spectrum, document the sampling
conditions, the sampling time (while the cell was being
filled), the time the spectrum was recorded, the
instrumental conditions (path length, temperature, pressure,
resolution, signal integration time), and the spectral file
name. Keep a hard copy of these data sheets.
8.9 Signal Transmittance. While sampling, monitor the
signal transmittance. If signal transmittance (relative to
the background) changes by 5 percent or more (absorbance =
-.02 to .02) in any analytical spectral region, obtain a new
background spectrum.
8.10 Post-test CTS. After the sampling run, record another
CTS spectrum.
8.11 Post-test QA.
8.11.1 Inspect the sample spectra immediately after the run
to verify that the gas matrix composition was close to the
expected (assumed) gas matrix.
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34
8.11.2 Verify that the sampling and instrumental parameters
were appropriate for the conditions encountered. For
example, if the moisture is much greater than anticipated,
it may be necessary to use a shorter path length or dilute
the sample.
8.11.3 Compare the pre- and post-test CTS spectra. The
peak absorbance in pre- and pos.t-test CTS must be ± 5
percent of the mean value. See appendix E of the FTIR
Protocol.
9.0 Quality Control.
Use analyte spiking (sections 8.6.2, 9.2 and 13.0 of
this method) to verify that the sampling system can
transport the analytes from the probe to the FTIR system.
9.1 Spike Materials. Use a certified standard (accurate to
± 2 percent) of the target analyte, if one can be obtained.
If a certified standard cannot be obtained, follow the
procedures in section 4.6.2.2 of the FTIR Protocol.
9.2 Spiking Procedure. QA spiking (section 8.6.2 of this
method) is a calibration procedure used before testing. QA
spiking involves following the spike procedure of sections
9.2.1 through 9.2.3 of this method to obtain at least three
spiked samples. The analyte concentrations in the spiked
samples shall be compared to the expected spike
concentration to verify that the sampling/analytical system
is working properly. Usually, when QA spiking is used, the
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35
method has already been validated at a similar source for
the analyte in question. The QA spike demonstrates that the
validated sampling/analytical conditions are being
duplicated. If the QA spike fails then the
sampling/analytical system shall be repaired before testing
proceeds. The method validation procedure (section 13.0 of
this method) involves a more extensive use of the analyte
spike procedure of sections 9.2.1 through 9.2.3 of this
method. Spectra of at least 12 independent spiked and 12
independent unspiked samples are recorded. The
concentration results are analyzed statistically to
determine if there is a systematic bias in the method for
measuring a particular analyte. If there is a systematic
bias, within the limits allowed by Method 301 of this
appendix, then a correction factor shall be applied to the
analytical results. If the systematic bias is greater than
the allowed limits, this method is not valid and cannot be
used.
9.2.1 Introduce the spike/tracer gas at a constant flow
rate of * 10 percent of the total sample flow, when
possible. (Note; Use the rotameter at the end of the
sampling train to estimate the required spike/tracer gas
flow rate.) Use a flow device, e.g., mass flow meter (± 2
percent), to monitor the spike flow rate. Record the spike
flow rate every 10 minutes.
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36
9.2.2 Determine the response time (RT) of the system by
continuously collecting spectra of the spiked effluent until
the spectrum of the spiked component is constant for 5
minutes. The RT is the interval from the first measurement
until the spike becomes constant.. Wait for twice the
duration of the RT, then collect spectra of two independent
spiked gas samples. Duplicate analyses of the spiked
concentration shall be within 5 percent of the mean of the
two measurements.
9.2.3 Calculate the dilution ratio using the tracer gas as
follows:
DF = I. (3)
^
where:
CS = DF+Spike^ + Unspike(l-DF) (4)
DF =• Dilution factor of the spike gas; this value
shall be ilO.
D = SFs (°r tracer gas) concentration measured
directly in undiluted spike gas.
SF6(3pk) = Diluted SF6 (or tracer gas) concentration
measured in a spiked sample.
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37
Spikedir = Concentration of the analyte in the spike
standard measured by filling the FTIR cell
directly.
CS = Expected concentration of the spiked samples.
Unspike = Native concentration of analytes in unspiked
samples
10.0 Calibration and Standardization.
10.1 Signal-to-Noise Ratio (S/N). The RMSD in the noise
must be less than one tenth of the minimum analyte peak
absorbance in each analytical region. For example if the
minimum peak absorbance is 0.01 at the required DL, then
RMSD measured over the entire analytical region must be
<; 0.001.
10.2 Absorbance Path length. Verify the absorbance path
length by comparing reference CTS spectra to test CTS
spectra. See appendix E of the FTIR Protocol.
10.3 Instrument Resolution. Measure the line width of
appropriate test CTS band(s) to verify instrument
resolution. Alternatively, compare CTS spectra to a
reference CTS spectrum, if available, measured at the
nominal resolution.
10.4 Apodization Function. In transforming the sample
interferograms to absorbance spectra use the same
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38
apodization function that was used in transforming the
reference spectra.
10.5 FTIR Cell Volume. Evacuate the cell to * 5 mmHg.
Measure the initial absolute temperature (TJ and absolute
pressure (Pi) . Connect a wet test meter (or a calibrated
dry gas meter), and slowly draw room air into the cell.
Measure the meter volume (VJ , meter absolute temperature
(TJ , and meter absolute pressure (PJ; and the cell final
absolute temperature (Tf) and absolute pressure (P£) .
Calculate the FTIR cell volume Vss/ including that of the
connecting tubing, as follows:
v m
111 rr*
m
P P
-L - -L
T T
l l
(5)
11.0 Data Analysis and Calculations.
Analyte concentrations shall be measured using
reference spectra from the EPA FTIR spectral library. When
EPA library spectra are not available, the procedures in
section 4.6 of the Protocol shall be followed to prepare
reference spectra of all the target analytes.
11.1 Spectral De-resolution. Reference spectra can be
converted to lower resolution standard spectra (section 3.3
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39
of this method) by truncating the original reference sample
and background interferograms. Appendix K of the FTIR
Protocol gives specific deresolution procedures. Deresolved
spectra shall be transformed using the same apodization
function and level of zero filling as the sample spectra.
Additionally, pre-test FTIR protocol calculations (e.g.,
FRU, MAU, FCU) shall be performed using the de-resolved
standard spectra.
11.2 Data Analysis. Various analytical programs are
available for relating sample absorbance to a concentration
standard. Calculated concentrations shall be verified by
analyzing residual baselines after mathematically
subtracting scaled reference spectra from the sample
spectra. A full description of the data analysis and
calculations is contained in the FTIR Protocol (sections
4.0, 5.0, 6.0 and appendices). Correct the calculated
concentrations in the sample spectra for differences in
absorption path length and temperature between the reference
and sample spectra using equation 6,
con-
where:
Ccorr = Concentration, corrected for path length.
Ccaic = Concentration, initial calculation (output of the
analytical program designed for the compound).
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40
Lr = Reference spectra path length.
Ls = Sample spectra path length.
T3 = Absolute temperature of the sample gas, K.
Tr » Absolute gas temperature of reference spectra, K.
Ps = Sample cell pressure.
Pr = Reference spectrum sample pressure.
12.0 Method Performance.
12.1 Spectral Quality. Refer to the FTIR Protocol
appendices for analytical requirements, evaluation of data
quality, and analysis of uncertainty.
12.2 Sampling QA/QC. The analyte spike procedure of
section 9 of this method, the QA spike of section 8.6.2 of
this method, and the validation procedure of section 13 of
this method are used to evaluate the performance of the
sampling system and to quantify sampling system effects, if
any, on the measured concentrations. This method is self-
validating provided that the results meet the performance
requirement of the QA spike in sections 9.0 and 8.6.2 of
this method and results from a previous method validation
study support the use of this method in the application.
Several factors can contribute to uncertainty in the
measurement of spiked samples. Factors which can be
controlled to provide better accuracy in the spiking
procedure are listed in sections 12.2.1 through 12.2.4 of
this method.
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41
12.2.1 Flow meter. An accurate mass flow meter is accurate
to ± 1 percent of its span. If a flow of 1 L/min is
monitored, with such a MFM, which is calibrated in the range
of 0-5 L/min, the flow measurement has an uncertainty of 5
percent. This may be improved by re-calibrating the meter
at the specific flow rate to be used.
12.2.2 Calibration gas. Usually the calibration standard
is certified to within ± 2 percent. With reactive analytes,
such as HCl, the certified accuracy in a commercially
available standard may be no better than ± 5 percent.
12.2.3 Temperature. Temperature measurements of the cell
shall be quite accurate. If practical, it is preferable to
measure sample temperature directly, by inserting a
thermocouple into the cell chamber instead of monitoring the
cell outer wall temperature.
12.2.4 Pressure. Accuracy depends on the accuracy of the
barometer, but fluctuations in pressure throughout a day may
be as much as 2.5 percent due to.weather variations.
13.0 Method Validation Procedure.
This validation procedure, which is based on EPA Method
301 (40 CFR part 63, appendix A), may be used to validate
this method for the analytes in a gas matrix. Validation at
one source may also apply to another type of source, if it
can be shown that the exhaust gas characteristics are
similar at both sources.
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42
13.1 Section 5.3 of Method 301 (40 CFR part 63, appendix
A), the Analyte Spike procedure, is used with these
modifications. The statistical analysis of the results
follows section 6.3 of EPA Method 301. Section 3 of this
method defines terms that are not defined in Method 301.
13.1.1 The analyte spike is performed dynamically. This
means the spike flow is continuous and constant as spiked
samples are measured.
13.1.2 The spike gas is introduced at the back of the
sample probe.
13.1.3 Spiked effluent is carried through all sampling
components downstream of the probe.
13.1.4 A single ETIR system (or more) may be used to
collect and analyze spectra (not quadruplicate integrated
sampling trains).
13.1.5 All of the validation measurements are performed
sequentially in a single "run" (section 3.26 of this
method).
13.1.6 The measurements analyzed statistically are each
independent (section 3.22 of this method).
13.1.7 A validation data set can consist of more than 12
spiked and 12 unspiked measurements.
13.2 Batch Sampling. The procedure in sections 13.2.1
through 13.2.2 may be used for stable processes. If process
emissions are highly variable, the procedure in section
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43
13.2.3 shall be used.
13.2.1 With a single FTIR instrument and sampling system,
begin by collecting spectra of two unspiked samples.
Introduce the spike flow into the sampling system and allow
10 cell volumes to purge the sampling system and FTIR cell.
Collect spectra of two spiked samples. Turn off the spike
and allow 10 cell volumes of unspiked sample to purge the
FTIR cell. Repeat this procedure until the 24 (or more)
samples are collected.
13.2.2 In batch sampling, collect spectra of 24 distinct
samples. (Each distinct sample consists of filling the cell
to ambient pressure after the cell has been evacuated.)
13.2.3 Alternatively, a separate probe assembly, line, and
sample pump can be used for spiked sample. Verify and
document that sampling conditions are the same in both the
spiked and the unspiked sampling systems. This can be done
by wrapping both sample lines in the same heated bundle.
Keep the same flow rate in both sample lines. Measure
samples in sequence in pairs. After two spiked samples are
measured, evacuate the FTIR cell, and turn the manifold
valve so that spiked sample flows to the FTIR cell. Allow
the connecting line from the manifold to the FTIR cell to
purge thoroughly (the time depends on the line length and
flow rate). Collect a pair of spiked samples. Repeat the
procedure until .at least 24 measurements are completed.
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44
13.3 Simultaneous Measurements With Two FTIR Systems. If
unspiked effluent concentrations of the target analyte(s)
vary significantly with time, it may be desirable to perform
synchronized measurements of spiked and unspiked sample.
Use two FTIR systems, each with its own cell and sampling
system to perform simultaneous spiked and unspiked
measurements. The optical configurations shall be similar,
if possible. The sampling configurations shall be the same.
One sampling system and FTIR analyzer shall be used to
measure spiked effluent. The other sampling system and FTIR
analyzer shall be used to measure unspiked flue gas. Both
systems shall use the same sampling procedure (i.e., batch
or continuous).
13.3.1 If batch sampling is used, synchronize the cell
evacuation, cell filling, and collection of spectra. Fill
both cells at the same rate (in cell volumes per unit time).
13.3.2 If continuous sampling is used, adjust the sample
flow through each gas cell so that the same number of cell
volumes pass through each cell in a given time (i.e. TCj =
TC2).
13.4 Statistical Treatment. The statistical procedure of
EPA Method 301 of this appendix, section 6.3 is used to
evaluate the bias and precision. For FTIR testing a
validation "run" is defined as spectra of 24 independent
samples, 12 of w.hich are spiked with the analyte(s) and 12
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45
of which are not spiked.
13.4.1 Bias. Determine the bias (defined by EPA Method 301
of this appendix, section 6.3.2) using equation 7:
B = Sm-CS
where:
B = Bias at spike level.
Sra = Mean concentration of the analyte spiked
samples.
CS = Expected concentration of the spiked samples.
13.4.2 Correction Factor. Use section 6.3.2.2 of Method
301 of this appendix to evaluate the statistical
significance of the bias. If it is determined that the bias
is significant, then use section 6.3.3 of Method 301 to
calculate a correction factor (CF). Analytical results of
the test method are multiplied by the correction factor, if
0.7 * CF i 1.3. If is determined that the bias is
significant and CF > ± 30 percent, then the test method is
considered to "not valid."
13.4.3 If measurements do not pass validation, evaluate the
sampling system, instrument configuration, and analytical
system to determine if improper set-up or a malfunction was
the cause. If so, repair the system and repeat the
validation.
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46
14.0 Pollution Prevention.
The extracted sample gas is vented outside the
enclosure containing the FTIR system and gas manifold after
the analysis. In typical method applications the vented
sample volume is a small fraction of the source volumetric
flow and its composition is identical to that emitted from
the source. When analyte spiking is used, spiked pollutants
are vented with the extracted sample gas. Approximately 1.6
x 10"4 to 3.2 x 1CT4 Ibs of a single HAP may be vented to the
atmosphere in a typical validation run of 3 hours. (This
assumes a molar mass of 50 to 100 g, spike rate of 1.0
L/min, and a standard concentration of 100 ppm). Minimize
emissions by keeping the spike flow off when not in use.
15.0 Waste Management.
Small volumes of laboratory gas standards can be vented
through a laboratory hood. Neat samples must be packed and
disposed according to applicable regulations. Surplus
materials may be returned to supplier for disposal.
16.0 References.
1. "Field Validation Test Using Fourier Transform Infrared
(FTIR) Spectrometry To Measure Formaldehyde/ Phenol and
Methanol at a Wool Fiberglass Production Facility." Draft.
U.S. Environmental Protection Agency Report, EPA Contract
No. 68D20163, Work Assignment 1-32, September 1994.
2. "FTIR Method Validation at a Coal-Fired Boiler".
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47
Prepared for U.S. Environmental Protection Agency, Research
Triangle Park, NC. Publication No.: EPA-454/R95-004, NTIS
No.: PB95-193199. July, 1993.
3. "Method 301 - Field Validation of Pollutant Measurement
Methods from Various Waste Media," 40 CF1 part 63, appendix
A.
4. "Molecular Vibrations; The Theory of Infrared and Raman
Vibrational Spectra," E. Bright Wilson, J. C. Decius, and P.
C. Cross, Dover Publications, Inc., 1980. For a less
intensive treatment of molecular rotational-vibrational
spectra see, for example, "Physical Chemistry," G. M.
Barrow, chapters 12, 13, and 14, McGraw Hill, Inc., 1979.
5. "Fourier Transform Infrared Spectrometry,". Peter R.
Griffiths and James de Haseth, Cheaical Analysis, 83, 16-
25, (1986), P. J. Elving, J. D. Winefordner and I. M.
Kolthoff (ed.), John Wiley and Sons.
6. "Computer-Assisted Quantitative Infrared Spectroscopy,"
Gregory L. McClure (ed.), ASTM Special Publication 934
(ASTM), 1987.
7. "Multivariate Least-Squares Methods Applied to the
Quantitative Spectral Analysis of Multicomponent Mixtures,"
Applied Spectroscopy, 39(10), 73-84, 1985.
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CAMPLE PRESENTATION OF SAMPLING DOCUMENTATION.
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49
Calibralion Ga* Line
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Figure 1. Extractive FTIR sampling system.
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50
.8-
.6-
0
FRU = SRMS(FU-FL)/BAV
SRMS = .00147
BAV = 3.662
FM = FRU = .086
p-xylene
1050
1000
950 900
Wavenumbers
850
800
750
Figure 2. Fractional Reproducibility. Top: average of ctslOSla and
ctsllOlb. Bottom: Reference spectrum of p-xylene.
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D-2 EPA FTIR PROTOCOL
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Page 1
PROTOCOL FOR THE USB OP EXTRACTIVE FOURIER TRANSFORM
INFRARED (FTIR) SPECTROMETRY FOR THE ANALYSES OF GASEOUS
EMISSIONS FROM STATIONARY SOURCES
INTRODUCTION
The purpose of this document is to set general guidelines
for the use of modern FTIR spectroscopic methods for the analysis
of gas samples extracted from the effluent of stationary emission
sources. This document outlines techniques for developing and
evaluating such methods and sets basic requirements for reporting
and quality assurance procedures.
1.0 NOMENCLATURE
1.1 Appendix A lists definitions of the symbols and terms
used in this Protocol, many of which have been taken directly
from American Society for Testing and Materials (ASTM)
publication E 131-90a, entitled "Terminology Relating to
Molecular Spectroscopy."
1.2 Except in the case of background spectra or where
otherwise noted, the term "spectrum" refers to a double-beam
spectrum in units of absorbance vs. wavenumber (cm"1).
1.3 The term "Study" in this document refers to a
publication that has been subjected to EPA- or peer-review.
2.0 APPLICABILITY AND ANALYTICAL PRINCIPLE
2.1 Applicability. This Protocol applies to the
determination of compound-specific concentrations in single- and
multiple-component gas phase samples using double-beam absorption
spectroscopy in the mid-infrared band. It does not specifically
address other FTIR applications, such as single-beam
spectroscopy, analysis of open-path (non-enclosed) samples, and
continuous measurement techniques. If multiple spectrometers,
absorption cells, or instrumental linewidths are used in such
analyses, each distinct operational configuration of the system
must be evaluated separately according to this Protocol.
2.2 Analytical Principle.
2.2.1 In the mid-infrared band, most molecules exhibit
characteristic gas phase absorption spectra that may be recorded
by FTIR systems. Such systems consist of a source of mid-
infrared radiation, an interferometer, an enclosed sample cell of
known absorption pathlength, an infrared detector, optical
elements for the .transfer of infrared radiation between
components, and gas flow control and measurement components.
Adjunct and integral computer systems are used for controlling
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BPA PTIR Protocol _ _
Page 2
the instrument, processing the signal, and for performing both
Fourier transforms and quantitative analyses of spectral data.
2.2.2 The absorption spectra of pure gases and of mixtures
of gases are described by a linear absorbance theory referred to
as Beer's Law. Using this law, modern FTIR systems use
computerized analytical programs to quantify compounds by
comparing the absorption spectra of known (reference) gas samples
to the absorption spectrum of the sample gas. Some standard
mathematical techniques used for comparisons are classical least
squares, inverse least squares, cross -correlation, factor
analysis, and partial least squares. Reference A describes
several of these techniques, as well as additional techniques,
such as differentiation methods, linear baseline corrections, and
non- linear absorbance corrections.
3.0 GENERAL PRINCIPLES OP PROTOCOL REQUIREMENTS
The characteristics that distinguish FTIR systems from gas
analyzers used in instrumental gas analysis methods (e.g.,
EPA Methods 6C and 7E) are: (1) Computers are necessary to
obtain and analyze data; (2) chemical concentrations can be
quantified using previously recorded infrared reference spectra;
and (3) analytical assumptions and results, including possible
effects of interfering compounds, can be evaluated after the
quantitative analysis. The following general principles and
requirements of this Protocol are based on these characteristics.
3.1 Verifiability and Reproducibility of Results. Store
all data and document data analysis techniques sufficient to
allow an independent agent to reproduce the analytical results
from the raw interferometric data.
3.2 Transfer of Reference Spectra. To determine whether
reference spectra recorded under one set of conditions (e.g.,
optical bench, instrumental linewidth, absorption pathlength,
detector performance, pressure, and temperature) can be used to
analyze sample spectra taken under a different set of conditions,
quantitatively compare "calibration transfer standards" (CTS) and
reference spectra as described in this Protocol. (Note; The CTS
may, but need not, include analytes of interest) . To effect
this, record the absorption spectra of the CTS (a) immediately
before *nd immediately after recording reference spectra and
(b) immediately after recording sample spectra.
3.3 Evaluation of FTIR Analyses. The applicability,
accuracy, and precision of FTIR measurements are influenced by a
number of interrelated factors, which may be divided into two
classes: v
3.3.1 Sample- Independent Factors. Examples are system
configuration and performance (e.g., detector sensitivity and
infrared source output) , quality and applicability of reference
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BPA FTIR Protocol
Paae
a
absorption spectra, and type of mathematical analyses of the
spectra. These factors define the fundamental limitations of
FTIR measurements for a given system configuration. These
limitations may be estimated from evaluations of the system
before samples are available. For example, the detection limit
for the absorbing compound under a given set of conditions may be
estimated from the system noise level and the strength of a
particular absorption band. Similarly, the accuracy of
measurements may be estimated from the analysis of the reference
spectra.
3.3.2 Sample -Dependent Factors. Examples are spectral
interferants (e.g., water vapor and C02) or the overlap of
spectral features of different compounds and contamination
deposits on reflective surfaces or transmitting windows. To
maximize the effectiveness of the mathematical techniques used in
spectral analysis, identification of interferants (a standard
initial step) and analysis of samples (includes effects of other
analytical errors) are necessary. Thus, the Protocol requires
post -analysis calculation of measurement concentration
uncertainties for the detection of these potential sources of
measurement error.
4.0 PRB-TEST PREPARATIONS AMD EVALUATIONS
Before testing, demonstrate the suitability of FTIR
spectrometry for the desired application according to the
procedures of this section.
4.1 Identify Test Requirements. Identify and record the
test requirements described below in 4.1.1 through 4.1.5. These
values set the desired or required goals of the proposed
analysis; the description of methods for determining whether
these goals are actually met during the analysis comprises the
majority of this Protocol.
4.1.1 Analytes (specific chemical species) of interest.
Label the analytes from i - 1 to I.
4.1.2 Analytical uncertainty limit (AU^ . The AUi is the
maximum permissible fractional uncertainty of analysis for the
i"1 analyte concentration, expressed as a fraction of the analyte
concentration in the sample.
4.1.3 Required detection limit for each analyte (DL^, pprn) .
The detection limit is the lowest concentration of an analyte for
which its overall fractional uncertainty (OFUj) is required to be
less than its analytical uncertainty limit (At^) .
4.1.4 Maximum expected concentration of each analyte
, ppm) .
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BPA PTIR ProtOCOl Darro A
A 1Qa
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BPA PTIR Protocol _
1*. "mfi Pa9e 5
4.5.3 At least one absorption CTS band within the operating
range of the FTIR instrument has an instrument -independent
linewidtn no greater than the narrowest analyte absorption band-
perform and document measurements or cite Studies to determine
analyte and CTS compound linewidths.
4.5.4 For each analytical region, specify the upper and
lower wavenumber positions (FFU_ and FFL^, respectively) that
bracket the CTS absorption band or bands for the associated
analytical region. Specify the wavenumber range, FNU to FNL,
containing the absorption band that meets the criterion of
Section 4.5.3.
4.5.5 Associate, whenever possible, a single set of CTS gas
cylinders with a set of reference spectra. Replacement CTS gas
cylinders shall contain the same compounds at concentrations
within 5 percent of that of the original CTS cylinders; the
entire absorption spectra (not individual spectral segments) of
the replacement gas shall be scaled by a factor between 0.95 and
1.05 to match the original CTS spectra.
4.6 Prepare Reference Spectra.
Note : Reference spectra are available in a permanent soft
copy from the EPA spectral library on the EMTIC (Emission
Measurement Technical Information Center) computer bulletin
board; they may be used if applicable.
4.6.1 Select the reference absorption pathlength (Lp) of
the cell.
4.6.2 Obtain or prepare a set of chemical standards for
each analyte, potential and known spectral interferants, and CTS.
Select the concentrations of the chemical standards to correspond
to the top of the desired range.
4.6.2.1 Commercially -Prepared Chemical Standards. Chemical
standards for many compounds may be obtained from independent
sources, such as a specialty gas manufacturer, chemical company,
or commercial laboratory. These standards (accurate to within
±2 percent) shall be prepared according to EPA Protocol l (see
Reference D) or shall be traceable to NIST standards. Obtain
from the supplier an estimate of the stability of the analyte
concentration; obtain and follow all the supplier's
recommendations for recertifying the analyte concentration.
4.6.2.2 Self -Prepared Chemical Standards. Chemical
standards may be prepared as follows: Dilute certified
commercially prepared chemical gases or pure analytes with ultra-
pure carrier (UPC) grade nitrogen according to the barometric and
volumetric techniques generally described in Reference A,
Section A4.6.
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EPA PTIR Protocol Paae> 6
'"-* 1A 1QQg ^
4.6.3 Record a set of the absorption spectra of the CTS
{Rl}, then a set of the reference spectra at two or more
concentrations in duplicate over the desired range (the top of
the range must be less than 10 times that of the bottom) ,
followed by a second set of CTS spectra {R2}. (If self -prepared
standards are used, see Section 4.6.5 before disposing of any of
the standards.) The maximum accepted standard concentration -
pathlength product (ASCPP) for each compound shall be higher than
the maximum estimated concentration-pathlength products for both
analytes and known interferants in the effluent gas. For each
analyte, the minimum ASCPP shall be no greater than ten times the
concentration-pathlength product of that analyte at its required
detection limit.
4.6.4 Permanently store the background and interferograms
in digitized form. Document details of the mathematical process
for generating the spectra from these interferograms. Record the
sample pressure (PR) , sample temperature (TR) , reference
absorption pathlength (LR) , and interferogram signal integration
period (tSR) . Signal integration periods for the background
interferograms shall be *tSR. Values of PR, LR, and tSR shall
not deviate by more than ±1 percent from the time of recording
{Rl} to that of recording {R2}.
4.6.5 If self -prepared chemical standards are employed and
spectra of only two concentrations are recorded for one or more
compounds, verify the accuracy of the dilution technique by
analyzing the prepared standards for those compounds with a
secondary (non-PTIR) technique as follows:
4.6.5.1 Record the response of the secondary technique to
each of the four standards prepared.
4.6.5.2 Perform a linear regression of the response values
(dependant variable) versus the accepted standard concentration
(ASC) values (independent variable) , with the regression
constrained to pass through the zero -response, zero ASC point.
4.6.5.3 Calculate the average fractional difference between
the actual response values and the regression-predicted values
(those calculated from the regression line using the four ASC
values as the independent variable) .
4654 If the average fractional difference value
calculated in Section 4.6.5.3 is larger for any compound than the
corresponding Alii, the dilution technique is not sufficiently
accurate and the reference spectra prepared are not valid for the
analysis.
4 7 Select Analytical Regions. Using the general
considerations in Section 7 of Reference A and the spectral
characteristics of the analytes and interferants, select the
analytical regions for the application. Label them m - 1 to M.
Specify the lower, center and upper wavenumber positions of each
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EPA FTIR Protocol
analytical region (FI^, FC^, and FUm, respectively) . Specify the
analytes and interferants which exhibit absorption in each
region. *
4.8 Determine Fractional Reproducibility Uncertainties
Using Appendix E, calculate the fractional reproducibility
uncertainty for each analyte (FRU^) from a comparison of {RI} and
{R2}. If FRUi > AUi for any analyte, the reference spectra
generated in Section 4.6 are not valid for the application.
4.9 Identify Known Interferants. Using Appendix B,
determine which potential interferant affects the analyte
concentration determinations. If it does, relabel the potential
interferant as "known" interferant, and designate these compounds
from k « 1 to K. Appendix B also provides criteria for
determining whether the selected analytical regions are suitable.
4.10 Prepare Computerized Analytical Programs.
4.10.1 Choose or devise mathematical techniques (e.g,
classical least squares, inverse least squares, cross-
correlation, and factor analysis) based on Equation 4 of
Reference A that are appropriate for analyzing spectral data by
comparison with reference spectra.
4.10.2 Following the general recommendations of Reference
A, prepare a computer program or set of programs that analyzes
all the analytes and known interferants, based on the selected
analytical regions (4.7) and the prepared reference spectra
(4.6). Specify the baseline correction technique (e.g.,
determining the slope and intercept of a linear baseline
contribution in each analytical region) for each analytical
region, including all relevant wavenumber positions.
4.10.3 Use programs that provide as output [at the
reference absorption pathlength (LR) , reference gas temperature
(TR) , and reference gas pressure (PR) ] the analyte
concentrations, the known interferant concentrations, and the
baseline slope and intercept values. If the sample absorption
pathlength (Lg) , sample gas temperature (Tg) or sample gas
pressure (Pg) during the actual sample analyses differ from LR/
TR/ and Pp, use a program or set of programs that applies
multiplicative corrections to the derived concentrations to
account for these variations, and that provides as output both
the corrected and uncorrected values. Include in the report of
the analysis (see Section 7.0) the details of any transformations
applied to the original reference spectra (e.g.,
differentiation) , in such a fashion that all analytical results
may be verified by an independent agent from the reference
spectra and data spectra alone.
4.11 Determine • the Fractional Calibration Uncertainty.
Calculate the fractional calibration uncertainty for each analyte
according to Appendix F, and compare these values to the
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_ Page 8
fractional uncertainty limits (AI^; see Section 4.1) . if
FCUi > AUi) , either the reference spectra or analytical programs
for that analyte are unsuitable.
4.12 Verify System Configuration Suitability. Using
Appendix C, measure or obtain estimates of the noise level
(RMSEST, absorbance) of the FTIR system; alternatively, construct
the complete spectrometer system and determine the values RMSo-
using Appendix G. Estimate the minimum measurement uncertainty
for each analyte (MAU^, ppm) and known interferant (MIUV, ppm)
using Appendix D. Verify that (a) MAU± < (AO.) (DI^) , FRUt < Am,
and FCUi < AUj_ for each analyte and that (b) the CTS chosen meets
the requirements listed in Section 4.5.
5.0 SAMPLING AND ANALYSIS PROCEDURE
5.1 Analysis System Assembly and Leak-Test. Assemble the
analysis system. Allow sufficient time for all system components
to reach the desired temperature. Then determine the leak- rate
(LR) and leak volume (VL) , where VL - LR tss. Leak volumes shall
be s4 percent of Vss .
5.2 Verify Instrumental Performance. Measure the noise
level of the system in each analytical region using the procedure
of Appendix 6. If any noise level is higher than that estimated
for the system in Section 4.12, repeat the calculations of
Appendix O and verify that the requirements of Section 4.12 are
met; if they are not, adjust or repair the instrument and repeat
this section.
5.3 Determine the Sample Absorption Pathlength. Record a
background spectrum. Then, fill the absorption cell with CTS at
the pressure P« and record a set of CTS spectra {R3}. Store the
background and unsealed CTS single beam interferograms and
spectra. Using Appendix H, calculate the sample absorption
pathlength (L«) for each analytical region. The values Lg shall
not differ from the approximated sample pathlength Ls^ (see
Section 4.4) by more than 5 percent.
5.4 Record Sample Spectrum. Connect the sample line to the
source. Either evacuate the absorption cell to an absolute
pressure below 5 mmHg before extracting a sample from the
effluent stream into the absorption cell, or pump at least ten
cell volumes of sample through the cell before obtaining a
sample. Record the sample pressure Ps. Generate the absorbance
spectrum of the sample. Store the background and sample single
beam interferograms, and document the process by which the
absorbance spectra are generated from these data. (If necessary,
apply the spectral transformations developed in Section 5.6.2) .
The resulting sample spectrum is referred to below as Ss.
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BPA PTIR Protocol
Multiple sample spectra may be recorded according to
the procedures of Section 5.4 before performing Sections 5.5
and 5.6.
5.5 Quantify Analyte Concentrations. Calculate the
unsealed analyte concentrations RUAi and unsealed interferant
concentrations RUI~ using the programs developed in Section 4.
To correct for pathlength and pressure variations between the
reference and sample spectra, calculate the scaling factor
RLPS • (LRPRTS^ / (LSpSTs) ' Calculate the final analyte and
interferant concentrations RSAi - R^gRUAi and RSIk - RLPSRUIk.
5.6 Determine Fractional Analysis Uncertainty. Fill the
absorption cell with CTS at the pressure Pg. Record a set of CTS
spectra {R4}. Store the background and CTS single beam
interf erograms . Using Appendix* H, calculate the fractional
analysis uncertainty (FAU) for each analytical region. . If the
FAU indicated for any analytical region is larger than the
required accuracy requirements determined in Section 4.1, then
comparisons to previously recorded reference spectra are invalid
in that analytical region, and the analyst shall perform one or
both of the following procedures:
5.6.1 Perform instrumental checks and adjust the instrument
to restore its performance to acceptable levels. If adjustments
are made, repeat Sections 5.3, 5.4 (except for the recording of a
sample spectrum), and 5.5 to demonstrate that acceptable
uncertainties are obtained in all analytical regions.
5.6.2 Apply appropriate mathematical transformations (e.g.,
frequency shifting, zero- filling, apodization, smoothing) to the
spectra (or to the interf erograms upon which the spectra are
based) generated during the performance of the procedures of
Section 5.3. Document these transformations and their
reproducibility. Do not apply multiplicative scaling of the
spectra, or any set of transformations that is mathematically
equivalent to multiplicative scaling. Different transformations
may be applied to different analytical regions. Frequency shifts
shall be smaller than one-half the minimum instrumental
linewidth, and must be applied to all spectral data points in an
analytical region. The mathematical transformations may be
retained for the analysis if they are also applied to the
appropriate analytical regions of all sample spectra recorded,
and if all original sample spectra are digitally stored. Repeat
Sections 5.3, 5.4 (except the recording of a sample spectrum),
and 5.5 to demonstrate that these transformations lead to
acceptable calculated concentration uncertainties in all
analytical regions.
6.0 POST-ANALYSIS EVALUATIONS
Estimate the overall accuracy of the analyses performed in
Section 5 as follows:
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BPA PTIR Protocol , Paqe 10
~
IQOfi
6.1 Qualitatively Confirm the Assumed Matrix. Examine each
analytical region of the sample spectrum for spectral evidence of
unexpected or unidentified interf erants . If found, identify the
interfering compounds (see Reference C for guidance) and add them
to the list of known interf erants . Repeat the procedures of
Section 4 to include the interferants in the uncertainty
calculations and analysis procedures. Verify that the MAU and
FCU values do not increase beyond acceptable levels for the
application requirements. Re-calculate the analyte
concentrations (Section 5.5) in the affected analytical regions.
6.2 Quantitatively Evaluate Fractional Model Uncertainty
(FMU) . Perform the procedures of either Section 6.2.1 or 6.2.2:
6.2.1 Using Appendix I, determine the fractional model
error (FMU) for each analyte.
6.2.2 Provide statistically determined uncertainties FMU
for each analyte which are equivalent to two standard deviations
at the 95% confidence level. Such determinations, if employed,
must be based on mathematical examinations of the pertinent
sample spectra (not the reference spectra alone) . Include in the
report of the analysis (see Section 7.0) a complete description
of the determination of the concentration uncertainties.
6.3 Estimate Overall Concentration Uncertainty (OCU) .
Using Appendix J, determine the overall concentration uncertainty
(OCU) for each analyte. If the OCU is larger than the required
accuracy for any analyte, repeat Sections 4 and 6.
7.0 REPORTING REQUIREMENTS
[Documentation pertaining to virtually all the procedures of
Sections 4, 5, and 6 will be required. Software copies of
reference spectra and sample spectra will be retained for some
minimum time following the actual testing.]
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BPA PTIR Protocol Page 11
lufjuat- 1 A 1QQC _____ _
8.0 RBFERENCSS
A) Standard Practices for General Techniques of Infrared
Quantitative Analysis (American Society for Testing and
Materials, Designation E 168-88).
B) The Coblentz Society Specifications for Evaluation of
Research Quality Analytical Infrared Reference Spectra
(Class II); Anal. Chemistry 4J7, 945A (1975); Appl.
Spectroscopy 444. pp. 211-215, 1990.
C) Standard Practices for General Techniques for Qualitative
Infrared Analysis, American Society for Testing and
Materials, Designation E 1252-88.
D) "Traceability Protocol for Establishing True Concentrations
of Gases Used for Calibration and Audits of Continuous
Emissions Monitors (Protocol Number D," June 1978, Quality
Assurance Handbook for Air Pollution Measurement Systems,
Volume III, Stationary Source Specific Methods, EPA-600/4-
77-027b, August 1977.
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BPA PTIR Protocol -
ing"**- i* •""»* _ . _ . _ Page 12
APPENDIX A
DEFINITIONS OP TERMS AND SYMBOLS
A.I Definition* of Terns
absorption band - a contiguous wavenumber region of a spectrum
(equivalently, a contiguous set of absorbance spectrum data
points) in which the absorbance passes through a maximum or
a series of maxima.
absorption pathlengta - in a spectrophotometer, the distance,
measured in the direction of propagation of the beam of
radiant energy, between the surface of the specimen on which
the radiant energy is incident and the surface of the
specimen from which it is emergent.
analytical region - a contiguous wavenumber region (equivalently,
a contiguous set of absorbance spectrum data points) used in
the quantitative analysis for one or more analyte.
The quantitative result for a single analyte may be
based on data from more than one analytical region.
apodization - modification of the IL3 function by multiplying the
interferogram by a weighing function whose magnitude varies
with retardation.
background spectrum - the single beam spectrum obtained with all
system components without sample present.
baseline - any line drawn on an absorption spectrum to establish
a reference point that represents a function of the radiant
power incident on a sample at a given wavelength.
Beers' a law - the direct proportionality of the absorbance of a
compound in a homogeneous sample to its concentration.
calibration transfer standard (CTS) gas - a gas standard of a
compound used to achieve and/or demonstrate suitable
quantitative agreement between sample spectra and the
reference spectra; see Section 4.5.1.
compound - a substance possessing a distinct, unique molecular
structure.
concentration (c) - the quantity of a compound contained in a
unit quantity of sample. The unit "ppm" (number, or mole,
basis) is recommended.
concentration-pathlength product - the mathematical product of
concentration of the species and absorption pathlength. For
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EPA FTIR Protocol _
Page 13
reference spectra, this is a known quantity; for sample
spectra, it is the quantity directly determined from Beer's
law. The units B centimeters-ppm" or "meters-ppm" are
recommended.
derivative absorption spectrum - a plot of rate of change of
absorbance or of any function of absorbance with respect to
wavelength or any function of wavelength.
double beam spectrum - a transmission or absorbance spectrum
derived by dividing the sample single beam spectrum by the
background spectrum.
Note: The term "double-beam" is used elsewhere to denote a
spectrum in which the sample and background interferograms
are collected simultaneously' along physically distinct
absorption paths. Here, the term denotes a spectrum in
which the sample and background interferograms are collected
at different times along the same absorption path.
fast Fourier transform (FFT) - a method of speeding up the
computation of a discrete FT by factoring the data into
sparse matrices containing mostly zeros.
flyback - interferometer motion during which no data are
recorded.
Fourier transform (FT) - the mathematical process for converting
an amplitude-time spectrum to an amplitude-frequency
spectrum, or vice versa.
Fourier transform infrared (FTIR) spectrometer - an analytical
system that employs a source of mid-infrared radiation, an
interferometer, an enclosed sample cell of known absorption
pathlength, an infrared detector, optical elements that
transfer infrared radiation between components, and a
computer system. The time-domain detector response
(interferogram) is processed by a Fourier transform to yield
a representation of the detector response vs. infrared
frequency.
Note; When FTIR spectrometers are interfaced with other
instruments, a slash should be used to denote the interface;
e.g., GC/FTIR; HPCL/FTIR, and the use of FTIR should be
explicit; i.e., FTIR not IR.
frequency, v - the number of cycles per unit time.
infrared - the portion of the electromagnetic spectrum containing
wavelengths from approximately 0.78 to 800 microns.
interf erogram, Kff} - record of the modulated component of the
interference signal measured as a function of retardation by
the detector.
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BPA PTIR Protocol
interferometer - device that divides a beam of radiant energy
into two or more paths, generate an optical path difference
between the beams, and recombines them in order to produce
repetitive interference maxima and minima as the optical
retardation is varied.
linewidth - the full width at half maximum of an absorption band
in units of wavenumbers (cm"1) .
mid- infrared - the region of the electromagnetic spectrum from
approximately 400 to 5000 cm"1.
pathlength - see "absorption pathlength. "
reference spectra - absorption spectra of gases with known
chemical compositions, recorded at a known absorption
pathlength, which are used in the quantitative analysis of
gas samples.
retardation,
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BPA PTIR Protocol _
inury u.f iQQg Page 15
wavenumber, v - the number of waves per unit length.
Hate.: The usual unit of wavenumber is the reciprocal
centimeter, cm"-1. The wavenumber is the reciprocal of the
wavelength, X, when X is expressed in centimeters.
xero- filling - the addition of zero- valued points to the end of a
measured inter ferogram.
Performing the FT of a zero- filled interferogram
results in correctly interpolated points in the computed
spectrum.
A. 2 Definitions of Mathematical Symbols
A, absorbance - the logarithm to the base 10 of the reciprocal of
the transmittance (T) .
= -log10T (1)
- band area of the ith analyte in the mtn analytical
region, at the concentration (CL^) corresponding to the
product of its required detection limit (DLj) and analytical
uncertainty limit (AU^) .
- average absorbance of the itn analyte in the mth
analytical region, at the concentration (CLj) corresponding
to the product of its required detection limit (DI^) and
analytical uncertainty limit (AU^) .
ASC, accepted standard concentration - the concentration value
assigned to a chemical standard.
ASCPP, accepted standard concentration-pathlength product - for
a chemical standard, the product of the ASC and the sample
absorption pathlength. The units "centimeters-ppm" or
"meters -ppm" are recommended.
AUj, analytical uncertainty limit - the maximum permissible
fractional uncertainty of analysis for the irn analyte
concentration, expressed as a fraction of the analyte
concentration determined in the analysis.
AVTn - average estimated total absorbance in the mtn analytical
region.
CKWNk • estimated concentration of the ktn known interferant.
- estimated maximum concentration of the itn analyte.
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EPA PTIR Protocol ~
IA laag Page 16
CPOTj - estimated concentration of the jtn potential interferant.
DLlf required detection limit - for the ith analyte, the lowest
concentration of the analyte for which its overall
fractional uncertainty (OFm) is required to be less than
the analytical uncertainty limit
• center wavenumber position of the mth analytical region.
, fractional analytical uncertainty - calculated uncertainty
in the measured concentration of the i"1 analyte because of
errors in the mathematical comparison of reference and
sample spectra.
, fractional calibration uncertainty - calculated uncertainty
in the measured concentration of the i"1 analyte because of
errors in Beer's law modeling of the reference spectra
concentrations .
- lower wavenumber position of the CTS absorption band
associated with the mclT analytical region.
PPTJm - upper wavenumber position of the CTS absorption band
associated with the nra analytical region.
- lower wavenumber position of the mtn analytical region.
, fractional model uncertainty - calculated uncertainty in
the measured concentration of the itn analyte because of
errors in the absorption model employed.
PHL - lower wavenumber position of the CTS spectrum containing an
absorption band at least as narrow as the analyte absorption
bands .
- upper wavenumber position of the CTS spectrum containing an
absorption band at least as narrow as the analyte absorption
bands.
, fractional reproducibility uncertainty' - calculated
uncertainty in the measured concentration of the itn analyte
because of errors in the reproducibility of spectra from the
FTIR system.
PUm - upper wavenumber position of the mtn analytical region.
lAIj- - band area of the jth potential interferant in the mth
analytical region, at its expected concentration (CPOTj).
IAVj_ - average absorbance of the itn analyte in the mth
analytical region, at its expected concentration (CPOTj).
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SPA PTIR Protocol
i /
Isci or k' indicated standard concentration - the concentration
from the computerized analytical program for a single-
compound reference spectrum for the i"1 analyte or kt^ known
interf erant .
kPa - kilo- Pascal (see Pascal) .
Lgf - estimated sample absorption pathlength.
LR - reference absorption pathlength.
LS - actual sample absorption pathlength.
" mean of tne MAUim over the appropriate analytical regions.
MAUim' »iai»w» analyte uncertainty - the calculated minimum
concentration for which the analytical uncertainty limit
(AUj_) in the measurement of the itn analyte, based on
spectral data in the mtn analytical region, can be
maintained.
- mean of the MIUjm over the appropriate analytical regions.
MIUjm/ minimum interferant uncertainty - the calculated minimum
concentration for which the analytical uncertainty limit
CPOTj/20 in the measurement of the jtn interferant, based on
spectral data in the mtn analytical region, can be
maintained.
MIL, minimum instrumental linewidth - the minimum linewidth from
the FTIR system, in wavenumbers.
Note; The MIL of a system may be determined by observing an
absorption band known (through higher resolution
examinations) to be narrower than indicated by the system.
The MIL is fundamentally limited by the retardation of the
interferometer, but is also affected by other operational
parameters (e.g., the choice of apodization) .
N! - number of analytes.
Na - number of potential interf erants .
Mk - number of known interf erants .
Nscan " tne number of scans averaged to obtain an interf erogram.
OPTJj • the overall fractional uncertainty in an analyte
concentration determined in the analysis
Pascal (Pa) - metric -unit of static pressure, equal to one Newton
per square meter; one atmosphere is equal to 101,325 Pa;
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BPA FTZR Protocol
i.,j.,.i. iAr iQog _ _ _ __ Page 18
7 ** Sre ^^ T°rr/ °r °nS millimeter H9> is equal
to133
the
Pgf - estimated sample pressure.
PR - reference pressure.
Pg - actual sample pressure.
RHSjSm • measured noise level of the FTIR system in the mth
analytical region.
RMSD, root mean square difference - a measure of accuracy
determined by the following equation:
RMSD
(*)£ •
(2)
where :
n - the number of observations for which the accuracy is
determined.
«i =« the difference between a measured value of a property
and its mean value over the n observations.
Note; The RMSD value "between a set of n contiguous
absorbance values (AJ) and the mean of the values" (AM) is
defined as ™
(3)
- the (calculated) final concentration of the itn analyte.
RSIfc - the (calculated) final concentration of the ktn known
interferant.
taca_, scan time - time used to acquire a single scan, not
including flyback.
ts, signal integration period - the period of time over which an
interferogram is averaged by addition and scaling of
individual scans. In terms of the number of scans Nscan and
scan time tgcan/ ts - Ngcantscan.
fcSR " signal integration period used in recording reference
spectra.
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RPA PTIR Protocol Paae 19
iiijuat- 1Af IQQfi 3
tgg - signal integration period used in recording sample spectra.
TR - absolute temperature of gases used in recording reference
spectra.
Tg - absolute temperature of sample gas as sample spectra are
recorded.
TP, Throughput • manufacturer's estimate of the fraction of the
total infrared power transmitted by the absorption cell and
transfer optics from the interferometer to the detector.
Vsa - volume of the infrared absorption cell, including parts of
attached tubing.
*ik " weight used to average over analytical regions k for.
quantities related to the analyte i; see Appendix D.
Note that some terms are missing, e.g., BAVm, OCU, RMSSm, SUBS/
, Ss
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BPA FTZR Protocol
. ^ Page 20
APPENDIZ B
IDENTIFYING SPECTRAL INTERFERANTS
B.1 General
B.l.l Assume a fixed absorption pathlength equal to the
value Ls' . = 1
B.I.2 Use band area calculations to compare the relative
absorption strengths of the analytes and potential interferants
In the mcn analytical region (FI^ to FUm), use either rectangular
or trapezoidal approximations to determine the band areas
described below (see Reference A, Sections A.3.1 through A.3.3);
document any baseline corrections applied to the spectra.
B.I.3 Use the average total absorbance of the analytes and
potential interferants in each analytical region to determine
whether the analytical region is suitable for analyte
concentration determinations.
Note; The average absorbance in an analytical region is the
band area divided by the width of the analytical region in
wavenumbers. The average total absorbance in an analytical
region is the sum of the average absorbances of all analytes
and potential interferants.
B.2 Calculations
B.2.1 Prepare spectral representations of each analyte at
the concentration CLj - (DLj_) (AUj_) , where DLj is the required
detection limit and AU* is the maximum permissible analytical
uncertainty. For the nr11 analytical region, calculate the band
area (AAI^m) and average absorbance (AAV£m) from these scaled
analyte spectra.
B.2.2 Prepare spectral representations of each potential
interferant at its expected concentration (CPOT^). For the mtft
analytical region, calculate the band area (lAIjjJ and average
absorbance (lAV^) from these scaled potential interferant
spectra.
B.2.3 Repeat the calculation for each analytical region,
and record the band area results in matrix form as indicated in
Figure B.I.
B.2.4 If the band area of any potential interferant in an
analytical region is greater than the one-half the band area of
any analyte (i.e., lAI^ > 0.5 AAIim for any pair ij and any m) ,
classify the potential Interferant as known interferant. Label
the known interferants k - 1 to K. Record the results in matrix
form as indicated in Figure B.2.
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EPA PTIR Protocol Facie 21
- 3
B.2.5 Calculate the average total absorbance (AVTm) for
each analytical region and record the values in the last row of
the matrix described in Figure B.2. Any analytical region where
AVTm >2.0 is unsuitable.
FIGURE B.I Presentation of Potential Interferant Calculations
Analytical Regions
1 .... M
Analyte Labels
Potential Interferant
Labels
. AAI1M
AAIZ1 . . . AAIIM
IAIn • • • IAI1M
FIGURE B.2 Presentation of Known Interferant Calculations
Analytical Regions
1 .... M
Analyte Labels
• AAI1M
AAIZ1
Known Interferant
Labels
1 IAI-L! .... IAI1M
• *
K IAIK1 . • . . li-
Total Average
Absorbance AVT-, AVTM
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EPA FTIR Protocol
Af IQQg
Page 22
APPENDIX C
ESTIMATING NOISE LEVELS
C.I General
C.I.I The root -mean- square (RMS) noise level is the
standard measure of noise in this Protocol. The RMS noise level
of a contiguous segment of a spectrum is defined as the RMS
difference (RMSD) between the absorbance values which form the
segment and the mean value of that segment (see Appendix A) .
C.I. 2 The RMS noise value in double-beam absorbance
spectra is assumed to be inversely proportional to: (a) the
square root of the signal integration period of the sample single
beam spectra from which it is formed, and (b) to the total
infrared power transmitted through the interferometer and
absorption cell.
C.I. 3 Practically, the assumption of C.I. 2 allow the RMS
noise level of a complete system to be estimated from the
following four quantities:
(a)
- the noise level of the system (in absorbance
units) , without the absorption cell and transfer optics,
under those conditions necessary to yield the specified
minimum instrumental linewidth. e.g., Jacquinot stop
size.
(b) t
- the manufacturer's signal integration time used
to"3etermine RMSMAN.
(c) tss - the signal integration time for the analyses.
(d) TP - the manufacturer's estimate of the fraction of the
total infrared power transmitted by the absorption cell
and transfer optics from the interferometer to the
detector.
C.2 Calculation*
C.2.1 Obtain the values of RMSu^, t^^, and TP from the
manufacturers of the equipment, or determine the noise level by
direct measurements with the completely constructed system
proposed in Section 4.
C.2.2 Calculate the noise value of the system (RMSEST) as
follows:
RMS
BST
RMS
MAN
TP
'as
'MAN
(4)
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SPA PTIR Protocol Paae 23
*"tr-*- •**- 10<><; _ , _
APPENDIX D
ESTIMATING MINIMUM CONCENTRATION MEASUREMENT
UNCERTAINTIES (MAU and MIU)
D . 1 General
Estimate the minimum concentration measurement uncertainties
for the itn analyte (MAU.^ and jtn interferant (MIU-s) based on
the spectral data in the mtn analytical region by comparing the
analyte band area in the analytical region (AAIim) and estimating
or measuring the noise level of the system (RMSEST or RMSSm) .
Note; For a single analytical .region, the MAU or MIU value
is the concentration of the analyte or interferant for which
the band area is equal to the product of the analytical
region width (in wavenumbers) and the noise level of the
system (in absorbance units) . If data from more than one
analytical region is used in the determination of an analyte
concentration, the MAU or MIU is the mean of the separate
MAU or MIU values calculated for each analytical region.
D . 2 Calculations
D.2.1 For each analytical region, set RMS - RMSsm if
measured (Appendix G) , or set RMS - RMSEST if estimated (Appendix
C) .
D.2.2 For each analyte associated with the analytical
region, calculate
= (RMS)
D.2.3 If only the mth analytical region is used to
calculate the concentration of the itn analyte, set MAUi - MAUim.
D.2.4 If a number of analytical regions are used to
calculate the concentration of the icn analyte, set MAUi equal to
the weighted mean of the appropriate MAUim values calculated
above; the weight for each term in the mean is equal to the
fraction of the total wavenumber range used for the calculation
represented by each analytical region. Mathematically, if the
set of analytical regions employed is {m' } , then the MAU for each
analytical region is
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SPA PTIR Protocol Page 24
Wik MAUik
where the weight Wj^ is defined for each term in the sum as
Wik=(FMk-FLk)( £ [FMp-Figr1 (7)
*pe{m'J '
D*2.5 Repeat Sections D.2.1 through D.2.4 to calculate the
analogous values MIU-i for the interferants j - 1 to J. Replace
the value (AUj) (DL^ in . the above equations with CPOTj/20;
replace the value AAI^ in the above equations with !AIjm.
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SPA PTIR Protocol Paae 25
- 3
APPENDIX B
DETERMINING FRACTIONAL REPRODUCIBILITY UNCERTAINTIES (FRU)
E.I General
To estimate the reproducibility of the spectroscopic results
of the system, compare the CTS spectra recorded before and after
preparing the reference spectra. Compare the difference between
the spectra to their average band area. Perform the calculation
for each analytical region on the portions of the CTS spectra
associated with that analytical region.
B.2 Calculations
E.2.1 The CTS spectra {Rl} consist of N spectra, denoted by
Slif i-1, N. Similarly, the CTS spectra {R2} consist of N
spectra, denoted by 32±, i-l, N. Each Ski is the spectrum of a
single compound, where i denotes the compound and k denotes
the set {Rk} of which SJH is a member. Form the spectra S3
according to S3j_ » S2i"li for eacn *• Form the spectra S4
according to S4i - [S2i+SliJ/2 for each i.
E.2.2 Each analytical region m is associated with a portion
of the CTS spectra S2i and SJH/ for a particular i, with lower
and upper wavenumber limits PPI^ and FFUm, respectively.
E.2.3 For each m and the associated i, calculate the band
area of S4i in the wavenumber range FFUm to FFI^. Follow the
guidelines of Section B.I. 2 for this band area calculation.
Denote the result by BAVm.
E.2.4 For each m and the associated i, calculate the RMSD
of S3.j between the absorbance values and their mean in the
wavenumber range FFUm to FFI^. Denote the result by SRMSm.
E.2.5 For each analytical region m, calculate the quantity
- SRMSm(FFUm-FFLm)/BAVm
E.2.6 If only the mth analytical region is used to
calculate the concentration of the itn analyte, set FRUt
E 2.7 If a number p.. of analytical regions are used to
calculate the concentration of the icn analyte, set FRUt equal to
the weighted mean of the appropriate FNL values calculated above.
Mathematically, if the set of analytical regions employed is
{m' } , then
Wlk FMk (8)
where the Wik are calculated as described in Appendix D.
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BPA FTIR Protocol -
26
APPENDIX F
DETERMINING FRACTIONAL CALIBRATION UNCERTAINTIES (FCU)
F . 1 General
F.l.l The concentrations yielded by the computerized
analytical program applied to each single -compound reference
spectrum are defined as the indicated standard concentrations
(ISC's). The ISC values for a single compound spectrum should
ideally equal the accepted standard concentration (ASC) for one
analyte or interferant, and should ideally be zero for all other
compounds. Variations from these results are caused by errors in
the ASC values, variations from the Beer's law (or modified
Beer's law) model used to determine the concentrations, and noise
in the spectra. When the first two effects dominate, the
systematic nature of the errors is often apparent; take steps to
correct them.
F.I. 2 When the calibration error appears non- systematic,
apply the following method to estimate the fractional calibration
uncertainty (FCU) for each compound. The FCU is defined as the
mean fractional error between the ASC and the ISC for all
reference spectra with non- zero ASC for that compound. The FCU
for each compound shall be less than the required fractional
uncertainty specified in Section 4.1.
F.I. 3 The computerized analytical programs shall also be
required to yield acceptably low concentrations for compounds
with ISC-0 when applied to the reference spectra. The limits
chosen in this Protocol are that the ISC of each reference
spectrum for each analyte or interferant shall not exceed that
compound's minimum measurement uncertainty (MAU or MIU) .
F . 2 Calculations
F.2.1 Apply each analytical program to each reference
spectrum. Prepare a similar table as that in Figure F.I to
present the ISC and ASC values for each analyte and interferant
in each reference spectrum. Maintain the order of reference file
names and compounds employed in preparing Figure F.I.
F.2.2 For all reference spectra in Figure F.I, verify that
the absolute value of the ISC's are less than the compound's MAU
(for analytes) or MIU (for interferant s) .
F.2.3 For each analyte reference spectrum, calculate the
quantity (ASC- ISC) /ASC. For each analyte, calculate the mean of
these values (the FCU.: for the icn analyte) over all reference
spectra. Prepare a similar table as that in Figure F.2 to
present the FCU^ and analytical uncertainty limit (AU^ for each
analyte .
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RPA PTIR Protocol
>iigri«1- 14,
Page 27
FIGURE F.I
Presentation of Accepted Standard Concentrations (ASC's)
and Indicated Standard Concentrations (ISC's)
Compound
Name
Reference
Spectrum
File Name
•
ASC
(ppm)
Anafytes
ISCfcpm)
In
... ]
terfenu
t
T
its
HGURE F.2
Presentation of Fractional Calibration Uncertainties (FCU's)
and Analytical Uncertainties (AU's)
Analyte
Name
FCU
(%)
AU
(*>
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BPA PTIR Protocol
ingulf 1*.
APPENDIX 6
MEASURING NOISE LEVELS
G.I General
The root -mean -square (RMS) noise level is the standard
measure of noise. The RMS noise level of a contiguous segment of
a spectrum is the RMSD between the absorbance values that form
the segment and the mean value of the segment (see Appendix A) .
G . 2 Calculation*
G.2.1 Evacuate the absorption cell or fill it with UPC
grade nitrogen at approximately one atmosphere total pressure.
G.2.2 Record two single beam spectra of signal integration
period tss.
G.2.3 Form the double beam absorption spectrum from these
two single beam spectra, and calculate the noise level RMSSm in
the M analytical regions.
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BPA PTIR Protocol n
ing,,*!- id ion* _ _ _ _ _ . Page 29
APPENDIX H
DETERMINING SAMPLE ABSORPTION PATHLENGTH (L0) AND
FRACTIONAL ANALYTICAL UNCERTAINTY (FAUJ
H.I General
Reference spectra recorded at absorption pathlength (Lp) ,
gas pressure (PR) , and gas absolute temperature (TR) may be used
to determine analyte concentrations in samples whose spectra are
recorded at conditions different from that of the reference
spectra, i.e., at absorption pathlength (Ls) , absolute
temperature (Ts) , and pressure (Pg) . Appendix H describes the
calculations for estimating the fractional uncertainty (FAU) of
this practice. It also describes the calculations for
determining the sample absorption pathlength from comparison of
CTS spectra, and for preparing spectra for further instrumental
and procedural checks.
H.I.I Before sampling, determine the sample absorption
pathlength using least squares analysis. Determine the ratio
LS/LR by comparing the spectral sets {Rl} and {R3}, which are
recorded using the same CTS at Ls and LR, and TS and TR, but both
at PR.
H.I. 2 Determine the fractional analysis uncertainty (FAU)
for each analyte by comparing a scaled CTS spectral set, recorded
at Ls, Ts, and Pg, to the CTS reference spectra of the same gas,
recorded at LR, TR, and PR. Perform the quantitative comparison
after recording the sample spectra, based on band areas of the
spectra in the CTS absorbance band associated with each analyte.
H.2 Calculations
H.2.1 Absorption Pathlength Determination. Perform and
document separate linear baseline corrections to each analytical
region in the spectral sets {Rl} and {R3}. Form a one-
dimensional array AR containing the absorbance values from all
segments of {Rl} that are associated with the analytical regions;
the members of the array are ARJ, i = 1, n. Form a similar one-
dimensional array Ag from the absorbance values in the spectral
set {R3}; the members of the array are Ag^^, i - l, n. Based on
^
the model AC - rAR + B, determine the least -squares estimate of
r' , the value or r which minimizes the square error E2 .
Calculate the sample absorption pathlength Lg - r' (TS/TR)LR.
H.2. 2 Fractional Analysis Uncertainty. Perform and
document separate linear baseline corrections to each analytical
region in the spectral sets {Rl} and {R4}. Form the arrays Ag
and AR as described in Section H.2.1, using values from {Rl} to
form AR, and values from {R4} to form Ag. Calculate the values
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BPA FTIR Protocol
Page 30
12
(9)
and
(10)
The fractional analytical uncertainty is defined as
FAU »
(ID
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BPA PTIR Protocol
Paap
^
APPENDIX I
DETERMINING FRACTIONAL MODEL UNCERTAINTIES (FMU)
I . 1 General
To prepare analytical programs for FTIR analyses, the sample
constituents must first be assumed; the calculations in this
appendix, based upon a simulation of the sample spectrum, verify
the appropriateness of these assumptions. The simulated spectra
consist of the sum of single compound reference spectra scaled to
represent their contributions to the sample absorbance spectrum;
scaling factors are based on the indicated standard
concentrations (ISC) and measured (sample) analyte and
interferant concentrations, the sample and reference absorption
pathlengths, and the sample and reference gas pressures. No
band- shape correction for differences in the temperature of the
sample and reference spectra gases is made; such errors are
included in the FMU estimate. The actual and simulated sample
spectra are quantitatively compared to determine the fractional
model uncertainty; this comparison uses the reference spectra
band areas and residuals in the difference spectrum formed from
the actual and simulated sample spectra.
I . 2 Calculations
1.2.1 For each analyte (with scaled concentration RSA.^) ,
select a reference spectrum SA^ with indicated standard
concentration ISC^ Calculate the scaling factors
R L3 P3 RSAt
Ts LR PR ISCt
and form the spectra SAC± by scaling each SAA by the factor
1.2.2 For each interferant, select a reference spectrum Slk
with indicated standard concentration ISCk. Calculate the
scaling factors
Ls Ps
ISCk
and form the spectra SICk by scaling each SIk by the factor RIk.
I 2.3 For each' analytical region, determine by visual
inspection which of the spectra SACi and SICk exhibit absorbance
bands within the analytical region. Subtract each spectrum SACi
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EPA PTIR Protocol Paqe 32
- -
and SICfc exhibiting absorbance from the sample spectrum So to
form the spectrum. SUBS. To save analysis time and to avoid* the
introduction of unwanted noise into the subtracted spectrum, it
is recommended that the calculation be made (1) only for those
spectral data points within the analytical regions, and (2) for
each analytical region separately using the original spectrum Sg.
1.2.4 For each analytical region m, calculate the RMSD of
SUBg between the absorbance values and their mean in the region
FFUm to FFLjn. Denote the result by RMSSm.
1.2.5 For each analyte i, calculate the quantity
RMSSm(FFUa-FFLn)AUiDLi
for each analytical region associated with the analyte.
1.2.6 If only the mtn analytical region is used to
calculate the concentration of the itri analyte, set
1.2.7 If a number of analytical regions are used to
calculate the concentration of the itft analyte, set m± equal to
the weighted mean of the appropriate FM,. values calculated above.
Mathematically, if the set of analytical regions employed is
(m' } , then
Wi* ™k (15)
where Wi]c is calculated as described in Appendix D.
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EPA PTIR Protocol Paqe 33
liijiiat- 1A.[ IQQg _____^_^ _^
APPENDIX J
DETERMINING OVERALL CONCENTRATION UNCERTAINTIES (OCU)
The calculations in previous sections and appendices
estimate the measurement uncertainties for various FTIR
measurements. The lowest possible overall concentration
uncertainty (OCU) for an analyte is its MAU value, which is an
estimate of the absolute concentration uncertainty when spectral
noise dominates the measurement error. However, if the product
of the largest fractional concentration uncertainty (FRU, PCU,
FAU, or FMU) and the measured concentration of an analyte exceeds
the MAU for the analyte, then the OCU is this product. In
mathematical terms, set OFUj_ - MAX{FRUi, FCU^ FAUif FMU-J and
- MAX{RSAi*OFUi,
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BPA PTIR Protocol „_„ ...
*"0"-«- 1A. 1aag . age 34
APPENDIX K
SPECTRAL DE-RESOLUTION PROCEDURES
K.I General.
High resolution reference spectra can be converted into
lower resolution standard spectra for use in quantitative
analysis of sample spectra. This is accomplished by truncating
the number of data points in the original reference sample and
background interferograms.
De-resolved spectra must meet the following requirements to
be used in quantitative analysis.
(a) The resolution must match the instrument sampling
resolution. This is verified by comparing a de-resolved CTS
spectrum to a CTS spectrum measured on the sampling instrument.
(b) The Fourier transformation of truncated interferograms
(and their conversion to absorbance spectra) is performed using
the same apodization function (and other mathematical
corrections) used in converting the sample interferograms into
absorbance spectra.
K.2 Procedures
This section details three alternative procedures using two
different commercially available software packages. A similar
procedures using another software packages is acceptable if it is
based on truncation of the original reference interferograms and
the results are verified by Section K.3.
K.2.1 KVB/Analect Software Procedure - The following
example converts a 0.25 cm"1 100 ppm ethylene spectrum (cts0305a)
to 1 cm"1 resolution. The 0.25 cm"1 CTS spectrum was collected
during the EPA reference spectrum program on March 5, 1992. The
original data (in this example) are in KVB/Analect FX-70 format.
(i) d«comp cta0305a.aif,0305dres,1,16384,1
"decomp" converts cts0305a to an ASCII file with name
0305dres. The resulting ASCII interferogram file is truncated to
16384 data points. Convert background interferogram
(bkg0305a.aif) to ASCII in the same way.
(ii) compos* 0305dr«a,0305dres.aif,1
"Compose" transforms, truncated interferograms back to spectral
format.
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SPA PTIR Protocol _
35
(iii) IG2SP 0305dres.aif,0305dres.dsf,3,l,low cm'1, high on'1
n •
'IG2SP" converts interferogram to a single beam spectrum
using Norton-Beer medium apodization, 3, and no zero filling i
De-resolved interferograms should be transformed using the same
apodization and zero filling that will be used to collect sample
spectra. Choose the desired low and high frequencies, in cm"1.
Transform the background interferogram in the same way.
(iv) DVDR 0305dre«.d»f,bkg0305a.daf,0305dres.dl£
"DVDR" ratios the transformed sample spectrum against the
background.
(v) ABSB 0305dr««.dlf,0305dres.dlf
"ABSB" converts the spectrum to absorbance.
The resolution of the resulting spectrum should be verified
by comparison to a CTS spectrum collected at the nominal
resolution. Refer to Section K.3.
K.2.2 Alternate KVB/Analect Procedure -- In either DOS
(FX-70) or Windows version (FX-80) use the "Extract" command
directly on the interferogram.
(i) EXTRACT CTS0305a.aif,0305dres.aif,1,16384
"Extract" truncates the interferogram to data points from to
16384 (or number of data points for desired nominal resolution).
Truncate background interferogram in the same way.
(ii) Complete steps (iii) to (v) in Section K.2.1.
K.2.3 Grams™ Software Procedure - Grams™ is a software
package that displays and manipulates spectra from a variety of
instrument manufacturers. Ib^8 procedure assumes familiarity
with basic functions of Grams™.
This procedure is specifically for using Grams to truncate
and transform reference interferograms that have been imported
into Grains from the KVB/Analect format. Table K-l shows data
files and parameter values that are used in the following
procedure.
The choice of all parameters in the ICOMPUTE.AB call of step
3 below should be fixed to the shown values, with the exception
of the "Apodization" parameter. This parameter should be set
(for both background and sample single beam conversions) to the
type of apodization function chosen for the de-resolved spectral
library.
TABLE K-l. GRAMS DATA PILES AND DE-RESOLUTION PARAMETERS.
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EPA PTIR Protocol Pacre 36
"3
Desired Nominal Spectral
Resolution (cm"1)
0.25
0.50
1.0
2.0
Data File Name
Z00250.sav
ZOOSOO.sav
ZOlOOO.sav
Z02000.sav
Parameter "N"
Value
65537
32769
16385
8193
(i) Import using "File/Import" the desired *.aif file. Clear
all open data slots.
(ii) Open the resulting *.spc interferogram as file #1.
(iii) Zflip - If the x-axis is increasing from left to right,
and the ZPD burst appears near the left end of the trace, omit
this step.
In the "Arithmetic/Calc" menu item input box, type the text
below. Perform the calculation by clicking on "OK" (once only),
and, when the calculation is complete, click the "Continue"
button to proceed to step (iv) . Note the comment in step (iii)
regarding the trace orientation.
xflip:*•-*•(*0,*N)+50
(iv) Run ICOMPUTB.AB from "Arithmetic/Do Program" menu.
Ignore the "subscripting error," if it occurs.
The following menu choices should be made before execution
of the program (refer to Table K-l for the correct choice of
"N":)
First: M Last: 0 Type: Single Beam
Zero Fill: None Apodization: (as desired)
Phasing: User
Points: 1024 Interpolation: Linear Phase :
Calculate
(v) As in step (iii), in the "Arithmetic/Gale" menu item
enter and then run the following commands (refer to Table 1 for
appropriate "PILE," which may be in a directory other than
"c:\mdgrams.")
setffp 7898.8805, 0 t loadspc «c:\mdgrams\ FILB" : #2«#s+#2
(vi) Use "Page Op" to activate file #2, and then use the
"File/Save A»" menu item with an appropriate file name to save
the result. . .
K.3 Verification of New Resolution
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BPA PTIR Protocol Paae
Ar 1QQ«! _ ^
K.3.1 Obtain interferograms of reference sample and
background spectra. Truncate interferograms and convert to
absorbance spectra of desired nominal resolution.
K.3.2 Document the apodization function, the level of zero
filling, the number of data points, and the nominal resolution of
the resulting de- resolved absorbance spectra. Use the identical
apodization and level of zero filling when collecting sample
spectra.
K.3.3 Perform the same de-resolution procedure on CTS
interferograms that correspond with the reference spectra
(reference CTS) to obtain de- resolved CTS standard spectra (CTS
standards) . Collect CTS spectra using the sampling resolution
and the FTIR system to be used for the field measurements (test
CTS) . If practical, use the same pathlength, temperature, and
standard concentration that were used for the reference CTS.
Verify, by the following procedure that CTS linewidths and
intensities are the same for the CTS standards and the test CTS.
K.3.4 After applying necessary temperature and pathlength
corrections (document these corrections) , subtract the CTS
standard from the test CTS spectrum. Measure the RMSD in the
resulting subtracted spectrum in the analytical region (s) of the
CTS band(s) . Use the following equation to compare this RMSD to
the test CTS band area. The ratio in equation 7 must be no
greater than 5 percent (0.05).
RMSS-RMSD in the itn analytical region in subtracted result, test
CTS minus CTS standard.
n-number of data points per cm"1. Exclude zero filled points.
FFUj &-The upper and lower limits (cm"1), respectively, of the
analytical region.
. erg-band area in the ith analytical region of the test CTS.
-------
TECHNICAL REPORT DATA
{Pleat read Instructions on Hit revent be fort completing)
REPORT NO.
EPA-454/R-99-031
13. RECIPIENT'S ACCESSION NO..
TITLE AND SUBTITLE
FUR Emissions Test at an Iron Foundry - GM Pdwsrtrain Group,
Motors Corp. Saginaw Metal Casting Operations Saginaw Michigan
REPORT DATE
SEPTEMBER 1999
PERFORMING OROANIZATIOM CODE
AUTHORIS)
EMAD
8. PERFORMING ORGANIZATION-REPORT NO.
PERFORMING ORGANIZATION NAME ANO ADDRESS
10. PROGRAM ELEMENT NO..
11. CONTHACT/GRA,NT NO. •
Midwest 'Research Institute (MRI)
EPACont. 68D98027
2. SPONSORING AGENCY NAME AND ADDRESS
US EhvironriEntal Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Emission Test Report
14. SPONSORING AGENCY CODE
EPA/200/04
5. SUPPLEMENTARY NOTES
e. ABSTRACT The US EPA is investigating iron and steel foundries to identify and quantify -HAPS emitted from
cupolas; electric arc furnaces; & pouring, cooling and shakedown operations of sand mold casting processes
GM Corpora Lion, Saginaw Casting Operations (GMC) Saginaw, MI was selected by EPA as the host facility at
which to 1)characterize HAP emissions from cupolas that are controlled by wet scrubbers, and 2) assess wet
scrubber performance in controlling HAP emissions from cupolas. GMC was selected because EPA deemed this
facility to be representative of a large segrent of the sand casting foundry industry and GMC operates a
relatively large cupola that is controlled by a wet scrubber.
Fourier Transform Infrared emission test runs were conducted at the cupola inlet and outlet locations.
Additionaly, MRI collected tedlar bag samples from pouring, cooling, shake-out ducts and analyzed by H1H.
7. MACT Rule support
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Fidd/Group
MACT Support for the Iron
& Steel Foundry Industry
18. DISTRIBUTION STATEMENT
RELEASE UNLIMITED
19. SECURITY CLASS i This Report I
21. NO. OF PAGES
382
20. SECURITY CLASS ,'Tliiipagei
22. PRICE
EPA Form 2220-1 (R«». 4-77) PREVIOUS EDITION is OBSOLETE
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