United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA-454/R-99-034
September 1999
Air
FTIR AND METHOD 25A EMISSIONS TEST
EPA AT AN INTEGRATED IRON AND STEEL
MANUFACTURING PLANT
Youngstown Sinter Company of WCI Steel, Inc.
Youngstown, Ohio
-------
EMISSIONS TEST
AT AN INTEGRATED IRON AND STEEL MANUFACTURING PLANT
Youngstown Sinter Company of WCI Steel, Inc.
Youngstown, Ohio
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
Michael L. Toney
Work Assignment Manager
EPA Contract No. 68-D-98-027
Work Assignment 2-12
MRI Project No. 104951-1-012-04
September, 1999
-------
Previous Page Blank
PREFACE
This 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. 2-12. 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. 4-20 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 4-20 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 11.
This report presents the procedures, schedule, and test results for an emissions test
performed at Youngstown Sinter Company in Youngstown, Ohio. The emissions test used
Fourier transform infrared (FTIR) sampling procedures to measure hazardous air pollutants
(HAP's) and other pollutants and Method 25A to measure hydrocarbon species.
This report consists of one volume (396 pages) with seven sections and four appendices.
Midwest Research Institute
John Hosenfeld
Program Manager
Approved:
Jeff Shu lar
Director, Environmental Engineering Division
September 30, 1999
111
-------
Previous Page Blank
TABLE OF CONTENTS
1.0 INTRODUCTION 1-1
1.1 BACKGROUND 1-1
1.2 PROJECT SUMMARY 1-1
1.3 PROJECT PERSONNEL 1-5
2.0 YOUNGSTOWN SINTER COMPANY'S SINTER PLANT 2-1
2.1 OVERVIEW 2-1
2.2 PROCESS DESCRIPTION 2-1
2.3 EMISSION CONTROL EQUIPMENT 2-5
2.4 MONITORING RESULTS DURING THE TESTS 2-7
2.5 ANALYSIS OF MONITORING AND TEST RESULTS 2-11
3.0 TEST LOCATIONS 3-1
3.1 BAGHOUSE INLET DUCT 3-1
3.2 BAGHOUSE OUTLET (STACK) 3-1
3.3 VOLUMETRIC FLOW 3-1
4.0 RESULTS 4-1
4.1 TEST SCHEDULE 4-1
4.2 FIELD TEST PROBLEMS AND CHANGES 4-1
4.3 METHOD 25A RESULTS 4-2
4.4 FTIR RESULTS 4-3
4.5 ANALYTE SPIKE RESULTS 4-3
4.6 ESTIMATED UNCERTAINTIES 4-7
5.0 TEST PROCEDURES 5-1
5.1 SAMPLING SYSTEM DESCRIPTION 5-1
5.1.1 Sample System Components 5-1
5.1.2 Sample Gas Stream Flow 5-3
5.2 FTIR SAMPLING PROCEDURES 5-3
5.2.1 Batch Samples 5-4
5.2.2 Continuous Sampling 5-4
5.3 ANALYTE SPIKING 5-5
5.3.1 Analyte Spiking Procedures 5-5
5.3.2 Analysis of Spiked Results 5-7
5.4 ANALYTICAL PROCEDURES 5-7
5.4.1 Computer Program Input 5-10
5.4.2 EPA Reference Spectra 5-10
5.5 FTIR SYSTEM 5-10
-------
TABLE OF CONTENTS (CONTINUED)
Page
5.6 CONTINUOUS EMISSIONS MONITORING FOR TOTAL
HYDROCARBONS (THC) 5-12
5.6.1 Total Hydrocarbon Sampling Procedures 5-12
5.6.2 Hydrocarbon Emission Calculations 5-13
6.0 SUMMARY OF QA/QC PROCEDURES 6-1
6.1 SAMPLING AND TEST CONDITIONS 6-1
6.2 FTIR SPECTRA 6-2
6.3 METHOD 25A 6-3
6.3.1 Initial Checks 6-3
6.3.2 Daily Checks 6-3
7.0 REFERENCES 7-1
LIST OF APPENDICES
APPENDIX A A-l
A-l METHOD 25A RESULTS A-2
A-2 METHOD 25A CALIBRATION AND QA CHECK DATA A-3
A-3 VOLUMETRIC FLOW DATA A-4
APPENDIX B B-l
B-l FTIR RESULTS B-2
B-2 FTIR FIELD DATA RECORDS B-29
B-3 FTIR FLOW AND TEMPERATURE READINGS B-30
APPENDIX C C-l
C-l CALIBRATION GAS CERTIFICATES C-2
C-2 ENVIRONICS MASS FLOW METER CALIBRATIONS C-3
APPENDIX D D-l
D-l EPA METHOD 320 D-2
D-2 EPA FTIR PROTOCOL D-3
D-3 EPA METHOD 25A D-4
D-4 EPA DRAFT METHOD 205 D-5
D-5 HC1 VALIDATION PAPER D-6
VI
-------
TABLE OF CONTENTS (CONTINUED)
• ' ' . • ' ' Page
LIST OF FIGURES
Figure 2-1. Schematic of material flow in sinter plant 2-3
Figure 2-2. Schematic of pick-up points for a baghouse 2-8
Figure 3-1. Test locations on the baghouse inlet duct 3-2
Figure 3-2. Test locations on the baghouse outlet stack 3-3
Figure 4-1. Example of a sample spectrum and its subtracted residual spectrum 4-8
Figure 5-1. Sampling system schematic 5-2
LIST OF TABLES
TABLE 1 -1. SUMMARY OF FTM RESULTS AT WCI BAGHOUSE
INLET AND OUTLET 1-3
TABLE 1 -2. SUMMARY OF METHOD 25A RESULTS FOR
HYDROCARBON EMISSIONS 1-4
TABLE 1-3. PROJECT PERSONNEL 1-5
TABLE 2-1. SUMMARY OF SINTER MIX (FEED) COMPONENTS 2-2
TABLE 2-2. SUMMARY OF SINTER COMPOSITION 2-5
TABLE 2-3. TYPICAL BAGHOUSE PARAMETERS 2-6
TABLE 2-4. PROCESS PARAMETER RANGES DURING THE TESTS 2-9
TABLE 2-5. CONTROL DEVICE OPERATING PARAMETERS —
WINDBOX BAGHOUSE 2-10
TABLE 2-6. PRESSURE DROP ACROSS EACH COMPARTMENT
OFTHE WINDBOX BAGHOUSE 240
TABLE 2-7. PRESSURE DROP ACROSS EACH COMPARTMENT
OF "A" BAGHOUSE 2-12
TABLE 2-8. STRAND BAGHOUSE SUMMARY OF RESULTS FOR
EACH TEST RUN 2-12
TABLE 2-9. A BAGHOUSE SUMMARY OF RESULTS FOR EACH TEST RUN .. . 2-13
TABLE 2-10. STRAND BAGHOUSE SUMMARY OF RESULTS
FOR PARTICULATE MATTER AND METAL HAPS 2-15
TABLE 2-11. STRAND BAGHOUSE SUMMARY OF RESULTS
FOR PAHS AND DIOXIN/FURANS 2-16
TABLE 2-12. DISCHARGE END BAGHOUSE ("A") - RESULTS FOR
PARTICULATE MATTER AND METAL HAPS 2-18
TABLE 3-1. SOURCE GAS COMPOSITION AND FLOW SUMMARY 3-4
TABLE 4-1. TEST SCHEDULE AT WCI STEEL 4-1
TABLE 4-2. MINIMUM AND MAXIMUM AND AVERAGE THC
CONCENTRATIONS 4-2
TABLE 4-3. SUMMARY OF SPIKE RESULTS 4-5
VII
-------
TABLE OF CONTENTS (CONTINUED)
'Jage
TABLE 4-4. COMPARISON OF EPA REFERENCE SPECTRA TO SPECTRA OF
TOLUENE CYLINDER STANDARD 4-6
TABLE 4-5. AVERAGE UNCERTAINTIES (ppm) OF UNDETECTED
ANALYTES AT WCI STEEL 4-7
TABLE 5-1. PROGRAM INPUT FOR ANALYSIS OF SAMPLE SPECTRA 5-8
TABLE 5-2. PROGRAM INPUT FOR ANALYSIS AND CTS SPECTRA
AND PATH LENGTH DETERMINATION 5-11
TABLE 5-3. RESULTS OF PATH LENGTH DETERMINATION 5-11
Vlll
-------
1.0 INTRODUCTION
1.1 BACKGROUND
The Emission Measurement Center (EMC) of the U. S. EPA directed Midwest Research
Institute (MRI) to conduct emissions testing at iron and steel manufacturing facilities,
specifically on sintering processes. The test request was initiated by 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). The test program was performed in August, 1997, under Work
assignment No. 4-20, under EPA Contract No. 68-D2-0165. A draft report was submitted under
Work Assignment No. 2-08, under Contract 68-W6-0048.
Initially, the project included two field tests: (1) a screening test with FTIR Method 320
to evaluate the data for detected HAP's, and (2) a separate FTIR emissions test at the same site
after additional preparation based on the screening results. The emissions test was to include
performance of the Method 301 spiking procedure with method validation for any detected
HAP's. Immediately before the field test the EPA altered the Scope of Work for this project to
include only one test for HAP screening and emissions measurements. No validation testing was
performed.
The test was performed on the sintering process at the Youngstown Sinter Company of
WCI Steel, Inc., in Youngstown, Ohio, using EPA Draft FTIR Method 3201 and EPA
Method 25A. Method 320 is an extractive test method based on Fourier Transform infrared
spectroscopy, which uses quantitative analytical procedures described in the EPA FTIR
Protocol.2 Data were used to quantify and characterize HAP and other detected emissions and
the performance of the control unit for MACT standard development for this industry.
1.2 PROJECT SUMMARY
The sintering process is used to agglomerate fine raw materials into a product suitable for
charging into a blast furnace. It is a potentially significant source of HAP emissions, including
both metal and organic compounds. The principal emission point at a sinter plant is the exhaust
from the sintering machine windboxes. Air pollution controls for the Youngstown Sinter
Company of WCI Steel, Inc. include a Strand baghouse to control particulate emissions from the
1-1
-------
sintering machine windboxes. Testing was conducted at the stack (outlet) and inlet to the Strand
baghouse to determine the measurable emissions released during the sintering process.
Three test runs were conducted by MRI at each location over a 3 day period concurrently
with manual method testing conducted by Eastern Research Group, Inc. (ERG). The FTIR
testing was done by alternating sampling between the Strand baghouse inlet and stack; the
Method 25 A testing was continuous at both locations. Summaries of the FTIR and Method 25A
results are presented in Tables 1-1 and 1-2, respectively. Average estimated uncertainties for
some target analytes, identified in the test request, and for some other HAP's, are presented in
Section 4.5.
The emission include hydrocarbon compounds that were represented primarily by
"hexane" in the draft report results. Since the draft report was submitted, MRI has measured
laboratory reference of some non-HAP hydrocarbon compounds. The new reference spectra
were included in the revised analysis of the WCI FTIR data. The revised results presented in
Tables 1-1, B-l, and B-2 include measurements of 2-methyl-2-butene, but eight other non-HAP
hydrocarbons were not detected. The hexane concentrations are slightly lower in the revised
results, but the draft hexane results were fairly accurate. The toluene concentrations in the
revised results are also lower compared to the draft report results.
The EPA Method 320 uses an extractive sampling procedure. A probe, pump, and heated
line are used to transport gas from the test port to a gas distribution manifold in a trailer that
contains the FTIR equipment. Infrared spectra of a series of samples are recorded. Quantitative
analysis of the spectra was performed after the FTIR data collection was completed. All spectral
data and results were saved on computer media. A compact disk containing all spectral data is
provided with this report.
The EPA Method 25A also uses an extractive sampling procedure. The same sample
transport system was used for both the FTIR and Method 25A testing. Volume concentration
data and results obtained from the samples were recorded and saved on computer media and
reviewed after the test was completed.
1-2
-------
TABLE 1-1. SUMMARY OF FTIR RESULTS AT WCIBAGHOUSE INLET AND OUTLET
Compound
Toluene • ppm
Ib/hr
kg/hr
Hexane ppm
Ib/hr
kg/hr
Ethylene ppm
Ib/hr
kg/hr
Methane ppm
Ib/hr
kg/hr
Sulfur Dioxide ppm
Ib/hr
kg/hr
Carbon Monoxide ppm
Ib/hr
kg/hr
Ammonia ppm
Ib/hr
kg/hr
Formaldehyde ppm
Ib/hr
kg/hr
Hydrogen Chloride ppm
Ib/hr
kg/hr
2-Methyl-2-butene ppm
Ib/hr
kg/hr
Baghouse Inlet
Run 1
0.88
4.1
1.9
11.4
49.4
22.4
5.70
8.03
3.64
121
97.5
44.2
175
563
255
1531
2153
976.1
4.51
3.86
1.75
4.46
6.73
3.05
6.67
12.2
5.54
0.97
3.45
1.56
Run 2
4.84
21.0
9.54
10.8
43.9
19.9
6.30
8.33
3.78
125
943
42.8
182
551
250
1558
2057
932.7
0.46
0.37
0.17
4.43
6.28
2.85
ND
1.88
6.30
2.86
Run 3
9.64
44.7
20.3
8.8
38.0
17.2
5.64
7.95
3.60
107
86.2
39.1
149
478
217
1486
2091
948.1
2.25
1.93
0.87
5.55
8.38
3.80
0.98
1.79
0.81
0.76
2.72
1.23
Baghouse Outlet
Run 1
1.37
5.91
2.68
11.3
45.4
20.6
6.02
7.88
3.57
124
93.1
42.2
166
497
225
1548
2022
916.8
5.34
4.24
1.92
4.06
5.P9
2.58
6.16
10.5
4.75
1.60
5.31
2.41
Run 2
3.06
12.8
5.80
108
42.4
19.2
6.45
8.21
3.72
127
92.9
42.1
175
507
230
1548
1968
892.3
0.64
0.49
0.22
3.68
5.01
2.27
ND
1.73
5.60
2.54
Run 3
10.3
43.3
19.6
9.2
36.3
16.5
5.38
6.90
3.13
107
78.7
35.7
132
387
175
1490
1907
864.9
2.55
198
0.90
5.27
7.23
3.28
1.33
2.22
1.01
ND
a The absorbance intensity in the CO reference
these average concentrations are approximate
more accurate concentrations.
spectrum was much less than the intensities in the sample spectra so
Measuring high concentration CO reference spectra may produce
1-3
-------
TABLE 1-2. SUMMARY OF METHOD 25A RESULTS FOR HYDROCARBON EMISSIONS
Test Data
Run Number
Date
Time
Baghouse inlet
Gaseous Concentration
THCa Concentration, ppm
(wet basis)
Methane Concentration, ppm
(wet basis)
Emissions Data
THCa Emission Rate, Ib/hr
TGNMOCb
Emission Rate, Ib/hr
Baghouse stack
Gaseous Concentration
THC a Concentration, ppmc
(wet basis)
Methane Concentration, ppm
(wet basis)
Emissions Data
THC a Emission Rate, Ib/hr
TGNMOCb
Emission Rate, Ib/hr
1
12-Aug-97
1335-2000
248.7
121.4
149.8
76.7
197.7
124.7
110.7
40.9
2
13-Aug-97
1055-1736
244.3
125.0
138.2
67.5
211.5
127.8
115.3
45.6
3
14-Aug-97
0810-1029
220.9
107.3
133.2
68.5
172.6
107.6
94.7
35.7
Average
238.0
117.9
140.4
70.9
194.0
120.0
106.9
40.7
a THC = Total hydrocarbons (ppm carbon).
b TGNMOC = Total gaseous non-methane organic carbon.
1-4
-------
1.3 PROJECT PERSONNEL
The EPA test program was administered by the EMC. The test request was initiated by
the Metals Group of the ESD and the Source Characterization Group of the EMAD, both in
OAQPS. Some key project personnel are listed in Table 1-3.
TABLE 1-3. PROJECT PERSONNEL
Organization and Title
WCI Steel. Inc.
Manger, Environmental Control
ofYSC
WCI Steel, Inc.
Environmental Engineer
Environmental Control of WCI
U. S. EPA, EMC
Work Assignment Manager
Work Assignment 4-20
Work Assignment 2-12
U. S. EPA, EMC
Work Assignment Manager
Work Assignment 2-08
MRI
Work Assignment Leader
Work Assignment 4-20
Work Assignment 2-12
MRI
Work Assignment Leader
Work Assignment 2-08
Name
Thomas O. Shepker
Keith McGlaughlin
Michael K. Ciolek
Michael L. Toney
Thomas J. Geyer
John Hosenfeld
Phone Number
(330) 841-8392
(330)841-8162
(919)541-4921
(919)541-5247
(919)851-8181
Ext 3 120
(816)753-7600
Ext 1336
1-5
-------
2.0 YOUNGSTOWN SINTER COMPANY'S SINTER PLANT
The material in Section 2 was prepared by Eastern Research Group (ERG) and provided
to MRI by the EMC. It is included in this report without MRI review.
2.1 OVERVIEW
The primary purpose of the sinter plant is to recover the iron value from waste materials
generated at iron and steel plants by converting the materials to a product that can be used in the
blast furnace (as burden material). Many of these wastes have little or no value otherwise and
would require disposal if they could not be recycled by this process. A secondary purpose of the
sinter plant is to recover lime from wastes and to convert limestone to lime, which is used as a
fluxing agent in the blast furnace. The raw material feed (sinter mix) consists of iron ore fines,
chips from iron ore pellets, fine limestone, slag from the steelmaking furnace, scale from the
steel rolling mill, blast furnace flue dust, coke breeze (undersize coke that cannot be used in the
blast furnace), and dolomite.
There are currently 10 sinter plants in operation in the U.S. A total of 6 of these plants
use scrubbers to control emissions from the sinter plant windbox, and 4 use a baghouse. The
sinter plant at Youngstown Sinter Plant, Youngstown, OH, a wholly owned subsidiary of WCI
Steel Company, was chosen for testing to evaluate hazardous air pollutants and emission control
performance associated with sinter plants that use baghouses.
2.2 PROCESS DESCRIPTION
The Youngstown sinter plant is operated by Youngstown Sinter Company, a wholly
owned subsidiary of WCI Steel. The plant was purchased from LTV Steel Company and was
brought on line in June 1991. The sinter plant is located a few miles from the WCI Steel
integrated iron and steel plant in Warren, OH. The integrated plant includes one blast furnace, a
basic oxygen furnace (EOF) shop containing two EOF vessels, ladle metallurgy, continuous
casting, rolling mills, and galvanizing lines. The sinter plant has a capacity of 60,000 tons per
month (tpm) and operates 24 hours per day with 2 days scheduled downtime every seven days
for routine maintenance. The major processing steps in the sinter plant include preparation of the
sinter mix (feed material), sintering, discharge end operations (crushing and screening), and
cooling of the sinter product. Figure 2-1 is a simplified schematic of the sintering process.
2-1
-------
The typical feed composition of the sinter mix during the emission tests is shown in
Table 2-1.
TABLE 2-1. SUMMARY OF SINTER MIX (FEED) COMPONENTS
Feed material
Ore fines
Mill scale
Limestone
Hue dust
Coke breeze
EOF slag
Pellet chips
Dolomite
Composition (% of feed)
27.70
12.79
12.15
9.07
0.63
16.51
19.73
1.42
Feed Rate (tons/day)
880
406
385
288
20
524
625
4.5
The raw materials are brought into the sinter plant by truck and are stored at the site.
Two feeder tables blend mill scale, BOF slag, and crushed ore pellets by volume, and the mixture
is transferred by conveyor to the sinter plant and fed into the sinter machine through a series of
bins. Limestone, dolomite, coke fines, and cold fines recycled from the sintering process are also
contained in bins and are blended into the mix. A "hearth layer" of material, which is undersize
sinter material that is recycled from the screening operation, is first deposited on the grate bars of
the sinter pallets so that the sinter mixture does not burn through to the grate, and then the feed
mix is added to a depth of about 17 inches. The plant has found that a deeper bed results in
fewer fines being generated.
The sinter feed passes through an ignition furnace, and the surface of the sinter feed is
ignited with natural gas. The sinter pallets move continually through the ignition furnace at
2-2
-------
Stack
Raw materials
[preblend (consisting of mill
scale, BOF slag, and crushed
ore pellets); coke breeze;
limestone; dolomite; and
flue dust]
Fugitives from various
transfer points, conveyors, etc.
Chemical dust
suppressant
Figure 2-1. Schematic of material flow in sinter plant.
-------
about 6.3 to 7.0 feet per minute over 21 vacuum chambers called "windboxes." A vacuum is
created in the windbox by a fan that draws heat through the sinter bed and creates the fused
"sintered" product.
The red hot sinter from the furnace continues to be transported on the pallets to the
breaker, where it is crushed, screened, and discharged to a 250-foot linear four-stack sinter
cooler. The sinter is removed from the cooler and transported by covered conveyor to the track
loadout station. The sinter plant has two truck loadout stations, and all of the sinter is transported
to the blast furnace by truck. The larger station is evacuated to a hood which goes to the cooler
baghouse; the building is open but has a curtain over each end to contain emissions with an
opening for the trucks to enter and exit.
The smaller truck loadout station is used to provide more capacity and is normally used to
handle production from the midnight shift; the station utilizes chemical dust suppression. The
sinter is transferred by a covered conveyor from the sinter cooler to a storage building as needed,
and is then transferred by a covered conveyor to the truck loadout station. Emissions from the
sinter storage building are evacuated to the A baghouse. SoLong, manufactured by Midwest, is
used for dust suppression at the truck loadout station. The chemical acts as a polymer and binds
the dust to the sinter during truck loading; SoLong is applied to the sinter as the product exits the
covered conveyor and drops into the bed of each truck. Very little emissions from the loading
process were observed to escape capture at the larger truck loadout station. Some emissions
were observed from the unenclosed area at the top of the conveyor and from the truck as the
sinter was being loaded. Dust emissions were minimal but were noticeable depending on the
track being loaded. Sinter material that passes through the screens ("fines") is returned to the
sinter process for use as the hearth layer or for addition to the sinter mix.
Several operating parameters are monitored and controlled to ensure proper operation of
the sinter machine. These parameters include the feed rate of each of the ten feed bins, the sinter
furnace temperature, the temperature profile through the various windboxes, draft on the
windboxes, speed of the grate, and percent water in the feed. The percentage of oil in each of the
feed materials is analyzed and the total amount of oil in the sinter feed is limited to less than 0.1
percent. To maintain the proper chemistry in the blast furnace, an important quality control
parameter that is monitored is the sinter basicity:
2-4
-------
(CaO+MgO)/(SiO2+Al2O3)
The sinter composition for the four tests days is summarized in Table 2-2 and shows that the
sinter basicity ranged from 2.72 to 2.92.
TABLE 2-2. SUMMARY OF SINTER COMPOSITION
Component
Fe
Si02
A1A
CaO
MgO
Sinter basicity
Percent of total
Test 1
(08/12/97)
53.23
4.82
0.90
14.69
2.09
2.90
Test 2
(08/13/97)
52.23
5.47
0.98
15.30
2.16
2.72
Test3
(08/14/97)
52.42
5.21
0.91
15.03
2.23
2.84
Test 4 (08/1 5/97)
52.20
5.17
0.89
15.40
2.28
2.92
2.3 EMISSION CONTROL EQUIPMENT
Emissions are generated in the process as sinter dust and combustion products are
discharged through the grates and the 21 windboxes to a common collector main and are then
collected by the strand baghouse. The pulse jet baghouse is manufactured by Environmental
Elements and uses Nomex® bags that are coated with an acid-resistant finish. There are fourteen
modules, each containing 306 bags. The bags are 6 inches in diameter and 15 feet in length, and
the total cloth area for each module is 7,215 square feet. The gross air-to-cloth ratio is
3.96 acfm/ft2 and the net air-to-cloth ratio, with one module off-line for cleaning is 4.26 acfm/ft2.
The flow to the baghouse is approximately 400,000 cubic feet per minute. A preheat
burner is used to minimize condensation and to bring the gas up to the desired inlet temperature.
The dust is removed from the baghouse by rotary screw to bins where it is stored on the ground
to gather moisture and is blended back into the sinter feed. The parameters associated with the
baghouse that are monitored include the pressure drop across the baghouse, inlet temperature,
stack temperature, damper percent, and fan amps.
2-5
-------
Typical operating conditions associated with the baghouse are summarized in Table 2-3.
Current State regulations limit particulate matter to 50 pounds per hour for the strand baghouse.
TABLE 2-3. TYPICAL BAGHOUSE PARAMETERS
Parameter
Pressure drop
Gas flow rate
Inlet temperature
Outlet temperature
Damper Percent
Fan Amps
Typical value
10 to 13 inches of water
400,000 scfm
235 to 270 F
120 F
90%
659-735
Three additional baghouses are used to control emissions from the sinter plant. The C
baghouse, a pulse jet baghouse utilizing polyester bags, is used to control emissions from the
material handling bins and the conveyors that transfer the sinter mix to the sinter machine. The
cooler baghouse controls emissions from the sinter cooler and from the main truck loadout
station. The baghouse is a shaker baghouse that utilizes Nomex® bags and contains nine
compartments. Eight of the compartments are used for the cooler and one compartment is used
for the truck loadout station. There are four 200 horsepower fans on the sinter cooler. The first
fan is the dirtiest fan and is directed back to hoods on the sinter machine and sent back through
as preheat air. The other 3 fans are ducted to the baghouse. In addition, the truck loadout station
has a 70,000 cubic feet per minute fan. These baghouses were not evaluated as part of this test
program.
The A baghouse that serves the discharge end of the sinter plant was evaluated as part of
this test program. A schematic of A baghouse is shown in Figure 2-2. This baghouse controls
emissions from discharge end emission points, including the hood before the sinter machine; the
hood over sinter discharge; the sinter breaker and hot screen which is enclosed by a cloth curtain;
the tail end of the sinter cooler; emissions from each of the ten sinter feed bins; a variety of
transfer points for the transport of sinter, dust, and fines; and emissions from sinter bins located
in the sinter overflow storage area. At any point where there is hot sinter, emissions are first
ducted to a cyclone before going to the baghouse.
2-6
-------
The plant sprays the roads twice per week to minimize dust emissions, except during the
winter months. All of the baghouses are monitored on a weekly basis by an outside contractor,
Fastway, Inc., to check the operation and for any visible opacity. A whole compartment is dye-
tested if there is more than 5 percent visible emissions observed, and the broken bags are then
replaced. Every other month, a complete compartment of either the strand or cooler baghouse is
replaced; each compartment is replaced approximately every 3 years.
2.4 MONITORING RESULTS DURING THE TESTS
The operating parameters associated with the process and control device were recorded at
15-minute intervals throughout each test day. The process parameters that were monitored
included the temperatures and the fan draft for the windboxes, percent water in the feed, sinter
machine speed, and the temperature of each of the four cooling fans. In addition, the turn
supervisor's report provided additional information, including tons per hour of pre-blend, and
tons per 8-hour turn of limestone, dolomite, coke fines, and cold fines. The emission control
device parameters that were monitored included the pressure drop across the baghouse, damper
percent, inlet temperature, stack temperature, fan amps, and the pressure drop of each of the
14 compartments of the baghouse. Tables 2-4 and 2-5 present a summary of the range of values
for these parameters for each test period. Table 2-6 presents a summary of the pressure drops of
each compartment of the baghouse for the four days of testing.
The process and control device appeared to be stable throughout the four test days;
consequently, sampling was conducted under normal and representative conditions. An
examination of the monitoring data showed that the average pressure drop across the baghouse
was 10.8, 12.0, 12.9 and 13.5 inches of water for the 4 test days. The pressure drop across the
baghouse did increase slightly during each day of testing. On the third day, the compartments
were double cleaned to try to reduce the pressure drop. The temperatures and draft of the
windboxes varied somewhat during the tests; plant operators stated that the temperature of
windboxes 19 and 20, should generally be 475° to 500 °F to achieve proper bumthrough of the
sinter bed.
2-7
-------
2 cold screens
to
00
Sinter storage bins
VVVVVYVVV' YVVVY
Y\
A Baghouse
Cooler tail
S = Sinter
D = Dust
B = Burden
Figure 2-2. Schematic of pick-up points for a baghouse.
-------
TABLE 2-4. PROCESS PARAMETER RANGES DURING THE TESTS
Parameter
Test 1
(8/12/97)
Test 2
(8/13/97)
Test 3
(8/14/97)
Test 4
(8/15/97)
Feed rate:
Pre-blend (ore) (tons/hour)
Limestone (tons/turn)
Dolomite (tons/turn)
Coke fines (tons/turn)
Cold fines (tons/turn)
120
144
43
19
1738
120
114
39
17
1545
120
167
43
18
1787
120
Other parameters:
Percent water
Grate speed (feet/min)
Windbox 1 temperature ( F)
Windbox 1 draft (in, H20)
Windbox 3 temperature ( F)
Windbox 3 draft (in. H20)
Windbox 13 temperature ( F)
Windbox 13 draft (in. H2O)
Windbox 1 8 temperature ( F)
Windbox 18 draft (in. H2O)
Windbox 19 temperature ( F)
Windbox 19 draft (in. H2O)
Windbox 20 temperature ( F)
Windbox 20 draft (in. H2O)
Windbox 21 temperature ( F)
Windbox 21 draft (in. H2O)
7.0-7.2
—
177-211
18.0-22.1
167-195
16.2-20.3
187-266
—
327-463
14.7-18.3
396-542
16.4-21.1
373-580
14.5-18.9
—
14.9-17.7
6.7-7.6
—
150-202
20.3-23.5
108-186
18.6-21.5
184-233
—
251-459
16.649.9
357-513
18,4-21.9
391-546
17.0-20,7
360-465
15.749.3
6.8-7.0
—
157-207
19.5-22.3
149-181
18.1-20.5
169-231
—
288-457
15.748.5
350-460
18.0-20.4
372-496
16.2-18.9
332-429
15.147.5
6.7 - 6.8
6.3 - 7.0
166-220
19,5-21,8
159498
-18.0-20.1
165-342
—
301-521
16.0-17.8
363-545
17.2-20.5
385-545
16.5-18.6
355-443
15.3-17.2
Cooling Fan Temperatures (°F)
A
B
C
D
420-463
505-546
430-460
185-243
411-460
405-544
205458
116-237
395-415
456-530
372-440
157-200
376-413
456-507
385-435
172-192
2-9
-------
TABLE 2-5. CONTROL DEVICE OPERATING PARAMETERS - WINDBOX BAGHOUSE
Parameter
Pressure drop (in. H2O)
Inlet Temp. ( F)
Stack Temp. ( F)
Fan amps
Damper (%)
Test 1 (08/12/97)
9.30-11.87
242 - 265
243 - 248
684 - 735
88.9-90.1
Test 2 (08/13/97)
10.60-12.59
217-253
231-248
667-690
89.5-91.2
Test 3 (08/14/97)
11.61-13.57
211-245
216-243
667-694
88.8-90 9
Test 4 (08/1 5/97)
12.09-14.12
217-236
227-248
659-690
89.0-90.8
TABLE 2-6. PRESSURE DROP ACROSS EACH COMPARTMENT
OF THE WINDBOX BAGHOUSE
Compartment
Pressure Drop
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Total
Test 1 (08/12/97)
7.0-8.6
8.2-9.2
7.1-8.6
5.6-8.0
7.1-8.5
6.6-7.9
6.4-8.0
67-8.4
7.6-9.4
7.1-9.0
6.8-8.9
7.6-9.4
64-9.0
6.4-9.2
9.9-11.5
Test 2 (08/1 3/97)
6.8-9.3
6.7-9.6
8.6-9.8
6.8-8.8
8.0-9.8
7.8-9.3
7.1-9.4
6.0-8.8
8.6-9.9
7.8-9.7
7.3-9.4
8.8-10+
7.6-10+
76-10+
10.0-11.5
Test 3 (08/14/97)
7.0-9.6
6.9-9.8
9.4-10+
7.4-9.8
9.1-10+
8.3-9.9
8.9-10.0
7.7-9.7
9.4-10+
9.3-10+
8.5-10+
9.6-10+
9.8-10+
9.4-10+
11.4-12.3
Test 4 (08/15/97)
8.6-9.9
8.0-10.0
9.9-10+
7.9-10+
10.0-10+
8.9-10+
9.7-10+
7.2-10+
9.5-10+
9.9-10+
8.2-10+
10+
10.0-10+
8.5-10+
12.0-13.0
2-10
-------
During each run of testing performed on A baghouse, the pressure drops of each
compartment and the pressure drop across the baghouse were monitored periodically, generally
every 20 to 30 minutes. The plant does not monitor any other parameters on A baghouse; since
the A baghouse is responsible for the capture and control of dust sources throughout the sintering
process, malfunctions are readily apparent. Table 2-7 presents a summary of the pressure drops
of each compartment and the pressure drop across the baghouse during each test period.
2.5 ANALYSIS OF MONITORING AND TEST RESULTS
Table 2-8 summarizes the emission results for each run for key pollutants from the outlet
of the control device on the sinter strand, along with selected parameters that were monitored
during the test. Only a few comparisons can be made because the process operated stably and
consistently during the 3 test runs. One difference is that the pressure drop across the strand
baghouse increased over the four days of testing, from an average of 10.78 on the first day of
testing, to an average of 13.48 on the final day of testing. However, the results were fairly stable
and did not appear to be impacted by the increased pressure drop over the course of testing.
Table 2-9 presents emission results for each run for key pollutants from the A baghouse outlet.
Particulate matter and HAP metal emissions were fairly steady over three runs. One
interesting factor is that while particulate matter emissions during Run 2 were three times lower
than during Run 1, and two times lower than during Run 3, HAP metal emissions were steady
over the course of the three runs. The major metal HAPs that were found were lead and
manganese; both were effectively captured and controlled by both the Strand baghouse and A
baghouse.
Another interesting result is the very low emission rate of dioxins, relative to what had
been reported from testing at German sinter plants. The German study reported concentrations of
23 to 68 ng TEQ/m3 from their initial studies and a range of 5 to 10 ng TEQ/m3 for plants that
optimized and improved their operation. The results for this sinter plant was much lower, with
an average concentration of 0.807 ng TEQ/m3. On the basis of sinter production, the Germans
reported emission levels in the range of 10 to 100 Mg/Mg of sinter compared to a measured level
of 0.6 /zg/Mg of sinter for this plant. The WCI sinter plant had emissions of dioxins and furans
that were on the order of 10 to 100 times less than that reported for German sinter plants.
2-11
-------
TABLE 2-7. PRESSURE DROP ACROSS EACH COMPARTMENT OF "A" BAGHOUSE
Compartment
1
2
3
4
Total
Test 1 (08/15/97)
2.6-3.8
2.8-3.7
4.7-5.5
4.4-6.0
7.7-8.1
Test2&3(08/16/97)
3.0-4.7
3.7-5.5
1 5-2.0
5.5-7.4
7.9-10.9
TABLE 2-8. STRAND BAGHOUSE SUMMARY OF RESULTS FOR EACH TEST RUN
Test Day
Sinter production
Baghouse AP
Windbox 20 Temp.
Baghouse Inlet Temp.
Baghouse Outlet Temp.
Parameter
PM" — outlet
Pb — outlet
Mn — outlet
HAP metals — outlet
Units
tons/hour
in. H2O
F
F
F
Units
Ib/hr
Ib/hr
Ib/hr
Ib/hr
Dioxin/furan congeners'1
Dioxin/furan TEQC
7PAHsd
16PAHs
Total PAHs
g/hr
g/hr
g/hr
g/hr
g/hr
Day 1
110
10.78
474
252
246
Runl
2.35
0.0220
0.0080
0.0628
Runs 1 & 2
Questionable
data;
unacceptable
leak checks
Day 2
110
12.00
467
240
240
Run 2
0.71
0.0209
0.0661
0.1224
Run 3
2,142
342
28.90
510
691
Day 3
110
12.88
446
230
230
Run 3
1.30
0.0229
0.0158
0.0681
Run 4
2,444
404
34.75
457
634
Day 4
110
13.48
457
231
238
Runs 4 & 5
Not
necessary to
do more
than 3 runs
RunS
2,186
375
33.88
575
755
Average
110
12.28
461
238
238
Average
1.45
0.0219
0.0300
0.0845
Average
2,257
374
32.51
514
693
a PM = particulate matter
b D/F congeners are those dioxins and furans that have a toxicity equivalent factor relative to 2,3,7,
c D/F TEQ is the toxicity equivalent expressed relative to 2,3,7,8-TCDD
d PAH = polycyclic aromatic hydrocarbons
8-TCDD
2-12
-------
TABLE 2-9. A BAGHOUSE SUMMARY OF RESULTS FOR EACH TEST RUN
Parameter
PMa — outlet
Mn — outlet
HAP metals — outlet
Units
Ib/hour
Ib/hour
Ib/hour
Run 1
0.53
0.0033
0.012
Run 2
0.67
0.036
0.046
Run 3
0.26
0.016
0.028
Average
0.48
0.019
0.029
a PM = particulate matter
The dioxin results are not unexpected because there are basic differences between the
operation of WCI's sinter plant and the German plants. The German study attributed the
formation of dioxin to the presence of chlorinated organics, primarily in cutting oils, that were in
the waste materials fed to the sintering process. In addition, they stated that the use of
electrostatic precipitators contributed to recombination and formation of dioxin. In contrast, the
WCI plant, like most U.S. integrated plants, has eliminated the purchase and use of chlorinated
organics in their facility. Their rolling mill oils (lubricants and hydraulic fluids) do not contain
chlorinated compounds. In addition, routine analysis of waste materials going to the sinter plant
have not detected chlorinated solvent. Finally, the WCI plant does not use an electrostatic
precipitator. Consequently, dioxin rates at WCI that are much lower than those reported by
German sinter plants appear to be reasonable and explainable.
A surprising result is the emission rate of polycyclic aromatic hydrocarbons (PAHs) that
was measured during the testing. Emissions for PAHs were slightly higher than particulate
matter emissions from the outlet of the strand baghouse. These results were consistent over all
test runs; even though the first two test runs resulted in questionable data, the results still are
consistent with the remaining three test runs. It is not known if the higher emissions were
present in the inlet stream or if the baghouse performed poorly in the capture and control of
PAHs emissions, since inlet testing for PAHs was not performed. The major PAHs present in
the outlet stream were naphthalene and 2-methylnaphthalene, with 3,660 and 2,920 pounds per
year being emitted respectively.
Table 2-10 presents a summary of particulate matter and metal HAP results for the strand
baghouse, including concentrations, efficiencies, annual emission rates, and emissions factors for
each metal HAP. Table 2-11 presents similar results for polycyclic aromatic hydrocarbons and
dioxins and furans. Table 2-12 presents a summary of results for the A baghouse for particulate
2-13
-------
matter and metal HAPs. The information contained in Tables 2-11 and 2-12 does not contain
efficiencies since inlet testing was not performed.
1-14
-------
TABLE 2-10. STRAND BAGHOUSE SUMMARY OF RESULTS FOR PARTICIPATE MATTER AND METAL HAPS
Partkulate Matter
Pollutant II A P
Metals
Mercury
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Manganese
Nickel
Lead
Antimony
Selenium
HAP metals
Inlet
Ib/hr
1,520
g/dscm
1.23
Concentration
(/^g/dscra)
Inlet
6.23
8.27
0,075
32.2
9.35
90.2
2230
18.3
7153
2.48
23.1
9,573
Outlet
5.02
0.452
0.038
0.180
0.135
4.47
29.1
2.07
21.3
1.21
18.0
82
Outlet
Ib/hr
1.45
g/dscra
0.0014
Emission rate
(g/hr)
Inlet
3.5
4.6
0,04
18.0
5.2
50.5
1,247
10.2
4,001
1.4
12.9
5,354
Outlet
2.35
0.21
0.02
0.08
0.06
2.09
13.62
0.97
9.97
0.57
8.42
38
Efficiency
%
99.9
Efficiency
(%)
32.5
95.4
57.7
99.5
98.8
95.9
98.9
90.5
99.8
59.3
34.7
99.3
Annual Rate,1* tpy
Inlet
5,700
Outlet
5.36
Annual rate (tpy)
Inlet
0.03
0.04
0.00
0.15
0.04
0.41
10.16
0.08
32.61
0.01
0.11
44
Outlet
0.02
0.00
0.00
0.00
0.00
0.02
0.11
0,01
0.08
0.00
0.07
0.31
Emission Factor (Ib/ton of sinter)
Inlet
13.8
Outlet
0.013
Emission factor {lb/t sinter)
Inlet
7.0 x 10~5
9,3 x 1Q"$
8.4 x ID'7
3.6 x 10 "
1.0 x 10"
1.0 x lO'3
2.5 x 10'2
2,0 x 104
8.0 x 10'2
2.8 x 10 5
2.6 x 1Q-4
1.1 x 10'1
Outlet
4.7 x 10'5
4.2 x 10 5
3.6 x 107
1.7x 10 6
1.3x 10'6
4.2 x 10 5
2.7 x 10"
1.9x 10'
2.0 x 10'4
1.1 x 10's
1.7x 10-"
7.7 x 10-4
" PM = paniculate matter
b Based on operation for 24 hours per day, 6 days per week, 52 weeks per year (7400 hours/year).
-------
TABLE 2-11. STRAND BAGHOUSE SUMMARY OF RESULTS
FOR PAHS AND DIOXIN/FURANS
Pollutant — Polycyclic Aromatic
Hydrocarbons (PAHs)
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Ideno( 1 ,2,3-cd)pyrene
7 PAHs (Total)
Acenaphthene
Acenaphthylene
Anthracene
Benzo(g,h.i)perylene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
16 PAHs (Total)
2-methylnaphthalene
2-chloronaphthalene
Benzo(e)pyrene
Perylene
Total PAHs
Outlet
g/hr
9.79
0.956
4.07
1.29
16.0
<0,273
<0.200
32.6
8.80
16.0
20.4
<0,194
56.3
18.8
221
115
25.3
514
176
0.804
1.98
<0,257
693
Mg/dsc
m
21.2
2.07
8.81
2.79
34.6
0590
0.433
70,7
19.0
34.5
44.2
0419
122
40.3
478
250
54.8
1114
382
1.74
4.27
0.557
1503
Annual Emissions,
Outlet of Control
Device"
tpy
0.0799
0.0078
0.0332
0.0105
0.1305
0.0022
0.0016
0.266
0.072
0.1305
0.1664
0.0016
0.459
0.1534
1.80
0.938
0.206
4.19
1.44
0.0066
0.0162
0.0021
5.65
Emission
Factor, Sinter
Basis
Outlet of
Control Device
Ib/ton
1.96xlO-4
1.92xlO~5
8.16x10°"
2.58xlO'5
3.21xlO-4
5.47xlO-s
4.01xlO-6
6,53xlO~4
1.76xlO~4
3.21xlO'4
4.09x1 0-4
3.89x10-'
1.13X10"3
3.77xia4
4.43xlO'3
2.30x10-'
5.07xlO'4
1.03xlO-z
3.53x10-'
1.61xlQ-5
3.97X10'5
5.15x10'*
1.39xlO'2
2-16
-------
TABLE 2-11. (CONTINUED)
Pollutant — Polycyclic Aromatic
Hydrocarbons (PAHs)
Pollutant — Dioxin/Furans
D/F congeners'1
D/FTEQC
Outlet
g/hr
/Lig/dsC
ni
Outlet
^g/hr
2,257
374
ng/dsc
in
4.877
0.807
Annual Emissions,
Outlet of Control
Device3
tpy
Annual Emissions,
Outlet of Control
Devicd"
grams/year
16.70
2.77
Emission
Factor, Sinter
Basis
Outlet of
Control Device
Ib/ton
Emission
Factor, Sinter
Basis
Outlet of
Control Device
Ib/ton
S.llxlO'8
8.48x10-"
' Based on operation for 24 hours per day, 6 days per week, 52 weeks per year (7400 hours/year).
b D/F congeners are those dioxins and furans that have a toxicity equivalent factor relative to 2,3,7,8-TCDD.
c D/F TEQ is the toxicity equivalent expressed relative to 2,3,7,8-TCDD.
2-17
-------
TABLE 2-12. DISCHARGE END BAGHOUSE ("A") - RESULTS FOR
PARTICIPATE MATTER AND METAL HAPS
Pollutant — Participate
Matter
PM"
Pollutant — Metal HAPs
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Mercury
Manganese
Nickel
Lead
Antimony
Selenium
HAP metals
Outlet
Ib/hr
0.48
gr/dscf
0.0007
Outlet
g/hr
0.10
0.013
0.017
0.039
1.2
0.29
8.4
1.0
1.1
0.48
0.43
13.1
^g/dscm
0.755
0.098
0.126
0.292
8.92
2.13
62.3
7.59
7.88
3.57
3.21
96.9
Emissions'"
tpy
1.8
Emissions'"
tpy
0.0008
0.0001
0.0001
0.0003
0.0099
0.0024
0.070
0.0084
0.0086
0.0040
0.0036
0.11
Emission Factor
Ib/ton sinter
0.0044
Emission Factor
Ib/ton sinter
2.4 xlO6
2.6 x 10'7
3.4 x 10'7
7.8 x 1C'7
2.4 x 105'
5.8 x 10-6
1.7 x 10'4
2.0 x 10'5
2.2 x 10'5
9.6 x 10 6
8.6 x 10 6
2.6 x 10'4
" PM = particulate matter.
b Based on operation for 24 hours per day, 6 days per week, 52 weeks per year (7400 hours/year).
2-18
-------
3.0 TEST LOCATIONS
Figures 3-1 and 3-2 are drawings of the baghouse inlet and outlet test locations. The
baghouse outlet stack and the baghouse inlet duct were sampled from the same trailer position.
3.1 BAGHOUSE INLET DUCT
The inlet location is a rectangular, horizontal, steel duct approximately 35 feet (ft) above
the ground level. The duct dimensions are 11 ft inside height by 10 ft inside width.
One 3-in. test port on the top of the duct was used for the FITR and Method 25A
sampling. Other ports installed on the side walls of the duct were used for the manual testing.
3.2 BAGHOUSE OUTLET (STACK)
The test platform and test ports on the stack were located approximately 60-70 ft above
ground level. Access to the stack platform was provided by a ladder on the exterior of the stack.
One 3-in. test port was installed 2 ft above the platform for the FUR and Method 25A
sampling. The four existing ports in the stack were used for the manual testing.
3.3 VOLUMETRIC FLOW
Table 3-1 summarizes the gas composition and flow data provided by ERG. ERG
provided volumetric flow rates, moisture content, gas molecular weight, etc. as part of their
manual testing; therefore, MRI did not conduct these tests.
3-1
-------
SINTERING PLANT
3-INCH PORT FOR
SAMPLING FOR FTIR &
25A TESTING
SUPPORT BEAM
FLOW
MANUAL
SAMPLING
PORTS
O
•O
O
O
APPROX.
2 FEET
•*-»
STAIRS-
BAGHOUSE
TO OUTLET STACK-
Figure 3-1. Test locations on the baghouse inlet duct.
-------
SAMPLE
PLATFORM'
MANUAL
SAMPLING
PORT
OPACITY MONITOR
3-INCH PORT FOR FTIR
& METHOD 25 A TESTING
• LADDER
Figure 3-2. Test locations on the baghouse outlet stack.
-------
TABLE 3-1. SOURCE GAS COMPOSITION AND FLOW SUMMARY
Test Data
Run Number
Date
Baghouse inlet duct
Oxygen, %
Carbon Dioxide, %
Moisture Content, %
Gas Stream Velocity, fpm
Volumetric Flow Rate, dscfm"
Baghouse outlet (stack)
Oxygen, %
Carbon Dioxide, %
Moisture Content, %
Gas Stream Velocity, fpm
Volumetric Flow Rate, dscfmb
1
12-Aug-97
18.5
2.0
6.2
5,375
302,348
19.0
2.0
7.4
6,463
277,347
2
13-Aug-97
18.5
2.0
5.1
4,822
287,397
18.5
2.5
7.0
6,255
271,179
3
14-Aug-97
18.0
2.0
6.7
5,116
301,113
17.5
3.5
6.5
6,235
274,572
a The flow data sheets in Appendix A incorrectly show the stack cross-sectional area of 9,160 in2 and an incorrect
volumetric flow was calculated. The correct inlet duct cross-sectional area was 12,690 in2. This was confirmed
in verbal communications with ERG, Inc., on 2/18/98. The corrected inlet duct cross-sectional area was used to
calculate the inlet volumetric flow rates shown.
b The outlet flows in Table 3-1 are averages of the two or three manual train results from each run.
3-4
-------
4.0 RESULTS
4.1 TEST SCHEDULE
The test program at WCI Steel was run from August 11 to August 14, 1997. Table 4-1
summarizes the sampling schedule. A complete record of all Method 25A and FTIR sampling is
in Appendices A and B. The FTIR and Method 25 A sampling was coordinated with the manual
sampling conducted by ERG.
TABLE 4-1. TEST SCHEDULE AT WCI STEEL
Date
8/11/97
8/12/97
8/13/97
8/14/97
Taska
Arrive on site, attend safety meeting, and setup at inlet and outlet.
Test Run 1. FTIR and Method 25 A in conjunction with manual methods
ERG.
13:35-20:00
Test Run 2. FTIR and Method 25A in conjunction with manual methods
ERG.
10:55-17:37
Test Run 3. FTIR and Method 25A in conjunction with manual methods
ERG.
08:10-10:29
Pack equipment and depart site
by
by
by
a AH of the testing was conducted at the baghouse inlet and outlet, which are described in Section 2.2.
4.2 FIELD TEST PROBLEMS AND CHANGES
During Run 2 the FTIR mercury/cadmium/tellunde (MCT) liquid nitrogen cooled
detector warmed up, and some data were lost. No results are reported for this period because the
spectra could not be analyzed. These spectra are included on the data back-up disk and are noted
in the data records. The MCT detector warming up had no effect on the 25A results, which are
reported for the same period.
Run 3 was abbreviated to about two hours because the manual sampling runs could not be
completed that day. The manual runs were redone the following day, but the EPA observer
decided that enough FTIR data had already been collected and did not require MRI to continue
testing on the following (fourth) day.
4-1
-------
4.3 METHOD 25A RESULTS
Table 1-2 summarizes the Method 25A total hydrocarbon (THC) results at the baghouse
inlet and outlet. The mass emissions data are presented as both THC and total gaseous non-
methane organic (TGNMO) carbon. The TGNMO was calculated using the procedures outlined
in Section 5,6,2 of this report using methane concentrations from the FTIR analysis.
The THC emissions were fairly steady during each test run except Run 3 at the baghouse
outlet. Table 4-2 shows the minimum and maximum 1-minute average THC concentrations, as
carbon, and the average concentration for each test run. At the baghouse inlet, the THC
concentration ranged from 199.8 ppm carbon during Run 1 to 287.4 ppm carbon also during Run
1. At the baghouse outlet, the THC concentration ranged from 66.9 ppm carbon during Run 3 to
242.7 ppm carbon during Run 1. Without accounting for process variations during the testing
periods, no absolute determinations can be made.
TABLE 4-2. MINIMUM AND MAXIMUM AND AVERAGE THC
CONCENTRATIONS (ppmc)
Run No.
Baehouse inlet
1
2
3
Baehouse stack
1
2
3
Minimum
199.8
2085
2043
153.9
174.6
66.9
Maximum
287.4
265.2
262.8
242,7
225.3
207.3
Average
248.7
244.2
220.8
197.7
211.5
172.5
The complete Method 25A results are included in Appendix A. The concentrations
presented were measured by MRI, and the mass emissions data, presented in Section 1.2, were
calculated using volumetric flow results provided by ERG. The pre- and post-run calibrations
and QA checks met the Method 25A criteria in all cases. Calibration QA results are included in
Appendix A.
4-2
-------
4.4 FTIR RESULTS
A summary of the FTIR results is presented in Table 1-1. Complete FTIR results at the
inlet and outlet are presented in Tables B-l to FJ-2 in Appendix B. The infrared spectra showed
evidence of water vapor, carbon dioxide (CO2), CO, methane, formaldehyde, sulfur dioxide
(SO2), toluene, ethylene, hexane, hydrogen chloride (HC1), 2-methyl-2-butene, and ammonia.
The FTIR results are from a revised analysis that included reference spectra of eight additional
hydrocarbon compounds. 2-methyl-2-butene was the only additional hydrocarbon compound
detected, but the revised hexane and toluene concentrations are slightly lower compared to the
draft report results. A description of the analytical procedures used to prepare the FTER results is
given in Section 5.4. The mass emission rates were calculated using flow data provided by ERG.
Mass emission calculations for toluene include only the results from unspiked samples.
Initially, the computer program was set to report as zero any concentration that was less
than four times the uncertainty. After the initial analysis there was clear evidence of HC1
remaining in some of the residual spectra. The evidence for HC1 is shown in the expanded
portion of Figure 4-1 at the end of Section 4. The analytical program was then modified to
measure HC1 and to report any concentrations that were greater than 1.0 times the uncertainty.
Note that in analysis both the calculated concentrations and uncertainties were the same. The
only mathematical difference between the analyses was in how many of the concentrations the
program actually reported (the other difference is that the first analysis did not account for HC1 at
all). The second analysis detected HC1 only in the first run. It was first measured at the inlet
about 3:00 PM, which was just prior to a process shut down at about 3:20 PM. The HC1 was
then measured for the remainder of the run at both locations even after the process restarted.
Note that the calculated uncertainty for HC1 is very similar for all of the spectra. The HC1
concentrations reported Tables B-l and B-2 were during periods when the HC1 concentrations
exceeded 1.0 times the uncertainties.
4.5 ANALYTE SPIKE RESULTS
For quality control a toluene gas standard was used for analyte spiking experiments.
Preferably, a spike standard combines the analyte and the tracer gas in the same cylinder, but the
SF6 and toluene were contained in two separate cylinders. Therefore, the two components (SF6
and toluene) were quantitatively mixed before being introduced into the sample gas stream.
4-3
-------
The analyte spike results are presented in Table 4-3. Samples were spiked with a
measured flow of toluene vapor during each run and at each location. The SF6 tracer gas was
spiked into the gas stream to determine the spike dilution factor. A description of the spike
procedure is given in Section 5.3.1.
In most cases the calculated spike recoveries (using deresolved reference spectra from the
EPA library) were greater than 130 percent, which is above the range allowed by Method 301 for
a validation correction factor (between 70 and 130 percent). This does not reflect on the
accuracy of the emissions results in reported in Appendix B. The residual spectra (Figure 4-1),
which show no significant (or negative) remaining absorbances, indicate that the computer
program correctly measured the absorbances from the interfering species and the analytes.
An important factor contributing to the (calculated) high spike recoveries relates to the
use of the toluene reference spectra. Method 320 specifies that library reference spectra be used
in the spectral analysis. The toluene spike recoveries and all of the toluene results were obtained
using reference spectra in the EPA library. Spectra of the toluene (spike) cylinder standard were
recorded on site during the test. If these on-site spectra are used in the analysis, one obtains
results about 38 percent lower (far right column in Table 4-3) than those obtained using the
reference spectra.
4-4
-------
TABLE 4-3. SUMMARY OF SPIKE RESULTS
Baghouse Inlet
Run
1
2
3
Toluene
Average
Spike
26.0
43.9
40.1
Unspike
7.1
9.5
9.7
Tol(calc)
spike -
unspike
18.9
34.3
30.4
SF6
Average
Spike
0.361
0.367
0.346
Unspike
0.000
0.000
0.000
spike -
unspike
0.361
0.367
0.338
DF
5.6
3.6
4.0
Cexp
10.9
22.2
20.4
Tol
(calc)
Cexp
8.0
12.1
10.0
Library
spectra"
%
Recovery
174
155
149
Standard
spectra15
%
Recovery
107
95
92
Baghouse Outlet (Stack)
Run
1
2
3
Toluene
Average
Spike
23.1
39.0
40.3
Unspike
8.5
7.5
10.8
Tol(calc)
spike -
unspike
14.6
31.5
29.6
SF6
Average
Spike
0.297
0.328
0.322
Unspike
0.000
0.000
0.000
spike -
unspike
0.297
0.328
0.322
DF
6.8
4.1
4.2
Cexp
9.0
19.8
19.4
Tol
(calc)
Cexp
5.6
11.7
10.1
Library
spectra"
%
Recovery
163
159
152
Standard
spectra15
%
Recovery
100
98
94
Calculations of the dilution factor, DF and the expected toluene spike concentration, Cexp, are described in
Section 5.3.
a These recoveries were obtained using EPA library reference spectra for toluene.
b These were obtained using spectra of the toluene cylinder standard measured on site.
Table 4-4 presents measured band areas of the EPA toluene reference spectra (deresolved
to 2.0 cm"1) and the spectra of the toluene cylinder standard measured while at the WCI test site.
The comparison of the band areas does not agree with the comparison of the concentrations
(corrected for path length and temperature). The comparisons differ by about 38 percent. This
observed difference predicts that, if the spectra of the toluene cylinder standard are used in the
analysis rather that the EPA library spectra, then the result would give a toluene concentration
that is about 38 percent lower. This in fact happens when the computer program is modified to
include the cylinder standard spectra.
This type of discrepancy is compound specific and the information in Table 4-4 does not
apply to the results for any of the other compounds detected. In fact, the deresolved CTS
(ethylene calibration) spectra give a path length result (Section 5.4.1) that is consistent with the
observed number of laser passes and the instrument resolution. Additionally, this observed
4-5
-------
TABLE 4-4. COMPARISON OF EPA REFERENCE SPECTRA TO SPECTRA OF
TOLUENE CYLINDER STANDARD3
Toluene Spectra
153a4ara
(2.0cm'1)
153a4arc
(2.0 cm'1)
ToldirA
ToldirB
ToldirC
153a4ara
(2.0 cm-1)
153a4arc
(2.0cm'1)
ToldirA
ToldirB
ToldirC
Source
EPA
library
EPA
library
WCI
WCI
WCI
EPA
library
EPA
library
WCI
WCI
WCI
Band
Area
23.4
4.3
21.2
21.1
21.0
12.1
2.6
11.0
11.2
11.2
Region
(cm'1)
3160.8-
2650.1
761.9-
670.1
Spectra comparison
based on band areas
Ratio
(Ra)
5.4
1.0
4.9
4.9
4.9
4.8
i.O
4.3
4.4
4.4
=l/Ra
0.184
1.000
0.203a
0.204
0.205
0.210
1.000
0.232
0.228
0.227
Comparison of spectra based on
standard concentrations
(ppm-m)/K
4.94
1.04
3.13
3.13
3.13
4.94
1.04
3.13
3.13
3.13
Ratio
(Re)
4.8
1.0
3.0
3.0
3.0
4.8
1.0
3.0
3.0
3.0
=l/Rc
0.210
1.000
0.332a
0.332
0.332
0.210
1.000
0.332
0.332
0.332
a The relevant comparison is Rc/Ra for spectra "ToldirA, ToldirB, and ToldirC" (about 61 percent).
discrepancy is not an artifact of the deresolution procedure because the band areas in the original
0.25 cm"1 toluene spectra are nearly equal to the band areas in the deresolved 1.0 cm'1 and
2.0 cm'1 versions of these spectra.
A discrepancy of this type has the greatest affect on the difference, "spike - unspike"
when the unspiked concentration is near zero. This is because two sets of reference spectra that
disagree will yield the same answer for a zero concentration, but they will yield different answers
for nonzero concentrations.
A similar disagreement between reference and standard spectra has been observed at least
once previously.4 In that study, which is included in Appendix D, HC1 was the analyte. The
spike recovery results were not significantly affected because there was a stable unspiked HC1
concentration and because both the spiked and unspiked HC1 concentrations were large
compared to the disagreement between the reference spectra and the spectra of the cylinder
standard.
4-6
-------
4.6 ESTIMATED UNCERTAINTIES
Estimated uncertainties for undetected HAP's are reported in Table 4-5. The spectra
were analyzed for the target analytes listed in the test request and for other, principally
hydrocarbon, species, which are in the EPA library of FTIR reference spectra. The procedure for
estimating the uncertainties is described in Section 5.4. The compounds for which the spectra
were analyzed and the analytical region(s) for each compound are given in Section 5.4. The
reported uncertainties can be interpreted as the practical measurement limits imposed by the
sampling conditions. The method of calculating uncertainties was identical to that used for the
compounds reported in Appendix B and depends on the noise in the residuals (Figure 4-1).
TABLE 4-5. AVERAGE UNCERTAINTIES (ppm) OF UNDETECTED
ANALYTES AT WCI STEEL
Compound"
Benzene (ch)
Methyl bromide (fp)
Methyl chloride (ch)
Methyl chloroform (fp)
1,1-Dichloroethane (fp)
1.3-Butadiene (fp)
Carbon tetrachloride (fp)
Chlorobenzene (fp)
Cumene (ch)
Ethyl benzene (ch)
Methylene chloride (fp)
Propionaldehyde (ch)
Styrene (fp)
1,1,2,2-Tetrachloroethane (fp)
p-Xylene (fp)
o-Xylene (ch)
m-Xylene (ch)
HC1 (ch)
2,2,4-Trimethylpentane (ch)
Run 1
Inlet
3.51
11.99
9.99
1.00
1.37
1.40
0.24
3.28
3.77
9.87
2.01
2.14
2.73
0.97
4.24
7.05
15.36
detected
0.85
Outlet
3.46
12.02
9.86
1.00
1.37
1.40
0.24
3.29
3.72
9.74
2.02
2.11
2.73
0.97
4.25
6.96
15.15
detected
0.84
Run 2
Inlet
3.24
11.72
9.24
0.98
1.34
1.37
0.23
3.21
3.49
9.13
1.97
1 98
2.66
0.95
4.15
6.52
14.20
3.2
0.79
Outlet
3.26
11.85
9.30
0.99
1.35
1.38
0.24
3.24
3.51
9.19
1.99
1.99
2.69
0.96
4.19
6.50
14.29
3.2
0.79
Run 3
Inlet
2.94
10.89
8.37
0.91
1.24
1.27
0.22
2.98
3.16
8.27
1.83
1.80
2.48
0.88
3.85
5.91
12.87
2.8
0.71
Outlet
2.88
10.74
8.21
0.90
1.23
1.25
0.21
2.94
3.10
8.11
1.80
1.76
244
0.87
3.80
5.79
12.61
2.8
0.70
Analytical Regions
(ch)-2,650.1-3,160.8 cm
(fp)-789.3-1275.0cm'1
Procedure for estimating uncertanties is described in Section 5.4.3
4-7
-------
-------
5.0 TEST PROCEDURES
The procedures followed in this field test are described in EPA Method 320 for using
FTIR spectroscopy to measure HAP's, the EPA Protocol for extractive FTIR testing at industrial
point sources, and EPA Method 25A. for measuring total gaseous organics. 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 FTER reference spectrum library, conduct analyte spiking for quality control,
and analyze the spectra for compounds not in the EPA library. Additionally, manual
measurements of gas temperature, gas velocities, moisture, CO2, and O2 by ERG were used to
calculate the mass emissions rates.
The extractive sampling system shown in Figure 5-1 was used to transport sample gas
from the test ports to the FTIR instrument and the THC analyzers.
5.1 SAMPLING SYSTEM DESCRIPTION
5.1.1 Sample System Components
The sampling system consists of three separate components:
• two sample probe assemblies
• two sample lines and pumps
• a gas distribution manifold cart
All wetted surfaces of the system are made of nonreactive 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 pilot 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 efficiency at 0.1 //m. The actuated spike
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.
5-1
-------
Vent
Vent
1
Data Storage & Analysis FTIR Spectrometer
Data Removal & Processing
Calibration Gas /
Spike Lira
Secondary PM Filter
Heated Manifold Box
20 ft of heated line
20 ft of heated Ira
Calibration Standards
Heated Probe Box #1
Bundles are 50-300+ ft long.
MFM • Mats Flow Molar
Calibration Qu / Spike Una
Sample Transfer Line (Heated Bundle) #1
Heated Probe Box *2
Bundles are 50-300+1 long.
Calibration Gas / Spike Una
Sample Transfer Line (Heated Bundle) #2
Figure 5-1. Sampling system schematic
-------
The sample lines are standard heated sample lines with three % inch Teflon tubes in
10, 25, 50, and 100 ft lengths. The pumps are heated single-head diaphragm pumps
manufactured by either KNF Neuberger or Air Dimensions. These pumps are capable of
sampling at rates up to 20 Lpm depending on the pressure drop created by the upstream
components.
The heated gas distribution manifold was specially constructed for FTIR sampling by
MRI. It is built onto a cart that can be operated inside the MRI mobile lab or elsewhere, 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.
Also included on the cart is 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 at both the inlet duct and outlet stack of the Strand baghouse
through the sample probe and transported to the gas distribution manifold. Inside the manifold
the gas passed through separate secondary particulate filters. Downstream of the secondary
filters, a portion of each sample gas stream was directed to separate THC analyzers; one to
measure concentration of the inlet sample and another to measure concentration of the outlet
sample. A portion of the remaining sample gas from each stream was either sent to the FTIR
instrument for analysis or exhausted with the remaining portion of the gas stream being sampled
(i.e., when the inlet sample was analyzed, the stack sample was exhausted and visa versa). This
was accomplished by rotating the gas selection valves to allow the appropriate sample gas to pass
to the instrument inlet port. The gas flow to the instruments was regulated by needle valves on
rotameters at the manifold outlets.
The FTIR instrument was used to sample each location alternately, while the two THC
analyzers were used to sample both locations simultaneously.
5.2 FTIR SAMPLING PROCEDURES
Figure 5-1 shows a schematic of the FTIR instrument and connections to the sample
distribution manifold.
5-3
-------
Sampling was conducted using either the batch or the continuous sampling procedures.
All data were collected according to Method 320 sampling procedures, which are described
below.
5.2.1 Batch Samples
In this procedure, a 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 as many samples as possible during Run 1.
Batch sampling has the advantage that every sample is an independent sample. The time
resolution of the measurements is limited by the interval required to pressurize the cell and
record the spectrum. For this test the time resolution was 4 to 5 minutes. All of the spiked
samples and all of the samples in Run 1 were collected using this procedure.
5.2.2 Continuous Sampling
The cell was filled as in the batch sampling procedure, but the cell inlet and outlet valves
were then opened to keep gas continuously flowing through the cell. The inlet and outlet flows
were regulated to keep the sample at ambient pressure. The flow through the cell was maintained
at about 5 Lpm (about 0.7 cell volumes per min). The cell volume was about 7 L.
The FTIR instrument was automated to record spectra of the flowing sample about every
2 minutes. The analytical program was revised after the field tests and the spectra were analyzed
to prepare the results reported in Section 4.
This procedure with automated data collection was used for all of the unspiked testing
during Runs 2 and 3. 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) depended on the sample flow rate (through the cell), and
the cell volume. The following explanation is taken from Performance Specification 15, for
continuous operation of FTIR systems.
"The Time Constant (TC) 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
5-4
-------
depends on the sampling rate (Rs in Lpm), the cell volume (Vcel, m L) and the analyte's chemical
and physical properties." Therefore,
V
ceil
Performance Specification 15 defines 5 * TC as the minimum interval between independent
samples. In this test, 5 *TC was about 7 minutes.
A stainless steel tube ran from the cell inlet connection point to the front 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.
5.3 ANALYTE SPIKING
Since no information about possible HAP emissions or flue gas composition was
available for this source before the test, validation of specific HAP's at this test was not planned.
MRI conducted spiking for QA purposes using a toluene (121 ppm in air) standard.
5.3.1 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 quality assurance check that the sampling
system can transport the spiked analyte(s) 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 validation3. No validation was performed at this field test.
The spike procedure follows Sections 9.2 and 13 of EPA draft 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 comprises about 1/10 or less of the spiked sample. The actual dilution ratio depends on the
sample flow rate and the spike gas flow rate. The expected concentration (Cexp, the calculated
100 percent recovery) 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
5-5
-------
used as the spike dilution factor (DF). The analyte standard concentration divided by DF gives
the "expected" value (100 percent) of the spiked analyte recovery.
In this test the analyte (121 ppm toluene in air) and the tracer gas (4.01 ppm SF6 in
nitrogen) were in separate cylinders. Flows from the two gas standards were passed through
separate mass flow meters and then combined into one flow that was directed up the spike line
and introduced into the sample stream at the back of the sampling probe. Because the two gases
were mixed, the concentrations of each component were reduced in the combined spike gas flow.
This had to be accounted for in the calculation of the spike dilution factor, DF. For example, the
SF6 concentration in the combined spike stream was
F
~ — Z * ^^6 (standard) (2)
toluene SF,
where:
SF6(direct) = SF6 in the spike mixture. This is used in place of the cylinder standard
concentration.
FSF6 and Ftoluene = the measured flows from the toluene and SF6 cylinder standards.
SF6(standard) = the concentration of the SF6 cylinder standard.
The toluene concentration in the combined spike flow is calculated in the same way.
•p
toluene(direct) = p '""TV * toluene(standa,d) (3)
rtoluene rSF6
The value, SF6(spike) is compared to the measured SF6 concentration in the spiked samples to
determine the spike dilution factor:
DF = SF(S(direct) (4)
SF
0 6(spike)
5-6
-------
Where DF is the spike dilution factor in Section 9.2,2 of Method 320 and SF6(direct) is calculated
using Equation 2.
The calculated 100 percent recovery of the toluene spike is analogous to the expected
concentration in Section 9.2,2 of Method 320. In this case:
toluene,, ,.
where:
Cexp= expected toluene concentration in the spiked samples (100 percent
recovery).
toluene(direct) = from Equation 3.
DF = from Equation 4.
5.3.2 Analysis of Spiked Results
The toluene and SF6 concentrations used in the evaluation of the spike recoveries in
Table 4-3 were taken directly from the sample analyses reported in Appendix B. The
concentrations in the spiked samples included a contribution from the spike gas and from any
analyte present in the flue gas. The component of the toluene concentration attributed to the
spike was determined by subtracting the average of the unspiked samples from the measured
concentration in each spiked sample ("spiked - unspiked" in Table 4-3). The percent recovery
was determined by comparing the differences, spiked - unspiked, to the calculated 100 percent
recovery, Cexp in Section 5.3.1.
5.4 ANALYTICAL PROCEDURES
Analytical procedures in the EPA FTER Protocol were followed for this test. A computer
program was prepared with reference spectra shown in Table 5-1. The computer program5 used
mathematical techniques based on a K-matrix analysis.6
5-7
-------
TABLE 5-1. PROGRAM INPUT FOR ANALYSIS OF SAMPLE SPECTRA
Compound name
Water
Carbon monoxide
Sulfur dioxide
Carbon dioxide
Formaldehyde
Benzene
Methane
Methyl bromide
Toluene
Methyl chloride
Methyl chloroform
1 , 1 -dichloroethane
1,3 -butadiene
Carbon tetrachloride
Chlorobenzene
Cumene
Ethyl benzene
Methylene chloride
Propionaldehyde
Styrene
1 , 1 ,2,2-telrachloroethane
p-Xylene
o-Xylene
m-Xylene
Ethylene
SF6
Ammonia
Hexane
butane
n-heptane
pentane
1-pcntenc
2-methyl- 1 -pentene
2-methyl-2butene
2-methyl-2-pentene
Isooctane
3-methvlDentane
File name
194clbvh
co20829a
198clbsc
193b4a_a
087clanb
015a4ara
196clbsb
106a4asb
153a4arc
107a4asa
108a4asc
086b4asa
023a4asc
029a4ase
037a4arc
046a4asc
077a4arb
117a4asa
140b4anc
147a4asb
150b4asb
173a4asa
171a4asa
172a4arh
CTS0813d
Sf60811a
174a4ast
0950709a
but0715a
hep0716a
pen0715a
Ipe0712a
2mlp716a
2m2b716a
2m2p713a
1650715a
3mo0713a
Region No.
1,2,3
1
2
1,2,3
3
3
3
2
3
3
2
2
2
2
2
3
3
2
3
2
2
2
3
2
2
2
2
3
3
3
3
3
3
3
3
3
3
ISCa
10011
167.1
89.5
415a
100.0
4966
80.1
485.3
103.0
501.4
98.8
499 1
98.4
20.1
502.9
963
5155
498.5
99.4
550.7
493.0
4882
497.5
497.8
20.1
4.01
500.0
46.9
100.0
49.97
49.99
501
50.08
50.04
51.4
50.3
50.0
Reference
Meters | T (K)
22
22
11.25
3
22
3
3
3
3
225
3
3
3
3
3
3
2.25
3
225
3
3
3
10.4
104
3
103
11.25
10.3
10.3
103
10.3
10.3
10.3
103
103
394
394
373
298
394
298
298
298
298
373
298
.298
298
298
298
298
373
298
373
298
298
298
394
394
298
399
397.8
3983
3979
399
398.2
3982
3986
3983
3985
Region No
1
2
3
Upper cm" '
2.142.0
1,275 0
3,1608
Lower cm" '
2,035.6
789.3
2,650.1
a Indicates an arbitrary concentration was used for the interferant.
5-8
-------
Initially, the spectra were reviewed to determined suitable input spectra for the computer
program. Next an analysis was run on all of the sample spectra using all of the reference spectra
listed in Table 5-1. The estimated uncertainty results for the undetected species were reported in
Table 4-4. Finally, the undetected compounds were removed from the analysis and the spectra
were analyzed again using reference spectra only for the detected compounds. The results from
this second analytical run are summarized in Table 1-1 and reported in Appendix B. In addition
to the detected compounds shown in Table 5-1, the spectra were analyzed for
2-methyl-2-pentene, 3-methylpentane, butane, 2-methyl-l-pentene, n-heptane, 1-pentene,
2-methyl-2-butene, and n-pentane in the revise danalysis.
The same program that performed the analysis 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.
The concentrations were corrected for differences in absorption path length and
temperature between the reference and sample spectra using equation 6.
L
\
]J": «,. (6)
where:
CCorr = concentration, corrected for path length and temperature.
CCalc = unconnected sample concentration.
Lr = cell path length(s) (meters) used in recording the reference spectrum.
Ls = cell path length (meters) used in recording the Sample spectra.
Tr = absolute temperature(s) (Kelvin) of gas cell used in recording the reference
spectra.
Ts = absolute temperature (Kelvin) of the sample gas when confined in the FTIR gas
cell.
5-9
-------
The ambient pressure recorded over the three days of the test averaged about 746 mm Hg.
Because the sample pressure in the gas cell is equivalent to the ambient pressure, an addition
concentration correction factor of about 2 percent was included in the reported concentrations.
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 calibration transfer standard (CTS)
spectra to CTS spectra in the EPA FTIR reference spectrum library. The reference CTS spectra,
which were recorded with the toluene reference spectra and are included in the EPA library, were
used as input for a K-matrix analysis of the CTS spectra collected at the WCI field test.
5.4.1 Computer Program Input
Table 5-1 presents a summary of the reference spectra input for the computer program
used to analyze the sample spectra. Table 5-2 summarizes the program input used to analyze the
CTS spectra recorded at the field test. The CTS spectra were analyzed as an independent
determination 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 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'1. Table 5-3 summarizes
the results of the CTS analysis. The cell path length from this analysis was used as Ls in
equation 2.
5.4.2 EPA Reference Spectra
The 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 were chosen to agree with those used to collect the sample absorbance
spectra. The new 2.0 cm"1 toluene 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 that were included in the analysis.
5-10
-------
5.5 FTIR SYSTEM
A KVB/Analect Diamond 20 spectrometer was used to collect all of the data in this field
test. The gas cell is a heated variable path (D-22H) gas cell from Infrared Analysis, Inc. The
path length of the cell was set at 20 laser passes and measured to be about 10.4 meters using
-------
The optical path length was measured by shining a He/Ne laser through the cell and
adjusting the mirror tilt to obtain the desired number of laser spots on the field mirror. Each laser
spot indicates two laser passes through the cell. The number of passes was recorded on the field
data sheets in Appendix B. The path length in meters was determined by comparing CTS
(ethylene in nitrogen) spectra, measured in the field, to CTS spectra in the EPA reference
spectrum library. The procedure for determining the cell path length is described in Section 4.4.
5.6 CONTINUOUS EMISSIONS MONITORING FOR TOTAL HYDROCARBONS (THC)
The guidelines set forth in Method 25A were followed during the sampling at WCI with
two exceptions. Section 7.2 of Method 25A specifies that the mid-level calibration gas be used
for the drift determination. For this test program, the high-level calibration gas was used for the
drift determination because it more closely approximated the measured THC concentrations.
Also, Section 7.2 of Method 25A specifies an analyzer drift determination hourly during the test
period, but this instruction was not followed.
There are two reasons the drift determination was not completed as specified. The first
reason is for continuity in the FTIR and THC sampling. With run length exceeding four hours,
this hourly drift determination would have involved off-line periods of up to 10 minutes each
hour for the THC analyzers and possibly the FTIR instrument. The loss of this time could affect
the results if significant process events had occurred during these periods. The second reason is
that experience with the analyzers MRI was using show them to be stable over extended periods
when they are operated in a climate controlled environment.
The need to do hourly drift determinations is somewhat diminished when the stability of
the analyzer is known and when the possibility that being off-line could affect the
representativeness of both the FTIR and THC results.
5.6.1 Total Hydrocarbon Sampling Procedures
The THC sampling was conducted continuously from both locations by using of two
separate analyzers. The same sample systems used for the FTIR sampling were used for the THC
sampling. Sample gas was directed to the analyzers through a separate set of rotameters and
control valves. Each test run was conducted from the start to the end of the manual test runs
completed by ERG. A summary of specific procedures used is given below.
A brief description of each system component follows.
5-12
-------
• THC Analyzer- The THC concentration was measured using a flame ionization
detector (FED). MRI used two J.U.M. Model VE-7 analyzers. The THC analyzers
were operated on the zero to 100 ppm range throughout the test period. The fuel
for the FDD is 40 percent hydrogen and 60 percent helium mixture.
• Data Acquisition System- MRI used LABTECH notebook (Windows version),
which is an integrated system that provides data acquisition, monitoring and
control. The system normally writes data to a disk in the background while
performing foreground tasks or displaying data in real time. The averaging period
set for this test was one minute.
• Calibration Gases- Calibration gases were prepared from an EPA Protocol
i cylinder of propane (5278 ppm propane in nitrogen) using an Environics •
Model 2020 gas dilution system that complies with the requirements of EPA
Method 205. High, medium, and low standard gases were generated to perform
analyzer calibration checks. The raw data are recorded in ppm as propane but are
converted to an as carbon basis for reporting. Appendix C contains copies of
mass flow meter calibration records and calibration gas certifications
5.6.2 Hydrocarbon Emission Calculations
The hydrocarbon data is presented as both THC and TGNMO emissions in Table 4-1. To
do this the THC emission data was first converted to an as carbon basis using Equation 7, and
then the THC emission rate was calculated using Equation 9.
(7)
where:
Cc = organic concentration as carbon, ppmv.
Cmeas = organic concentration as measured, ppmv.
K = carbon equivalent correction factor, 3 for propane.
The TGNMO concentration was calculated by subtracting the methane concentration
measured by the FTIR from Cc (Equation 8). The emission rate was then calculated using
Equation 9.
5-13
-------
^TGNMO C ^CH4 (8)
where:
CTGNMO = iota\ gaseous nonmethane organic concentration, ppmv.
CCH4 = methane concentration in gas stream, ppmv.
CTGNMO/CC ^W x Q td x 60
td
(1-BJ (9)
where:
ETGNMO/THC ~ TGNMO or THC mass emission rate, Ib/hr.
Bws = moisture fraction in gas stream
MW = molecular Weight of Carbon, 12 Ib/lb-mole.
Qstd = volumetric Flowrate corrected to standard conditions, dscfm.
60 = conversion to hours, min/hr.
385.3 = molar Volume, ftVmole at standard conditions.
106 = conversion for decimal fraction to ppm.
5-14
-------
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
was 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, spectra of at least 10 different samples were collected during each hour
(five at each of two locations).
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 of all flue gas measurements, such as sample flow,
temperature, moisture and diluent data.
Effluent was allowed to flow through the entire sampling system for at least 5 minutes
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). Whenever this condition occurred, sampling was
interrupted and a new background spectrum was collected. The run was then be 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 CTS spectrum 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 were 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
spectra were stored on separate computer disks. Additional copies of sample and CTS
absorbance spectra were also stored for data analysis. Sample absorbance spectra can be
regenerated from the raw interferograms, if necessary.
To measure HAP's detected in the gas stream, MRI used spectra from the EPA library,
when available.
6-2
-------
6.3 METHOD 25A
6.3.1 Initial Checks
Before starting the first run, the following system checks were performed:
1. Zero and Span check of the analyzer;
2. Analyzer linearity check at intermediate levels; and
3. Response time of the system.
Calibration criteria for Method 25A is ±5 percent of calibration gas value.
6.3.2 Daily Checks
The following checks were made for each test run.
1. Zero/Span calibration and Linearity check before each test run; and
2. Final Zero and Span calibrations of the analyzer at the end of each test run.
The difference between initial and final zero and span checks agreed within ±3 percent of
the instrument span.
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 Part 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. "Validation of EPA FTIR Method For Measuring HC1," T. J. Geyer and G. M. Plummer, Ajr
and Waste Management Association Paper Number 97-MP74.05, 1997.
5. "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.
6. "Computer-Assisted Quantitative Infrared Spectroscopy," Gregory L. McClure (ed.), ASTM
Special Publication 934 (ASTM), 1987.
7-1
-------
APPENDIX A
METHOD 25A AND VOLUMETRIC FLOW DATA
A-l
-------
A-l METHOD 25A RESULTS
A-2
-------
WCI
Run 1
Date: 8/12/37
Project No.: 3804-20-03-02-02/4701-08-10
Operator; Gulick
Time (24 hour)
1335
1336
1337
1338
1339
1340
1341
1342
1343
1344
1345
1346
1347
1348
1349
1350
1351
1352
1353
1354
1355
1356
1357
1358
1359
1400
1401
1402
1403
1404
1405
1406
1407
1408
1409
1410
1411
1412
1413
1414
1415
1416
1417
1418
1419
1420
1421
THC inlet (ppm)
83.4
83.7
83.7
83.1
83.5
83.1
83.4
84.4
84.5
86.9
87.2
87.8
87.8
87.7
87.1
86.8
86.4
85.7
86.0
84.6
84.5
84.6
85.7
86.4
86.2
86.5
87.9
88.2
88.4
87.6
87.7
86.9
87.1
86.7
84.9
84.9
85,1
86.5
86.2
85.2
84.9
84.3
84.6
88.5
89.1
88.4
88.3
THC outlet (ppm)
68.7
67.9
68.9
68.4
68.1
68.6
68.2
68.4
68,9
69.8
70.8
70.9
71.0
70.9
70.7
70.6
69.9
69J
69.6
69.7
68.8
69.1
69.3
70.1
70.2
70.2
70.3
72.0
71.3
71.1
70.8
71.0
70.8
71.1
69.5
69.1
69.0
69.5
70.1
69.2
69.2
68.7
68.7
71,3
72.7
72,1
72.5
runl, Page 1
-------
WCI
Run 1
Date: 8/12/97
Project No.: 3804-20-03-02-02/4701-08-10
Operator: Gulick
Time (24 hour)
1422
1423
1424
1425
1426
1427
1428
1429
1430
1431
1432
1433
1434
1435
1436
1437
1438
1439
1440
1441
1442
1443
1444
1445
1446
1447
1448
1449
1450
1451
1452
1453
1454
1455
1456
1457
1458
1459
1500
1501
1502
1503
1504
1505
1506
1507
1508
THC inlet (ppm)
88,0
95.8
90.5
87.6
88.6
87.4
88.2
90.1
87.7
88.3
88.6
89.6
90.5
89.9
89.3
86,6
84.8
84.8
87.4
84.7
83.4
81.5
81.5
82.2
84.8
85.9
85.9
85.5
84.6
83.1
82.4
82.5
81.6
80.9
80.4
80.5
78.3
80.0
81.5
81.7
82.2
82.2
82.8
84.3
83.5
84.3
84.9
THC outlet (ppm)
71.1
80.9
74.8
71.5
71.8
70.9
70.4
72.0
71.1
70.9
71.4
71.1
73.0
71.7
72.7
71.1
69.6
69.6
71.8
70.9
69.5
67.3
66.9
67.1
67.5
69.5
89.7
69.5
68.9
66.1
61.4
62.4
62.4
60.2
61.4
63.2
61.5
60.6
61.5
64.5
66.7
67.0
67.6
68.2
69.1
68.7
69,4
runl, Page 2
-------
WC1
Run 1
Date; S/12/t7
Project No.: 3804-20-03-02-02/4701-08-10
Operator. Gulick
Time (24 hour) THC inlet (ppm) THC outlet (ppm)
1509
1510
1511
1512
1513
1514
1515
1516
1517
1518
1519
1520
1521
Process off Line
(1522-1551)
1552
1553
1554
1555
1556
1557
1558
1559
1600
1601
1602
1603
1604
1605
1606
1607
1608
1609
1610
1611
1612
1613
1614
1615
1616
1617
1618
1619
1620
1621
1622
1623
84.7
85.5
85.3
86,8
87.6
89,4
90.4
90.4
90.7
90.0
89.7
91,0
92.0
81.0
80.4
82.6
81 .9
79.7
79.8
79.0
83,2
83.9
85.5
87.0
89.0
90.0
90.4
91.1
91.0
90.4
89.6
89.2
88.8
89.1
89.2
88.3
88.7
89.0
88.3
88.2
87.8
88.1
87.6
86.6 "
85.6
69.5
69.1
69.5
70.0
70.7
72.1
73.6
73.2
73.4
72.7
72.3
72.1
74.6
58.9
58.6
61.7
65.8
61.8
60.6
57.9
63.3
64.9
67.9
69.3
70.4
71.7
71.9
72.0
72.4
72.0
71.6
71.3
71.1
71.1
71.8
71.3
71.1
71.5
71.4
71.0
70.7
71.2
71.2
69.9
63.3
runl, Page 3
-------
WCI
Run 1
Date: 8/12/97
Project No.: 3804-20-03-02-02/4701 -08-10
Operator: Gulick
Time (24 hour)
1624
1625
1626
1627
1628
1629
1630
1631
1632
1633
1634
1635
1636
1637
1638
1639
1640
1641
1642
1643
1644
1645
1646
1647
1648
1649
1650
1651
1652
1653
1654
1655
1656
1657
1658
1659
1700
1701
1702
1703
1704
1705
1706
1707
1708
1709
1710
THC inlet (ppm)
85.0
85.2
84.1
88.2
89.6
88.7
89.2
89,3
90.2
90.4
89.7
89.0
84.4
83.0
82.7
82.9
83.0
83.6
85.4
87.3
88.6
90.3
90.8
91.4
92.4
95.2
93.8
92.7
91.6
89.9
88.0
89.8
86.6
84,6
88.0
84.4
77.1
73.8
70.6
68.4
66.8
68.4
66.6
67.2
67.5
68.6
68.8
THC outlet (ppm)
66.5
63.9
61.5
66.8
70.7
70.3
69.6
71.8
72.6
72.0
72.1
72.0
64.2
61.3
60.6
60.3
60.4
60.8
61.2
68.2
70.2
72.0
73.1
73.7
74.2
75.8
76.2
75.2
74.1
73.3
71.5
71.8.
71.8
70.0
70.0
67.4
61.4
57.3
55.1
53.5
52.0
52.1
51.3
51.8
51.7
52.6
52.9
runl, Page 4
-------
WCI
Run 1
Date: 8/12/97
Project No.: 3804-20-03-02-02/4701-08-10
Operator: Gulick
Time (24 hour)
1711
1712
1713
1714
1715
1716
1717
1718
1719
1720
1721
1722
1723
1724
1725
1726
1727
1728
1729
1730
1731
1732
1733
1734
1735
1736
1737
1738
1739
. 1740
1741
1742
1743
1744
1745
1746
1747
1748
1749
1750
1751
1752
1753
1754
1755
1756
1757
THC inlet (ppm)
70.3
72,3
72.6
72,4
73,0
73.9
74.1
74.7
75.9
77.1
78.7
80.6
81.0
82.6
83.7
84.4
85.0
85.9
87.0
83.8
82.6
81.4
81.7
84.3
86.5
87.5
87.9
88.2
87.8
86.2
85.2
82.3
79.4
78.5
76.7
75.8
75.2
75.2
75.6
76.2
77.5
76.1
76.2
78.7
79.7
81.6 •
83.0
THC outlet (ppm)
53.5
54.7
55.4
55.2
55.3
56.1
56.4
56.6
57.2
58.2
58.5
59.7
60.3
60.8
61.9
62.1
62.3
62.9
69.3
66.5
62.6
60.5
60.2
62.3
68.9
70.8
72.0
71.6
72.4
71.3
70.1
69,1
62.9
59.7
58.6
57.2
57.2
56.8
56.7
56.9
58.1
57.2
56.8
57.9
59.0
59.8
60.7
runl, Pages
-------
WCI
Run 1
Date: 8/12/97
Project No,; 3804-20-03-02-02/4701-08-10
Operator; Gulick
Time (24 hour)
1758
1759
1800
1801
1802
1803
1804
1805
1806
1807
1808
1809
1810
1811
1812
1813
1814
1815
1816
1917
1818
1819
1820
1821
1822
1823
1824
1825
1826
1827
1828
1829
1830
1831
1832
1833
1834
1835
1836
1837
1838
1839
1840
1841
1842
1843
1844
THC inlet (ppm)
83,7
88,8
92.1
91,0
89.1
86.3
81.8
80,5
79,3
77.5
77.4
76.9
76.9
76.3
75.8
76.2
75.8
76.2
76.1
76.2
76.4
77.2
78,0
78.1
78.5
79.9
82.0
81.8
81.5
81,6
80.1
79.9
80,6
80.5
81.5
80.6
81.7
81.8
82.2
82.3
81.1
82.5
80.3
80.3
78.4
75.7 -
74.6
THC outlet (ppm)
61.5
65.7
73.2
73.4
72.6
70.6
64.3
60.2
59.2
57.9
57.6
57.5
57.4
56.9
56.8
56.6
56.6
56.8
56.9
56.8
57.0
57.5
57.5
57.9
57,5
57.8
64,0
66.3
65.4
66,0
65.9
64.9
65,5
65.9
66.3
66.5
66.6
67.2
67.0
67.6
67.1
67.4
66.6
65.9
65.8
58.4
57.2
mn1, Page 6
-------
WCI
Run 1
Date: 8/12/97
Project No.: 3804-20-03-02-02/4701-08-10
Operator: Gulick
Time (24 hour)
1845
1846
1847
1848
1849
1850
1851
1852
1853
1854
1855
1856
1857
1858
1859
1iOO
1901
1902
1903
1904
1905
1906
1907
1908
1909
1910
1911
1912
1913
1914
1915
1916
1917
1918
1919
1920
1921
1922
1923
1924
1925
1926
1927
1928
1929
1930
1931
THC inlet (ppm)
73.8
73.5
73.5
73.8
74.9
74.3
74.8
74.9
77.0
79.1
78,8
79,9
78.8
78.1
79.8
80.7
80.9
81.7
83.2
84.6
83.7
84.5
82.9
82.6
82.0
82.8
81.8
80.8
80.2
80.6
80.1
80.1
80.4
80.4
79.3
78.8
78.1
78.3
77.9
78.1
78.3
78.6
79.2
79.5
80.7
81.5 •
81.9
THC outlet (ppm)
56.0
55.6
55.3
55.5
55.8
56.2
56.0
56.5
59.2
64.4
62.9
64.8
63.0
59.7
60.8
65.5
66.2
66.3
67.5
69.5
68.7
69.1
68.4
68.0
67.7
68.0
68.1
67.1
66.6
66.8
66.4
66.5
66.1
66.8
66.1
65.1
65.1
65.1
65.0
65.1
65.3
65.3
66.0
66.1
66.6
67,4
68,1
runl, Page 7
-------
WCI
Run 1
Date: 8/12/97
Project No.: 3804-20-03-02-02/4701-08-10
Operator: Gulick
Time (24 hour)
1932
1933
1934
1935
1936
1937
1938
1939
1940
1941
1942
1943
1944
1945
1946
1947
1948
1949
1950
1951
1952
1953
1954
1955
1956
1957
1958
1959
2000
Minimum
Maximum
Average
THC inlet (ppm)
81.9
82.4
82.9
83.4
83.7
82.9
83.1
83.8
82.0
82.9
81.8
82.1
81.8
82.4
84.2
82.4
81.8
81.6
80.5
79.5
79.3
76.9
76.8
76.4
76.6
77.7
79,2
81.7
81.6
Inlet
66.6
95.8
82.9
THC outlet (ppm)
68.3
68.3
68.8
69.1
69.4
69.4
69.0
69.5
69.4
69.1
68.9
68.3
68.7
68.6
69.2
70.4
68.8
68.2
67.5
66.6
66.3
63.0
58.7
58.0
58.1
58.1
63.6
63,2
68.6
Outlet
51,3
80.9
65,9
runl, PageS
-------
100
80
60
i
o.
a.
*HP
E
40
20 -
0
THC Concentrations vs. Time (Run 1,8/12/97)
-*- THC inlet (ppm) -a- THC outlet (ppm)T]
13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00
Time
-------
WCI
Run 2
Date: 8/13/97
Project No.: 3804-20-03-02-01
Operator: Gulick
Time (24 hour)
1055
1056
1057
1058
1059
1100
1101
1102
1103
1104
1105
1106
1107
1108
1109
1110
1111
1112
1113
1114
1115
1116
1117
1118
1119
1120
1121
1122
1123
1124
1125
1126
1127
1128
1129
1130
1131
1132
1133
1134
1135
1136
1137
1138
THC inlet (ppm)
82.5
83.0
81.6
81.4
81.0
80.2
80.8
79.8
79.9
79.8
79.0
79.9
81.3
81.4
81.7
81.6
81.8
83.3
83.2
83.0
84.1
83.9
84.2
84.6
84.4
84.8
85.4
85.7
85.7
84.2
82.6
81.1
82.1
83.1
80.9
80.2
78.4
79.0
79.2
79.5
79.5
79.8
79.2
79.8
THC outlet (ppm)
70.5
71.5
70.3
70.0
69.8
69.5
69.8
6i.2
69.0
69.3
68.9
69.3
69.9
70.5
70.2
70.6
70.6
71.4
71.7
71.2
72,3
72.3
72.4
72.7
72.5
72.7
72.6
73.2
73.9
73.1
72.0
70.9
71.2
72.1
71.4
70,1
65.8
68.6
69.0
69.4
69.7
69.8
69.6
69.7
run2, Page 1
-------
WCI
Run 2
Date: 8/13/97
Project No.: 3804-20-03-0241
Operator: Gulick
Time (24 hour)
1139
1140
1141
1142
1143
1144
1145
1146
1147
1148
1149
1150
1151
1152
1153
1154
1155
1156
1157
1158
1159
1200
1201
1202
1203
1204
1205
1206
1207
1208
1209
1210
1211
1212
1213
1214
1215
1216
1217
1218
1219
1220
1221
1222
THC inlet (ppm)
79.4
79.7
80.3
79.9
80,8
81.9
82.8
82.5
83.1
83.1
82.4
83.1
84.5
84.2
82.5
81.5
81.5
80.8
80.3
80.3
81.6
81.8
81.8
83.2
83.1
84.3
85.0
82.5
84.6
84.7
85.6
84.9
85.2
83.2
82.0
82.1
82.1
83.0
81,2
83.2
81.5
81.8
83.3
81.3
THC outlet (ppm)
69.6
69.7
70.0
69.8
70.0
70.9
72.2
71.6
72.2
72.1
71.7
71.6
72.2
74.0
71,7
71.0
70.8
70.9
69.9
70.1
70.3
71.0
70.4
71.2
71.1
71.6
73.1
71.6
72.5
72.7
71.9
72.6
72.1
71.1
70.3
70.1
69.8
70.7
69,9
70.4
70.3
70.0
71.1
69.3
run2, Page 2
-------
WC!
Run 2
Date: 8/13/97
Project No.: 3804-20-03-02-01
Operator: Gulick
Time (24 hour)
1223
1224
1225
1226
1227
1228
1229
1230
1231
1232
1233
1234
1235
1236
1237
1238
1239
1240
1241
1242
1243
1244
1245
1246
1247
1248
1249
1250
1251
1252
1253
1254
1255
1256
1257
1258
1259
1300
1301
1302
1303
1304
1305
1306
THC inlet (ppm)
80.7
82.0
85.0
88.4
86.0
83.6
82.0
82.8
84.4
84.7
84.0
81.6
80.1
7i.8
79.4
78.7
81.8
80.0
80.6
80.1
79.7
80.1
81.1
82.3
82.0
82.5
83.5
82.2
80.5
78.6
78.7
78,9
79.0
78.8
78.8
78.9
79.2
79.6
79.8
81.1
82.4
82.2
82.4
84.3
THC outlet (ppm)
69.1
69.8
72.3
75.1
74.5
72.1
71.1
70.4
72.4
72.9
72.7
70.8
69.8
68.7
69.1
68.3
70.1
69.8
69.1
70.3
68.9
69.2
69.6
70.5
71.2
71.1
72.7
71.7
70.6
69.1
68.2
68.8
69.2
68.9
68.8
68.9
68.8
69.3
69.3
702
71 2
71,8
71.5
72.5
mn2, Page 3
-------
WCI
Run 2
Date: 8/13/37
Project No.: 3804-20-03-02-01
Operator: Gulick
Time (24 hour)
1307
1308
1309
1310
1311
1312
1313
1314
1315
1316
1317
1318
1319
1320
1321
1322
1323
1324
1325
1326
1327
1328
1329
1330
1331
1332
1333
1334
1335
1336
1337
1338
1339
1340
1341
1342
1343
1344
1345
1346
1347
1348
1349
1350
THC inlet (pprn)
84.5
84.9
85.6
84,6
84.5
84.1
83.9
84.9
85.1
84.4
84.2
83.9
83.7
84.1
83.9
84.0
84.1
84.0
83.7
83.2
83.3
83.0
82.9
83.8
83.0
83.6
83.9
84.3
85.1
83.9
84.0
84.3
84,5
83.0
82.1
82.7
88.2
84.8
81.6
82.8
81.9
81.5
81.9
82.5
THC outlet (ppm)
73.0
72.7
73.5
72.8
72.i
72.4
72.2
72.7
73.1
72.6
72.0
72.3
72,2
72.3
72.3
72.4
72.5
72,6
72.4
72.1
71,8
72,1
71.8
72.1
72,1
72.0
73.0
71.9
73.7
72.7
72.3
73.0
72.7
72.0
71.0
70.9
74.7
74.4
70,6
71.8
70.6
70.7
70.3
70.9
run2, Page 4
-------
WC1
Run 2
Date: 8/13/9?
Project No.: 3804-20-03-02-01
Operator: Gulick
Time (24 hour) THC inlet (ppm)
1351
1352
1353
1354
Manual Sampling Down
(1355-1529)
1530
1531
1532
1533
1534
1535
1536
1537
1538
1539
1540
1541
1542
1543
1544
1545
1546
1547
1548
1549
1550
1551
1552
1553
1554
1555
1556
1557
1558
155i
1600
1601
1602
1603
1604
1605
1606
1607
82.1
82,2
83.1
82.3
78.9
79.4
79.2
79.9
80.7
81.7
81.4
81.1
82.7
81.8
81.8
81.8
81.1
81.2
80.5
79.5
79.1
78,1
78.0
76.7
77.1
76.3
74.8
74.0
73.4
71.3
70.4
73.2
73.2
72.8
73.2
73.8
75.5
76.6
77.9
78.5
82,6
83.6
71.0
70.5
71.0
70.7
68.5
68.9
68.8
69.2
69.9
70.8
70.8
70.0
71.2
71.1
70.6
70.6
70.3
70.5
70,1
69.3
69.1
68.3
68.4
67.6
67.6
67.8
66.8
65.9
65.7
63.4
58.2
62.7
64.5
65.0
65.3
66.1
67.3
68.5
69.4
69.7
72.0
73.6
run2, Page 5
-------
WCI
Run 2
Date: 8/13/97
Project No,; 3804-20-03-02-01
Operator: Gulick
Time (24 hour) THC inlet (ppm) THC outlet (ppm)
1608
1609
1610
1611
1612
1613
1614
1615
1616
1617
1618
1619
1620
1621
1622
1623
Process Down
(1624-1659)
1700
1701
1702
1703
1704
1705
1706
1707
1708
1709
1710
1711
1712
1713
1714
1715
1716
1717
1718
1719
1720
1721
1722
1723
1724
1725
84.9
84.3
83.6
83.7
83.2
84.7
83.8
83.2
83.1
82.9
82.5
82.1
82.0
81.2
81.1
81.6
69.5
70,8
72,7
75.0
77.4
79.9
81.9
83.7
85.2
86.7
86.0
84.1
81.6
80.0
79.2
79.5
78.8
80.6
80.0
79.7
79.3
79.4
78.3
77.8
77.2
76.8
74.3
74.2
73.8
73.1
73.2
73.6
73.1
72.8
72.3
72.3
72.2
71.7
71.7
71.1
70.9
.71.5
61.9
62.4
64.0
65.6
66.8
69.2
70.6
72.0
72.9
74.2
74.2
72.7
70.8
69.3
68.4
68.9
68.2
68.9
69.3
69.1
68.6
68.5
68.1
67.8
67.4
67.0
run2, Page 6
-------
WCI
Run 2
Date: 8/13/S7
Project No.: 3804-20-03-02-01
Operator: Gulick
Time (24 hour) THC inlet (ppm) THC outlet (ppm)
1726 76.7 66.9
1727 77.5 67.6
1728 78.6 68.5
1729 79.6 69.3
1730 80.7 70.0
1731 81.2 70.3
1732 82.7 71.8
1733 82.7 71.6
1734 83.9 71.9
1735 84.5 73.6
1736 81.9 71,4
Inlet Outlet
Minimum 69,5 58,2
Maximum 88.4 75.1
Average 81.4 70,5
run2, Page 7
-------
100
THC Concentrations vs. Time (Run 2, 8/13/97)
THC inlet (ppm)
THC outlet (ppm)
80 -
60 -
a
a
\~s
U
E
40
20
0
10
:30
11:30
12:30
13:30
14:30
15:30
16:30
17:30
Time
-------
WC1
Run 3
Date: 8/14/97
Project No, 3804-20-02-02-01
Operator: Gulick
Time (24 hour)
810
811
812
813
814
815
816
817
818
819
820
821
822
823
824
825
826
827
828
829
830
831
832
833
834
835
836
837
838
839
840
841
842
843
844
845
846
847
848
849
850
851
852
853
THC inlet (ppm)
71,5
78.2
77.1
75.2
78.3
79.1
77.0
76.9
79.3
80.8
81.6
81.7
82.3
82.9
85.2
81.7
82.8
85.1
87.6
82.4
79.4
77.9
75.7
74.6
75.2
73.9
73.5
72.8
72.5
72.4
72.9
74.7
74.7
76.5
74.6
72.6
72.5
73.2
72.7
72.8
71.7
71.8
71.7
71.2
THC outlet (ppm)
56.5
60.2
62.8
5i.5
60.5
22.3
27.9
58,8
60.6
62.4
64.0
63.1
64.6
64.2
66.1
64.8
63.5
65.1
69.1
66.2
63.0
61.0
60.5
58.5
58.9
58.5
57.8
57.9
57.2
57.0
57.2
58.5
59.7
59.8
60.2
58.0
57.1
57.7
57.8
57.8
57.5
57.0
57.0
57.2
run3, Page 1
-------
WCI
Run 3
Date: 8/14/97
Project No, 3804-20-02-02-01
Operator; Gulick
Time (24 hour)
854
855
856
857
858
859
900
901
902
903
904
905
906
907
908
909
910
911
912
913
914
915
916
917
918
919
920
921
922
923
924
925
926
927
928
929
930
931
932
933
934
935
938
937
THC inlet (ppm)
70.9
71.2
70.0
69.4
68.5
68.1
69.0
69.0
69.0
69.7
70.2
70.9
72.0
72.5
73.6
74.4
74.9
75.9
76.0
75.1
73.4
71.8
70.8
71.0
71.0
70.4
69.8
69.9
70.0
70.7
70.7
71.0
71.6
72.8
71.9
72.7
73.4
73.4
73,8
75.8
75.2
74.0
73.5
72.9
THC outlet (ppm)
56.7
56.7
56.7
55.5
55.4
54.7
55.0
55.5
55.4
56.0
56.6
56.8
57.4
57.6
58.3
58.5
58.4
68.3
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
run3, Page 2
-------
WCI
Run 3
Date: 8/14/97
Project No. 3804-20-02-02-01
Operator: Gulick
Time (24 hour)
938
939
940
941
942
943
944
945
946
947
948
949
950
951
952
953
954
955
956
957
958
959
1000
1001
1002
1003
1004
1005
1006
1007
1008
1009
1010
1011
1012
1013
1014
1015
1016
1017
1018
1019
1020
1021
THC inlet (ppm)
71.9
71,5
71.6
71.9
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
Spike
72.5
71.6
76.1
71.6
70.5
70.5
70.4
72.3
71.8
71.0
70.7
70.6
70.9
THC outlet (ppm)
Spike
Spike
Spike
56.6
55.5
55.2
54.1
53.8
52.8
53.1
53.3
53.4
53.8
53.5
54.0
53.8
54.4
55.6
55.0
55,4
55.2
56.9
57.1
58.2
57.5
56,7
57.4
58.1
58.0
58.1
57.6
59.8
58.8
62.5
61,2
57.7
58.4
57.8
58.8
59.2
58.4
57.9
57.6
58.3
mn3, Page 3
-------
WCI
Run 3
Date: 8/14/97
Project No. 3804-20-02-02-01
Operator. Gulick
Time (24 hour) THC inlet (ppm) THC outlet (ppm)
1022 70.2 56.6
1023 70.9 56.7
1024 71.1 57.4
1025 70.0 56.2
1026 69.4 56.1
1027 70.0 56.0
1028 70.3 56.2
1029 72.1 57.1
Inlet Outlet
Minimum 68.1 22.3
Maximum 87.6 69.1
Average 73,6 57.5
run3, Page 4
-------
90
THC Concentrations vs. Time (Run 3,8/14/97)
• THC inlet (ppm) -e- THC outlet (ppm)
70
50
a
Q.
Q.
N.X
u
E
30
10
-10
8:00
8:30
9:00 9:30
Time
10:00
10:30
-------
A-2 METHOD 25A CALIBRATION AND QA CHECK DATA
A-3
-------
THC1
Iniet
THC 2
Outlet
Cat Gas
Value
0.0
90.4
50.4
35.2
0.0
90.4
50.4
35.2
Measured
Value
0.0
91.0
50.7
34.7
0.1
92.4
50.8
34.8
Calibration Error Determination For 8/12/97
Difference as
%ofCalGas
0.0
0.7
0.6
1.4
0.1
2.2
0.8
1.1
Pass/ Fail
Pass
Pass
Pass
Pass
Pass
Pass
Pass
Pass
Pass/Fail Criteria is +/- 5% of Calibration gas.
Calibration Drift Determination for 8/12/97
Zero Drift
THC1
Inlet
THC2
Outlet
Initial
Value
0.0
0.1
Final
Value
-1.3
0.6
Difference as
% of Span
1.3
0.5
Pass/ Fail
Pass
Pass
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +/- 3% of Instrument Span.
Span Drift
THC1
Inlet
THC 2
Outlet
Initial
Value
91.0
92.4
Final
Value
91.4
90.6
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +1- 3% of Instrument Span.
Difference as
% of Span
0.4
1.8
Pass/ Fail
Pass
Pass
-------
Calibration Error Determination For 8/13/97
THC1
Inlet
THC2
Outlet
Cal Gas
Value
0.0
90.4
50.4
35.2
0.0
90.4
50.4
35.2
Measured
Value
0.3
90.4
49.8
34.1
0.5
91.4
50.8
35.1
Difference as
% of Cal Gas
0.3
0.0
1.2
3.1
0.5
1.1
0.8
0.3
Pass/ F
Pass
Pass
Pass
Pass
Pass
Pass
Pass
Pass
Pass/Fail Criteria is •*•/- 5% of Calibration gas.
Calibration Drift Determination for 8/13/97
Zero Drift
THC1
Inlet
THC2
Outlet
Initial
Value
0.3
0.5
Final
Value
0.0
1.8
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +/- 3% of Instrument Span.
Difference as
% of Span
0.3
1.3
Pass/ Fail
Pass
Pass
Span Drift
THC1
Inlet
THC 2
Outlet
Initial
Value
90.4
91.4
Final
Value
90.5
92.0
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +/- 3% of Instrument Span.
Difference as
% of Span
0.1
0.6
Pass/ Fail
Pass
Pass
-------
Calibration Error Determination For 8/14/97
CalGas Measured Difference as Pass/Fail
Value Value % of Cal Gas
THC1 0.0 0.3 0.3 Pass
Inlet 90.4 90.7 0.3 Pass
50.4 51.1 1.4 Pass
35.2 35.8 1.7 Pass
THC2 0.0 0.6 0.6 Pass
Outlet 90.4 91.5 1.2 Pass
50.4 50.4 0.0 Pass
35.2 34.4 2.3 Pass
Pass/Fail Criteria is +/- 5% of Calibration gas.
Calibration Drift Determination for 8/14/97
Zero Drift
Initial Final Difference as Pass/Fail
Value Value % of Span
THC1 0.3 -0.1 0.4 Pass
Inlet
THC2 0.6 0.3 0.3 Pass
Outlet
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +/- 3% of Instrument Span.
Span Drift
Initial Final Difference as Pass/Fail
Value Value % of Span
THC1 90.7 89.5 1.2 Pass
Inlet
THC 2 91.5 90.5 1.0 Pass
Outlet
Instrument Span for THC 1 and THC 2 is 100 ppm.
Pass/Fail Criteria is +/- 3% of Instrument Span.
-------
Response Times
THC 1 47 seconds
Inlet
THC 2 55 seconds
Outlet
-------
A-3 VOLUMETRIC FLOW DATA
A-4
-------
08/1 2/9t
.Sta<*. /''••;' v
Date:
Location;.
Run
Total Sampling time (mln)
Corrected Barometric Pressure (In Hg)
Absolute Stack Pressure (In H2O)
Stack Static Pressure (in H2O)
Average Stack Temperature (°F)
Stack Area (sq In)
Actual Meter Volume (cu ft)
Average Meter Pressure (In H2O)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (In)
Pilot Constant
Average Sampling Rate (dscfrn)
Standard Metered Volume (dtcf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isoklnette
Percent Excess, Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/hr)
240.0
29.26
29.23
-0.40
246.09
9160,88
224.695
2.77
99.06
368.50
3,5
17.5
79.0
0.9880
0.193
0.84
0.860
206.501
5.848
7.76
0.922
29,26
28.39
6473.79
1973,21
411844.44
11683.43
277479.87
7858.23
97.10
519.01
0.00
0.00
0.00
0.00
-------
C,- 3RXP;iJ- 3-97 ; 5:'1PM :
3134511573-
acility:
Date;
Location; . <.
Run Nuffibid !
WCl '
Qfl/W87
-SladC' ,'-.'•'
Total Sampling Time (min)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (In H2O)
Stack Static Pressure (In H2O)
Average Stack Temperature (*F)
Stack Area (sq in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H2O)
Average Meter Temperature (*F)
Moisture Collected (a)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pitot Constant
Average Sampling Rate (dscfm)
Standard Metered Volume (dsef)
Standard Metered Volume (d«cm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isoklnetic
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissioni (Ib/hr)
240.0
29,00
29.04
0.60
238.50
9160.88
213.980
2.55
77.34
341.00
3,5
17.§
79.0
0,9680
0.193
0.84
0.844
202.664
5.739
7.35
0.928
29,29
28.43
6326.64
1928.38
402483.68
11398.34
273586.26
7747.96
96.65
519,01
0.00
0.00
0.00
0.00
-------
SEN
EARCH 3RCUPMG- 3-97 : SM'PM
9196773065;* 4
Location:..; Stack
Run NumJiirF"" "':,-.;
Sample Type: Metals
Total Sampling Time (min)
Corrected Barometric Pressure (In Hg)
Absolute Stack Pressure (in H2O)
Stack static Pressure (In H2O)
Average Stack Temperature (*F)
Stack Area (sq in)
Actual Meter Volume (eu ft)
Average Meter Pressure (in H20)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pltot Constant
Average Sampling Rate (dsctm)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gat Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isokinetlc
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emisalona Hb/hr)
240,0
29,04
29.08
0.00
230.91
9160.88
209.8S5
2.48
86.61
283,00
3.S
1?.S
7i.O
0.9880
0.193
0.84
0,815
195.872
5.541
6.38
0.936
29,26
28.54
6224.21
1897.14
395967.06
11213.79
275333.02
7797.43
92.72
519.01
0.00
0.00
0,00
0.00
-------
SEN: 3v:EAS""ERN RESEARCH 3ROUP;iQ- 3-97 : 5:12PM
i1i4611579-
i'3677QQ65;S 5
Facility: WCI
Date; -Li, 08/12/07— ,; , -
Location: iN/Inlef.
Run Number: 1
SamDJety&ej. Metal* ..' am ,
Total Sampling Time (min)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (in H20)
Average Stack Temperature (*F)
Stack Area (sq In)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H20)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pftot Constant
Average Sampling Rate (dscfm)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isoklnetlc
Percent Excess Air
Concentration (g/dicm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/hr)
240,0
29,30
27.08
-30.00
257.53
9160.88
107.497
0.87
90.61
140.10
2.0
18.5
79.5
0.9840
0.150
0.84
0.415
99.613
2,821
8.22
0.938
29.06
28.37
5375.30
1638.39
341962.03
9664.36
213664.28
6050.97
100,70
738.85
0.00
0.00
0.00
0.00
-------
SEN" 3Y:EASTERN RESEARCH jROUPMQ- 3-9?
3134511573-
Facility:
Dater : . r
Location: ••
Run Number; -
WCI
Total Sampling Time (min)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (In H2O)
Stack Static Pressure (in H20)
Average Stack Temperature (9F)
Stack Area (sq in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H20)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pilot Constant
Average Sampling Rate (dscfm)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gaa
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isokinetlc
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/hrt
240,0
29,06
26,85
-30.00
218,96
9160.88
104.344
0.58
78,21
111.60
2.0
18.5
79,5
0.9840
0.150
0.84
0.408
97.867
2,772
5.10
0,949
29.06
28.50
4821.75
1469.67
306746,70
8687.07
203150.98
5753,24
104,06
738.85
0,00
0.00
0,00
0.00
-------
SENT 3v:EA5~ERN RESEARCH 2ROUPJ10- 8-97 ; 5M3PM
9194611579-
919B770C65:» 7
08/1,4/W1
Facility: ;:
Date: •!•:,••
Location:
Run Numbers
Sample. Tvce; Metala.:.
Total Sampling Time (min)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (in H2O)
Average Stack Temperature (*F)
Stack Area (sq In)
Actual Meter Volume (cu ft)
Average Meter Pressure (In H2O)
Average Meter Temperature (°F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pilot Constant
Average Sampling Rate (dscfm)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gaa
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dscmm)
Percent Isokinetic
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/hr)
240.0
29.10
28.89
-30.00
216.67
9180.88
109.508
0.81
80.08
157.20
2.0
18.0
80.0
0.9840
0.150
0.84
0.430
103.200
2.923
6.70
0.933
29.04
28.30
5116.05
1559.37
325469.09
9217.26
212954.17
6030.86
104.66
573.98
0.00
0.00
0.00
0.00
-------
SENT SY: EASTERN RESEARC,- aRCUPHO- 8-97 : 5: UPM
Facility:
Date;
Location: - . Stack
RunNumbeY;,,;
Total Sampling Time (min) 240 0
Corrected Barometric Pressure (In Hg) 29 26
Absolute Stack Pressure (In H2O) 29 26
Stack Static Pressure (in H2O) .Q 04
Average Stack Temperature (*F) 25019
Stack Area (tq in) 9160*88
Actual Meter Volume (cu ft) 228.017
Average Meter Pressure (in H2O) 2,63
Average Meter Temperature (*F) 99*53
Moisture Collected (g) 34140
Carbon Dioxide Concentration (%V) 0.5
Oxygen Concentration (%V) 20.5
Nitrogen Concentration (%V) 79,0
Dry Gas Meter Factor 0.9960
Nozzle Diameter (in) 0.193
Pltot Constant 0.84
Average Sampling Rate (dscfm) 0.878
Standard Metered Volume (dscf) 210.832
Standard Metered Volume (dscm) 5.971
Stack Moisture (%V) 7,09
Mote Fraction Dry Stack Gas 0.929
Dry Molecular Weight 28.90
Wet Molecular Weight 28.13
Stack Gas Velocity (fpm) 6452.52
Stack Gas Velocity (mpm) 1966.73
Volumetric Flow Rate (acfm) 410491.39
Volumetric Flow Rate (acmm) 11625.12
Volumetric Flow Rate (dscfm) 277213.98
Volumetric Flow Rate (dtcrnm) 7850.70
Percent laokinetic 99.23
Percent Excess Air 5513.72
Concentration (g/dscm) 0.00
Concentration (kg/hr) 0.00
Concentration (ppmv) 0.00
Emissions (Ib/hrt : 0.00
-------
S£NT 3v: EASTERN RESEARCH 3ROUFMO- 8-37 J 5: UPH ;
3194611573-
S'3677Q065;» 3
Facility; ,
Date;
Location: ',
Run Numb
vci
Total Sampling Time (mln)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (in H2O)
Average Stack Temperature (*F)
Stack Area (sq in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H2O)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (In)
Pttot Contttnt
Average Sampling Rate (dscfm)
Standard Metered Volume (dtcf)
Standard Metered Volume (daem)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gaa Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dicfm)
Volumetric Flow Rate (dacmm)
Percent Isokinetic
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/Tir)
120.0
29,00
29,04
0.60
24S.89
9160,88
107.856
2.27
79,38
148.70
0,5
20,5
79.0
0,9960
0.193
0.84
0.854
102.513
2,903
6.32
0,937
26.90
28.21
6188.65
1886.30
393704,79
11149.72
267835.10
7585.09
99.88
5513.72
0.00
0.00
0.00
0.00
-------
SEN' 3Y:EASTERN '.ESEARCh 3RGUP;'Q- 8-87 : 5:15PM
I1S161157S-
91i671Q355;«10
aeiitty: •,-•--
Dati; "£•-
Locaitim ""':
Run Number!
Sample Type*
WCI
y'WW.
Total Sampling Time (mln)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (In H2O)
Average Stack Temperature ("F)
Stack Area (so; in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H20)
Average Meter Temperature (*F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Phot Constant
Average Sampling Rate (dscfm)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dscfm)
Volumetric Flow Rate (dicmm)
Percent Isokinetlc
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (IWhrt
240.0
29,00
29,04
0,60
233.63
§160,88
224.147
2,53
81,05
3S8.40
3.5
17.5
79.0
0.9960
0,193
0.84
0.886
212.543
8.019
7.37
0,926
29,26
28.43
8249,71
1904,91
397589.40
11259.73
272118.18
7706.33
101.91
519.01
0.00
0.00
0.00
0.00
-------
SENT 3Y:cA5T£RN RESEARCH GROUP!10- 8-97 : 5'ISPM
9134611579-
319677C065;*M
Date; :;•„.!• .Oad^Sl?^-.,,,?^./^,-;'.'-" .':;:-- i-v/^X .-•... • -. • ,.
loeationr^Stiffiiir^ - '•' ,-• •; ''•?... ' ,'' .
RunNymbA-^«^^ ; --.=•-, • .- •
SimDte;l^:t3Joxla:vV/1t^,--'-:'J!:.;.: ::•,_ ' ;•*$ m; ,,; ; '; , • • :
Total Sampling Time (min)
Corrected Barometric Pressure (In Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (In H2O)
Average Stack Temperature (*F)
Stack Area (sq in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H20)
Average Meter Temperature ("F)
Moisture Collected (g)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pttot Constant
Average Sampling Rate (dscfm)
Standard Mete red Volume (dscf)
Standard Metered Volume (dscrn)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (daefmj
Volumetric Flow Rate (dscmm)
Percent Isokinetic
Percent Excess Air
Concentration (g/dscrn)
Concentration (kg/hr)
Concentration (ppmv)
Emissions (Ib/hrt
240.0
29.04
29.08
0.60
235.66
9160.88
222.820
2.51
89,59
310.80
3.5
17.S
79.0
0.9960
0.193
0.84
0.868
208.287
5.899
8.67
0.934
29.26
28.52
6245.02
1903.48
397290.73
11251,27
273811.90
77S4.35
99.25
519.01
0.00
0.00
0.00
0.00
-------
SEN" 3Y:£A5~=SN RESEARO 3ROUP;10- 3-97 : 5:15PM
9194511579-
9196770Q65:»'.2
acility;
Dite;: • 'f',H
Locatlortir
Run Number
WCI
Total Sampling Time (mm)
Corrected Barometric Pressure (in Hg)
Absolute Stack Pressure (in H2O)
Stack Static Pressure (In H2O)
Average Stack Temperature (T)
Stack Area (sq in)
Actual Meter Volume (cu ft)
Average Meter Pressure (in H2O)
Average Meter Temperature (*F)
Moisture Collected (fl)
Carbon Dioxide Concentration (%V)
Oxygen Concentration (%V)
Nitrogen Concentration (%V)
Dry Gas Meter Factor
Nozzle Diameter (in)
Pitot Constant
Average Sampling Rate (dscfrn)
Standard Metered Volume (dscf)
Standard Metered Volume (dscm)
Stack Moisture (%V)
Mole Fraction Dry Stack Gas
Dry Molecular Weight
Wet Molecular Weight
Stack Gas Velocity (fpm)
Stack Gas Velocity (mpm)
Volumetric Flow Rate (acfm)
Volumetric Flow Rate (acmm)
Volumetric Flow Rate (dadm)
Volumetric Flow Rate (dscmm)
Percent Isokinetic
Percent Excess Air
Concentration (g/dscm)
Concentration (kg/nr)
Concentration (ppmv)
Emissions (ib/hr)
240,0
28.96
29.00
0.60
232,06
9160.88
222.592
2.41
86.34
297,40
3.5
17.5
79.0
0.9960
0.193
0.84
0.869
208.642
5.909
6.30
0.937
29.26
28.55
6112.46
1863.08
388858,13
11012.46
269443.87
7830,65
101.03
519.01
0,00
0.00
0.00
0.00
-------
APPENDIX B
FTDR DATA
B-l
-------
B-1FTIR RESULTS
B-2
-------
TABLE B-l. FTIR RESULTS (ppm) AT THE WCI BAGHOUSE INLET
Date
8/12/97
Time
10:35
10:37
10:41
10:43
10:53
11:00
11:02
11:05
11:07
13:32
13:34
13:37
13:39
13:41
13:43
13:46
13:48
13:50
13:53
13:55
13:57
13:59
14:01
14:03
14:05
14:32
File Name"'b
ISM11A
IS0811B
IS0811C
IS08UD
IU0811A
IU0811B
IU0811C
IU0811D
IU0811E
18120022
18120023
18120024
18120025
18120026
18120027
18120028
18120029
18120030
18120031
18120032
18120033
18120034
18120035
18120036
18120037
18120049
Toluene Unc c
26.2 1.6
26.1 1.6
25.9 1.5
25.8 1.5
6.2 1.6
6.9 1.8
7.5 2.1
7.7 2.2
7.8 2.2
5.5 2.3
5.5 2.3
5.3 2.3
5.1 2.3
5.0 2.3
5.3 2.3
5.5 2.3
5.4 2.3
5.2 2.3
5.2 2.3
5.0 2.3
4.9 2.3
5.2 2.3
5.0 2.3
4.9 2.3
4.9 2.3
3.9 2.4
Hexane Unc
6.1 0.19
5.9 0.19
5.6 0.19
5.4 0.19
6.1 0.20
7.2 0.22
8.3 0.48
9.0 0.50
9 3 0.50
11.3 0.52
11.2 0.52
11.1 0.52
11.1 0.52
11.2 0.52
11.3 0.53
11.6 0.53
11.7 0.53
11.7 0.53
11.6 0.53
11.5 0.53
11.5 0.53
11.6 0.54
11.8 0.54
11.8 0.54
11.8 0.54
11.5 0.55
Ethylene Unc
35 0.75
3.1 0.75
2.9 0.74
2.8 0.73
3.5 0.72
4.1 0.76
4.9 0.83
5.2 0.86
5.3 0.87
6.3 0.92
6.1 0.91
5.9 0.90
5.9 0.90
5.9 0.90
6.0 0.90
6.2 0.92
6.2 0.91
6.1 0.91
6.1 0.90
6.0 0.90
6.0 0.90
6.1 0.91
6.1 0.91
6.1 0.91
6.1 0.91
6.4 0.93
Methane Unc
*OJ 1.1
78.1 1.1
75.7 1.0
72.4 1.0
80.6 1.1
96.4 1.2
1131 13
119.2 1.4
122.5 1.4
129.2 1.5
126.5 1.4
125.6 1 4
125.0 1.4
124.9 1.4
126.1 1.5
129.6 1.5
129.0 1.5
128.4 1.5
127.9 1.5
126.4 1.5
127.0 1.5
128.2 1.5
130.4 1.5
131.1 1.5
131.1 1.5
132.0 1.5
SO2 Unc
115.0 IS
114.7 2.9
106.6 2.9
101.4 2.9
115.6 3.1
140.3 3.3
168.9 3.6
176.6 3.7
183.7 3.7
196.2 3.9
191.1 3.9
181.8 3.8
174.5 3.8
167.8 3.8
167.3 3.8
175.4 3.9
181.8 3.9
187.0 3.9
184.7 3.9
179.8 3 8
178.0 3.9
176.1 3.9
173.3 3.9
176.1 3.9
177.8 3.9
164.1 4.0
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/12/97
Time
14:34
14:36
14:37
14:40
14:42
14:44
14.46
14:48
14:50
14:52
14:54
14:57
14:59
15:01
15:03
15:05
15:07
15:09
16:48
16:50
16:52
16:54
16:56
16:58
17:00
17:02
File Name1'1"
18120050
18120051
18120052
18120053
18120054
18120055
18120056
18120057
18120058
18120059
18120060
18120061
18120062
18120063
18120064
18120065
18120066
18120067
18120091
18120092
18120093
18120094
18120095
18120096
18120097
18120098
Toluene Unc c
3.8 2.4
3.8 2.4
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.8
0.0 2.8
0.0 2.8
0.0 2.8
0.0 2.8
0.0 2.8
0.0 3.8
0.0 3.7
Hexane Unc
11.6 0.55
11.8 0.55
11.5 0.54
11.3 0.54
11.2 0.54
11.1 0.54
11.2 0.54
11.4 0.54
11.3 0.54
11.1 0.54
11.0 0.54
10.9 0.54
10.8 0.53 '
10.9 0.54
11.0 0.54
11.1 0.54
11.1 0.54
11.3 0.54
12.3 0.59
12.6 0.60
12.6 0.59
12.4 0.59
12.3 0.59
12.0 0.58
11.9 0.27
10.8 0.27
Ethylene Unc
6.4 0.93
6.4 0.93
6.3 0.93
6.1 0.93
6.1 0.93
5.9 0.91
6.0 0.91
6.1 0.92
6.1 0.92
6.0 0.92
5.9 0.91
5.8 0.91
5.7 0.90
5.8 0.91
5.9 0.91
5.9 0.91
6.0 0.92
6.0 0.92
6.3 1.0
6.5 1.0
6.5 1.0
6.3 1.0
6.2 1.0
5.9 0.95
4.9 0.91
4.2 0.88
Methane Unc
133.1 1.5
134.8 1.5
130.6 1.5
131.4 1.5
129.6 1.5
125.1 1.5
126.3 1.5
128.5 1.5
128.3 1.5
126.7 1.5
125.7 1.5
124.5 1.5
123.9 1.5
125.7 1.5
126.6 1.5
128.3 1.5
128.9 1.5
129.3 1.5
130.3 1.7
134.6 1.7
133.8 1.7
129.7 1.7
128.3 1.7
128.1 1.6
128.4 1.6
120.9 1.5
SO2 Unc
168.7 4.0
176.3 4.0
182.6 4.0
178.0 3.9
176.0 3.9
171.2 3.9
173.5 3.9
179.3 3.9
175.4 3.9
172.2 3.9
179.1 3.9
183.4 3.9
179.1 3.9
179.5 3.9
177.5 3.9
176.3 3.9
172.1 3.9
167.7 3.9
182.4 4.1
193.2 4.2
206.5 4.2
2120 4.1
214.2 4.1
206.2 4.0
136.0 3.9
99.9 3.8
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/12/97
Time
17:05
17:07
17:09
17:11
17:13
17:15
17:17
17:20
17:22
17:24
17:26
17:28
17:30
17:32
17:34
17:37
17:39
17:41
17:43
17:45
17:47
17:49
17:52
17:54
18:19
18:21
File Name16
18120099
18120100
18120101
18120102
18120103
18120104
18120105
18120106
18120107
18120108
18120109
18120110
18120111
18120112
18120113
18120114
18120115
18120116
18120117
18120118
18120119
18120120
18120121
18120122
18120134
18120135
Toluene Unc c
0.0 3.6
0.0 3.6
0.0 3.6
0.0 3.6
0.0 3.7
0.0 3.7
0.0 3.8
0.0 3.8
0.0 3.8
0.0 3.9
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.1
0.0 4.1
0.0 4.1
0.0 4.1
0.0 4.0
0.0 3.9
0.0 3.9
0.0 3.9
0.0 4.0
0.0 3.7
0.0 3.7
Hexane Unc
10.1 0.27
10.0 0.26
10.1 0.26
10.3 0.26
10.6 0.27
10.9 0.27
10.9 0.28
11.1 0.27
11.4 0.28
11.8 0.28
12.1 0.29
12.4 0.29
12.5 0.29
12.2 0.29
12.2 0.29
12.5 0.29
12.8 0.30
12.7 0.29
12.2 0.29
11.7 0.29
11.4 0.29
11.2 0.29
11.3 0.29
11.4 0.29
9.9 0.28
9.9 0.28
Ethylene Unc
4.4 0.87
4.4 0.87
4.5 0.87
4.6 0.88
4.9 0.89
5.0 0.90
5.0 0.90
5.1 0.89
5.4 0.91
5.6 0.92
5.8 0.94
5.9 0.95
6.0 0.95
5.8 0.94
5.9 0.94
6.2 1.0
6.2 1.0
6.1 1.0
5.8 0.95
5.6 0.93
5.4 0.93
5.4 0.93
5.4 0.93
5.5 0.94
4.9 0.89
5.0 0.89
Methane Unc
112.8 1.5
107.0 1.5
105.5 1.5
105.9 1.5
108.9 1.5
111.4 1.6
113.4 1.6
114.4 1.6
117.9 1.6
120.5 1.6
122.6 1.6
124.9 1.6
124.9 1.6
122.2 1.6
123.1 1.6
129.5 1.7
130.8 1.7
128.5 1.7
123.7 1.7
118.9 1.6
115.7 1.6
114.7 1.6
116.0 1.6
116.9 1.6
103.8 1.6
105.0 1.6
SO2 Unc
162.8 3.7
191.6 3.7
193.1 3.7
189.1 3.7
182.0 3.8
172.5 3.9
160.2 3.8
150.9 3.8
150.9 3 9
152.6 3.9
161.9 40
185.0 4.0
200.5 4.0
186.1 4.0
172.2 4.0
172 1 41
181.6 4.1
186.1 4.1
175.7 4.1
162.2 4.0
150.7 3.9
146.7 3.9
144.0 4.0
135.8 4.0
153.1 3.8
154.6 3.8
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/12/97
Time
18:24
18:26
18:28
18:30
18:32
18:34
18:36
18:38
18:41
18:43
18:45
18:47
18:49
18:51
18:53
18:56
18:58
19:00
19:02
19:04
19:08
19:10
19:13
19:15
19:17
19:19
File Name'- b
18120136
18120137
18120138
18120139
18120140
18120141
18120142
18120143
18120144
18120145
18120146
18120147
18120148
18120149
18120150
18120151
18120152
18120153
18120154
18120155
18120156
18120157
18120158
18120159
18120160
18120161
Toluene Unc c
0.0 3.9
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.1
0.0 4.1
0.0 4.1
0.0 4.0
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3.9
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
Hexane Unc
10.9 0.28
11.6 0.29
11.9 0.29
11.8 0.29
11.9 0.29
12.0 0.29
12.0 0.30
12.0 0.30
11.8 0.30
11.5 0.30
11.2 0.29
10.9 0.29
10.9 0.29
10.8 0.29
10.3 0.29
10.6 0.29
10.5 0.29
10.6 0.29
11.1 029
11.5 0.30
11.5 0.30
11.5 0.30
11.4 0.30
11.2 0.30
11.2 0.29
11.2 0.29
Ethylene Unc
5.3 0.91
5.6 0.93
5.7 0.94
5.6 0.93
5.7 0.94
5.7 0.94
5.8 0.95
5.8 1.0
5.7 0.95
5.5 0.94
5.2 0.92
5.1 0.92
5.1 0.92
5.1 0.92
5.2 0.92
5.4 0.93
5.3 0.92
5.5 0.93
5.7 0.95
5.9 1.0
5.9 1.0
5.8 10
5.7 1.0
5.7 1.0
5.7 0.95
5.6 0.95
Methane Unc
112.8 1.6
118.8 1.6
119.3 1.7
117.9 1.6
118.3 1.7
119.3 1.7
120.4 1.7
120.7 1.7
119.6 1.7
117.5 1.7
113.4 1.7
111.6 16
112.2 1.7
112.1 1.7
110.1 1.6
114.1 1.6
111.2 1.6
113.6 1.7
117.2 1.7
121.0 1.7
119.0 1.7
118.8 1.7
116.8 1.7
116.8 1.7
115.8 1.7
114.9 1.7
SO2 Unc
167.9 3.9
181.6 4.0
183.6 4.0
181.2 4.0
178.6 4.0
173.7 4.0
174.4 4.0
176.9 4.1
181.9 4.0
179.9 4.0
171.0 3.9
164.2 3.9
161.6 3.9
159.1 3.9
167.3 3.9
180.2 4.0
169.5 3.9
161.6 4.0
163.2 4.0
164.9 4.1
166.5 4.1
166.0 4.1
168.6 4.1
169.6 4.1
180.6 4 0
189.3 4.0
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/12/97
Time
19:21
19:23
19:25
19:28
19:30
19:32
19:34
19:36
19:38
19:40
19:42
19:45
File Name1- b
18120162
18120163
18120164
18120165
18120166
18120167
18120168
18120169
18120170
18120171
18120172
18120)73
8/12/97 Average— >
Toluene Unc c
0.0 3.9
0.0 3.9
0.0 3.9
0.0 3,9
0.0 3.9
0.0 3.9
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.0 4.0
0.9 3.4
Hexane Une
11.0 0.29'
11.0 0.29
11.1 0.29
11,1 0.29
11.4 0.29
11.9 0.29
12.0 0.29
12.1 0.29
12.1 0.30
12.1 0.30
12.0 0.30
11.9 0.30
11.4 0.39
Ethylene Unc
5,5 0.94
5.5 0.94
5.5 0.93
5.5 0.93
5.6 0.94
5,6 0.94
5.7 0.94
5.7 0.94
5.7 0.94
5.7 0.94
5.7 0,94
5.7 0.94
5.7 0.93
Methane Unc
113.3 1.7
112.8 1.7
113,1 1.7
114.0 1.7
115,9 1.7
117.9 1.7
119.2 1.7
120.2 1.7
120.6 1.7
120.6 1.7
119.5 1.7
119,6 1.7
121.4 1.6
SO2 Unc
187.2 4.0
178.0 4:0
171.1 4.0
171.6 4.0
181.6 4.0
187.3 4.0
188.3 4.0
191.3 4.0
194.0 4,0
195.8 4.0
195.0 4.0
194.9 4,0
175.2 3.9
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/13/97
Time
9:30
9:36
9:42
9:45
10:00
10:06
10:11
10:16
11:23
11:25
11:28
11:30
11:32
11:34
11:36
11:38
11:40
11:42
11:45
11:47
11:49
11:51
11:53
12:43
12:45
12:48
File Name"- b
IU0813A
IU0813B
IU0813C
IU0813D
ISOS13A
ISOS13B
IS0813C
IS0813D
18130001
18130002
18130003
18130004
18130005
18130006
18130007
18130008
18130009
18130010
18130011
18130012
18130013
18130014
18130015
18130038
18130039
18130040
Toluene Unc c
9.3 2.1
9.8 2.1
9.7 2.1
9.5 2.1
43.9 M
44.3 1.6
43.8 1.6
43.4 1.6
7.7 2.3
7.5 2.3
7.2 2.3
6.9 2.3
6.8 2.3
6.6 2.3
6.7 2.3
6.6 2.3
6.6 2.3
6.5 2.3
6.5 2.3
6.6 2.3
6.7 2.3
6.5 2.3
6.4 2.3
4.9 2.3
4.7 2.3
4.6 2.3
Hexane Unc
8.4 0.47
9.0 0.49
9.3 0.49
9.3 0.49
6.8 0.41
6.9 0.20
6.8 OJO
6.6 OJO
11.2 0.53
11.1 0.54
11.0 0.53
10.9 0.53
10.7 0.53
10.7 0.53
10.8 0.52
10.8 0.52
10.8 0.52
10.9 0.52
11.0 0.53
11.1 0.53
11.1 0.53
11.1 0.53
11.2 0.53
10.7 0.53
10.9 0.53
11.1 0.53
Ethylene Unc
5.4 0.83
5.7 0.85
5.7 0.86
5.7 0.86
3.2 0.78
3.1 0.77
3.0 0.77
2.9 0.77
6.7 0.93
6.6 0.91
6.4 0.91
6.3 0.91
6.2 0.90
6.2 0.90
6.3 0.90
6.4 0.90
6.3 0.90
6.3 0.90
6.5 0.90
6.5 0.91
6.5 0.91
6.5 0.91
6.5 0.91
6.3 0.91
6.3 0.91
6.4 0.92
Methane Unc
110.3 1.3
113.9 1.3
113.8 1.3
112.3 1.3
81.4 1.1
81.1 1.1
803 1.1
78.6 1.1
131.5 1.5
129.5 1.5
129.7 1.5
127.8 1.5
125.1 1.5
124.3 1.5
124.0 1.5
123.7 1.5
124.4 1.5
124.8 1.5
127.8 1.5
129.0 1.5
128.9 1.5
130.9 1.5
129.9 1.5
126.6 1.5
125.6 1.5
128.1 1.5
S02 Unc
127.9 3.6
127.1 3.6
138.2 3.7
146.2 3.7
115.4 3.0
108.6 3.0
109.3 3.0
104.4 3.0
204.2 3.9
202.0 3.9
192.4 3.9
184.4 3.9
179.2 3.9
184.8 3.9
188.1 3.9
187.3 3.9
184.2 3.8
182 1 3.9
179.4 3.9
181.2 3.9
181.0 3.9
184.6 3.9
192.3 3.9
170.2 3.9
167.5 3.9
174.3 3.9
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Dale
8/13/97
Time
12:50
12:52
12:54
12:56
12:58
13:00
13:02
15:53
15:55
15:57
16:00
16:04
File Name* *
18130041
18130042
18130043
18130044
18130045
18130046
18130047
18130094
18130095
18130096
18130097
18130098
8/13/97 Average -->
Toluene Unc c
4.6 2.4
4.5 23
4.2 2.3
4.1 2.3
3.9 2.3
4.0 2.3
40 23
0.0 2.5
0.00 2.5
0.00 2.5
0.00 2.6
00 27
4.8 2.4
Hexane Unc
11.2 0.54
11.1 0.54
11.0 0.53
10.9 0.53
10.8 0.53
10.9 0.53
10.9 0.54
10.4 0.25
9.8 0.25
9.5 0.25
9.9 0.26
10.5 0.28
108 0.49
Ethylene Unc
6.5 0.92
6.5 0.92
6.3 0.91
6.3 0.90
6.3 0.90
6.3 0.90
6.3 0.91
6.0 0.88
5.7 0,86
5.6 0.86
5.8 0.88
5.9 I.I
6.3 0.91
Methane Unc
130.7 1.5
128.2 1.5
125.1 1.5
125.0 1.5
124.7 1.5
125.0 1.5
126.2 1.5
116.8 1.4
110.9 1.4
109.6 1.5
114.7 1.5
121.6 1.6
125.0 1.5
SO2 Unc
181.9 3.9
195.2 3.9
193.3 3.9
183.9 3.9
183.0 3.9
185.2 3.9
185.5 3.9
169.3 3.8
162.3 3.7
162.7 3.7
174.2 3.8
181.9 4.2
182.6 3.9
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/14/97
8/14/97
Spike On
Spike Off
Time
8:32
8:34
8:36
8:38
8:40
8:42
8:50
8:52
8:54
8:56
8:59
9:36
9:38
9:40
9:42
9:44
9:46
9:48
9:50
9:53
9:55
9:57
9:59
10:01
10:03
10:05
File Name1"
18140001
18140002
18140003
18140004
18140005
18140006
18140007
18140008
18140009
18140010
18140011
18140028
18140029
18140030
18140031
18140032
18140033
18140034
18140035
18140036
18140037
18140038
18140039
18140040
18140041
18140042
Toluene Unc c
12.1 1.9
11.7 2.1
11.7 2.1
11.6 2.1
11.4 2.1
11.4 2.1
10.8 2.1
10.7 2.1
10.4 2.1
10.3 2.1
10.0 2.0
9.0 2.0
8.7 2.0
8.4 2.0
8.8 1.9
7.4 1.8
24-3 1.7
36.9 1.5
39.6 1.5
40.2 1.5
40.4 IS
403 IS
23.6 1.7
10.0 1.8
7.1 1.8
6.5 1.8
Hexane Unc
8.5 0.23
8.6 0.49
8.8 0.48
8.8 0.48
8.9 0.48
9.1 0.49
9.1 0.48
9.1 0.48
9.0 0.47
9.0 0.47
8.8 0.47
9.1 0.24
9.0 0.24
8.9 0.24
8.8 0.24
8.1 0.23
64 0.20
5.7 0.19
5.4 0.19
53 0.1»
53 0.19
53 0.1»
6.4 0.21
7.4 0.22
7.7 0.23
7.9 0.23
Ethylene Unc
7.5 0.86
6.2 0.87
5.8 0.87
5.7 0.86
5.7 0.86
5.8 0.86
5.6 0.85
5.5 0.84
5.4 0.84
5.4 0.84
5.3 0.83
5.6 0.97
5.5 0.97
5.5 0.96
5.2 0.94
4.7 0.90
3.5 041
2.8 0.75
2.6 0.74
2.6 0.74
1.6 0.74
2.6 0.74
3.6 0.81
4.5 0.87
4.7 0.87
5.1 0.79
Methane Unc
111.6 1.3
112.8 1.3
111.5 1.3
109.8 1.3
109.4 1.3
112.6 1.3
107.9 1.3
107.1 1.3
106.3 1.3
105.2 1.3
102.8 1.3
113.2 1.4
109.9 1.3
107.6 1.3
103.6 13
94.2 13
77.1 1.1
66* 1.0
64.9 1.0
64.5 1.0
65.0 1.0
65.7 1.0
79.7 1.1
92.5 1.2
93.6 1.3
94.9 1.3
SO2 Unc
133.9 3.7
142.7 3.7
144.0 3.7
141.0 3.7
135.1 3.7
132.2 3.7
141.5 3.6
151.3 3.6
164.0 3.6
167.4 3.6
154.6 3.5
147.5 3.7
158.9 3.7
162.4 3.7
158.9 3.6
149.6 3.5
121.9 3.1
101.0 2.9
93.4 2.9
92.5 2.9
93.8 2.8
94.7 24
1173 3.1
1333 3.4
136.8 3.4
139.1 3.4
-------
TABLE B-l. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Inlet Results)
Date
8/14/97
Time
10:08
10:10
10:12
File Name*1'
18140043
18140044
18140045
8/14/J7 Avemge— >
Toluene Unc s
6.4 1.9
73 2.0
7.6 2.0
9.6 2.0
Hexane Unc
8.1 0.23
8.9 0.24
9.3 0.25
8.8 0.36
Ethylene Unc
5.2 0.80
5.7 0.83
5.9 0.85
5.6 0.86
Methane Unc
97.4 1.3
108.2 1.3
116.0 1.4
107.3 1.3
SO2 Unc
146.7 3.4
162.4 3.6
164.1 3.6
148.7 3.6
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/12/97
Time
10:35
10:37
10:41
10:43
10:53
11:00
11:02
11:05
11:07
13:32
13:34
13:37
13:39
13:41
13:43
13:46
13:48
13:50
13:53
13:55
13:57
13:59
14:01
14:03
14:05
14:32
File Name 1-b
ISOtllA
ISM11B
ISMUC
ISMUD
IU0811A
IU0811B
IU0811C
IU0811D
IU0811E
18120022
18120023
18120024
18120025
18120026
18120027
18120028
18120029
18120030
18120031
18120032
18120033
18120034
18120035
18120036
18120037
18120049
CO Unc c
1202 22.5
1183 22.1
1153 21 J
1132 20 J
1 186 22.7
1308 26.0
1456 31.2
1507 33.4
1531 34.4
1588 36.5
1566 35.7
1556 35.2
1554 35.3
1553 35.4
1559 35.7
1579 36.7
1580 36.5
1585 36.7
1572 36.3
1559 35.9
1569 36.2
1578 36.5
1583 36.8
1583 36.8
1574 36.4
1563 36.8
Ammonia Unc
0.0 0.4
0.0 0.4
0.0 0.4
0.0 0.4
0.0 0.4
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
5.6 0.5
4.6 0.5
4.1 0.5
3.9 0.5
4.0 0.5
4.3 0.5
4.9 0.5
5.4 0.5
5.5 0.5
5.0 0.5
4.5 0.5
4.6 0.5
4.6 0.5
4.7 0.5
5.0 0.5
5.6 0.5
6.7 0.6
Formal-
dehyde Unc
S3 1.0
5.1 1.0
5.0 0.9
4.8 0.9
5.8 1.0
70 1.1
7.9 1.2
8.7 1.2
9.5 1.2
5.6 1.3
5.6 1.3
5.6 1.3
5.7 1.3
5.7 1.3
5.6 1.3
5.7 1.3
5.7 1.3
5.8 1.3
5.7 1.3
5.7 1.3
5.9 1.3
5.7 1.3
5.7 1.3
5.7 1.3
5.6 1.3
4.8 1.4
HC1 Unc
0.0 2.4
0.0 2.4
0.0 2J
0.0 2J
0.0 2.4
0.0 2.6
0.0 2.9
0.0 3.0
0.0 3.0
0.0 3.1
0.0 3.1
0.0 3.0
0.0 3.0
0.0 3.0
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
3.5 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
2-Methyl-
2-butene Unc
0.0 1.1
0.0 1.1
0.0 1.1
0.0 1.0
0.0 1.1
0.0 1.2
1.8 1.3
2.3 1.3
2.6 1.3
2.7 1.4
2.4 1.4
2.3 1.4
2.3 1.4
2.3 14
2.3 1.4
2.5 1.4
2.6 1.4
2.5 1.4
2.4 1.4
2.3 1.4
2.4 1.4
2.6 1.4
2.5 1.4
2.6 1.4
2.4 1.4
2.1 1.5
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/12/97
Time
14:34
14:36
14:37
14:40
14:42
14:44
14:46
14:48
14:50
14:52
14:54
14:57
14:59
15:01
15:03
15:05
15:07
15:09
16:48
16:50
16:52
16:54
16:56
16:58
17:00
17:02
File Name ^
18120050
18120051
18120052
18120053
18120054
18120055
18120056
18120057
18120058
18120059
18120060
18120061
18120062
18120063
18120064
18120065
18120066
18120067
18120091
18120092
18120093
18120094
18120095
18120096
18120097
18120098
CO Unc c
1572 37.0
1578 37.2
1565 37.2
1537 36.3
1525 36.0
1522 35.7
1547 36.5
1564 37.1
1554 37.0
1542 36.5
1534 36.1
1529 36.0
1520 35.7
1537 36.2
1556 36.7
1561 36.9
1565 37.2
1578 37.5
1600 40.7
1615 41.6
1626 41.7
1610 40.9
1584 40.0
1544 38.3
1327 31.1
1216 28.3
Ammonia Unc
6.8 0.6
6.8 0.6
6.3 0.6
5.7 0.5
5.2 0.5
5.1 0.5
5.1 0.5
5.0 0.5
4.9 0.5
5.2 0.5
5.6 0.5
5.3 0.5
4.7 0.5
4.3 0.5
4.4 0.5
4.3 0.5
4.1 0.5
4.0 0.5
5.7 0.6
6.0 0.6
6.0 0.6
5.5 0.6
4.8 0.6
3.9 0.6
3.5 0.5
4.0 0.5
Formal-
dehyde Unc
4.9 1.4
5.3 1.4
5.1 1.4
5.2 1.4
5.3 1.4
5.2 1.3
5.2 1.4
5.1 1.4
5.1 1.4
5.0 1.4
5.0 1.3
5.0 1.3
5.0 1.3
4.9 . 14
5.0 1.4
4.9 1.4
4.9 1.4
4.9 1.4
4.7 1.5
4.8 1.5
4.9 1.5
4.9 1.5
4.9 1.5
4.8 1.5
4.5 1.4
4.1 1.4
HC1 Unc
0.0 3.2
0.0 3.2
3.7 3.2
4 1 3.2
4.2 3.2
4.4 3.2
4.4 3.2
4.5 3.2
4.6 3.2
4.5 3.2
4.4 3.2
4.6 3.2
5.0 3.2
5.3 3.2
5.2 3.2
5.2 3.2
5.3 3.2
5.4 3.2
7.8 3.5
7.2 3.5
7.0 3.5
7.3 3.5
7.7 3.5
8.7 3.5
9.5 3.3
9.5 3.2
2-Methyl-
2-buiene Unc
2.2 1.5
2.4 1.5
3.4 1.4
3.1 1.4
3.0 1.4
2.8 1.3
2.9 1.3
3.0 1.4
3.0 1.4
2.8 1.3
2.6 1.3
2.4 1.3
2.2 1.3
2.4 1.3
2.5 1.3
2.6 1.4
2.6 1.4
2.7 1.4
25 1.5
2.6 1.5
2.5 1.5
2.3 1.5
2.0 1.5
18 15
0.0 1.4
0.0 1.4
-------
TABLE B-l. Continued, (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/12/97
Time
17:05
17:07
17:09
17:11
17:13
17:15
17:17
17:20
17:22
17:24
17:26
17:28
17:30
17:32
17:34
17:37
17:39
17:41
17:43
17:45
17:47
17:49
17:52
17:54
18:19
18:21
File Name*"
18120099
181 20100
18120101
18120102
18120103
18120104
18120105
18120106
18120107
18120108
18120109
18120110
18120111
18120112
18120113
18120114
18120115
18120116
18120117
18120118
18120119
18120120
18120121
18120122
18120134
18120135
CO Uncc
1319 30.4
1387 31.8
1410 32.7
1422 33.0
1438 33.8
1474 35.3
1495 35.8
1498 36.0
1527 37.2
1540 37.9
1544 38.2
1560 39.3
1561 39.3
1526 38.1
1515 37.8
1543 39.2
1565 40.2
1565 40.1
1536 39.0
1501 37.6
1491 37.3
14S4 37.0
1486 36.9
1499 37.5
1431 33.9
1437 34.2
Ammonia Unc
3.4 0.5
2.7 0.5
2.5 0.5
2.7 0.5
2.8 0.5
3.3 0.5
3.8 0,5
4.2 0.5
4.2 0.5
4.4 0.5
5.0 0.6
5.4 0.6
5.1 0.6
4.5 0.6
4.3 0.6
4.6 06
4.7 0.6
4.5 0.6
4.2 0.6
3.8 0.6
3.4 0.5
3.3 0.5
3,1 0.5
3.1 0.6
4.6 0.5
4.8 0.5
Formal-
dehyde Unc
4.2 1.4
4.2 1.3
4.2 1.3
4.2 1.4
4,3 1.4
4,4 1.4
4.3 1.4
4,2 1.4
4.2 1.4
4.3 1.4
4.2 1.5
4.5 1.5
4.6 1.5
4.5 1.5
4.3 1.5
4.5 1.5
4.8 1.5
5.0 1.5
4.9 1.5
4.9 1.5
4.9 1.5
4.7 1.5
4.7 1.5
4.7 1.5
2.8 1.4
2.8 1.4
HC1 Unc
10.3 3.2
11.7 3.2
1 1.8 3.2
11.1 3.2
10.7 3.2
10.1 3.3
9.2 3.3
8.8 3.3
8.4 3.4
7.9 3.4
7.0 3.4
6.6 3.5
6.9 3.5
7.8 3.5
7.6 3.5
7.1 3.5
6.7 3.6
6.8 3.5
7.2 3.5
7.6 3.5
8.4 3.5
8.3 3.5
8.3 3.5
8.3 3.5
11.0 3.3
10.5 3.3
2-Methyl-
2-butene Unc
0.0 1.4
0.0 1.3
0.0 1.3
0.0 1.4
0.0 1.4
0.0 1.4
0.0 1.4
0.0 1.4
00 1.4
0.0 1.4
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0,0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.4
0.0 1.4
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/12/97
Time
18:24
18:26
18:28
18:30
18:32
18:34
18:36
18:38
18:41
18:43
18:45
11:47
18:49
18:51
18:53
18:56
18:58
19:00
19*2
19:04
19:08
19:10
19:13
19:15
19:17
19:19
File Name *•"
18120136
18120137
18120138
18120139
18120140
18120141
18120142
18120143
18120144
18120145
18120146
18120147
18120148
1X120149
18120150
1X120151
18120152
18120153
18120154
18120155
18120156
18120157
18120158
18120159
18120160
18120161
CO Uncc
1486 36.3
1524 38.0
1534 38.5
1531 38.3
1538 38.7
1542 39.0
1546 39.5
1546 39.5
1543 39.4
1526 38.6
1508 37.6
1496 37.1
1490 36.9
1488 36.9
1489 36.4
1521 37.5
1491 36.4
1508 37.2
1543 38.6
1560 39.2
1551 39.2
1552 39.0
1544 38.7
1544 38.6
1550 38.7
1550 3X.6
Ammonia Unc
5.1 0.5
5.0 0.6
4.6 0.6
4.3 0.6
3.9 0.6
3.7 0.6
3.5 0.6
3.5 0.6
3.3 0.6
2.7 0.6
2.4 0.5
2.2 0.5
2.1 0.5
2.3 0.5
3.0 0.5
3.1 0.6
3.3 0.5
3.5 0.6
3.8 0.6
4.3 0.6
4.8 0.6
5.0 0.6
5.3 0.6
5.6 0.6
5.7 0.6
5.8 0.6
Formal-
dehyde Unc
3.8 1.5
4.5 1.5
4.8 1.5
4,7 1.5
48 1.5
4.9 1.5
5.0 1.5
5.0 1.5
5.0 1.5
49 1.5
5.0 1.5
4.9 1.5
4.6 1.5
4.5 1.5
3.1 1.5
2.8 1.5
2.8 1.5
2.9 1.5
2.8 1.5
2.8 1.5
2.8 1.5
2.9 1.5
2.8 1.5
2.7 1.5
2.7 1.5
2.7 1.5
HC1 Unc
9.4 3.4
8.7 3.5
8.5 3.5
8.3 3.5
8.2 3.5
8.0 3.5
7.9 3.6
7.6 3.6
7.8 3.6
8.3 3.6
8.9 3.5
9.1 3.5
9.2 3.5
8.9 3.5
9.2 3.5
9.5 3.5
9.9 3.5
10.0 3.5
9.9 3.5
9.5 3.6
9.5 3.6
9.7 3.6
9.5 3.6
9.7 3.6
9.6 3.5
9.5 3.5
2-Methyl-
2-butene Unc
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Dale
8/12/97
Time
19:21
19:23
19:25
1928
19:30
19:32
19:34
19:36
19:38
19:40
19:42
19.45
FUeName*'1'
18120162
18120163
18120164
18120165
18120166
18120167
18120168
18120169
18120170
18120171
18120172
18120173
8/12/97 Average— >
CO Unc c
1546 38.3
1544 38.3
1543 38.2
1544 38.1
1556 38.5
1570 39.1
1572 39.3
1573 39.4
1565 39.1
1563 39.1
1558 38.9
1560 39.0
1531 37.2
Ammonia Unc
5.9 0.6
5.7 0.6
5.5 0.6
S.7 0.6
5,8 0.6
5.4 0.6
5.3 0.6
5.3 0.6
5.3 0.6
4.8 0.6
4.3 0.6
4.1 0.6
4.5 0.5
Formal-
dehyde Unc
2.6 1.5
2.6 1.5
2,7 1.5
2.6 1.5
2.8 1.5
3.5 1.5
3.8 1.5
3.8 15
3.8 1.5
3.8 1.5
3.8 1.5
3.8 1.5
45 1.4
HCi Unc
9.7 3.5
10.0 3.5
10.3 3.5
10.1 3.5
9.8 3.5
9.4 3.5
S.9 3.5
8.4 3.5
8.2 3.6
8.3 3.6
8.5 3.6
85 3.6
6.7 3.4
2-Methyl-
2-butene Unc
0.0 1.5
0.0 I.S
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
1.0 1.4
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/13/97
Time
9:30
9:36
9:42
9:45
10:00
10:06
10:11
10:16
11:23
11:25
11:28
11:30
11:32
11:34
11:36
11:38
11:40
11.42
11:45
11:47
11:49
11:51
11:53
12:43
12:45
12:48
File Name lb
IU0813A
IU0813B
IU0813C
[U0813D
IS0813A
1S0813B
IS0813C
IS0813D
18130001
18130002
18130003
18130004
18130005
18130006
18130007
18130008
18130009
18130010
18130011
18130012
18130013
18130014
18130015
18130038
18130039
18130040
CO Unc c
1411 30.0
1451 31.5
1451 31.6
1448 31.5
1212 22.9
11(4 22.2
11» 22.0
117* 21.9
1602 37.8
1599 37.4
1577 36.6
1562 36.2
1558 35.9
1565 36.2
1566 36.2
1571 36.4
1577 36.5
1580 36.6
1585 36.7
1594 37.1
1591 36.9
1585 36.8
1582 36.8
1536 34.8
1549 35.6
1567 36.5
Ammonia Unc
0.0 0.5
0.6 0.5
1.3 0.5
1.7 0.5
0.6 0.4
0.0 0.4
0.0 0.4
0.0 0.4
0.7 0.5
0.0 0.5
0.0 0.5
00 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.5 0.5
0.8 0.5
1.1 0.5
1.3 0.5
1.5 0.5
1.7 0.5
1.6 0.5
Formal-
dehyde Unc
6.4 1.2
6.4 1.2
6.3 1.2
6.1 1.2
5.4 1.0
5J 1.0
5J 1.0
5.2 1.0
5.5 1.3
5.5 1.3
5.5 1.3
5.6 1.3
5.4 1.3
5.5 1.3
5.5 1.3
5.4 1.3
5.3 1.3
5.3 1.3
5.3 1.3
53 1.3
5.2 1.3
5.2 1.3
5.4 1.3
4.1 1.3
4.4 1.3
5.0 1.3
HC1 Unc
0.0 2.8
00 2.9
0.0 2.9
0.0 2.9
0.0 2.4
0.0 2.4
0.0 2.4
0.0 2.4
0.0 3.2
00 3.2
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
2-Methyl-
2-butene Unc
1.6 1.3
1.9 1.3
2.0 1.3
2.0 1.3
1.2 1.1
0.0 1.1
0.0 1.1
0.0 1.1
2.6 1.4
2.5 1.4
2.4 1.4
2.3 1.4
2.1 1.4
2.2 1.4
2.2 1.4
2.2 1.4
2.1 1.4
2.2 14
2.4 14
2.5 1.4
2.5 1.4
2.7 1.4
2.6 1.4
1.7 1.4
1.9 1.4
2.3 1.4
-------
TABLE B-l. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Inlet Results)
Date
8/13/97
Time
12:50
12:52
12:54
12:56
12:58
13:00
13:02
15:53
15:55
15:57
16:00
16:04
File Name *•"
18130041
18130042
18130043
18130044
18130045
18130046
18130047
18130094
18130095
18130096
18130097
18130098
8/13/97 Average— >
CO Unc c
1568 36,7
1570 36.7
1555 36,0
1547 35,7
1546 35.7
1550 35.9
1560 36,3
1518 33.4
1473 31.7
1459 31.5
1501 33.2
1544 36.3
1558 35.9
Ammonia Unc
1.7 0.5
1.8 0.5
0.9 0.5
0.0 0.5
0.0 0,5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 05
0.0 0.6
0.5 0.5
Formal-
dehyde Unc
5.2 1.3
5.3 1.3
5.3 1.3
5.2 1.3
5.2 1.3
5.2 1.3
5.2 1.3
1.8 1-3
0.0 1.3
0.0 1.3
0.0 1. 4
0.0 1.4
4.4 1.3
HC1 Unc
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3,1
0.0 3,1
0.0 3.1
0.0 3.1
0.0 3.0
0.0 3.1
0.0 3.2
0.0 3.4
0.0 3.1
2-Melhyl-
2-butene Unc
2.3 1.4
2,2 1,4
2.1 1.4
2.0 1.4
2.1 1.4
1.9 1.4
2.1 1.4
0.0 1.4
0.0 1,4
0.0 1.4
0.0 1.5
0.0 1.6
1.9 1.4
-------
TABLE B-1. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyi-2-butene Inlet Results)
Date
8/14J97
Spike On
Spike Off
Time
8:32
8:34
8:36
8:38
8:40
8:42
8:50
8:52
8:54
8:56
8:59
9:36
9:38
9:40
9:42
9:44
9:46
9:4*
9:50
9:53
9:55
9:5?
9:59
10:01
10:03
10:03
File Name *•"
18140001
18140002
18140003
18140004
18140005
18140006
18140007
18140008
18140009
18140010
18140011
18140028
18140029
18140030
18140031
18140032
18140033
18140034
18140035
1814003*
1X140037
18140038
18140039
18140040
18140041
18140042
CO Unc°
1451 31.1
1489 32.8
1493 32.9
1492 32.9
1487 32.8
1498 33.2
1504 33.1
1495 32.7
1489 32.4
1485 32.3
1468 31.6
1530 34.5
1524 34.4
1522 34.4
1485 32.8
1416 30.1
1270 24.8
1177 22.0
1157 21J5
1158 21.5
1170 21.7
1175 21.8
1297 25.5
1394 28.9
1419 29.8
1427 30.2
Ammonia Unc
4.4 0.5
3.7 0.5
3.2 0,5
2.9 0.5
3.0 0,5
3.2 0,5
3.3 0.5
3.S 0.5
3.5 0.5
3.0 0,5
2.6 0,5
2.2 0.5
2.2 0,5
2.2 0.5
2.4 Oj
23 OJ
2,0 0.4
iJt 0.4
IS 04
1.4 0.4
13 0.4
1.1 04
0.« 0.4
0.6 0.5
0.0 0.5
0.0 OJ
Formal-
dehyde Unc
6.3 1.2
6.6 1.2
6.6 1.2
6.5 1.2
6,2 1.2
6.2 1.2
6 I 1.2
6,1 1.2
6.1 1.2
5.9 1.2
5.8 1.2
4.9 1.2
5.1 1.2 •
5.2 1.2
53 1.2
45 1.1
5.1 1.0
43 8.»
4.2 0.9
4.0 0.9
4.0 0.9
3.9 0.9
4.0 1.0
4.2 1.1
4.3 1.1
4.3 I.I
HC1 Unc
0.0 2.8
2.9 2.8
3.0 2.8
3.2 2.8
2.9 2.8
0.0 2.9
0.0 2.8
0.0 2.8
0.0 2.8
3.1 2.7
3.5 2.7
0.0 2.9
0.0 2.9
0.0 2.9
0.0 2.8
0.0 2.7
OJ 2.4
2J 2.2
2.6 2.2
2.6 2.2
2.5 . 2.2
23 2.2
0.0 2.4
0.0 2.6
0.0 2.7
0.0 2.7
2-Methyl-
2-butene Unc
0.0 1.3
1.6 1.3
1.6 1.3
1.6 1.3
1.5 1.3
1.5 1.3
1.4 1.3
1.3 1.3
1,3 1.3
1 3 1.3
1.3 1,2
0.0 1.4
0.0 1.3
0.0 1.3
0.0 13
1.0 13
0.0 1.1
0.0 1.04
0.0 1.02
0.0 1.02
0.0 1.02
0.0 1.02
0.0 1.1
0.0 1.2
0.0 1. 3
0.0 1.3
-------
TABLE B-l. Continued, (CO, Ammonia, Formaldehyde, HO and 2-Methyl-2-butene Met Results)
Date
8/14/97
Time
10.-08
10:10
10:12
File Name fcl>
18140043
18140044
18140045
8/14/97 Average— >
CO Unc *
1449 30.9
1504 33.2
1509 33.7
I486 32.6
Ammonia Unc
0.0 0.5
0.0 0.5
0.0 0.5
2.3 0.5
Formal-
dehyde Unc
4.3 1.2
4.4 1.2
4.5 1.2
5.6 1.2
HCI Unc
0.0 2.7
0.0 2.9
0.0 3.0
1.0 2.8
2-Methyl-
2-butene Unc
0.0 1.3
0.0 1.3
0.0 1.4
0.8 1.3
* Bold face type indicates umptej dial were ipiked wiih toluene or SPt
b Shaded row* indicate timei when the proceu wai down.
c Unc is the ettunated uncertainty in each meuunmenl. Typically the uncertainty is greater for lower concentrations.
-------
TABLE B-2. FTIR RESULTS (ppm) AT THE WCI BAGHOUSE OUTLET
Date
8/12/97
Process Down
Time
11:17
11:19
11:21
11:24
11:32
11:34
11:39
11:41
14:08
14:10
14:12
14:14
14:16
14:18
14:20
14:24
14:26
14:28
14:30
15:12
15:14
15:16
15:18
t&20
15:22
15:24
»&»
File Name ab
OU0811A
OU0811B
OU0811C
OU0811D
OS0811A
OSOS11B
OS0811C
OS0811D
18120038
18120039
18120040
18120041
18120042
18120043
18120044
18120045
18120046
18120047
18120048
18120068
18120069
18120070
18120071
1SIZ0073
18120073
18120074
im0Q75
Toluene Unc c
7.6 2.1
8.5 2.2
9.0 2.2
8.8 2.2
22.9 2.0
23.2 2.0
23.0 1.9
23.1 2.0
4.8 2.3
4.7 2.3
4.6 2.3
4.5 2.3
4.3 2.3
4.4 2.4
4.4 2.4
4.3 2.4
4.2 2.4
4.0 2.4
3.9 2.4
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0,0 2,e
ftO 2,6
0.0 2.5
ftO $4
Hexane Unc
8.8 0.5
9.6 0.5
10.1 0.5
10.0 0.5
O 0.5
8.7 0.4
8J 0.4
8.5 0.4
11.6 0.5
11.4 0.5
11.4 0.5
11.3 0.5
11.3 0.5
11.4 0.5
11.5 0.5
11.7 0.6
11.7 0.6
11.5 0.6
11.5 0.6
11.4 0.5
11.5 0.5
11.4 0.6
11.4 0.5
1 1.4 (US
11.2 04
Jftfc OS
KM 0<5
Eihylene Unc
5.0 0.8
5.6 0.9
6.0 0.9
5.9 0.8
43 0.9
4.2 0.9
4.0 0.8
4.1 0.9
6.1 0.9
6.0 0.9
5.9 0.9
6.0 0.9
6.0 0.9
6.1 0.9
6.3 0.9
6.4 0.9
6.4 0.9
6.4 0.9
6.3 0.9
6.1 0.9
6.2 0.9
6.4 0.9
6.3 0.9
6,3 0,9
JJ 0,9
4-8 <>.!»
4.5 0.9
Methane Unc
108.7 1.3
118.5 1.4
123.5 1.4
120.2 1.4
99.7 13
99.0 1.2
95.1 1.2
96.6 1.2
130.0 1.5
127.2 1.5
127.3 1.5
128.0 1.5
126.4 1.5
130.7 1.5
132.6 1.5
1410 1.5
139.3 1.5
132.9 1.5
132.9 1.5
129.7 1.5
132.3 1.6
134.0 1.6
134.4 1.6
135,2 1,6
m.o i.s
124.* 1,5
119,0 1,4
SO2 Unc
149.8 3.5
167.7 3 7
174.2 3.7
171.3 3.6
143.2 3J
141.5 33
1373 33
146.2 33
175.3 3.9
172.3 3.8
174.2 3.8
176.8 3.9
169.2 3.8
163.4 3.9
163.4 3.9
156.2 4.0
151.2 4.0
153.1 4.0
156.7 4.0
163.4 3.9
164.5 4.0
164.9 4.0
160.5 4.0
lte.4 4,0
l»4 3,9
8(M> 3.8
$14 5.7
-------
TABLE B-2. Continued, (Toluene, Hexane, Ethylene, Methane and SO2 Outlet Results)
Date
PfdOWiPowd
8/12/97
Time
i&3$ •'
'!»«
ijS^j
iWJT
15:54
15:56
16:03
16:05
16:07
16:09
16:11
16:14
16:17
16:19
16:21
17:56
17:58
18:00
18:02
18:04
18:06
18:09
18:11
18:13
18:15
18:17
File Name"-*
s;:iffi$8ii$i,'"
r'^S*'-!':';
' • '•• littwfifi' ' •
'.••IjJtoSQf
18120080
18120081
18120082
18120083
18120084
18120085
18120086
18120087
18120088
18120089
18120090
18120123
18120124
18120125
18120126
18120127
18120128
18120129
18120130
18120131
18120132
18120133
8/12/97 Average— >
Toluene Unc *
ftQ • &i '
fcO 23
ftO 33
9,0 . $3 •
0.0 2.5
0.0 2.5
0.0 2.7
0.0 2.7
0.0 2.7
0.0 2.7
0.0 2.7
0.0 2.7
0.0 2.7
• 0.0 2.7
0.0 2.7
0.0 4,0
0.0 4.0
0.0 4.1
0.0 4.2
0.0 4.0
0.0 3.8
0.0 3.8
0.0 3.7
0.0 3.7
0.0 3.7
0.0 3.7
1.4 TO
Hexane Unc
j§,6 Up '
9,1 ft*
$& 0.2
*,t •
4.J W
4v*.
-------
TABLE B-2. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Outlet Results)
Date
8/13/97
Time
10:34
10:38
10:44
10:49
11:02
11:07
11:12
11:18
11:55
11:58
12:01
12.03
12:05
12:07
12.09
12:11
12:13
12:16
12:18
12:20
12:22
12:24
12:26
12:28
12:30
12:33
12:35
File Name"
OSM13A
OSOS13B
OSOS13C
OS0813D
OU0813A
OU0813B
OU0813C
OU0813D
18130016
18130017
18130018
18130019
18130020
18130021
18130022
18130023
18130024
18130025
18130026
18130027
18130028
18130029
18130030
18130031
18130032
18130033
18130034
Toluene Unc c
37.0 1.6
39.6 1.8
39.7 1.8
39.8 1.8
7.6 2.3
7.4 2.3
7.5 2.3
7.5 2.3
6.2 2.3
6.2 2.3
6.3 2.3
6.4 2.3
6.5 2.3
6.4 2.3
6.4 2.3
6.4 2.4
6.2 2.3
6.0 2.3
5.9 2.3
5.8 2.3
5.7 2.3
5.6 2.3
5.9 2.3
6.0 2.4
5.8 2.3
5.7 2.3
5.4 2.3
Hexane Unc
6.9 0.2
7.9 0.2
8.2 0.2
83 0.2
10.3 0.5
10.4 0.5
10.6 0.5
10.8 0.5
110 0.5
10.9 0.5
10.8 0.5
10.8 0.5
10.9 0.5
11.0 0.5
11.0 0.5
11.0 0.5
10.9 0.5
10.9 0.5
10.9 0.5
10.9 0.5
10.9 0.5
10.8 0.5
11.1 0.5
11.2 0.5
11.1 0.5
11.1 0.5
11.0 0.5
Ethylene Unc
2.9 0.8
3.6 0.8
3.9 OJt
3.9 0.8
6.5 0.9
6.5 0.9
6.6 0.9
6.7 0.9
6.4 0.9
6.4 0.9
6.5 0.9
6.5 0.9
6.6 0.9
6.7 0.9
6.8 0.9
6.8 0.9
6.7 0.9
6.6 0.9
6.6 0.9
6.5 0.9
6.5 0.9
6.5 0.9
6.6 0.9
6.7 0.9
6.5 0.9
6.5 0.9
6.5 0.9
Methane Unc
81J 1.1
963 1.2
98.6 1.2
98J 1.2
124.8 1.4
124.1 1.5
1257 1.5
128.8 1.5
128.5 1.5
126.8 1.5
127.1 1.5
127.9 1.5
129.9 1.5
131.1 1.5
131.8 1.5
131.7 1.5
128.8 1.5
126.7 1.5
127.1 1.5
128.0 1.5
128.9 1.5
125.7 1.5
132.1 1.5
134.0 1.5
128.8 1.5
132.6 1.5
130.5 1.5
SO2 Unc
1153 3.0
137.8 33
145.4 33
127.9 33
188.4 3.9
180.6 3.9
176.6 3.9
186.5 3.9
195.6 3.9
197 0 3.8
190.4 3.9
182.8 3.9
180.1 3.9
182.4 3.9
190.8 4.0
202.0 4.0
204.0 3.9
202.1 3.9
206.4 3.9
205.4 3.9
193.9 3.9
183.0 3.9
186.8 3.9
190.7 4.0
191.3 3.9
187.6 3.9
186.3 3.9
-------
TABLE B-2. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Outlet Results)
Date
8/13/97
Time
12:37
12:39
12:41
13:05
13:07
13:09
13:11
13:13
13:15
13:17
13:20
13:22
13:24
13:26
13:28
13:30
13:32
13:34
13:37
13:39
13:45
13:47
13:49
13:52
15:00
15:02
15:04
File Name'"
18130035
18130036
18130037
18130048.
18130049
18130050
18130051
18130052
18130053
18130054
18130055
18130056
18130057
18130058
18130059
18130060
18130061
18130062
18130063
18130064
18130065
18130066
18130067
18130068
18130069
18130070
18130071
Toluene Unc c
5.2 2.3
5.1 2.3
5.0 2.3
4.3 2.3
4.5 2.4
4.7 2.4
4.8 2.4
4.7 2.4
4.6 2.4
4.6 2.4
4.5 2.3
4.6 2.4
4.5 2.4
4.4 2.4
4.2 2.3
4.2 2.4
4.2 2.4
4.1 2.4
4.0 2.4
4.0 2.4
0.0 2.6
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.6
0.0 2.6
0.0 2.5
Hexane Unc
10.9 0.5
10.8 0.5
10.8 0.5
11.1 0.5
11.0 0.5
11.0 0.5
11.1 0.5
11.0 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
11.1 0.5
10.7 0.5
10.6 0.5
10.6 0.5
10.6 0.5
10.6 0.5
10.5 0.5
10.5 0.5
Ethylene Unc
6.4 0.9
6.3 0.9
6.3 0.9
6.4 0.9
6.6 0.9
6.7 0.9
6.8 0.9
6.6 0.9
6.6 0.9
6.6 0.9
6.6 0.9
6.6 0.9
6.6 0.9
6.5 0.9
6.5 0.9
6.5 0.9
6.5 0.9
6.5 0.9
6.6 0.9
6.6 0.9
6.5 0.9
6.4 0.9
6.4 0.9
6.5 0.9
6.5 0.9
6.4 0.9
6.4 0.9
Methane Unc
125.2 1.5
123.9 1.5
126.6 1.5
128.5 1.5
129.5 1.5
131.1 1.5
132.0 1.5
130.5 1.5
130.6 1.5
129.5 1.5
129.0 1.5
129.4 1.5
130.0 1.5
129.3 1.5
128 1 1.5
128.0 1.5
128.8 1.5
130.2 1.5
131.0 1.5
131.0 1.5
132.9 1.5
129.6 1.5
127.0 1.5
126.9 1.5
133.3 1.5
129.4 1.5
127.2 1.5
SO2 Unc
184.1 3.9
181.7 3.9
177.8 3.9
185.8 3.9
188.3 4.0
190.3 4.0
186.6 4.0
190.7 3.9
198.0 4.0
196.7 3.9
194.2 3.9
193.1 3.9
190.9 3.9
190.3 3.9
187.7 3.9
185.0 3.9
177.3 3.9
169.9 4.0
167.2 4.0
170.0 4.0
176.6 3 9
173.3 3.9
170.9 3.9
171.7 3.9
143.8 3.9
147.5 3.9
148.8 3.9
-------
TABLE B-2. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Outlet Results)
Date
8/13/97
Time
15:06
15:08
15:10
15:13
15:15
15:17
15:19
15:21
15:23
15:25
15:28
15:30
15:32
15:34
15:36
15:38
15:40
15:42
15:45
15:47
15:49
15:51
File Name "•"
18130072
18130073
18130074
18130075
18130076
18130077
18130078
18130079
18130080
18130081
18130082
18130083
18130084
18130085
18130086
18130087
18130088
18130089
18130090
18130091
18130092
18130093
8/13/97 Average— >
Toluene Unc c
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.6
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.5
0.0 2.6
0,0 2.6
0.0 2.6
0.0 2.6
0.0 2.6
0.0 2.5
0.0 2.5
0.0 25
3.1 2.4
Hexane Unc
10.5 0.5
10.4 0.5
10.7 0.3
10,7 0.3
10.4 0.5
10.5 0.5
10,6 0.5
10,6 0.5
106 0.5
10.6 0.5
10.6 0.5
10.5 0.5
10.5 0.5
106 0.5
10.7 0.5
10.7 0.5
10.7 0.5
10.7 0.5
10.6 0.5
10.5 0.5
10.3 0.5
10.6 0.3
10.8 0.5
Ethylene Unc
6.4 0.9
6.2 0.9
6.1 0.9
6.0 0.9
6.1 0.9
6.2 0.9
6.3 0.9
6.3 0.9
6.3 0.9
6.2 0.9
6.2 0.9
6.1 0.9
6.1 0.9
6.2 0.9
6.4 0.9
6.5 0.9
6.5 0.9
6.4 0.9
6.3 0.9
6.3 0.9
6.2 0.9
6.1 0.9
6.4 0.9
Methane Unc
126.3 1.5
125.7 1.5
122.9 1.5
122.9 1.5
123.8 1.5
126.0 1.5
127.0 1.5
127.1 1.5
125.9 1.5
125.6 1.5
124.7 1.5
123,7 1.5
123.7 1.5
124 .8 1.5
126.8 1.5
127.6 1.5
127.1 1.5
126.1 1.5
124.7 1 5
122.4 1.5
120.1 1.5
119.4 1.5
127.8 1.5
SO2 Unc
155.0 3.9
151.8 3.9
145.7 3.9
145.1 3.9
147.4 3,9
147.5 3.9
148.0 3.9
154.3 3.9
159.8 3.9
160.7 3.9
157.7 3.9
153.8 3.9
149.8 3.9
148.0 3.9
145.5 3.9
142.2 3.9
147.0 3.9
154.7 .3.9
159.6 3.9
159.9 3.9
164.4 3.8
172.4 3.8
174.6 3.9
-------
TABLE B-2. Continued. (Toluene, Hexane, Ethylene, Methane and SO2 Outlet Results)
Date
8/U/97
Spike OD
5p»« off
Time
9:01
9:04
9:06
9:08
9:10
9:12
9:14
9:16
9:18
9:21
9:23
9:25
9:2?
9:29
9:31
9:33
File Name0
18140012
18140013
18140014
18140015
1X140016
U 1400 17
1S14M18
11140019
11140020
11140021
1X140022
1S140023
18140024
1X140025
18140026
18140027
8/14/97 Average — >
Toluene Unc c
10.7 1.9
10.6 1.9
10.9 1.9
10.9 1.9
10.8 1.9
18.4 2.0
36.9 1.7
40.0 1.7
48.4 1.7
40.4 1.7
40.6 1.7
363 1.7
16.2 1.9
10.4 1.9
9.3 2.0
9.1 2.0
10.3 1.9
Hexane Unc
9.2 0.2
9.2 0.2
9.4 0.2
9.7 0.2
9.8 0.2
*J 03
(.1 0.2
73 0.2
7.0 0.2
6.9 0.2
«J 0.2
7.0 OJ
8.4 6.2
8.9 0.2
9.0 0.2
9.1 0.2
9.2 0.2
Ethylene Unc
5.3 OJ
5.3 0.8
5.4 0.8
5.6 0.8
5.7 0.9
44 OJ
3.8 OJ
33 04
33 OJ
3.4 OJ
3.4 OJ
3.7 OJ
4.9 OJ
5.3 1.0
5.4 1.0
5.5 1.0
5.4 0.9
Methane Unc
103.5 1.3
104.6 1.3
106.0 1.3
108.0 1.3
110.4 1.3
983 13
903 1.2
85.7 1.1
843 1.1
833 1.1
82.6 1.1
86.2 1.1
1*2.6 13
108.5 1.3
110.0 1.3
112.6 1.3
107.6 1.3
SO2 Unc
140.5 3.5
126.8 3.5
120.1 3.6
121.2 3.6
130.8 3.7
1275 3.4
129.1 3.2
129.0 3.2
126.8 3.1
122.7 3.1
119.9 3.1
124.4 3.2
WSJ 33
143.1 3.7
136.8 3.7
137.1 3.7
132.2 3.6
-------
TABLE B-2, Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Outlet Results)
Dale
8/12/97
Time
11:17
11:19
11:21
11:24
11:32
11:34
11:39
11:41
14:08
14:10
14:12
14:14
14:16
14:18
14:20
14:24
14:26
14:28
14:30
15:12
15:14
15:16
15:18
1S3&
ts&?
J«M'
File Name ''b
OU0811A
OUOgllB
OU0811C
OU0811D
osasm
OS4S11B
OSC811C
OSflSllI)
18120038
18120039
18120040
18120041
1X120042
18120043
18120044
18120045
18120046
18120047
IS120048
18120068
18120069
18120070
18120071
18120072
W20073
iwawM
CO Unc c
1429 30.3
1508 33.3
1534 34.2
1517 33.3
1407 28.6
1401 2S.2
1368 27.2
1397 28.1
1554 35.7
1547 35.2
1546 35.3
1545 35.3
1539 35.1
1548 35.5
1561 36.2
1542 35.8
1534 35.7
1548 36.3
1551 36.4
1581 37.8
1592 38,1
1600 38.2
1596 38.1
JS83 37.7
1406 3&6
J2.8* • |t,5
Ammonia Unc
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.6 OJ
0.6 0.5
0,7 OJ
0.7 OJ
5.8 0.5
5.8 0.5
5.7 0.5
5.7 0.5
5.7 0.5
5.9 0.5
6.1 0.5
6.3 0.6
6.5 0.6
6.6 0.6
6.7 0.6
3.9 0.5
4.6 0.6
5.2 0.6
5.5 0.6
5,8 &&
&2 «.$
«.S 4)4 '
Formal-
dehyde Unc
7.0 1.2
7.0 1.2
6.6 1.3
6.5 1.2
6.1 1.1
6.1 1.1
5J 1.1
6.0 1.1
5.2 1.3
4.9 1.3
4.8 1.3
4.8 1.3
4.8 1.3 .
4.7 1.3
4.7 1.3
4.9 1.4
4.9 1.4
4.8 1.4
4.9 1.4
4.9 1.4
4.5 1.4
3.9 1.4
3.7 1.4
».* 1,4
•• 14 . J.3
' IJ . U
HC1 Unc
0.0 2.8
0.0 2.9
0.0 3.0
0.0 2.9
0.0 2.6
OJ) 2.6
3.4 2.6
34 2.6
0.0 3.1
3.6 3.1
3.8 3.1
3.8 3.1
3.9 3.1
3.8 3.1
3.7 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
5.4 3.2
5.0 3.3
5.3 3.3
55 3.3
S,6 3.3
SM 3,2
42 M
2-Methyl-
2-butene Unc
1.6 1.2
2.1 1.3
2.2 1.3
2.0 1.3
IJ 1.2
1.4 1.2
1.2 1.2
1.4 1.2
2.3 1.4
2.2 14
2.2 1.4
2.2 1.4
2.2 1.4
2.2 1.4
2.4 1.4
2.4 1.5
2.2 1.5
2.1 1.5
2.1 1.5
2.9 1.4
3.0 1.4
2.9 1.4
2.8 1.4
2,8 1.4
U J.3
JU5> U
-------
TABLE B-2. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Outlet Results)
Date
PipcwOwii i
Process Down
8/12/97
Time
'**$&.:.•;'
' !$*»••;
i5-3i':
1533
i$as •
15:54
15:56
16:03
16:05
16:07
16:09
16:11
16:14
16:17
16:19
16:21
17:56
17:58
18:00
18:02
18:04
18:06
18:09
18:11
18:13
18:15
File Name 1-b
.• ?'i?fS?T •
•iiwBi
. iftsaW''--
1*120078 •
'.\ 'tf 'im*t '•••
18120080
18120081
18120082
18120083
18120084
18120085
18120086
18120087
18120088
18120089
18120090
18120123
18120124
18120125
18120126
18120127
18120128
18120129
18120130
18120131
18120132
CO Unc c
123? - 33.1
J2JS i7.3
I30S #3
1339 . 2*.5
: US* 2
, $.0 2,9
W» 2,9
m &»
8.6 3.1
8.6 3.1
8.5 3.3
8.1 3.4
7.9 3.4
7.9 3.4
7.9 3.3
8.2 3.3
8.4 3.3
8.6 3.3
8.8 3.3
7.6 3.5
7.1 3.5
7.0 3.6
7.1 3.6
7.7 3.5
8.8 3.4
9.6 3.4
10.1 3.3
10.6 3.3
108 3.3
2-Methyl-
2-butene Unc
U. J4
0,0 U
ao jua
0,0 1.2
04) U
0.0 1.3
0.0 1.3
2.1 1.4
2.3 1.4
2.4 1.4
2.3 14
2.2 1.4
2.2 1.4
2.2 14
2.2 1.4
2.1 1.4
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.5
0.0 1.4
0.0 1.4
0.0 1.4
0.0 1.4
0.0 1.4
-------
TABLE B-2. Continued, (CO, Ammonia, Formaldehyde, HCI and 2-Methyl-2-butene Outlet Results)
Date
8/12/97
Time
18:17
File Name *•"
18120133
8^12/97 Averap— >
CO Uncc
1428 33.8
1548 37.1
Ammonia Unc
4.3 0.5
5.3 0.6
Formal-
dehyde Unc
2.9 1.4
4.1 1.4
HCI Unc
11.0 3.3
6.2 3.3
2-Msahyl-
2-butene Unc
0.0 1.4
1.6 1.4
-------
TABLE B-2, Continued. (CO, Ammonia, Formaldehyde, HO and 2-Methyl-2-butene Outlet Results)
Date
8/13/97
Time
10:34
10:38
10:44
10:49
11:02
11:07
11:12
11:18
11:55
11:58
12:01
12:03
12:05
12.07
12;09
12:11
12:13
12:16
12:18
12:20
12:22
12:24
12:26
12:28
12:30
12:33
File Name '-b
OSOU3A
OS0813B
OSOS13C
OSOS13D
OU0813A
OU0813B
OU0813C
OU08I3D
18130016
18130017
18130018
18130019
18130020
I8I30021
18130022
18130023
18130024
18130025
18130026
18130027
18130028
18130029
18130030
18130031
18130032
18130033
CO Unc *
1173 21.8
1311 25.6
1329 26.1
1327 26.2
1544 35.6
1544 35.6
1560 36.5
1578 36.8
1574 36.4
1566 35.9
1559 356
1561 35,8
1575 36.3
1585 36.8
1590 36.9
1592 37.2
1583 36.8
1571 36.3
1564 36.0
1556 35.6
1542 35.1
1535 34.7
1556 35.7
1569 36.2
1564 35.9
1548 35.3
Ammonia Unc
0.0 0.4
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.6
1.3 0.5
1.2 0.5
1.1 0.5
1.0 0.5
1.1 0.5
1.4 0.5
1.7 0.5
1.9 0.6
1.6 0.5
1.2 0.5
0.9 0.5
0.8 0.5
0.6 0.5
0.0 0.5
0.7 0.5
1.1 0.6
1.5 0.5
1.4 0.5
Formal-
dehyde Unc
4.4 1.0
4J» 1.1
4.7 1.1
4.7 1.1
5.0 1.3
5.1 1.3
5.1 1.3
5.0 1.3
5.3 1.3
5.2 1.3
4.4 1.3
4.2 1.3
4.2 1.3 ,
4.2 1.3
4.3 1.3
4.3 1.3
4.4 1.3
4.4 1.3
4.4 1.3
4.4 1.3
4.4 1.3
4.2 1.3
4.3 1.3
4.3 1.3
4.3 1.3
4.3 1.3
HC1 Unc
0.0 2.4
0.0 2.6
0.0 2.7
0.0 2.7
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.2
2-Meihyl-
2-butene Unc
0.0 1.1
0.0 1.2
0.0 13.
0.0 1.2
2.0 1.4
2.1 1.4
2.2 1.4
2.3 1.4
2.5 1.4
2.4 1.4
2.1 1.4
2.1 1.4
2.1 1.4
2.1 1.4
2.2 1.4
2,1 1.4
2.0 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.8 1.4
1.8 1.4
2.1 14
2.1 1.4
1.9 1.4
2.0 1.4
-------
TABLE B-2. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Outlet Results)
Date
8/13/97
Time
12:35
12:37
12:39
12:41
13:05
13:07
13:09
13:11
13:13
13:15
13:17
13:20
13:22
13:24
13:26
13:28
13:30
13:32
13:34
13:37
13:39
•13:45
13:47
13:49
13:52
15:00
File Name *•"
18130034
18130035
18130036
18130037
18130048
18130049
18130050
18130051
18130052
18130053
18130054
18130055
18130056
18130057
18130058
18130059
18130060
18130061
18130062
18130063
18130064
18130065
18130066
18130067
18130068
18130069
CO Unc c
1545 35.2
1542 35.1
1537 34.8
1536 34.8
1566 36.5
1568 36.4
1571 36.4
1562 36.1
1564 35.9
1579 36.4
1573 36.2
1568 36.0
1565 35.9
1571 36.0
1563 35.8
1557 35.6
1559 35.8
1559 35.8
1556 35.8
1550 35.6
1549 35.6
1531 34.8
1522 34.5
1527 34.7
1526 34.7
1510 34.1
Ammonia Unc
1.3 0.5
1.3 0.5
1.4 0.5
1.4 0.5
0.0 0.5
0.0 0.6
0.0 0.6
0.0 0.6
0.6 0.5
0.7 0.5
0.0 0.6
0.0 0.6
0.0 0.6
0.0 0.5
0.7 0.5
0.9 0.5
1.0 0.5
10 0.5
1.2 0.5
1.4 0.6
1.6 0.6
1.8 0.5
1.7 0.5
1.4 0.5
1.3 0.5
0.8 0.5
Formal-
dehyde Unc
4.3 1.3
4.3 1.3
4.2 1.3
4.2 1.3
5.1 1.3
4.3 1.3
4.1 1.3
3.9 1.3
3.9 1.3
3.9 1.3
3.9 1.3
3.9 1.3
3.9 1.3
3.9 1.3
3.9 1.3
4.0 1.3
3.9 1.3
3.8 1.3
3.9 1.3
3.8 1.3
3.7 1.4
3.4 1.3
3.3 1.3
3.4 1.3
3.4 1.3
30 1.3
HC1 Unc
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 32
2-Methyl-
2-butene Unc
2.0 1.4
1.8 1.4
1.8 1.4
1.8 1.4
2.1 1.4
2.0 1.4
2.0 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.8 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.9 1.4
1.7 1.4
2.5 1.3
2.3 1.3
2.4 1.3
2.4 1.3
1.7 1.3
-------
TABLE B-2. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Outlet Results)
Date
8/13A>7
Time
15:02
15:04
15:06
15:08
15:10
15:13
15:15
15:17
15:19
15:21
15:23
15:25
15:28
15:30
15:32
15:34
15:36
15:38
15:40
15:42
15:45
15:47
15:49
15:51
File Name '•"
18130070
18130071
18130072
18130073
18130074
18130075
18130076
18130077
18130078
18130079
18130080
18130081
18130082
18130083
18130084
18130085
18130086
18130087
18130088
18130089
18130090
18130091
18130092
18130093
8/13/97 Average — >
CO Unc c
1508 34.0
1506 34.0
1514 34.4
1506 34.0
1507 33.9
1517 34.2
1530 34.8
1537 35.1
1547 35.3
1542 35.0
1528 34.7
1517 34.3
1521 34.3
' 1521 34.3
1517 34.3
1519 34.6
1525 35.0
1531 35.1
1541 35.4
1547 35.6
1552 35.5
1551 35.1
1547 34 8
1536 34.2
1548 35.4
Ammonia Unc
0.6 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.6
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.0 0.6
0.0 0.6
0.0 0.5
0.6 0.5
0.6 0.5
0.0 0.5
0.0 0.5
0.0 0.5
0.6 0.5
Formal-
dehyde Unc
2.9 1.3
3.0 1.3
3.1 1.3
3.1 1.3
3.0 1.3
3.0 1.3
3.1 1.3
2.9 1.3
2.9 1.3
3.1 1.3
3.0 1.3
3.0 1.3
2.9 1.3
2.9 1.3
3.0 1.3
2.9 1.3
2.9 1.3
2.8 1.3
2.9 1.3
2.9 1.3
2.8 1.3
2.6 1.3
2.4 1.3
2.2 1.3
3.7 1.3
HC1 Unc
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.1
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.2
0.0 3.1
00 3.1
0.0 3.1
0.0 3.1
2-Methyl-
2-butene Unc
1.6 1.3
1.5 1.3
1.5 1.3
1.4 1.3
0.0 1.3
0.0 1.3
1.4 1.3
1.4 1.3
1.5 1.3
1.6 1.3
1.5 1.3
1.4 1.3
1.4 1.3
1.4 1.3
1.4 1.3
1.4 1.3
1.5 1.3
1.4 1.3
1.5 1.3
1.5 1.3
1.4 1.3
1.4 1.3
1.4 1.3
0.0 1.4
1.7 1.4
-------
TABLE B-2. Continued. (CO, Ammonia, Formaldehyde, HC1 and 2-Methyl-2-butene Outlet Results)
Date
8/14/97
Spike On
Spike Off
Time
9:01
9:04
9:06
9:(M
9:10
9:12
9:14
9:16
9:18
9:21
9:23
9:25
9:27
9:29
9:31
9:33
File Name*'"
18140012
18140013
18140014
18140015
18140016
18140017
18140018
1S14001*
18140020
1*140021
18140022
18140023
18140024
18140025
18140026
18140027
8/14/97 Average — >
CO Unc c
1461 31.3
1465 31.4
1475 31.7
1494 32.6
1507 33.1
1414 29.2
1342 26.5
1309 25.4
1286 24.8
1282 24.7
1284 24,7
1317 25.7
145S 30.9
1498 33.0
1515 33.8
1523 34.2
1490 32.6
Ammonia Unc
2.6 0.5
2.8 0.5
3.2 0.5
3.4 0.5
3.5 0.5
3.7 OJ
3.7 0.4
3J 0.4
3.2 0.4
2.9 0.4
2.8 0.4
2.6 0.4
2.2 0,5
1.9 0.5
1.9 0.5
2.0 0.5
2.5 0.5
Formal-
dehyde Unc
5.8 1.1
5.6 1.2
5.3 1.2
5.4 1.2
5.3 1.2
S.S 1.1
5.4 1.1
S.2 I A
4.9 1.0
4.8 1.0
4.7 1.0
4.7 1.0
4.9 1.1
4.93 1.2
4.93 1.2
4.88 1.2
53 1.2
HCI Unc
3.4 2.7
3.1 2.7
2.8 2.8
0.0 2.8
0.0 2.8
0.0 2.7
0.0 2.5
2J 2.4
2.* 2.4
2.8 2.4
2.9 2A
2.9 2.4
0.0 2.7
0.0 2.8
0.0 2.9
0.0 2,9
1.3 2.8
2-Methyi-
2-butene Unc
0.0 1.2
0.0 1.2
0.0 1.3
0.0 1.3
0.0 1.3
1.7 1.2
0.0 1.1
0.0 1.1
0.0 I.I
0.0 1.1
0.0 1.1
0.0 1.1
0.0 1J
0.0 1.3
0.0 1.3
0.0 1.4
0.0 1.3
* Bold face type indicates samples that were spiked with toluene or SF6
* Shaded rows indicate tunes when the process was down.
c Unc is (lie estimated uncertainty in each measurement. Typically the uncertainty is greater for lower concentrations.
-------
Toluene Concentrations at WCI Inlet and Outlet (8/12/97)
30
-Inlet —Q— Oullei
25 -
20-
15
10
5 -
-5
4MMMBP
10:00 11:00 12:00 13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
Toluene Concentrations at WCI Inlet and Outlet (8/13/97)
-Inlet ~Q— Outlet
55
45
35 -
I25
I
15
9:00
10:00
11:00 12:00
13:00
Tine
14:00
15:00
16:00
-------
I
e
y
41
(U
"3
H
s
o
o
0>
s
o
do
8
(uidd) ananioj,
-------
Hexane Concentrations at WCI (8/12/97)
•Inlet -Q— Oultet
14
12-
10 -
8 -
S
CL
0
10:00 11:00 12:00 13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
Hexane Concentrations at WCI (8/13/97)
•Intel -G— Outlet
12
10
8 -
I 6^
4 -
\
9:00
10:00
11:00 12:00 13:00 14:00
Time
15:00 16:00
-------
Hexane Concentrations at WCI (8/14/97)
•Inlet -"©—Outlet
12
10-
I 6
8:00
8:30
9:00
9:30
Time
10:00
10:30
-------
Ethylene Concentrations at WCI (8/12/97)
-Inlet -&-Outlet |
4 -
a
a.
a
3 -
0
10:00 11:00 12:00 13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
Ethylene Concentrations at WCI (8/13/97)
-Inlet -^-Outlet
7 -
6-
5
B.4H
2 -
9:00
10:00
11:00
12:00
13:00
14:00
Time
15:00
16:00
-------
2 -
Ethylene Concentrations at WCI Inlet (8/14/97)
-Inlet -^—Outlet
6-
3
8:00
8:30
9:00
9:30
10:00
10:30
Time
-------
Methane Concentrations at WCI (8/12/97)
160
-Inlet -©—Outlet
140-
120
100
I. SO
60-
40
20-
0
10:00 11:00
12:00
13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
Methane Concentrations at WCI (8/13/97)
-Met -©—Outlet
140
120
100
e
D.
a
80 -
60
40
20
O
\
9:00
10:00
11:00
12:00
13:00
14:00
15:00
16:00
Time
-------
Methane Concentrations at WO (8/14/97)
•Inlet —©—Outlet
140
120-
100-
i
a.
3
80
60-
40-
20-
8:00
8:30
9:00
9:30
Time
10:00
10:30
-------
SO2 Concentrations at WCI (8/12/97)
250
-Inlet -0—Outlet
200-
150 i
B
a.
&
100-
50
0
10:00
11:00 12:00 13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
SO2 Concentrations at WCI (8/13/97)
•Inlet -©—Outlet
250
200 -
150
100
50
0
9:00 10:00
11:00 12:00 13:00 14:00 15:00 16:00
Time
-------
50
SO2 Concentrations at WCI (8/14/97)
-Mel -0~ Outlet
250
200
150
e
Q.
a
100
8:00
8:30
9:00
9:30
Tint
10:00
10:30
-------
1800
CO Concentrations at WCI (8/12/97)
-Inlet ~O—Outlet
1600-
1400-
1200-
1000 •
§
Q.
&
*
800
600-
400
200
10:00
11:00
12:00
13:00
14:00
15:00
Time
16:00
17:00
18:00
19:00
-------
B-2 FTIR FIELD DATA RECORDS
B-29
-------
Data Shed: FITR Balch Samples: WCI. EPA Work Assignment 4-20.
Dale
8/14/97
Samptotimo Filename
10.00 is0813a
10:05 'Is0813b
10:10 is0813c
10:15 is0313d
|msu0813d
1029 I
10:34 os0813a
10:39 osO813b
10:44 os0813c
10:49 080613d
10:51 !
10:55
11:02 ou0813a
11:07 ou0813b
11:12 ou0813c
11:17 ou0813d
1122
1124 180130001
11:55
11:58 18130016
12:15 -18130025
12:45 181300038
13.05 -18130047
13:06
13:54 18130068
1457 18130069
15:30 18130079
15:56 -18130094
1623 18130106
1624 18130106
1700
1715
17:37
17:40 '
17.45
17:49 CTS0813C
17:51 CTS0813D
17:54
726
8.21 bkg0814a
! 6:22 cts0814c
' 826 cts0814d
828 i
8:30
845 18140006
848
I 8.50 18140007
! 8:03 -18140012
Path
Location/Notes
First spiked into! sampb
Second spiked Intel sample
Third spiked inlet sample
Fourth spiked MM sample
Spfced minus unspiked; tol largai than yesterday (OKI)
•scans fles (cm-1
'
•
Start to) (121 ppm) (low 2.00 1pm , SF6 (4 Oppm) 1 .0 Ipm to outlet spite, total flow -14 51pm
Firat spited oUtet sample
Second spited outlet sample
Third spiked outlet sample
Fourth apiked outlet sampte
Spike gasas off, valve dosed
Run 2 starts at outlet
First unspikad owlet sample
Second unspikad outlet sample
Third unspiked outlet sample
Fourth unspikad outlet sampte
Switch to continuous mode at inlet
First ol Run 2 continuous mode spectra
rM port swKch starts
Switch to continuous mode at outlet
inlet port switch ends
Switch to continuous mode at inlet
Outlet port sw«ch starts
Switch to continuous mode at outlet
Slop analysis. Waiting (or repairs to outlet dioxin train and test restart
Start continuous mode at outlet
Re start manual testing at outlet
Start continuous mode at inlet
Manual testing stoppad because ot process cksruption
Start continuous mode at outlet (process down]
Manual testing restarted
Inlet port switch starts
l- I IR run ends (manual testing to continue)
250 ' 20
Start GTS tow to cell 7.5 £m P-745 [
Data since 1628 lost - detector warmed up - 1 5 minutes ot manual test comparison lost
20 ppm ETY
20 ppm ETY
Start N2 low to cell
InttiaJ CTS (a,b) with old bkg no good; NH3 seams to be gone
P-747.1
Start inlet tow to cell
Start of FTIR Run 3
Stop lor data check
Data check OK
Restart FTIR testing
Switch to continuous mode at outlet
500 2.0
1'
1
Cat Tamp (F)
130C
Spk/Unsp
S
S
S
S
u
I
130C
t
|
'
Sampte Cond Sample Flow
^
H/W 331pm
4 Olpm
301pm
35lpm
4 51pm
BKG
AjSOO)
A
WCILOG02 Xls, WCI
-------
Data Sheet: FTIR Batch Samples: WCI. EPA Work Assignment 4-20,
Oats Sample lima File name
9.10 -18140016
925 -18140022
9-40 -18114028
9 43 -18140030
9 58 -18140037
10 13 -18140045
I 1021 cts0814e
1
Path
LacalioiVNotm
tecans Res («m-1]
Slart spike flow to outlet 1 .0|>m SFS (4.0 ppm) * 2.00(pm TOLj12liggn)£total flow ~t 0.51pm
Spite flows off
Switch to continuous mode at Intel
Start spike flow to intel 1 .Olpm SFS (4 0 ppm) t 2.0CHpm TOL (121ppmj; total flow -9.01pm
Spite flows ofl
Stop for data check
Cell T«»£jF)J Spk/Unsp
Sample Cond. Sampte Row
3.5lpm
I
BKG
WCILOG02 xls, WCI
-------
Data Sheet: FOR Batch Samples WCI. EPA Woik Assignment 4-20-
Date
8/11/97
8/12/97
Sample time' Filename
8:00
-930
11.30 '
12:30
-14:30
-15:00 bkgratcd.asf
-17:00
until 21 :00
5:45 i
902 GTS0811A.I
9:18 '
921 BKG0811F
925 !
927
9-28 CTS0811C
931 CTS0811D
9:33 '
10:16
1021 SF60811a
1024
1029
10 35 isOSIIa
1038 is0811t»
1040 isQB11c
1042 is0811d
1045
1052 tuOSHa
1054
1100 iu0811b
1102 iu0811c
! 11:04 iu0811d
1 11:07 fu0811»
11:08 '
11:09
11:16 ouOSIIa
11:19 ouOSUb
1121 OU0811C
1124 ouOSHd
1127 ,
1132 os811a
11:34 os811b
11 38
11 39
11 41
11 44
11 51 lottra
Path
20 passes
Location/Notes
Truck location
Safety briefing
Computer failure, Syquesl mistakenly plugged into MIDAC card.
Discover MIDAC card and cable destroyed.
System running w/o Syquest (removed MIDAC card)
*scans Res (cm \
BKG nearly identical to KG 8/6/97 'A," RMS 2500-2600 -.0001 AU lor two 250 scan ratio '
System running ml Syquesl (naw M/F 25 pm cable)
ntefoulet setup; final inlet probe set-up and samp sys leak checks remain;
LH has re-plumbed and tested spiking system.
Spreadsheet prep
20 ppm ETY 7.51pm 5 mln: P-748.5 N2 BKG081 1e 500 scans
CTSA.B show Islon outgasses and features in CH region
Switch to N2 7.5 Ipm P-748 9 (or new BKG
Switch to 20ppm ETY 6 0 1pm P.749.3
nit* and outlet systems pass teak checks
CTS comparison and quality jood; switch to N2
Start SF6 4 0 ppm direct flow 51pm
SF6 direct 4.0ppm 5.51pm P-748 9 recorded as inlet spec
SF6 absorbanca -0.67AU; switch to N2
250 2.0
500
250
250
250
Start tol (121ppm) flow 1.00 Ipm, SF6 (4 Oppm) 1 0 Ipm to inlet spike, total flow 101pm
Start first spiked inlet stack spectrum 41pm
Start second spiked inlet slack spectrum
Start third spiked Met stack spectrum
Start fourth spiked inlet stack spectrum
Spite gases oH
First unspiksd inlet slack spectrum 4 Ipm;
Can see SF6 and tol in calc'd spectrum smuOSI la
Second unspiked inlol stack spectrum
Third unspiked inlet slack spectrum
Fourth unspiked inlet slack spectrum
Fourth unspiked into! stack spectrum
Intel filer T and flow have dropped; repairs begun
Switch to outlet stream 3.0 Ipm
First unspiked outlet stack spectrum 4.0 Ipm, P-746.5
Second unspjted outlet stack spectrum
Third unspiked outlet stack spectrum
Fourth unspiked outlet slack spectrum
250
Star) tol (121 ppm) low 1 .00 Ipm, SF6 (4 Oppm) 1 0 Ipm to outlet spike; total Dow - 12 Oipm
First spiked outlet stack spectrum 4.0 Ipm: P-746 6
Second spiked outlet slack spectrum
Can see SF6 and tol in calc'd spectrum smuOS1 1 b
Third spiked outlet slack spectrum
Fourth spiked outlet slack spectrum
Slart fol direct 121ppm S.OIpm
Toluene direct 121ppm 6 51pm P=749, recorded as outlet spec
Call Temp (F)
130C
Spk/Unsp
!
I
_ ^ _.
Sample Cond. Sample Flow
i
BKG
E
F
WCILOG02xls, WCI
-------
Data Sheet FTIR Batch Samples, WCI EPA Work Assignment 4-20.
Dale Sample time Fite name
1 1 .54 toldirb
1 1 '59 toldirc
12.03
1204
12:07
i 12.14
! 12:40
1H50
1252
I 1259
13'07
, 13'21
8/12/97 ( 1335 18120022
1349
j 14t>7 18120038
i 1435 18120049
!_ 1435
1 14.45
' 1515
1522
15.37
15:52
15:53
Path
15.53 181200(80,81)
: 16t>3 18120082
j 16.18
i 16.19
16.20
16:47 18120091
I 16-50
I 17:03
L 1746
| 17:52 ,-18120120
i 17.58
j 18'22
1824
8/1 3/97 ;
9:00 ;
9:25
i_ 9:30 tu08l3a
9.35 Iu0813b
9:41 iu0813c
9:45 iu0813d
9:52
i 9-56
Location/Notes
Toluene direct 12 1ppm 6.51pm P.749; recorded as ouflet spec 4
Toluene direcf 121ppm 6.51pm P-749; recorded as outlet spec
Switch to inlet flow 2 5 Ipm
Switching to continuous mode 250 scans
Start conlinous mode ; slop to change # scans from 50
Discovered error in date) Reset date In computer to Tuesday, August 1 2
Start conlinous mode again In 081 2 sub-dir, 50 scans
May have a througput problem, stopping to check
No throughput problem "man* mode actually reset gain to 2R (was at 4R)
Re HI detector
fccans Res (cm-1j
Started cent mod w/ 50 scans per spectrum as set in wti.aqp, sill wrong, aborted
Edited wd.prm fie to sat aqp ffle (tr* was tha problem) and gain to proper values
Inlet samples: Back on line using gain -4R, 250scans, T-130C, P=745.4
Run 1 start, continuous mode, pimfte-WCI, AQP-WCI
May have had data glitch caused by inadvertent keyboard entry altar file 27
Switch to outM (4 Ipm) and record meterbox data
Switch to inlet (4 Ipm) and record meterbox data
Manual method port change at inlet starts
Manual method inlet train back on line
Switch to oulM (5 Ipm) and record metwtoox data
AudMejjrocess change, outlet cteNa(p) (prev. steady at 2.4) drops to 0.7;
this Is the first of me usual paltetle (pellef'chartges
FTIR data check for first 'half of Run 1 .
250 ; 20
Gain actually at 8 in these data; wll need to scale and transform BKG* alt, regenerate stos flies
Process back on line after 30 mki delay
Record meterbox data
Re-start monitor mode for gain test, two spectra completed
Resume FTIR outlet analysis
Manual method port change at outlet starts.
Record meterbox data
Manual method port change at inlet starts
Resume FTIR testing at inlet
Record meterbox data
Re-fM detector
Record meterbox data
250 ,
Manual method port change at outlet completed: Isstlno resumed without notice from ERG or EPA
Switch FTIR sampjlng to outlet (unaware of test resumption)
Switch FTIR sampling to inlet
Record meterbox data
Record several "ice" and other spectra; note NH3 contamination in system
Start inlet sample flow to cell 3.0 Ipm
First unspked Inlet sample
Second unspked Inlet sample
hire) unsplked inlet sample
Fourth unsplked inlet sample
250
250 2.0
Start tol (121ppm) flow 2.00 Ipm, SF6 (4 Oppm) 1.0 Ipm to inlet spike, total flow ~12.0lpm
SF6 clearly in Ista* spectrum [
Cell Temp (F)
130C
130C
Spk/Unsp
U
u
U
u
u
u
u
Sample Cond Sample Flow
H/W 4.01pm
401pm
4.51pm
I
HW , S.Wpm
j
BKG
F(500)
F(500)
F(500)
A{500)
WCILOG02 xls, WCI
-------
HCI Concentrations at WCI (8/14/97)
[-4— Inlet
3 -
I 2
a
o-
-i
8:00
8:30
9:00 9:30
Time
10:00
10:30
-------
HC1 Concentrations at WCI (8/12/97)
13
-Inlei -0— Outlet
11 -
9-
i
a.
5 -
-1
10:00 11:00 12:00 13:00 14:00
15:00
Time
16:00 ' 17:00 18:00 19:00
-------
9-
7 -
5 -
I
&
HC1 Concentrations at WCI (8/13/97)
•Inlet —•—Outlet
9:00 10:00 11:00 12:00
13:00
14:00 15:00
16:00
Time
-------
Formaldehyde Concentrations at WCI (8/13/97)
•Inlet -^-Outlet
i, 3
-1
9:00
10:00
11:00
12:00
13:00
14:00
15:00
16:00
Time
-------
I 3H
Formaldehyde Concentrations at WCI (8/14/97)
j—»— Inlet -^-Outlet
-1
8:00
8:30
9:00
9:30
Time
10:00
10:30
-------
Ammonia Concentrations at WCI (8/14/97)
•Inlet -O— Outlet
3 -
2 -
-1
8:00
8:30
9:00
9:30
Time
10:00
10:30
-------
Formaldehyde Concentrations at WCI (8/12/97)
11
9 -
7 -
I 5i
3 -
-1
i
10:00 11:00 12:00 13:00 14:00
15:00
Time
16:00 17:00 18:00 19:00
-------
Ammonia Concentrations at WCI (8/12/97)
-Inlet -O~ Outlet
5 -
3 -
Qw
-1
10:00
11:00
12:00
13:00
14:00
15:00
Time
16:00
17:00
18:00
19:00
-------
3 -
Ammonia Concentrations at WCI (8/13/97)
•Inlet -O— Outlet
e
o.
a
2 -
GB9© oeeo
-i
9:00
10:00
11:00
12:00
13:00
14:00
15:00
16:00
Time
-------
1000-
I
a.
a
800 -
600
400
MO-
CO Concentrations at WCI (8/13/97)
•Inlet -^—Outlet
1800
1600
1400
1200-
9:00
10:00
11:00
12:00
13:00
14:00
Time
15:00
16:00
-------
1000
1
a
800 -
600-
400
200
CO Concentrations at WCI (8/14/97)
-Inlet ~O— Outlet
1800
1600-
1400
1200 -
8:00
8:30
9:00
9:30
10:00
10:30
Time
-------
B-3 HYDROCARBON REFERENCE SPECTRA
-------
Reference Spectra of Hydrocarbon Compounds
The purpose of measuring reference spectra of some hydrocarbon confounds 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 FTTR 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 fo Do wing 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
Pas
1.0 INTRODUCTION ., j
i.l 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
111
-------
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
FTTH reference spectra is comprised primarily of hazardous air pollutants (HAPs) identified in
Title ffl 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 (FTTR) 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, MRJ Work Assignments 2-12 and 2-13
Draft Juifc 14, 1999 RaSe '
-------
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 m 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 50 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 h'llK 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 PaSe 2
-------
TABLE 1. ORGANIC COMPOUNDS SELECTED FOR THE LABORATORY STUDY
Compound Name
n-hexanea
n-heptane
Pentane
isooctane3
1-pentene
2-methyl, 1 -pentene
2-methyl,2-butene
2-methyl,2-pentene
3-methylpentane
Butane
Boiling Point (QC)
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 arabient'temperature.
The instrument is an Analect Instruments (Orbital Sciences) RFX-65 optical bench
equipped with a mereury-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
(CIS) 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, MM Work Assignments 2-12 and 2-13
Draft June 14. 1999 Page
-------
Cylinder gas inlets
Calibration
manifold
• Heated line
(250 F)
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" .
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 MIST 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.
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 Repotting
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, Mil Work Assignments 2-12 and 243
Draft June 14.1999 pa*e6
-------
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 and2-J3
Draft June 14,1999
-------
DTRANSFER
D EXCHANGE
TO A\v4.U>est
SuiT-E /OO
Me
SHIPPING ORDER
MIDWEST RESEARCH INSTITUTE
425 Voiker Boulevard, Kansas City, Missouri 64110
D RETURN FOR CREDIT
D RETURN FOR REPAIR
DATE
144099
REFER TO THIS NO. IN
ALL CORRESPONDENCE
(
a
a P.M.
D PREPAID
D COLLECT
INSURE: D YES
AMOUNT
Q NO
REQUESTED BY
04 f
Charge No.
or
Bill Recipient Acct. No.
REFERENCE
QUANTITY
DESCRIPTION OF MATERIAL
PRESENT LOCATIO!
2_{
SIGNED
PACKING SLIP
MRM1 (Rev. 8/92)
-------
Code: MRI-0701
Revision: 3
Effective: 10/23/98
Page: 12 of 12
Attachment 1
Instrument Found Out of Tolerance
Instrument: /-Slo itetic^ivc cu£H/\ U/4ffdiil/|
Manufacturer: £a
iMRI Number: ~T
Serial Number:
Acceptance Criteria:
f
Date of calibration or test that revealed the out of tolerance condition: i"-6-?f
Date of previous calibration: HtHCMtwtt
Responsible person: I Q**^ ^c^W (Must receive a copy of this report)
Tested/Calibrated by^J>^—e— JJ/JS&J Date: _
^^~ rfrf' j$ ^if^Zs
Reviewed by: .x_^£^^^t/. *^£^&^-. Date: _
i>
/H-£*
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: (^Jw«^/f^L/^ (Responsible person)
Date:
MW"QA\MR!-
-------
Code: MRI-0722
Revision. 0
Effective: 03/22/99
Page: 6 of 6
MRINo.
Report No.
Noun fe/°c«tf (ri'SSu.f*-
Attachment 1
Pressure Gauge Calibration Data Sheet
No-;TvP« /*"?o SerialNo._f£237
Ambient Temperature "7.3*^ Ambient Humidity
Applied Pressure
Initial Check
Final Check
Tolerance i
Pass
Fad
SOPS
600
l.H
?oo
?oo
'.7
foo
1060
Cumuiaove uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMRI-070! and ISO IOOI2-1.
Standards Used: MRI No
Notes/ Adjustments/Repairs/Modifications;
o.ecu/-qey »^
-------
Code: MRJ-Q72!
Revision; 0
Effective: 01/29/99
Page: 9 of 9
Attachment
Calibration Data Sheet
MRI No.:
Noun: T
Model No/Type:
-ISs-JZ. Serial No.:TfllM
rature: if f
No.:
Ambient Humidity: j| /a
Applied temperature
Initial check
Final check
Tolerance ±
Pass
Fail
/.o
0.0
Jjfl.
ISO*
AJO.O
AS"
Joo.O
5.2
Cumulative uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMRJ-0701 and ISO 10012-1.
Standards used: MRI No.
V-S835"
0/3.40/
a/a&ao
o/SWJ
Date calibrated
/s-y-iz
S-'2t,-?B
-------
Code: MRI-0721
Revision: 0
Effective: 01/29/99
Page: 9 of 9
Attachment
Calibration Data Sheet
MRINo.: -
Model No./Type: H H2l
Ambient Temperature: _
Serial No.: T-
Report No.:.
Ambient Humidity:
Applied temperature
Initial check
Final check
Tolerance±
Pass
Fail
id
0.7'c.
o'c
0.6'c
' IOC °C
LZ^_
G.ltt,
o.g'c
Cumulative uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMR]-070l and ISO 10012-1.
Notes/Adjustments/Repairs/Modifications:
Limitations for use:
j)
Date Calibrated: 5"- 7"
Date Due Recalibration:
Calibration Performed bvc^ps
Reviewed by: ^^
Cal Interval: /
Date:
-------
UJ
Sill
Scott Specialty Gases
pped
From:
6141 BASTON ROAD, BLDG 1 PO BOX 310
PLUMSTEADVILLE PA 18949-0310
Phone: 215-766-8861 Fax: 21i-766-2070
CERTIFICATE
O P
ANALYST
MIDWEST RESEARCH
SCOTT KLAMM
425 VOLKER BLVD
KANSAS CITY
MO 64110
PROJECT #: 01-01788-OOi
P0#: 033452
ITEM #: 01021951 SAL
DATE: 3/31/98
CYLINDER #: ALMQ25384
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +/-5%
BLIND TYPE
COMPONENT
ETHYLENE
NITROGEN
CERTIFIED WORKING STD
REQUESTED GAS
CONC MOL1S
20.
PPM
BALANCE
ANALYSIS
(MOLgS)
20.0
PPM
BALANCE
ANALYST:
-------
Scott Specialty Gases
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 #: 12-34162-005
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.XBECTON
-------
Scott Specialty Gases
pped
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 #: 12-34162-004
P0#: 038546
ITEM #: 12Q22232 1AL
DATE: 5/25/99
27511
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
CONC MOLES
50.
PPM
BALANCE
ANALYSIS
(MOLES)
49.6
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L. BAYLOR
-------
Scott Specialty Gases
'pped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE OF
Fax: 91S-22Q-Q8Q3
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
CARY NC 27511
PROJECT #: 12-34167-006
POth 038545
ITEM #: 1202M2034951AL
DATE: 5/27/99
CYLINDER #: ALM037409
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/27/2QOO
BLEND TYPE :
COMPONENT
3-METHYLPENTANE
NITROGEN
GRAVIMETRIC
MASTER GAS
REQUESTED GAS
CONC MOLES
50 .
PPM
BALANCE
ANALYSIS
_JMOLES)
50.0
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
TAYLOR
-------
Scott Specialty Gases
trpped
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 #: 12-34162-006
P0#: 038546
ITEM #: 1202P20008C1AL
DATE: 5/27/99
CYLINDER f: ALM041358
FILL PRESSURE: 2000 FSIG
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
MIST TRACEABLE BY WEIGHT
ANALYST:
-------
Scott Specialty Gases
ipped
rom:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE
0 F
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE 100
CARY NC 27511
PROJECT #: 12-34167-005
P0#: 038545
ITEM #: 1202M2034941AL
DATE: 5/26/99
CYLINDER #: ALMO54078
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000'
BLEND TYPE :
COMPONENT
2-METHYL-2-PENTENE
NITROGEN
,C MASTER GAS
REQUESTED GAS
CONC MOLES
50.
PPM
BALANCE
ANALYSIS
(MOLES)
51.4
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
-------
Scott Specialty Gases
Tpped
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 #: 12-34167-004
P0#: 038545
ITEM #: 1202M2034961AL
DATE: 5/26/99
CYLINDER #: ALM005876
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/26/2000
BLEND TYPE
"COMPONENT
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONC MOLES
ANALYSIS
(MOLES)
2-METHYL 2-BUTENE
NITROGEN
50.
PPM
BALANCE
50.04
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L.
LOR1
-------
Scott Specialty Gases
ITpped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE
0 F
Pax: 919-220-0808
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
COMPONENT
GRAVIMETRIC MASTER GAS
REQUESTED GAS
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
Tppeci
From:
1750 EAST CLUB 3LVD
DURHAM
Phone: 919-220-0803
NC 27704
CERTIFICATE OP
Fax: 919-22Q-08C:
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITE
CARY
.00
NC
27511
PROJECT #: 12-34167-002
P0#: 038545
ITEM #: 1202P2019421AL
DATE: 5/27/99
CYLINDER fh ALM041929
FILL PRESSURE: 2000 PSIG
BLEND TYPE : GRAVIMETRIC
COMPONENT
1-PENTENE
NITROGEN
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/27/2000
MASTER GAS
REQUESTED GAS
CONC MOLES
50 .
PPM
BALANCE
ANALYSIS
(MOLES)
50.1 PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
B.M. BECTON
-------
Scott Specialty Gases
Dped
From:
1750 EAST CLUB BLVD
DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE
0 F
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
T7MT">
COMPONENT
N-HEPTANE
NITROGEN
GPJiV"rME'T'RTC MASTER GAS
REQUESTED GAS
CONC MOLES
ANALYSIS
(MOLES)
50.
PPM
BALANCE
49.97
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
L. TAYLOR
-------
Code: MRI-0721
Revision: 0
Effective: 01/29/99
Page: 9 of 9
Attachment
Calibration Data Sheet
MRI No.: r
Model No/rype: H H£\
Ambient Temperature: _
Serial No.: T-£obfZt Report No.: _
Ambient Humidity: £•_$.'
Applied temperature
Initial check
Final check
Tolerance ±
Pass
Fail
o*c
2*0
o.g'c
J
Cumulative uncertainties of the standards used to perform this calibration did not exceed the requirements
ofMRI-0701 and ISO 10012-1.
Notes/Adjustments/Repairs/Modifications;
Limitations for use:.
Date Calibrated: 'S'-1'
-------
Scott Specialty Gases
Tpped 1750 EAST CLUB BLVD
From: DURHAM NC 27704
Phone: 919-220-0803
CERTIFICATE
0 F
Fax: 919-220-0808
ANALYSIS
MIDWEST RESEARCH
CROSSROADS CORP PARK
5520 DILLARD RD,SUITS 100
GARY NC
PROJECT #: 12-341S2-001
P0#: 038546
ITEM t: 12021152 1AL
DATE: 5/25/99
27511
CYLINDER #: ALM020217
FILL PRESSURE: 2000 PSIG
ANALYTICAL ACCURACY: +-1%
PRODUCT EXPIRATION: 5/25/2000
BLEND TYPE
COMPONENT
N-BUTANE
NITROGEN
GRAVIMETRIC MASTER GAS
REQUESTED GAS
CONG MOLES
ANALYSIS
(MOLES!
PPM
BALANCE
51.3
PPM
BALANCE
NIST TRACEABLE BY WEIGHT
ANALYST:
B.M. BECTON
-------
Project No
I 2-
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE:
OPERATOR:
Check cell temperature
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure in cell, (PJ
i Check Procedure: £ fos^cj-e ?rf r$ u^j )
Evacuate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (P^ lf'-o~? •
Leave cell isolated for one Tn'Ti"»» Time
Record time and cell pressure (?„») /f:o(t ',<<'
Calculate "leak rate" for 1 minute Time
Calculate "leak rate" as percentage of total pressure
%VL = (AP/Pb)*100
|% VL| shouldbe<4
77 if./
AP
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 Spectra
Record Cell path length setting
EvaenMeCett
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 u
It •.
-inft
i OdlU
Jam iL
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum File Name
Reviewed by:
rr 5 otol A
Date:.
-------
Project No V93(-/X^ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
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 ceil, (Pj
Vacuum Leak Check Procedure:
Evacuate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (P^J
Leave cell isolated for one minute Time
Record time and cell pressure (P^
Calculate "leak rate" for 1 mimit,, Time
Calculate "leak rate" as percentage of total pressure Ap
. ' %VL = (AP/Pb)« 100
|% VL| should be < 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 (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
Record Cell path length setting . (
EvacoateCell «,
Fill Cell with CTS gas /i
Open cell outlet and purge cell with CTS at sampling rate (I to 5LPM)
Record cylinder ID Number
Record CTS gag cylinder identity and concentration yo.o
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file. - rffyfr
Record Barytron pressure during collect ^^7^
•-Record J^OHaaaqa-aB^BHcfcgroaad^ad-CalibiaUuui" Jala tlmL " Jb
Verify that spectrum and interferogram were copied to directories. _____
Record CTS Spectrum File Name rrs»?n ft
Reviewed by; tS\(t'*\A/ Date: 7pfl °>
T-J/ r
-------
Project No . - \1
DATE 1
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
OPERATOR: 7~
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
Vamiiaa Leak Check Procedure:
"°> u>* _ Ev£«2le cell to btsriSSt pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (P^J (o'.IW 711,°
Leave cell isolated for one minute Time p^
Time
/> *Vt
f) i**-~ —
0
Record time and cell pressure (?„„)
Calculate "leak rate" for I miniit»
Calculate "leak rate" as percentage of total pressure
|%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 (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
Record Cell path length setting
777. ?
rn»
6*
JTfl Cell with CTS gu
Open cell outlet and purge ceil with CTS at sampling rate (1 toSLPM)
Record cylinder ID Number
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 interferognm were copied to directories.
Record CTS Spectrum File Name
Reviewed by:.
Date:.
-------
Project No
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE
OPERATOR:
Check
temperature
Verify temperature using thermocouple probe and hand-held readout
Purge cell with dry nitrogen and vent to ambient pressure
Record ambient pressure IB cell, (P»)
.VjMoimi Leak Check Procedure:, ' 4
ijA^f i-. —T*
^^- ^*^^^%*»w|*^
•1* Evacuate cell to* baseiiae pressure.
ii^yi A***
' 'Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (T^J
Leave cell isolated for one minute
Record time and cell pressure (r^
Calculate "leak rate" for 1 minute
Initials
Time
Time
Calculate "leak rate" as percentage of total pressure
%VL = (AP/Pb)MOO
|%VL| should be<4
AP
*
%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 (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 path length setting
4*
.0 3
Fill Cell with CTS gu
Open cell outlet and purge cell with CTS at sampling rate (1 to S LPM)
Record cylinder ID Number
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
Reviewed bjr
Dale:
-------
Project No ^I-'V^ MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DAm ""ll~' OPERATOR: ^
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 ceil, (PJ
jyaouufrLeak Check Procedure:
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 (P^
Calculate "leak rate" for 1 minute Time
Calculate "leak rate" as percentage of total pressure
%VL = (AP/Pb)* 100
%VL| should be < 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)
y(t
Collect Background (AQBK) under continuous flow and ambient pressure c^»
Record information in data book. w_
Copy Background to C-drive and backup using batch file.
Record CTS Spectral
Record Cell path length setting
•fiwcuateCelr
Fill Cell with CTS ga»
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM) gflft, f.n
Record cylinder CD 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: Q/H. ~+ C/2*, • Date:.
-------
Project No
MIDWEST RESEARCH tNSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE
OPERATOR: J^
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 ceo, (PJ
iLe
i& Evacuafecell to baseline pressure
L-^-^^
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
1tl.H
Time
Time
Calculate "leak rate" as percentage of total pressure
% VL-(AP/Pb)*100
|%VL| should be < 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 (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 Spectrum
Record Cell path length setting
Q*>4 jycaenateCell
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 interferogram were copied to directories.
Record CTS Spectrum File Name
4?
Reviewed by:
L
Date:
44*-
-------
Project No —"n5/- It-1 ft MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATS 7/,*/Tq OPERATOR: T.
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, (P^)
Vacuum Leak Check Procedure: v
a-j Evaeoate cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (Pnm) I[j2%it f
Leave cell isolated for one minute Time
Record time and cell pressure (?„„) H'. 21-o(
Calculate "leak rate" for 1 minute Time
Calculate "leak rate" as percentage of total pressure
. %VL = (AP/Pb)*100
|% VL| should be < 4
Record NHrogen 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 SpectruB
Record Cell path length setting
Fill Cell with CTS gu
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: ^ V " Dat*
-------
Project No
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Start up Procedure
DATE:
*"
OPERATOR: *
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;
^O"-*f§vaettste cell to baseline pressure.
Isolate cell (close cell inlet and cell outlet)
Record time and baseline pressure (?^)
Leave cell isolated for one minute
Record time and cell pressure (1^)
Calculate "leak rate" for 1 minute
AP= P™.-P,»
?:$/.'VO
Time
0.1
Calculate "leak rate" as percentage of total pressure
%VL=«(AP/Pb)*100
|%VL| should be < 4
Record Nitrogen Background
Purge cell with dry nitrogen
Verify cell is as dry as previous background
Record ambient pressure using cell Barocell gauge
Record nitrogen flow rate (about sampling flow rate)
Collect Background (AQBK) under continuous flow and ambient pressure
Record information in data book.
Copy Background to C-drive and backup using batch file.
Record CTS Spectrum
Record Cell path length setting
AP
Fill Cell with CTS gw
Open cell outlet and purge cell with CIS at sampling rate (1 toSLFM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file.
Record Barytron pressure during collect
Record information on 'Background and Calibrations" data sheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum Pile Name
Reviewed by:
Date:
-K7.1
-------
FTIR DATA FORM
PROJECT NO. 4951-12 and 13
Background and Calibration Spectra
BAROMETRIC: 7^% 1
SITE: NCO Laboratory DATE:
TIME
/*.-«
,,:V7
*,,'
J&^K—
IJW
:mc backSfyWW
W-07-99
FILE
NAME
0 KGo'tenA
cri*,*
^,
&ii r n-tn-tfl —
— IW-toU W (P
c.~$*ent*1 £
S
(Dial)
PATH
*.-3
ii
if
-C-fjtt —
' '
,*.,
NOTES
Jjn ^M«uk. t-tt£. (3 t>- f L f /^\
/o*4.*( ^P***1 f^i^**1* f t£)l-fs\
^.ff* 5%/- 1-.^
^
* Zf fcf'*'
,0.^ ,^ ^ ,0^
f/7/^ '
NUMBER
SCANS
r~
fT»
^
_G» —
^*-
•
Rrsolullon
(e»-l)
/.*
/.r.
/.*
f — , I, —
"" If**
i,o
G*t
TFMP(F)
««
^.
«..
* ^?J ^
«.*
OPERATOR: ^ <^*Y^
Gaa
PRESSURE
75-/.-T
^
„,»
^/.^
^.f
•KG
—
w,
707,
,.,.
951\I2Vefs\furdaU Jhecu for references.il> Reviewed b
Dsl
A POO
~^
((
'I
"
^%^
•
v -*y
c -7-7-1
00
-------
FTIR DATA FORM
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR: /.
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
Rcsolulkm
(cm-1)
Go
TBMPjJRf'
CM
PRESSURE
•KG
APOD
^o.o (Y-u. &(f*-l***»<3 o.to
ufa
'.O
W -ytt.
C.75
emcJ>«ckNfy99yl95I\12^rfsSflirdala iheeu for references.xli
07-07-99
Reviewed by _
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE: 7/?/y?
OPERATOR:
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
Resolution
(cm- 1)
Ou
TEMP (F)
Gas
PRESSURE
BKG
APOD
C-SW
Ae
fexo -
•-0
75^.0
'. t>
l.O
752.
ft
0.10
6-
/,/(
foo
0
a
emc_b»ck'>/y99vl9Sl\12VefiNftir dau sheeu (ot refeiences,)ili
07-07^99
Reviewed by
-------
PROJECT NO. 4951 12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR: 77
TIME
FILE
NAME
(DM)
PATH
NOTES
NUMBER
SCANS
Ruolulloo
(em-1)
G*s
TEMP(F)
Gu
PRESSURE
•KG
APOD
8K60 7(2 A
/.O
, 3
te.o'b
/.ffft
7S4-/
-nz,
ft
/, 0
It)
/•O
C? 1.1
l.o
7S&.O
10. JO
•\
r?.o
rao
cmc bad6fy99vl951XJ2ycfs\ftirdu» shccu for refeicnoes.ils
07-07-99
Reviewed by
//5/I1
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FT1R DATA FORM
Background and Calibration Spectra
DATE:
BAROMETRIC:
OPERATOR:
TIME
FILE
NAME
(DM)
FATH
NOTES
NUMBER
SCANS
Resolution
(cm-1)
Gu
TEMP(F)
Gw
PRESSURE
•KG
APoo
(64 j
-.0
. f
f,o
Ceo
1- O
75V.
l.o
fttr
70C
***
cmc b«kNfy99M951\12Sref$Sftirdala jheeu for references
07-07-99
Reviewed by
Pile
-------
PROJECT NO. 4951-12 and 13
SITE; NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
'
V
DATE: 7
OPERATOR:
T.
TIME
FILE
NAME
(DM)
FATH
NOTES
NUMBER
SCANS
Rnoldttoo
Gm
TEMP(F)
Gm
KESSURE
•IG
APOD
(\\t4o
•. o
. \
f. o
is-7.1
1. 0
**•<>
tr
5*
t.o
tmc h«i\/y^M95 l\l ^n-f j\Wr d«u ihecu for rrfcra>ces xli
07-07-99
Reviewed by
J_L
-------
PROJECT NO, 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Background and Calibration Spectra
BAROMETRIC:
DATE:
OPERATOR: T.
TIME
FILE
NAME
(DM)
FATH
NOTES
NUMBER
SCANS
RCMlllllOB
PRESSURE
•KG
APOD
foo
(.O
$«>
,*'.«<
I3S.2
!$<*.(
5°°
1,0
emc_b»cWy95M951MZ*ef»*ftir
-------
Project No. '* '' fc / MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
OPERATOR:
~ Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting >g 9t,
Record Background Spectrum File Name SHAatrf &
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 S
Adjust sample flow through cell to 0,5 lo 1 LPM, Record flow rate /, oo
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 laterferogram to backup directories
End Time
at-
Reviewed by; i/lloAl— Date:,
-------
No. — /-^,^ MIDWEST RESEARCH INSTITUTE
FTIR Reference Specman Checklist
DATE: 7'V?^ OPERATOR:
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting g^, «
Record Background Spectrum Ftle Name i&te*M fe q backup directories
End Time
Reviewed by:
-------
Project No. 1">I' , j— MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE: I'l^'l"! OPERATOR:
Reference Spectrum Sample
Start Tax
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 boot
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by:
-------
Prsjeet No IW'fl- ^ MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE: 7/^fyt OPERATOR:
I ,b*t+t
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting /a.o>
Record Background Spectrum Fde Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum fate Name
HI! 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 L/& \*Ji»Q k^m, $e Jl>
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in date book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by:.
-------
P^ct No flS/"'V__ MIDWEST RESEARCH INSTITUTE
FliK Reference Spectrum Checklist
OPERATOR:
— Initials
Reference Spectrum Sample -**£FreP ft- lu/U*»
StanTime ""^"
Record Cell path length setting
Record Background Spectrum File Name ? W4»i il, ft
Record CTSSpectrum Hie Nam.
Record Compound Name
Record Cylinder Identification Number *
Record Cylinder Concentration
Record Spectrum Rle Name a, j>Bl< 4 ft
Fill cell to ambient pressure with gas from cylinder standard ^i *
Open ceU outlet vent valve g^
Adjust sample flow througi cell to 0.5 to I LPM, Record flow rate |,gg if*
Allow to equilbraa for 5 minutes ^
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book -fl;,
Copy Spectrum and Interferogram to backup directories •fyt
End Time ff ;
Reviewed bv: Of t V*\/*~^ Date:
-------
No n^l "'t_ji ' MIDWBST flESEARCH INSTrrUTE
FTIR Reference Spectrum Checklist
DATE: 1(l*\n OPERATOR:
Initials
Reference Spectrum Sample ^ - {,^fo»
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Spectrum FUe Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Specoum 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 £^*£i ut*»*£ pw 4
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: < *J*«~t^~"^ Date:.
-------
Project No. ''I 3*1'' t £» MIDWBST RESEARCH INSTITUTE
FITR 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 ry
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
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: V \\OJAsf— Date:
-------
Project No MliillL^ MIDWEST RESEARCH [NSTITUTE
FITR Reference Spectrum Checklist
DATE: i -i • • i • • OPERATOR:
Reference Spectrum Sample
Start Time
Record Cell path length setting /p.o^
Record Background Spectrum File Name
Record CTS Spectrum Hie Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum File Name
Fdl 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 £^&t**4tM$ £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
Initials
Reviewed by:
-------
No. ^lll'll ^ MIDWEST RESEARCH INSTITUTE
FTTJR Reference Spectrum Checklist
DATE: -?/)?> ft OPERATOR:
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting / * .
Record Background Spectrum File Name j(^(,o7f> g-
Record CIS Spectrum File Name ntolrtlK I % «7(? /*
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration 5*0.0
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 mir"*** •
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 bjr * lif~tA'*^~ Date:
-------
Project No. mSM* ('?. MIDWEST RESEARCH INSTITUTE
FUR Reference Spectrum Checklist
DATE: Ij^fH OPERATOR:
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CIS Spectmm Hie Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum Rle 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 LFM. Record flow rate (JA1
Allow to equilibrate for 5 minutes Le$v****9 jp*' H $fo
Record sample pressure in cell
Record sample flow rate through cell
Start spectrum collect program
Record information in data book
Copy Spectmm and Interferogram to backup directories
End Time
Reviewed by:
-------
Projecthfa M1>l-'*(l? MIDWEST RESEARCH INSTmJTE
FTTJR Reference Spectrum Checklist
DATE IjtSJT'r OPERATOR: T", (s>
- Initials
/
Reference Spectrum Sample
Start Time I*?"**} ru**t*'i
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 (low 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 dkectories
End Time
Reviewed by:
-------
Project No, —I*51' dl_ MIDWEST RESEARCH INSTITUTE
FITJR Reference Spectrum Checklist
DATE:
OPERATOR:
. 6**,
Initials
Reference Spectrum Sample
Stan Time
Record Cell path length setting M,«%
Record Background Spectrum File Name
Record CTS Spectrum Me 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 rate through cell
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: v l^^T . Dttto:
-------
Project No \7 \ ' f ? MIDWEST RESEARCH INSTITUTE
FITR Reference Spectrum Checklist
DATS m»m OPERATOR:
Reference Spectrum Sample
t
Initials
rt-
Start Time lt/: •
Record Cell path length setting ,_
Record Background Spectrum File Name
Record CIS Spectrum File Nan» Ctta"7/SB , > fit* tn & ^ ^
Record Compound Nam*
Record Cylinder Identification Number •
Record Cylinder Concentralion
Record Spectnim FUe 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 ra»
Allow to equilibrate for 5 minutes
Record sample pressure in cell
Record sample flow rate through cell ; / pg
Stan spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories -f \
End Time
Reviewed by: ___MJ24£±±! ' Date: _J/Lk
31.
-------
: No. Tl>,,/- C2- ^ MIDWEST RESEARCH [NSTITUTE
FTlR Reference Spectrum Checklist
DATE
iM OPERATOR: T~/6 «*1
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration ,5/3
Record Spectrum Hie 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:
-------
Project No. r7>( ' t L MIDWEST RESEARCH INSTTTUTE
KF1K Reference Spectrum Checklist
OPERATOR:
Initials
Reference Spectrum Sample i#v— \| 1Ju7&*a
Start Time .prry
Record Cell path length setting /0.°'
Record Background Spectrum File Name ^ f ^ ft
Record CIS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number
Record Cylinder Concentration
Record Spectrum Me Name
Fill cell to ambient pressure with gas from cylinder standard
Opea cell outlet vent valve
Adjust sample flow through cell to 0,5 to 1 LPM. Record flow rate
Allow to equilibrate for 5
Record sample pressure in cell
Record sample flow rate through cell l.a'k
Start spectrum collect program
Record information in data book
Copy Spectrum and Interferogram to backup directories
End Time
Reviewed by: \L\V **T Date:-
-------
Project No Tj > ' '' *".. ' y MIDWEST RESEARCH INSTITUTE
FTlK Reference Spectrum Checklist
PATH: I ((ffll OPERATOR: T.
Initials
Reference Spectrum Sample % -^
Start Time
Record Cell path length setting I0.
Record Background Spectrum File Name
RecordCTS Spectrum File Name . Cli£lli»ii& i
-------
^J^ No- —III —J MIDWEST RESEARCH INSTITUTE
FtlK Reference Spectrum Checklist
DATE- 'f'"in 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 sell to ambient pressure with gas from cylinder standard
Open cell outlet vent valve jfc
Adjust sample flow through cell to 0.5 to 1 LPM. Record flow rite
Allow to equilibrate for 5 minutes
Record sample pressure in cell ' -jft»
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: VH l> if _ Date:.
-------
No -- , — MIDWEST RESEARCH INSTITUTE
FUR Reference Spectrum Checklist
OPERATOR:
Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
Record CTS Specttum 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
Cepy Spectrum and Interferogram to backup directories
End Time
.Reviewed by: Date:.
-------
Project No U^l'tt ,>"*? MIDWEST RESEARCH INSnTUTE
FOR Reference Spectrum Checklist
DATE: ~7|'U^1 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 Hie 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 ..__rf/(tf
Record information in data book _____
Copy Spectrum and Interfax)gram to backup directories ______
End Time ^___
Reviewed by: ' Date:,
-------
Project No. ^\'\T- }I"? MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DAT1: -'f.*|n OPERATOR:
Initials
Reference Spectrum Sample / vt, • ^-v\Sft^(- ( -P
. rf . /? L«t n '
Start Time
Record Cell path length setting t/(.fr
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 gfy
End Time ' (ffC
Reviewed by: Date:.
-------
Project No. —"11*1 -1^| MIDWEST RESEARCH INSTITUTE
FTIR Reference Spectrum Checklist
DATE: •7/1U 19 OPERATOR: T.
— Initials
Reference Spectrum Sample
Start Time
Record Cell path length setting
Record Background Spectrum File Name
RecordCTS Spectrum File Name r-urtiu* itW7i<-A
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 mmv'**
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:.
-------
No. q- MIDWEST RESEARCH INSTITUTE
FITR Reference Spectrum Checklist
OPERATOR: T-
— Initial!;
Reference Spectrum Sample
Start Time
Record Cell path length setting (f)
Record Background Spectrum File Name
Record CTS Spectrum File Name
Record Compound Name
Record Cylinder Identification Number la^
Record Cylinder Concentration ua
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:.
-------
FTIR DATA FORM
Sampling Data
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
Time
,<•-*<
,*-.,«.
File
Name
******
0^4
i
(DM)
Pilh
,...^
,,.^
DATE:
NOTES
H*^ £-/>!
/(.*/*» MS fl*-
•
7/t/YT
Scans
<*e
f«o
Resolution
t (cro-1)
,-
1.0
•
BAROMETRIC: /5f. V
OPERATOR
Gas
Temp CO
y-^j^l—^b
1 9
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Sampling Data
DATE:
BAROMETRIC:
OPERATOR:
Time
Flic
Name
P»lh
NOTES
HeMJUlklD
Gn
TempfC)
Flow
Rale
Pressure
•KG
tf'i*
1.0
. 6
ft
u
emc_bacWy99vl95 l\12«f JHfiir
-------
FTIR DATA FORM
Sampling Data
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
DATE:
BAROMETRIC:
OPERATOR: '
Time
File
Name
(DW)
Pith
NOTES
Sans
Rettolutloi
Gu
TtmpCC)
Flow
R.t«
Gu
BKG
l.o
1.0
'1
emc_b«ckNfy99vl951\12NrefWtird«i« sheets for i
0707-99
Reviewed by
Due
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Sampling Data
BAROMETRIC:
DATE:
OPERATOR: 7~.
Time
Nine
(Dbd)
P*tb
NOTES
Scout
Kodultoo
Gm
Temp (*C)
Flow
Rate
Gat
Pressure
BKC,
Ao
to, e -
$<*>
&
(.0
12M-1
•11*0
(.0
Jff
cmc_backMy99v<951\1 yrehSitir dau iheeti for references.*!*
07-07-99
Reviewed by
-------
PROJECT NO. 4951-12 and 13
SITE: NCO Laboratory
FTIR DATA FORM
Sampling Data
DATE:
BAROMETRIC:
OPERATOR:
Time
Pile
Name
(DW)
Pith
NOTES
Sons
Resolution
. (cin-U
Gm
Temp <'C)
Flaw
Rile
Gu
Pressure
BKG
-i-
/.O
IK-
tO-o"*?
*<*>
75L..I*
7/fr/t
-I
( ,0
125.*
7/4
«O.o>
5**
o.tf
„
W/**
/.O
7ft* A
cmc_b»ckN|y9W495l\IZ*refiV«rd«la sheels for referencet.ili
07-07-99
Reviewed by
Dale
-------
Pr°Ject No H^]-11 ) j"l MTOWIST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
D ATE: ?" T~ ^ . . OPERATOR:
Initials
Purge sample from cell using ambient air or nitrogen
Record Nitrof en 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 rale)
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 LFM)
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 krw nitrogen purge or under vacuum
Fill MCT detwtof deww
Reviewed by:
-------
Project No
' I2- .
MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE
OPERATOR:
Initials
ctS
Purge sample from cell using ambient air or nitrogen
Record Nitrof en 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
Fill Cell with CTS gas
Open cell outlet and purge cell with. CTS at sampling rate (1 to S LPM)
Record cylinder ID Number
Record CTS gas cylinder identity and concentration
Record and copy spectrum and interferogram to C-dri ve 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 Pile Name
Close cylinders
Evacuate of Purge CTS from cell using nitrogen
Leave cell under tew nitrogea purge or under vacuum
RE MCT detector deww
Reviewed by:,
0. W Lfk.
-4*-
tt.
Date:,
JL1
-------
P^wt No L_ MIDWEST RESEARCH INSTITUTl
DAILY CHECKLIST
Shut Down Procedure
DAm •'-»'• OPERATOR:
Initials
Purge sample from ceil using ambient air or nitrogen
Record Nttrof en 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 CIS Spectrum
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 / (<* M .Art** - <>*e <&>£. <,Lt*.i .
Record and copy spectrum and Jnterferogram 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 uuerferogram 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 dewmr
Reviewed by:
-------
NO. _n?r'.r)n MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE Hi»p7 OPERATOR: T.
Initials
Purge sample from cell using ambient air or nitrogen
Record Nitrogen Background
Purge cell with dry nitrogen
Verily cell is as dry as previous background
Record ambient pressure using cell Barocell gauge .
Record nitrogen flow mte (about sampling flow rate)
\tr
Collect Background (AQBK) under continuous flow and ambient pressure ±
Record information in data book. i«F '
Copy Background to C -drive and backup using batch file.
Record CTS Spectrum
Fill Cell with CTS gas f^
Open ceE outlet and purge cell with CTS at sampling rate (1 to 5 LPM) i,(o
Record cylinder ID Number
Record CTS gas cylinder identity and concentration 3.0 Off/"*
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 &JJt
Leave cell under low nitrogen purge or under vacuum
Fill MCT detector drwmr
Reviewed by: _^ D** .
-------
*'?• ) ...... '1 MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE 1
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 • 0 „$
w*^ /u
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
Fill Cell with CTS gas
' Q
Open cell outlet and purge cell with CTS at sampling rate (1 to 5 LPM) j/Hp ALA* is -**i •»
g £*-X
Record cylinder ID Number fit,
Record CTS gas cylinder identity and concentration • fa *p-~
Record and copy spectrum and interferogram to C-drive and back up using CTS batch file. 3^
Record Barytron pressure during collect
Record information on "Background and Calibrations" date sheet
Verify that spectrum and interferogram were copied to directories.
Record CTS Spectrum Rl* Nam»
Close cylinders
Evacuate or Purge CTS from cell using nitrogen
Leave cell under low nitrogen purge or under vacuum
Fill MCT detector dewmr
B,vi»w«thv /fc**^-^ . Data,
-------
• r MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATSjlllfl^ OPERATOR:
Initials
Purge sample from cell using ambient ait or nitrogen
Record Nitroten 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 rite)
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
i&a€uate Cell
Fill Cell with CTS gas
Open cell outlet and purge ceil 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 Rls Nairn
Close cylinders
Evacuate or Purge CTS Cram cell using nitrogen
Leave cell under tow nilrogai p«^e or under vacuum
Fill MCT detector dewtr
Reviewed by: Y I Vf^ Date:
-------
Project No. *1^6I "it ft MIDWEST RESEARCH INSTITUTE
DAILY CHECKLIST
Shut Down Procedure
DATE lliuM 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) \ir\
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
Fill Cell with CTS gas
Open cell outlet and purge cell with CTS at sampling rate (t to 5 LPM)
Record cylinder ID Number
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 intetferogrsm were copied to directories.
Record CTS Spectrum File Name
Close cylinders
Evacuate or Purge CTS from cell using nitrogen
Leave cell under tow nitrogen purge or under vacuum
Fill MCT detector dewmr
R,view«rfhv- * V«Y~- . Date
-------
APPENDIX C
EQUIPMENT CALIBRATION CERTIFICATES
C-l
-------
C-l CALIBRATION GAS CERTIFICATES
C-2
-------
01 05 98 13,58 0215 T8f 0320 SCOTT
Scott Specialty Gases
6141 BASTQN 1QAD FO BOX 310
Prom: PLOMSTSADVILLE PA 18949-0310
Phom*: 21S-766-8861 Pax: 215-766-2070
CERTIFICATE OF ANALYSIS
MIDWEST RESEARCH fROCTECT f : 01-81796-005
DAVE ALBORTY, X1525 PO#: 029872
425 VOLXSR 1LVD IT8M #: 01023912 4AL
DATE: 5/13/97
KANSAS CITY MO 64110
CYLINDER #: AU«!057730 ANALYTICAL ACCURACY; +/- 2%
FILL PRESSURE: 2000 PSTG
BLEND TYPE : CERTIFIED MASTER QAS
REQUESTED GAS ANALYSIS
CQIPQKfgNT CQNC MOLSS
TOLUEKB 120. PPM 121. PPM
AIM BALANCE BALANCE
__ _ 3T_
%.
v
ANALYST;
GE3IYA
oui*tttt.!C.
-------
12 22 91
10: 39
FAI 1S1QS892134
SCOTT SPECIALTY
HOOT
Scott Specialty Gases
1290 CQMBERMERiE STREET
TROY MI 48083
Phone: 248-589
C E R T I P 1
-2950
C A T B
O P
Pax: 248-589-3134
ANALYSIS
MIDWEST RESEARCH
MELISSA TUCKER; # 026075
425 VOLKER BLVD
KANSAS CITY
MO 64110
PROJECT #; 05-97268-002
P0#: 026075
ITEM #: 05023822 4A
DATE: S/03/96
CYLINDER #: *7§53 ;
FILL PRESSURE: 2000 PSI
BLEND TYPE : CERTIFIED
COMPONENT
SULFUR HBXAFLUQRIDS-
NITROGBK
MAS
ANALYTICAL ACCURACY:
PRODUCT EXPIRATION:
TER GAS
REQUESTED OAS
CONG MOLES
+ /- 2%
6/03/1997
ANALYSIS
(MOLE3)
4.
PPM
BALANCE
4.01
PPM
BALANCE
CERTIFIED MASTER GAS
-------
01 OS 98 18.58 tt213 786 0320 SCOTT ->
«loos
Scott Specialty Gases
€141 SASTGN ROAD PO BOX 310
Fraiu PHJMST1ADVILLB PA 18549-0310
Phon»: 215-766-8861 Fax: 215-766-2070
CERTIFICATE OF ANALYSIS
__-. --- •««.«•»»»••«_»««__»-••».„«,„••__• --- ——-•- — • — *»-- — -.«.«••«••„„__ __ _•••««
MIDWEST RESEARCH PROJECT #; 01-88514-001
TOM G1YIR SQ#; 029257
42i VOLKER 8LVD ITEM #: 01021951 1AL
DATS: 3/25/97
KA8SAS CITY HO 64110
CYLINDER #: ALM023S40 ANALYTICAL ACCD1ACY: +-1%
FILL PRESSURE: 2000 PSIG
BLEND TYPE : ORAVIMBTRIC MASTER GAS
REQUESTED Q&£ ANALYSIS
COMNBNT CONC MOLBS
STHYLJOJK 20. PPM 20.01 9PM
NITRCX3BM BALANCE BALANCE
ANALYST:
GfiNYA
WMMT.CA S*MK«M»*WINO.C* UONOMOMT.OO CMC*«0. H
DUMUH.MC SOUTH »UUHfmO,tU *MNU.omMO M.UM9TIMWUJ.M P«»0»».«
-------
OCT-16-9* UIEB 10129
SPECIBUJV CP3ES
417
» wn* <•> ,
J
6.589
LIQUID CARBONIC
•TO •OUTH ALAUmA tm«T • 10* AMOOtt. CA WCW
nw. I ineurt. iiir.
COMMNUfl
tKtuit mn
PJ
MtlOfSt tti«um-1
CVUKDOMO.
U Wl
. 13
Z-Z000A1
COMMNXWT
ami
ac/ pyy« IOKIWTIOH
x o
• UlttlO
X 0
WM Utf't
»
co
C J717117
c tmias CONC. }»j 0*1
c trtstM cone. »m pp*
X M6MM COIIC. 5J7| ^t
MIAN TUT AMAT StTI MM
I
•
inc
IUtl9
uit
•
s
C
c
c
K
ai/n/vf
co»*c.
CONC.
CONC.
net ««H4 MtM 119 p«lf
TMUCVLMMBINO, M MS
n iun umt> ACCOIUXNO to atcnoM M».«oa/«ts/i2*
turr»cm)coi.Mo. t»». t/ti
PKOCKOUM tl
t 1 *NUt T1AC1IA1U
ION MH
CDnW9 Cvncxrr
MbMCt
•XraUtlONOAtS 04/OT/VI 7HM MIMTN
4AUUMEO
-------
C-2 ENVIRONICS MASS FLOW METER CALIBRATIONS
C-3
-------
ENVIRQNICS FLOW CONTROLLER CALIBRATION SHEET
Mf »: 4, Descrlotion; AIR
Size; 100,0
SCCM, K-factor; 1.0
SERIAL « ft&1)in 3*0*4
This flow controller was calibrated using a Sierra Cal Bench(TM), a traceable
Primary Flow Standard Calibration System. This calibration is referenced to
dry air at a temperature of 44F { C) and a pressure of 29.92 in.Hg (7SQTorr)s
5 X
10 %
20 X
30 %
40 91
50 %
60 X
70 X
80 X
90 51
100*
Set Flow
5.0
10.0
20.0
30.0
40.0
50,0
60.0
70.0
80.0
90,0
100,0
CCM
CCM
CCK
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
True Flow
5.236 CCM
10.269 CCM
20.434 CCM
30,524 CCM
40.606 CCM
50.636 CCM
60.683 CCM
70.779 CCM
80.917 CCM
91 .035 CCM
101.12 CCM
Calibration data was last savod on Friday 03 January 97
at 19:11:00
Verified by:
Date;
.--12.
-------
ENVIRONICS FLOW CONTROLLER CALIBRATION SHEET
Mf #: 3, Description; AIR
SSHIAL
Size; 1000,0 SCCM, K-factor; 1.0
This flow controller was calibrated using a Sierra Cal Bench(TM), a traceable
Primary Flow Standard Calibration System, This calibration is reftrenced to
dry air at a temperature of ftjtF < _ C) and a pressure of 29,92 in.Hg (76-QTorr}.
5 X
10 X
20 X
30 %
40 X
50 X
60 X
70 X
80 X
90 X
100*
Set Fl
50.0
100.0
200.0
300.0
400.0
500,0
§00.0
700.0
800.0
900,0
1000.0
ow
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
True Flow
50.515 CCM
101.84 CCM
204.84 CCM
306,67 CCM
408.82 CCM
510.43 CCM
611.44 CCM
713.39 CCM
816.61 CCM
918.19 CCM
1021 .3 CCM
Calibration data was last saved on Friday 03 January 97
at 17;55:OC
Verified by:
Date:
-------
ENVIEONICS FLOW CONTROLLER CALIBRATION SHEET
Mf *: 2, Description; AIS , Size: 10000. SCCM, K-factor: 1,0
SERIAL #
This flow controller was calibrated using a Sierra Cal Bench(TM), a traceable
Primary Flow Standard Calibration System. This calibration is referenced to
dry air at a temperature of SSL? ( C) and a pressure of 29.92 in.Hg (760Torr)
5 X
10 X
20 X
30 X
40 X
50 X
60 X
70 X
80 X
90 X
100X
Set Flow
500.0
1000.0
2000.0
3000.0
4000,0
5000.0
6000,0
7000.0
8000.0
9000 .0
10000.
COM
CCM
CCH
CCM
CCH
CCM
CCM
CCM
CCM
CCM
CCM
True F
510.51
1021 .4
2046.9
3074 .8
4103 .8
5135.6
6156.8
7182.5
8203 .3
9219.5
10233.
low
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
Calibration data was last saved on Friday 03 January 9?
at 17;09;OC
Verified by:.
cr
Date :
-------
ENVIRONICS FLOW CONTROLLER CALIBRATION SHEET
Mf *: 1, Description: AIR , Size: 10000. SCCM , K-f«ctor: 1.0
SERIAL « ......... A*}*jf£.&i:rto __
This flow controlier was calibrated using a Sierra Cal Bench(TM3, a traceable
Primary Flow Standard Calibration System. This calibration is referenced to
dry air at a temperature of 4JJLF ( _ C) and a pressure of 29.92 in.Hg (760Torr),
5 *
10 %
20 *
30 *
40 %
50 *
60 %
70 *
80 *
90 X
100%
Set Flow
500.0
1000.0
2000.0
3000,0
4000.0
5000.0
6000.0
7000.0
8000.0
9000.0
10000.
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
True Flow
498,79 COM
1009 .0 CCM
8
2
3
9
3
3
3
2029
3058
4088
5121
S143
7178
3206
9224,<
10252
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
CCM
Calibration data was last saved on
Friday 03 January 97
at 16:22:00
Verified by;
Date :
-------
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
BY EXTRACTIVE FOURIER TRANSFORM INFRARED (FTIH) SPECTSOSCOPY
1,0 Introduction.
Persona 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 urn) , 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 litait) 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
choice of detection limit (DLt) and analytical uncertainty
(AUs) 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 MAUlf 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
-------
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
(GEM) 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.
Al = at b c, (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.
Ct = 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.
-------
8
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.
-------
9
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
-------
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
-------
11 . . • . .
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
-------
12
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 refe'rence 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 ETIR system.
3.19 RMSD. Root Mean Square Difference, defined in EPA
ETIR Protocol, appendix A.
3,20 Sensitivity. The noise-limited compound-dependent
detection limit for the FTIR system configuration. This is
estimated by the MAD. 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
-------
.13
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 ia 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.
-------
14
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 FTIR 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
-------
15
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
-------
16
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 C03 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,
COj 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.
-------
17
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
-------
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 Aaencv.
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.
-------
19
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 ETIR 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
-------
20
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,
-------
21
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
-------
22
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 ETIR 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(3) at
concentrations within ± 2 percent of tire 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 ETIR 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
-------
23
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) AUt, DL1( overall
fractional uncertainty, OF0U maximum expected concentration
(CMAXJ , and t^, for each, (b) potential interferants, (c)
sampling system factors, e.g., minimum absolute cell
pressure, (PMIJ, FTIR cell volume (Vss) , estimated sample
absorption pathlength, Ls', estimated sample pressure, Ps',
Ts'» 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, FCra, and upper wavenumber
position, FUm, plus interferants, upper wavenumber position
of the CTS absorption band, FFU,,, lower wavenumber position
of the CTS absorption band, FFL,,, 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
-------
24
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 (DLi)
and the maximum permissible analytical uncertainty (AUt) for
each analyte (labeled from 1 to i). Estimate, if possible,
the maximum expected concentration for each analyte/ CMAXi-
The expected measurement range is fixed by DLt and CMAXi f°r
each analyte (i),
8.1.2 Potential Interferants. List the potential
interferants. This usually includes water vapor and CO2,
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 GTS.
8.1.4. Fractional Reproducibility Uncertainty (FRU^ . The
FRU is determined for each analyte by comparing CTS spectra
taken before and- after the reference spectra were measured.
-------
25
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 FRO 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 - ctslOSla)»
and S4 [(ctsllOlb + ctslOSla)/2]. The HMSD (SRMSJ 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
-------
26
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 FTIR 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 s 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 APy after 2 minutes.
8.2.2.2 For both the evacuated sample and purging
techniques, pressurize the system to about 100 mmHg above
-------
27
atmospheric pressure. Isolate the pump and determine the
change in pressure APp after 2 minutes.
9.2.2.3 Measure the barometric pressure, P0 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
APy or APP, as follows:
AP
= 50tss-J
r
ss
where 50 = 100% divided by the leak-check time of 2 minutes.
9.2.2.5 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 CIS 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.
-------
28
Compare the three CTS spectra. CTS band areas shall agree
to within the uncertainty of the cylinder standard and the
KMSD 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
-------
29
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, fable 1 gives a sample presentation of
documentation.
8,5 Background Spectrum. Evacuate the gas cell to <. 5
minHg, 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, SO2, CO, NH3, are readily available from cylinder
gas suppliers.
8.5.2 Water vapor spectra can be prepared by the following
-------
30
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 3 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
-------
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
-------
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
s 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
-------
33
achieve the required signal-to-noise ratio. Obtain an
absorbance spectrum by filling the cell with N2. Measure
the RMSD 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.
-------
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
-------
' 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.
-------
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 =
where:
CS =
Umpike(l-DF)
(4)
DF
SFS(dlt
SFS(3
S(3PR)
Dilution factor of the spike gas; this value
shall be ilO.
SF6 (or tracer gas) concentration measured
directly in undiluted spike gas.
Diluted SF6 (or tracer gas) concentration
measured in a spiked sample.
-------
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
Z 0,001.
10.2 Absorbance Path length. Verify the absorbance path
length by comparing reference GTS spectra to test CIS
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
-------
38
apodization function that was used in transforming the
reference spectra.
10.5 FTIR Cell Volume. Evacuate the cell to a 5 mitiHg.
Measure the initial absolute temperature (TJ and absolute
pressure (PJ . 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 (Pm); and the cell final
absolute temperature (T£) and absolute pressure (P£) .
Calculate the FTIR cell volume Vss, including that of the
connecting tubing, as follows:
v m
/7I rrt
m
(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
-------
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.,
FRO, MAU, FCO) 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,
^ca/c
\S» \'r)\rs)
where:
Ceorr = Concentration, corrected for path length.
Coalc = Concentration, initial calculation (output of the
analytical program designed for the compound).
-------
40
Lr - Reference spectra path length.
L5 = Sample spectra path length.
Ta = Absolute temperature of the sample gas, K.
Tt = Absolute gas temperature of reference spectra, K.
P3 = 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.
-------
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.
-------
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 FTIR 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
-------
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.
-------
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. 1Cl =
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 which are spiked with the analyte(s) and 12
-------
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.
Sm = 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 s CF s 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.
-------
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 1Q~4 to 3.2 x 10"4 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".
-------
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 CFM 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, Chemical 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.
-------
48
Table 1. EXAMPLE PRESENTATION OF SAMPLING DOCUMENTATION.
til* •*
VII* ••
Smmflm
Pr*c*M
Sm*flK ttm»
Sptclnm fll*
lnierr*ragriha
••••lutlMI
Stmma
Ap^izatiM
£•!•
CIS Spectra
-------
49
Vent Ve.
rii t
mFtow Hi Flow fflRow I
||MtUr |M*t»r [HMrtvr j
.. JTL 7r T^ T C^
Plata It ..f'^A"!.
rt
D
Row
Meter
h t£aa;
mm\ ! ®oSSl .
""^\r
»\
Slack !,_ -aJ {>i| ,"»«-.«. SanpleGa* Delivery MwiNold IfieT'
J*ILJ-«J 1 _ Togole
Balston ^rT^r- ~* \ . r*-| Ww
F*»r "I" ••"•' S»rrpl« Line »1 \(\( v
. PuniJll
Spike Line
T^flto,
Sample Line 12 f/^1 V"*
Calibration Gas Lma
Men Flow Cattiralion Gas MmVok)
Meier i i
^* -*
1
To CaJfcraUon
QaaCyimdert
Pump ii
Figure 1. Extractive FTIR sampling system.
-------
50
.8-
/•v ^
,4-
.2
0-
FRU « SRMS(FU-FL)/BAV
SRMS = .00147
BAV = 3.662
FM = FRU = .086
«*«BKJJ
MflAtowA^^
p-xylene
1050
1000
950 900 850
Wavenumbers
800
i
750
Figure 2. Fractional Reproducibility. Top: average of ctslOBla and
ctsllOlb. Bottom; Reference spectrum of p-xylene.
-------
D-2 EPA FTIR PROTOCOL
-------
Page 1
PROTOCOL FOR THE USI OP EXTRACTIVE FOURIER TRANSFORM
INFRARED (FTIRJ 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 PTIR 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 Cor 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 B 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~*).
1.3 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
-------
BPA FTIR Protocol
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 07 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 Verif lability 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 and 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
-------
SPA PTIR Protocol
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 PRE-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 AXJ^ is the
maximum permissible fractional uncertainty of analysis for the
jln analyte concentration, expressed as a fraction of the analyte
concentration in the sample.
4.1.3 Required detection limit for each analyte (DL^, ppm).
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 (AU^).
4.1.4 Maximum expected concentration of each analyte
(CMAX^, ppm). • "
-------
BPA fTim Protocol
4.2 Identify Potential Interf erants . Considering the
chemistry of the process or results of previous Studies, identify
potential interf erants , i.e., the major effluent constituents and
any relatively minor effluent constituents that possess either
strong absorption characteristics or strong structural
similarities to any analyte of interest. Label them 1 through
N|, where the subscript «j« pertains to potential interf erants .
Estimate the concentrations of these compounds in the effluent
(CPOTj , ppm) .
4.3 Select and Evaluate the Sampling System. Considering
the source, e.g., temperature and pressure profiles, moisture
content, analyte characteristics, and particulate concentration),
select the equipment for extracting gas samples. Recommended are
a particulate filter, heating system to maintain sample
temperature above the dew point for all sample constituents at
all points within the sampling system (including the filter) , and
sample conditioning system (e.g., coolers, water-permeable
membranes that remove water or other compounds from the sample,
and dilution devices) to remove spectral interf erants or to
protect the sampling and analytical components. Determine the
minimum absolute sample system pressure (Pmin' mmHg) and the
infrared absorption cell volume
-------
SPA PTIR Protocol
1 A iaqg
4.5.3 At least one absorption CTS band within the operating
range of the PTIR instrument has an instrument -independent
linewidth 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 (FFUm 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 (LR) 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 1 (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.
-------
IPA FTI* Protocol p
g
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 (P^) , sample temperature (TR) , reference
absorption pathlength (Im) , and interferogram signal integration
period (tSR) . Signal integration periods for the background
interferograms shall be *tgn« Values of P^» L«, and tg^ shall
not deviate by more than ±x percent from trie 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-FTIR) 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) .
4.6.5.4 If the average fractional difference value
calculated in Section 4.6.5.3 is larger for any compound than the
corresponding AUj, 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
-------
BPA FTIR Protocol
analytical region (PL,,,, 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 (WKU^ 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 analytea 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>l tne analyte
concentrations, the known interferant concentrations, and the
baseline slope and intercept values. If the sample absorption
pathlength (Lg) , sample gas temperature (Ts) or sample gas
pressure (Ps) during the actual sample analyses differ from LR,
TRf 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
-------
If* FTI8 Protocol _
B
fractional uncertainty limits (AUj_; see Section 4.1) . if
FCUi > AU^ , 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
(RMSsgT, absorbance) of the FTIR system; alternatively, construct
the complete spectrometer system and determine the values RMS*
using Appendix G. Estimate the minimum measurement uncertainty
for each analyte (MAUj, ppm) and known interferant (Mm., ppm)
using Appendix D. Verify that (a) ma± < (Aiij) (DL^) , FRU., < AUi ,
and FCU^ < AU,£ 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
(L^) and leak volume (VL) , where VL - LR tss. Leak volumes shall
be *4 percent of Vgg.
5.2 Verify Instrumental Performance. Measure the noise
level of the system in each analytical region using the procedure
of Appendix G. If any noise level is higher than that estimated
for the system in Section 4.12, repeat the calculations of
Appendix D 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 (Lg) 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 Pg. 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.
-------
BPA PTIR Protocol n*~« o
ii.g.,-1. I*. IPO* page 9
!2£S5 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 Rtm^ and unsealed interferant
concentrations RUIjr 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 "
-------
EPA FTIR Protocol Da
-------
SPA FTim Protocol Paae 11
mn.* i^ loaf; _ __ _ ___ _ ......... a
8.0 REFERENCES
A) Standard Practices for General Techniques of Infrared
Quantitative Analysis (American Society for Testing and
Materials, Designation I 168-88) .
B) The Coblentz Society Specifications for Evaluation of
Research Quality Analytical Infrared Reference Spectra
(Class II); Anal. Chemistry 4J7, 945A (1975); Appl.
Spcctroscopy 1*4 » 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 1) , " June 1978, Quality
Assurance Handbook for Air Pollution Measurement Systems,
Volume III, Stationary Source Specific Methods, EPA- 600/4-
77-027b, August 1977.
-------
BPA PTIR Protocol p
*..g»f.. i* lap* __ ____ _ rage 12
APPENDIX A
DEFINITIONS OF TERMS AND SYMBOLS
A.I Definitions of Terms
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 pathlength - 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.
Beer*' * 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- pa thlength product - the mathematical product of
concentration of the species and absorption pathlength. For
-------
EPA FTIR Protocol _
anjn.fr 1A 1QOS 9
reference spectra, this is a known quantity; for sample
spectra, it is the quantity directly determined from Beer's
law. The units "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 (FPT) - 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/FTIRj 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.
interferogram, I (o) '- " record of the modulated component of the
interference signal measured as a function of retardation by
the detector.
-------
BPA PTXR Protocol «,-«
i*. m* _ _____ ge
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.
1 in width - 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 SOOO 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,
-------
BPA PTIR Protocol _
1*. -mfi ___ ^age 15
wavenunber, v - the number of waves per unit length.
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.
zero- filling - the addition of zero-valued points to the end of a
measured interferogram.
Note; 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) .
A • loglo = -logloT (1)
- band area of the itn analyte in the mth analytical
region, at the concentration (CL^) corresponding to the
product of its required detection limit (DL^) and analytical
uncertainty limit (AU^) .
jn - average absorbance of the itn analyte in the mth
analytical region, at the concentration (CL^) corresponding
to the product of its required detection limit (DL^) and
analytical uncertainty limit (AUj_) .
ASC, accepted standard concentration - the concentration value
assigned to a chemical standard.
ASCPP, accepted standard concentration -pa thlength 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.
CKMNk - estimated concentration of the kth known interferant.
CMAXi - estimated maximum concentration of the ic analyte.
-------
it* FTIR protocol
- estimated concentration of the jtn potential interferant.
DL±f required detection limit - for the ith analyte, the lowest
concentration of the analyte for which its overall
fractional uncertainty (OFU^) is required to be less than
the analytical uncertainty limit
- center wavenumber position of the mtn analytical region.
L, fractional analytical uncertainty - calculated uncertainty
in the measured concentration of the itn analyte because of
errors in the mathematical comparison of reference and
sample spectra.
f fractional calibration uncertainty - calculated uncertainty
in the measured concentration of the ifc" 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 mtn analytical region.
P7Ua - upper wavenumber position of the CTS absorption band
associated with the nr analytical region.
- lower wavenumber position of the m*"" analytical region.
, fractional model uncertainty - calculated uncertainty in
the measured concentration of the itn analyte because of
errors in the absorption model employed.
• 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.
, fraction*! reproducibility uncertainty - calculated
uncertainty in the measured concentration of the icn analyte
because of errors in the reproducibility of spectra from the
PTIR system.
FUm - upper wavenumber position of the mtn analytical region.
IAIj_ - band area of the jtn potential interferant in the mth
analytical region, at its expected concentration (CPOTj).
IAVj_ - average absorbance of the ith analyte in the mc
analytical region, at its expected concentration (CPOTj } .
-------
ISA PTIS Protocol p
I-*, ma*? . rage i/
Isci or k' iQdicated standard concentration - the concentration
from the computerized analytical program for a single-
compound reference spectrum for the ith analyte or ktfi known
interferant.
kPa - kilo-Pascal (see Pascal).
Lg' - estimated sample absorption pathlength.
lia - reference absorption pathlength.
LS - actual sample absorption pathlength.
L - mean of the MAU^m over the appropriate analytical regions.
Ijj, minimum 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.
I - mean of the MIUjm over the appropriate analytical regions.
MlTJjm, minimum interf erant uncertainty - the calculated minimum
concentration for which the analytical uncertainty limit
CPOTj/20 in the measurement of the jtn interf erant, 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.
No_t e.; 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).
H^ - number of analytes.
NJ - number of potential interferants.
Hk - number of known interferants.
w - the number of scans averaged to obtain an interferogram.
OFCFj - the overall fractional uncertainty in an analyte
concentration determined in the analysis (OPU^ - MAXtFRU.^,
FCUif PAUlf FMCJ.JJ) .
Pascal (Pa) - metric unit of static pressure, equal to one Newton
per square meter; one atmosphere is equal to 101,325 Pa;
-------
ISA mm Protocol _
is
1/760 atmosphere {one Torr, or one millimeter Hg) is equal
to 133.322 Pa.
pmin " niinintum pressure of the sampling system during the
sampling procedure.
Pg' - estimated sample pressure.
PR - reference pressure.
Pg - actual sample pressure.
IMSgja - measured noise level of the FTIR system in the mth
analytical region.
IMSD, root mean square difference - a measure of accuracy
determined by the following equation:
m
where:
n - the number of observations for which the accuracy is
determined.
e^_ = the difference between a measured value of a property
and its mean value over the n observations.
Note; The EMSD value "between a set of n contiguous
absorbance values (Aj_) and the mean of the values" {Aj^} is
defined as
RMSD * .,
it V* /A4 - V <3)
£ - the (calculated) final concentration of the ich analyte.
, - the (calculated) final concentration of the ktn known
~lnterferant.
tgc , scan tin* - time used to acquire a single scan, not
including flyback.
ts, signal integration ptriod - the period of time over which an
interferogram is averaged by addition and scaling of
individual scans. In terms of the number of scans Ngcan and
scan time tacan, ts - Nacantgcan.
tga - signal integration period used in recording reference
spectra.
-------
1PA FTIR Protocol
Aj HO*
tsg - 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.
Vgg - 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, OCT. RMSSm, SUBS,
SACif Ss
-------
BPA PTIR Protocol
ing,..*, i* mag Page 20
APPENDIX B
IDENTIFYING SPECTRAL INTERFERANTS
B.1 General
B.I.I Assume a fixed absorption pathlength equal to the
value Lg'.
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 - (DL^) (AUj_) , where DLj is the required
detection limit and AUj is the maximum permissible analytical
uncertainty. For the m*" 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 (CPOTj). For the mcn
analytical region, calculate the band area (lAIjjJ and average
absorbance (IAV.jm) 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., IAI-jm > 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.
-------
SPA ?TXR Protocol
-I A 190*
B.2,5 Calculate the average total absorfaance (AVT-) 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
l .... M
Analyte Labels
. AAIIM
Potential Interferant
Labels
. IAI1M
FIGURE B.2 Presentation of Known Interferant Calculations
Analytical Regions
l .... M
Analyte Labels
1 AAI11 .... AAI1M
Known Interferant
Labels
1 IAI
ia>
IAIK1 .
Total Average
Absorbance AVT-, AVTM
-------
KPA FTIR Protocol
APPENDIX C
ESTIMATING NOISE LEVELS
C . 1 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) RMSvQUf - 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) tf^M - the manufacturer's signal integration time used
tod
ietermine
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 RMSj^, tj^jj, 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:
• RMSBST
(4)
-------
EPA PTIR Protocol
APPENDIX D
ESTIMATING MINIMUM CONCENTRATION MEASUREMENT
UNCERTAINTIES (MAU and MIU)
D.I General
Estimate the minimum concentration measurement uncertainties
for the icn analyte (MAU.^) and jtn interferant (MIU.. ) 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 ^f
measured (Appendix G) , or set RMS = RMSEg.p if estimated (Appendix
C) .
D.2. 2 For each analyte associated with the analytical
region, calculate
(RMS)
D.2. 3 If only the mtn analytical region is used to
calculate the concentration of the itn analyte, set MA^ - MAUim.
D.2. 4 If a number of analytical regions are used to
calculate the concentration of the ith analyte, set MAUj_ 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
-------
SPA FTIR Protocol Paoe 24
ingtuf 14. a
(6)
*€{»'}
where the weight W^^ is defined for each term in the sum as
D.2.5 Repeat Sections D.2.1 through D.2.4 to calculate the
analogous values MIU-s for the interferants j » l to J, Replace
the value (KU±) (DL/i in the above equations with CPOTj/20;
replace the value AAl^ in the above equations with !AIjm.
-------
BPA PTIR Protocol
A..g»«<- -IA TOOK — .
APPENDIX E
DETERMINING FRACTIONAL REPRODUCIBILITY UNCERTAINTIES (FRU)
E . 1 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.
E.2 Calculations
E.2.1 The CTS spectra {Rl} consist of N spectra, denoted by
sli' i-1» N> Similarly, the CTS spectra {R2} consist of N
spectra, denoted by S2_/ i»l, N. Each Sk_ 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 i- Form the spectra S4
according to S4j_ - [S2i+S1_]/2 for each i.
E.2. 2 Each analytical region m is associated with a portion
of the CTS spectra S?* and Sji_, for a particular i, with lower
and upper wavenumber limits FFI^ and FFUm, respectively.
E.2. 3 For each m and the associated i, calculate the band
area of S4^ 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_ 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-FFV/BAVm
E.2. 6 If only the mth analytical region is used to
calculate the concentration of the itft analyte, set
E.2. 7 If a number p± of analytical regions are used to
calculate the concentration of the i"1 analyte, set FRU_ equal to
the weighted mean of the appropriate FM_ values calculated above.
Mathematically, if the set of analytical regions employed is
{m' } , then
WikFMk
Ice (m'}
where the Wik are calculated as described in Appendix D.
-------
ISA FTIR frotoeol o-,«« or
Z6
APPENDIX F
DETERMINING FRACTIONAL CALIBRATION UNCERTAINTIES (FCU)
F . 1 General
P. l.l The concentrations yielded by the computerized
analytical program applied to each a ingle -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 (ASC5 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.
P. 1.2 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 P.I, verify that
the absolute value of the ISC's are less than the compound's MAU
(for analytes) or MIU (for interferants) .
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 FCUA and analytical uncertainty limit (AU^) for each
analyte .
-------
SPA FTIE Protocol
Page 27
FIGURE F.I
Presentation of Accepted Standard Concentrations (ASC's)
and Indicated Standard Concentrations (ISC's)
Compound
Name
Reference
Spectrum
Fife Name
ASC
(&sn)
Analytes
i=,l
r-
ISC (ppm)
In
.,.„]
=1
terferai
t
I
its
FIGURE F.2
Presentation of Fractional Calibration Uncertainties (FCU's)
and Analytical Uncertainties (AU's)
Analyte
Name
FCU
(*)
AU
(«)
-------
BPA FTIR Protocol
APPENDIX G
MEASURING NOISE LEVELS
G . 1 General
The root -mean -square (RMS) noise level is the standard
measure of noise. The IMS 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 Calculations
G.2.1 Evacuate the absorption cell or fill it with UFC
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 RMSgm in
the M analytical regions.
-------
SPA PTIR Protocol
tA laoe
APPENDIX H
DETERMINING SAMPLE ABSORPTION PATHLENGTH (Lc) AND
FRACTIONAL ANALYTICAL UNCERTAINTY (FAUJ
B.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 (Tg) , 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 Tg 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 PC, to the CTS reference spectra of the same gas,
recorded at LR, TR, and PR. Perform the quantitative comparison
after recording tne sample spectra, based on band areas of the
spectra in the CTS absorbance band associated with each analyte.
E.2 Calculation*
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 Asi, i - 1, n. Based on
the model Ag - rAR + B, determine the least -squares estimate of
r' , the value or r which minimizes the square error "&* .
Calculate the sample absorption pathlength Ls =• 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 AT, as described in Section H.2.1, using values from {Rl} to
form AR, and values from {R4} to form Ag. Calculate the values
-------
29A FTI* Protocol Paqe 30
»iMTn«j^j_4^_ir " '
NRMS. -
T
and
(10)
The fractional analytical uncertainty is defined as
FAU = -——5 (11)
-------
ISA FTIR Protocol
lA TOO*
APPENDIX 1
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.
1.2 Calculations
1.2.1 For each analyte (with scaled concentration RSAj_) »
select a reference spectrum SA^ with indicated standard
concentration ISC^. Calculate the scaling factors
m. . T* L3 P3 RSAi
1 Tg LR PR ISC4
and form the spectra SACA by scaling each SR.j_ by the factor RA^
1.2.2 For each interferant, select a reference spectrum SIk
with indicated standard concentration ISCk. Calculate the
scaling factors
T* LS P3
* Ts LR PR ISCk
and form the spectra SlCk by scaling each SIk by the factor RIk.
1.2.3 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
-------
EPA FTia Protocol
and SIC]g exhibiting absorbance from the sample spectrum S« to
form the spectrum SOTS. 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 So.
1.2.4 For each analytical region m, calculate the RMSD of
StJBg between the absorbance values and their mean in the region
FFUm to FFl^. Denote the result by RMSSm.
1.2.5 For each analyte i, calculate the quantity
for each analytical region associated with the analyte.
1.2.6 If only the mth analytical region is used to
calculate the concentration of the itn analyte, set
1,2.7 If a number of analytical regions are used to
calculate the concentration of the ith 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
FMUi = £ Wik FMk (15)
keCm'l
where Wi]c is calculated as described in Appendix D.
-------
SPA FTia Protocol Pace ^ 1
I..JM.J. 1A 180C ^
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 OFU^ - MAX{PRUj_, FCOif FAU^ FMU^} and
-------
EPA PTIR Protocol^ pagg 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) decomp eta0305a.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) compose 0305drea,0305dres.aif,1
"Compose" transforms truncated interferograms back to spectral
format.
-------
KPA PTIR Protocol
35
(iii) IG2SP 0305dres.aif,0305dres.daf,3,l,low cm'1, high on'1
"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 0305drea.daf,bkg0305a.dsf,0305dres.dlf
"DVDR" ratios the transformed sample spectrum against the
background.
(v) ABSB 0305drea.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. Ill&ia procedure assumes familiarity
with basic functions of Grams™.
This procedure is specifically for using Grains to truncate
and transform reference interferograms that have been imported
into Grams 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 FILES AND DE- RESOLUTION PARAMETERS.
-------
SPA FTIR Protocol Pacre
4, THfi ; ; ?
Desired nominal Spectral
Resolution (cm"1)
0.25
0.50
1.0
2.0
Data Pile Name
Z00250.aav
ZQQSOQ.sav
ZQlO'QQ.sav
Z02000.sav
Parameter UN"
Value
65537
32769
16385
8193
(i) laport using "File/Import" the desired *.aif file. Clear
all open data slots.
(ii) Open the resulting *.spc interferogram as file #1. •
(iii) Xflip - 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:#S-#fl(#0,#N)+50
(iv) Run ICOMPUTE.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
"H":)
First: H Last: 0 Type: Single Beam
Zero Fill: None Apodization: (a* desir«d)
Phasing: U«er
Points: 1024 Interpolation: Linear Phase :
Calculate
(v) As in step (iii), in the "ArittfflMtie/Calc" menu item
enter and then run the following commands (refer to Table l for
appropriate "PILS," which may be in a directory other than
"c:\mdgrams.")
s*t£fp 7898.880S, 0 i loadspe "oi\mdgraiM\ FIXiB* * i2»#8+f2
(vi) Use "Faf« Ujp" to activate file #2, and then use the
"File/Sav* A«" menu item with an appropriate file name to save
the result.
K.3 Verification of New Resolution
-------
SPA PTIR Protocol Pa ma T7
»,.T.... 1* lose _ rdge J '
K.3.1 Obtain interferograma of reference sample and
background spectra. Truncate interferograma 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).
RM3S, xrKFFUj - FFLj
^ (lg)
- ease
KMSS-RMSD in the ith analytical region in subtracted result, test
CTS minus CTS standard.
n-number of data points per cm"1. Exclude zero filled points.
&-The upper and lower limits (cm"1), respectively, of the
analytical region.
Atest-CTS"band area in the ith analytical region of the test CTS.
-------
D-3 EPA METHOD 25A
D-4
-------
EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METEOR
METHOI 25A-DETERMINATION OF TOTAL GASEOUS ORGANIC
CONCENTRATION USING A FLAME IONIZATION ANALYZER
1. Applicability and Principle
1.1 Applicability. This method applies to the measurement of total gaseous
organic concentration of vapors consisting primarily of alkanes, alkenes, and/or
arenes (aromatic hydrocarbons) . The concentration is expressed in terms of
propane (or other appropriate organic calibration gas) or in terms of carbon.
1.2 Principle. A gas sample is extracted from the source through a heated
sample line, if necessary, and glass fiber filter to a flame ionization analyzer
(FIA). Results are reported as volume concentration equivalents of the
calibration gas or as carbon equivalents.
2. Definitions
2.1 Measurement Systems. The total equipment required for the determination
of the gas concentration. The system consists of the following major subsystems:
2.1.1 Sanple Interface. That portion of the system that is used for one or more
of the following: sample acquisition, sample transportation, sample
conditioning, or protection of the analyzer from the effects of the stack
effluent.
2.1.2 Organic Aaalyzer. That portion of the system that senses organic
concentration and generates an output proportional to the gas concentration.
2.2 Spaa Valoe. The upper limit of a gas concentration measurement range that
is specified for affected source categories in the applicable part of the
regulations. The span value is established in the applicable regulation and is
usually 1.5 to 2.5 times the applicable emission limit. If no span value is
provided, use a span value equivalent to 1.5 to 2.5 times the expected
concentration. For convenience, the span value should correspond to 100 percent
of the recorder scale.
2.3 Calibration Gas. A known concentration of a gas in an appropriate diluent
gas.
2.4 Zero Drift. The difference in the measurement system response to a zero
level calibration gas before and after a stated period of operation during which
no unscheduled maintenance, repair, or adjustment took place.
2.5 Calibration drift. The difference in the measurement system response to
a midlevel calibration gas before and after a stated period of operation during
which no unscheduled maintenance, repair or adjustment took place.
2.6 Response Tine. The time interval from a step change in pollutant
Prepared by Enission Measurement Branch EMTIC TM-25A
Technical Support Division, OAQPS, EPA June 23, 1993
-------
EMTIC TM-25A EMTIC NSPS TEST METHOD page 2
concentration at the inlet to the emission measurement system to the time at
which 95 percent of the corresponding final value is reached as displayed on the
recorder.
2.7 Calibration Error, The difference between the gas concentration indicated
by the measurement system and the known concentration of the calibration gas.
3, Apparatus.
A schematic of an acceptable measurement system is shown in Figure 25A-1.
The essential components of the measurement system are described below:
3.1 Orgaaic Coaceatratioa Aaalyzer. A flame ionization analyzer (FIA) capable
of meeting or exceeding the specifications in this method.
3.1 Sample Probe. Stainless steel, or equivalent, three-hole rake type.
Sample holes shall be 4 mm in diameter or smaller and located at 16.7, 50, and
83.3 percent of the equivalent stack diameter. Alternatively, a single opening
probe may be used so that a gas sample is collected from the centrally located
10 percent area of the stack cross-section.
3.3 Sample Lia«. Stainless steel or Teflon * tubing to transport the sample
gas to the analyzer. The sample line should be heated, if necessary, to prevent
condensation in the line.
3.4 Calibratioa Valve Assembly. A three way valve assembly to direct the zero
and calibration gases to the analyzers is recommended. Other methods, such as
quick-connect lines, to route calibration gas to the analyzers are applicable.
3.S Particulate Filter. An in-stack or an out-of-stack glass fiber filter is
recommended if exhaust gas particulate loading is significant. An out-of-stack
filter should be heated to prevent any condensation.
* Mention of trade names or specific products does not constitute
endorsement by the Environmental Protection Agency.
3.6 Recorder. A strip-chart recorder, analog computer, or digital recorder for
recording measurement data. The minimum data recording requirement is one
measurement value per minute, Note: This method is often applied in highly
explosive areas. Caution and care should be exercised in choice of equipment and
installation.
4. Calibration ud Otker Gases.
Gases used for calibrations, fuel, and combustion air (if required) are
contained in compressed gas cylinders. Preparation of calibration gases shall
be done according to the procedure in Protocol No. 1, listed in Citation 2 of
Bibliography. Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than ±2 percent from the certified value. For
calibration gas values not generally available (i.e., organics between 1 and 10
percent by volume), alternative methods for preparing calibration gas mixtures,
such as dilution systems, may be used with prior approval of the Administrator.
Calibration gases usually consist of propane in air or nitrogen and are
determined in terms of the span value. Organic compounds other than propane can
-------
EMTIC TM-25A EMTIC NSPS TEST METHOD page 3
be used following the above guidelines and making the appropriate corrections for
response factor.
4.1 Fuel. A 40 percent H2/60 percent N2 gas mixture is recommended to avoid
an oxygen synergism effect that reportedly occurs when oxygen concentration
varies significantly from a mean value.
4.2 Zero Gas. High purity air with less than 0.1 parts per million by volume
(ppmv) of organic material (propane or carbon equivalent) or less than 0.1
percent of the span value, whichever is greater.
4.3 Low-level Calibration Gas. An organic calibration gas with a concentration
equivalent to 25 to 35 percent of the applicable span value.
4.4 Hid-level Calibration Gas. An organic calibration gas with a concentration
equivalent to 45 to 55 percent of the applicable span value.
4.5 High-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 80 to 90 percent of the applicable span value.
5. Measurement System Performance Specifications
5.1 Zero Brift. Less than ±3 percent of the span value.
5.2 Calibration Brift. Less than ±3 percent of span value.
5.3 Calibration Error. Less than ±5 percent of the calibration gas value.
6. Pretest Preparations
6.1 Selection of Sampling Site. The location of the sampling site is generally
specified by the applicable regulation or purpose of the test; i.e., exhaust
stack, inlet line, etc. The sample port shall be located at least 1.5 meters or
2 equivalent diameters upstream of the gas discharge to the atmosphere.
6.2 Location of Sample Probe. Install the sample probe so that the probe is
centrally located in the stack, pipe, or duct and is sealed tightly at the stack
port connection.
6.3 Measurement System Preparation. Prior to the emission test, assemble the
measurement system following the manufacturer's written instructions in preparing
the sample interface and the organic analyzer. Make the system operable.
FIA equipment can be calibrated for almost any range of total organics
concentrations. For high concentrations of organics (>1.0 percent by volume as
propane) modifications to most commonly available analyzers are necessary. One
accepted method of equipment modification is to decrease the size of the sample
to the analyzer through the use of a smaller diameter sample capillary. Direct
and continuous measurement of organic concentration is a necessary consideration
when determining any modification design.
6.4 Calibration Error Test. Immediately prior to the test series, (within 2
hours of the start of the test) introduce zero gas and high-level calibration gas
at the calibration valve assembly. Adjust the analyzer output to the appropriate
levels, if necessary. Calculate the predicted response for the low-level and
-------
EMTIC TM-25A SMTIC NSPS TEST METHOD Page 4
mid-level gases based on a linear response line between the zero and high-level
responses. Then introduce low-level and mid-level calibration gases successively
to the measurement system, Record the analyzer responses for low-level and nud-
level calibration gases and determine the differences between the measurement
system responses and the predicted responses. These differences must be less
than 5 percent of the respective calibration gas value. If not, the measurement
system is not acceptable and must be replaced or repaired prior to testing. No
adjustments to the measurement system shall be conducted after the calibration
and before the drift check (Section 7.3). If adjustments are necessary before
the completion of the test series, perform the drift checks prior to the required
adjustments and repeat the calibration following the adjustments. If multiple
electronic ranges are to be used, each additional range must be checked with a
mid-level calibration gas to verify the multiplication factor.
6.5 Response Tiae Test, Introduce Zero gas into the measurement system at the
calibration valve assembly. When the system output has stabilized, switch
quickly to the high-level calibration gas. Record the time from the
concentration change to the measurement system response equivalent to 95 percent
of the step change. Repeat the test three times and average the results.
7, Eaissioa Measureaeat Test Procedure
7,1 Orgaaic Measareaeat . Begin sampling at the start of the test period,
recording time and any required process information as appropriate. In
particular, note on the recording chart periods of process interruption or cyclic
operation.
7.2 Drift Deteraiaatioa. Immediately following the completion of the test
period and hourly during the test period, reintroduce the zero and mid-level
calibration gases, one at a time, to the measurement system at the calibration
valve assembly. (Make no adjustments to the measurement system until after both
the zero and calibration drift checks are made.) Record the analyzer response.
If the drift values exceed the specified limits, invalidate the test results
preceding the check and repeat the test following corrections to the measurement
system. Alternatively, recalibrate the test measurement system as in Section 6.4
and report the results using both sets of calibration data (i.e., data determined
prior to the test period and data determined following the test period) .
8. Orgaaic Coaceatratioa calcalatioas
Determine the average organic concentration in terms of ppmv as propane or
other calibration gas. The average shall be determined by the integration of the
output recording over the period specified in the applicable regulation If
results are required in terms of ppmv as carbon, adjust measured concentrations
using Equation 25A-1.
r = £
-------
EMTIC TM-25A EMTIC NSPS TEST METHOD Page 5
K = 2 for ethane.
K = 3 for propane,
K = 4 for butane.
K = Appropriate response factor for other organic calibration
gases.
9. Bibliography
1. Measurement of Volatile Organic Compounds-Guideline Series, U.S.
Environmental protection Agency. Research Triangle Park, NC.
Publication No. EPA-4SQ/2-7S-Q41. June 1978. p. 46-54.
2. Traceability Protocol for Establishing True Concentrations of Gases
Used for Calibration and Audits of Continuous Source Emission
Monitors (Protocol No. 1). U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Research Triangle
Park, NC. June 1978.
3. Gasoline Vapor Emission Laboratory Evaluation-Part 2. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6.
August 1975.
-------
EMTIC TM-25A
EMTIC NSPS TEST METHOD
Page 6
Probe
HesUd
Sampta
Un«
Calibration
Valv«
Pump
Sack
Figure 25A-1. Organic Concentration Measurement System.
-------
D-4 EPA DRAFT METHOD 205
D-5
-------
EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
TEST METIOi
DRAFT—DO NOT CITE OR QUOTE
The EPA proposes to amend Title 40, Chapter I, Part 51 of the Code of
Federal Regulations as follows:
1. The authority citation for Part 51 continues to read as follows:
Authority: Section 110 of the Clean Air Act as amended. 42 U.S.C. 7410.
2. Appendix M, Table of Contents is amended by adding an entry to read as
follows:
Method 205—Verification of Gas Dilution Systems for Field Instrument
Calibrations
3. By adding Method 205 to read as follows:
Method 205 - Verification of Gas iilutioa Systeas
for Field lastnueat Calibrations
i. iNTKOiucTiON
1.1 Applicability. A gas dilution system can provide known values of
calibration gases through controlled dilution of high-level calibration gases
with an appropriate dilution gas. The instrumental test methods in 40 CFR Part
60 — e.g., Methods 3A, 6C, 7E, 10, 15, 16, 20, 25A and 25B — require on-site,
multi-point calibration using gases of known concentrations. A gas dilution
system that produces known low-level calibration gases from high-level
calibration gases, with a degree of confidence similar to that for Protocol1
gases, may be used for compliance tests in lieu of multiple calibration gases
when the gas dilution system is demonstrated to meet the requirements of this
method. The Administrator may also use a gas dilution system in order to produce
a wide range of Cylinder Gas Audit concentrations when conducting performance
specifications according to Appendix F, 40 CFR Part 60. As long as the
acceptance criteria of this method are met, this method is applicable to gas
dilution systems using any type of dilution technology, not solely the ones
mentioned in this method.
1.2 Principle. The gas dilution system shall be evaluated on one analyzer once
during each field test. A precalibrated analyzer is chosen, at the discretion
of the source owner or operator, to demonstrate that the gas dilution system
produces predictable gas concentrations spanning a range of concentrations.
After meeting the requirements of this method, the remaining analyzers may be
calibrated with the dilution system in accordance to the requirements of the
applicable method for the duration of the field test. In Methods 15 and 16, 40
CFR Part 60, Appendix A, reactive compounds may be lost in the gas dilution
system. Also, in Methods 25A and 258, 40 CF-R Part 60, Appendix A, calibration
with target compounds other than propane is allowed. In these cases, a
laboratory evaluation is required once per year in order to assure the
Administrator that the system will dilute these reactive gases without
significant loss. Note: The laboratory evaluation is required only if the
source owner or operator plans to utilize the dilution system to prepare gases
mentioned above as being reactive.
2. SPECIFICATIONS
2.1 Gas Illation Systea. The gas dilution system shall produce calibration
gases whose measured values are within ±2 percent of the predicted values. The
predicted values are calculated based on the certified concentration of the
supply gas (Protocol gases, when available, are recommended for their accuracy)
and the gas flow rates (or dilution ratios) through the gas dilution system.
Prepared by Eaissioa Measurement franca EMTIC TM-205
Technical Support Division^ OAQPS, EPA
-------
EMTIC TM-205 EMTIC NESHAP TEST METHOD Page 3
injection shall differ by more than +2 percent from the average instrument
response for that dilution. 3.2.5 For each level of dilution, calculate the
difference between the average concentration output recorded by the analyzer and
the predicted concentration calculated in Section 3.2.2. The average
concentration output from the analyzer shall be within .+2 percent of the
predicted value.
3.2.6 Introduce the mid-level supply gas directly into the analyzer, bypassing
the gas dilution system. Repeat the procedure twice more, for a total of three
mid-level supply gas injections. Calculate the average analyzer output
concentration for the mid-level supply gas. The difference between the certified
concentration of the mid-level supply gas and the average instrument response
shall be within +2 percent.
3.3 If the gas dilution system meets the criteria listed in Section 3.2, the gas
dilution system may be used throughout that field test. If the gas dilution
system fails any of the criteria listed in Section 3.2, and the tester corrects
the problem with the gas dilution system, the procedure in Section 3.2 must be
repeated in its entirety and all the criteria in Section 3.2 must be met in order
for the gas dilution system to be utilized in the test.
4. REFERENCES
1. "EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards," EPA-600/R93/224, Revised September 1993.
-------
D-5 HC1 VALIDATION PAPER
D-6
-------
D-5 HC1 VALIDATION PAPER
D-6
-------
For Presentation at the Air & Waste Management Association's 90th Annual Meeting
& Exhibition, June 8-13,1997, Toronto, Ontario, Canada
97-MP74.05
Validation of EPA FTIR Method For Measuring HO
Thomas J. Geyer
Midwest Research Institute, Suite 350,401 Harrison Oaks Boulevard, Gary, North Carolina 27513
Grant M. Plummer
Rho Squared, 703 Ninth Street, Suite 183, Durham, North Carolina 27705
Introduction
In 1997 EPA is preparing to publish a sampling method (Draft Method 320)1 based on the use of Fourier
transform infrared (FTER) spectroscopy to measure emissions of hazardous air pollutants (HAPs). This
method establishes sampling procedures for measuring HAPs and employs analytical procedures in the
EPA FTIR Protocol.2
In 1996 EPA conducted a field test at a source with HC1 emissions. The test goal was to use the FTTR
Draft Method 320 to measure vapor phase pollutants at this source. Measurements were conducted on
the inlet and outlet of a control device. Hydrogen chloride (HC1) was a target pollutant for this source
and, for this reason, some samples were spiked from a cylinder containing a standard concentration of
103 ppm HC1. Results of HCl measurements are presented along with a Method 3013 statistical analysis
of spiked and unspiked samples, and a comparison of results obtained using EPA reference spectra and
results obtained using spectra of the HCl gas standard to measure the sample concentrations.
Experimental
The source tested in this project was a coal burning process with a relatively low moisture content (3 to
4% by volume). Flue gas temperatures were between 400 and 500°F. The principal components of the
gas stream were water vapor, COj, SOj, and NO.
Sampling System
The sampling system is depicted in Figure 1. The sample was extracted through a 4-ft long, 0.5-in
diameter stainless steel probe. Sample was transported through heated 3/8-in Teflon line using a KNF
Neuberger heated head sample pump (Model NO35 ST.111). A Balston paniculate filter (holder Model
Number 30-25, filter element Model Number 100-25-BH, 99 percent removal efficiency at 0.1 u,m) was
connected in-line at the outlet of the sample probe. The sample line was heat wrapped and insulated.
Temperature controllers were used to monitor and regulate the sample line temperature at about 350° F.
The stainless steel manifold contained 3/8-in tubing, rotameters and 4-way valves to monitor and control
the sample flow to the FTIR gas cell. The manifold temperature was maintained between 300 to 310°F.
-------
97-MP74.05
The FTIR system included an Analect instruments Model RFX-40 interferometer equipped with a broad
band MCT detector. Samples were contained in an Infrared Analysis Model D22H variable path gas cell.
The cell temperature was maintained at 250°F.
Sampling Procedure
A series of discreet batch samples was collected by filling the cell above ambient pressure and closing the
inlet valve to isolate the sample. An outlet valve was briefly opened to vent the sample to ambient
pressure. The spectrum of the static sample was recorded. Then the cell was evacuated for the next
sample. Each spectrum consisted of 50 co-added scans. The minimum time between consecutive
samples was about 2 minutes. Inlet and outlet runs were conducted at the same time: the two location
were sampled alternately with the one FTIR system. The minimum time between consecutive
measurements was about 3 to 5 minutes.
Path Length Determinations
Two path lengths were used in this test. The cell was adjusted to 40 beam passes for the first two test
runs and reduced to 20 beam passes for a third test run. The number of beam passes was measured by
shining a He/Ne laser through the optical path and observing the number of laser spots on the field
mirror. The path lengths in meters were determined by comparing CTS EPA reference spectra to the
CTS spectra collected at each path length.
Absorption path lengths were determined from a comparison of the field test CTS spectra and EPA
library CTS spectra of ethylene (C2H4). For high temperature spectra, the EPA library interferograms
ctsOl 15a.aif and bkgOl 15a.aif were de-resolved to the appropriate spectral resolution (either 1 or 2 cm"1)
according to the procedures of reference 2 (Appendix K). The same procedure was used to generate
low-temperature spectra from the original interferometric data in the EPA library files cts0829a.aif and
bkg0829a.aif. The resulting files were used in least squares fits to the appropriate field CTS spectra (see
reference 2, Appendix H) in two regions (the FP, or "fingerprint" region from 790 to 1139 cm"1 and the
CH, or "CH-stretch region" from 2760 to 3326 cm"1). The fit results for each region, test, and set of test
sampling conditions were averaged. They and their average uncertainties are presented in Table 1. The
CH values were used in analytical region 4 where HC1 was measured.
Analyte Spiking
Draft Method 3201 contains a procedure for spiking the flue gas with one or more of the target analytes.
The spike procedure closely follows Section 6.3 of reference 3. The primary purpose of analyte spiking
is to provide a quality assurance check on the sampling system to determine if analyte losses occur in
transport to the analyzer. A second purpose is to test the analytical program to verify that the analyte(s)
can be measured in the sample matrix. If at least 12 (independent) spiked and 12 (independent) unspiked
samples are measured then a Method 301 statistical analysis can be performed on the results to "validate"
the method.
Figure 1 shows the sampling configuration used for the analyte spike. This procedure is described in
detail elsewhere1. In this test, a measured flow of the gas standard was preheated to the sample line
temperature before being introduced into the extracted flue gas at the back of the probe. The spiked
sample then passed through all of the sample components to the gas cell where the spectrum was
recorded. A series of unspiked samples was measured, the spike was turned on and then a complete
2
-------
97-MP74.05
series of spiked samples was measured. The spike then was turned off to make additional unspiked
measurements. Ideally, the spike comprises 1/10 or less of the sample mixture. The dilution is estimated
by comparing the spike flow to the total flow, but the actual dilution is determined measuring a tracer
(SF6) concentration in the spiked samples and comparing that to tracer concentration in the undiluted gas
standard.1
Usually the tracer is spiked with the analyte standard. In this test the SFS standard and HC1 standard
were contained in separate cylinders so the SFS was spiked first, then the HC1 was spiked, and finally the
SF6 was spiked again. The total sample flow stayed constant during the entire sampling period. The
spike flow was also held constant to insure that the dilution ratio was the same when the SF6 was spiked
as when the HC1 was spiked.
Quantitative Analysis
FUR analysis is performed in two steps: (1) collecting spectra of samples, and (2) analyzing the spectra
to determine concentrations of detected compounds. The quantitative analysis step usually is performed
with an automated program that relates sample absorbance intensities to absorbance intensities at known
concentrations in reference spectra.2 The Protocol2 describes procedures for preparing reference spectra
and Method 3201 requires the analyst to use reference spectra prepared with the Protocol procedures. To
date, the only existing set of reference spectra for HC1 and most Clean Air Act HAPs is in the EPA FTIR
spectral library (httpVAnfo.amold.af.miVepa/welcome.htm).
The Calibration Transfer Standard2 is the key requirement in using reference spectra for quantitative
analysis. CTS spectra help the analyst characterize differences in resolution, path length, temperature,
and sample pressure between the instrument system used to coEect reference spectra and the system used
to collect the sample spectra. Table 1 illustrates how the CTS spectra were used to determine the optical
path lengths for the system used in this test The HC1 reference spectra were de-resolved in the same way
as the CTS reference spectra before they were used in the quantitative analysis.
References 4 through 8 comprise a thorough description of one technique for analyzing FTIR absorbance
spectra. Two different analytical routines were used in this study. The first was prepared by Rho
Squared using the programming language ARRAY BASIC™ (GRAMS,™ Version 3.02, Galactic
Industries Corporation, Salem, New Hampshire). The "classical least squares" (CLS) or "K-Matrix"
technique and the associated computer program "4FIT" are described in Reference 9. The terminology
and basic analytical approach employed in this work are described in the "EPA FTIR Protocol"
(Reference 2). The second routine used the K-matrix analytical program "MuMcornp" version 6,0
(Analect Instruments).
The two analyses were performed independently by different analysts and then compared without
modification.
Reference Spectra
The program "4FIT" used as input EPA FTIR library spectra of HC1 de-resolved to 1 cm"1 and
normalized for absolute temperature, concentration, and absorption path length. The resulting files were
-------
97-MF74.05
averaged to provide a "reduced absorptivity" (see Reference 9), which was stored in the spectral file
097 .alf and employed in all subsequent HC1 analyses. The HC1 analysis was applied to the de-resolved
EPA library Hd spectra to determine the fractional calibration uncertainty (FCU), which is presented in
Table 2.
During the test MRI recorded spectra of samples taken directly from an HC1 cylinder standard (103 ppm
HCl in nitrogen, ± 5% accuracy from Scott Specialty Gases). Four independent HC1 "calibration" spectra
were measured at each of the two instrument configurations used to collect the data presented in Figures
2 and 3. The Fractional Calibration Uncertainty for each set of four spectra and the analytical region for
the "Multicomp" analysis is presented in Table 2.
Even though the two sets of results are identified by the program names "4FIT" and "Mulitcomp," it is
important to note that the "Multicomp" results were reproduced by the program "4FIT" when the HCl
calibration spectra were used as input for "4FIT." Therefore, any differences in the analyses are not
attributable to the programs, but to the use of different input spectra,
Results
HCl Concentrations
Table 3 summarizes results from the three test runs at the two locations. The agreement between the
"4FTT' and the "Multicomp" analyses is very good except for the third run. This run was conducted after
the path length had been decreased from 40 to 20 laser passes.
The two comparisons plotted in Figures 2 and 3 are indicated in Table 3. The Run 2 outlet results
(Figure 2) are typical of those obtained for the Run 2 inlet results recorded on the same day and the Run
1 inlet and outlet results recorded a day earlier. The close agreement was typical also for two data sets
collected at another field test in one test ran. For 3 of the 6 data sets presented in Table 3, the results
obtained with program "4F1T," using de-resolved EPA library reference spectra and the CTS-derived
absorption path lengths, are nearly identical (within the 4 o uncertainty) to those obtained using
"Multicomp," which employed the field HCl calibration standard spectra without an explicit absorption
path length determination. The average percent difference of the Run 2 inlet results was slightly higher
than the 40 uncertainty, but this percent difference corresponded to an average difference of 1.7 ppm.
The error bars in Figures 2 and 3 correspond to the 40 statistical uncertainties in the "4FTT" HCl
concentrations.
Method 301 Analysis
Tables 4 and 5 present the results of the method 301 statistical analysis of the spiked and unspiked
"4FIT" and "Multicomp" Run 3 outlet results, respectively. Note that the nearly constant difference of
about 19 percent in the two analyses has almost no effect on the Method 301 statistical analyses, which
indicate no significant bias in the HCl measurements. This is because the statistical treatment analyzes
differences between spiked and unspiked measurements and compares the differences to an expected
value of the spike. Since the same offset is apparent in the "Multicomp" analysis of both the spiked and
unspiked results, the calculated bias is not affected.
-------
97-MP74.05
This is another indication that the difference in the "4FTT" and "Multicomp" run 3 results is not due to a
measurement or analytical error. It is likely due either to an anomaly in the Run 3 path length
determination for the CH stretch region or to an error associated with using the HC1 "calibration spectra
as Input for the "Multicomp" program. As stated above, the "4FIT" program reproduced the
"Multicomp" results when using the HC1 "calibration" spectra as input.
Discussion
The uncertainties for the four data sets in Runs 1 and 2 are approximately equal to the small differences
between the "4FIT" and "Multicomp" results. The excellent agreement of the two analyses is noteworthy
for several reasons. HC1 is notoriously difficult both in terms of sampling and data analysis, due
(respectively) to the compound's high chemical reactivity and the details of the infrared spectrum which
make the analysis susceptible to instrument resolution errors. The results also provide a direct
comparison between two fundamentally different analytical approaches, one relying on in situ calibration
of the instrument using actual calibration gas standards, and the other using the calibration transfer
concept
This comparison is somewhat clouded by the results depicted in Figure 3, which show the HC1
concentration determined during Run 3 at the outlet These are also typical of the results for another data
set recorded on the same day at the inlet Unlike the Runs 1 and 2 data, the Run 3 data indicate a
statistically meaningful difference of approximately 18% between the "4FTT' and "Multicomp" results.
We stress that this difference is not attributable to errors in the computer programs, which produced
reliable results in these and many independent test cases. Rather, the difference seems be related to an
anomaly in the absorption path length determinations presented in Table 1. Note that the CTS-derived
absorption path length for (nominally) 20 passes, corresponding to the Run 3 data, are 10.2 meters 14.3
meters for the CH-stretch and "fingerprint" (FP) analytical regions. The difference between the CH and
FP results is much larger for this particular day of tasting than on the other two test days, represented in
the table by the 16- and 40- pass results. (It is also anomalous with respect to results obtained using the
same instrument in another field test completed within nine days of the testing addressed here.)
Moreover, were the average of the CH and FP region values (12.2 meters) used for the HC1
concentration values rather than the CH region value of 10.2 meters, the level of agreement between the
two sets of analytical results for the Run 3 data would be comparable to that of the Run 1 and 2 data
discussed immediately above.
We have attempted to determine the cause of this difference by considering of a number of possible
operational and instrumental problems. However, no single systematic effect seems sufficient Because
consistent path length determinations were carried out both before and after the HCl measurements in
question, a sudden change in instrument performance must be ruled out Gas pressure and dilution
effects cannot cause the type of wavenumber-dependent effects observed in the CTS spectra; subsequent
laboratory measurements of C2Hi indicated that temperature variations, like pressure and dilution effects,
would lead to path length errors in the same direction for the CH and FP regions. Because the same EPA
CTS ethylene spectra were used in afl the path length determinations and led to excellent statistical results
in all cases, potential data processing errors in the deresoluton procedure are also insufficient to explain
-------
97-MP74.05
the anomalous results. However, we note that the observed 18% discrepancy still allows high confidence
in the data and the infrared technique, and the discrepancy is obvious mainly because of the overall high
quality of the data set and statistical results.
Conclusions
The evaluation presented in this paper demonstrates that the EPA FTIR Protocol analytical procedures
based on the use of laboratory reference spectra to determine analyte concentrations in sample spectra
give excellent, and verifiable, results. This is true even for HQ, which is difficult to sample, and even
when the reference spectra are deresolved to match the sample spectra.
Two independent analyses using different programs and different spectral input data were performed on 6
FTTR data sets collected at a site with HC1 emissions. The alternate analyses produced nearly identical
results in 4 of the data sets. In two of the data sets the apeement was also good, but the average
discrepancy of about 18 percent between results produced by the alternate analyses was larger than the
average measurement uncertainty of about 5.5 percent. A preliminary evaluation of this discrepancy has
not determined the exact cause, but it is probably attributable to an anomaly in the measurement of the
absorption path length for the one test run.
These results also demonstrate the need for careful instrument performance checks and preparation of
library reference spectra. Strict QA/QC standard procedures are required to produce accurate
measurements. The Method 301 validation results showed no significant bias in the Fl'lK measurements
of HQ at this test, but the validation procedure cannot reveal a constant offset "error" that is applied
equally to both spiked and un spiked samples.
Acknowledgments
The field test discussed in this paper was funded by the Emission Measurement Center of the United
States Environmental Protection Agency.
References
1) Draft Method 320, "Measurement of Vapor Phase Organic and Inorganic Emissions by Extractive
Fourier Transform Infrared (FTIR) Spectroscopy," EPA Contract No. 68-D2-0165, Work Assignment
3-08, My, 1996.
2) "Protocol For The Use of FTIR Spectrometry to Perform Extractive Emissions Testing at
Industrial Sources," EPA Contract No, 68-D2-0165, Work Assignment 3-12, EMTIC Bulletin Board,
September, 1996.
3) "Method 301 - Field Validation of Pollutant Measurement Methods from Various Waste Media," 40
CFR Part 63, Appendix A.
-------
97-MP74.05
4. D.M. Haaland and R.G, Easterling, "Improved Sensitivity of Infrared Spectroscopy by the Application
of Least Squares Methods," Appl.Spectrosc. 34(5):539-548 (1980).
5. D.M. Haaland and R.G. Easterling, "Application of New Least-Squares Methods for the Quantitative
Infrared Analysis of Multicomponent Samples," Appl. Spectrosc. 36(6):665-673 (1982).
6. D.M. Haaland, R.G. Easterling and D.A. Vopicka, "Multivariate Least-Squares Methods Applied to
the Quantitative Spectral Analysis of Multicomponent Samples," Appl. Spectrosc. 39(l):73-84 (1985).
7. W.C. Hamilton, Statistics in Physical Science. Ronald Press Co., New York, 1964, Chapter 4.
8. P.R. Griffiths and J.A. DeHaseth, Fourier Transform Infrared Spectroscopy. John Wiley and Sons,
New York, 1986, ISBN 0-471-09902-3.
9, G. M. Plummer and W. K. Reagen, "An Examination of a Least Squares Fit FITR Spectral Analysis
Method," Air and Waste Management Association. Paper Number 96-WA65.03, Nashville, 1996.
10. T. J. Geyer, "Method 301 Validation of Fourier Transform Infrared (FTIR) Spectroscopy
For Measuring Formaldehyde and Carbonyl Sulfide," Air and Waste Management Association. Paper
Number. 96-RA110.03, Nashville, 1996.
-------
97-MP74.05
Table 1, Pathlength Determination Results.
CIS Conditions
# Passes Temp(K)
16 293
Run 3 (Figure 3)
Run2 (Figure 2)
20 293
20 393
40 293
40 393
CH region
Result (m) % uncert.
6.5 2.9
11,0 2.6
10.2 2.5
19.2 5.5
20.2 2.6
FP region
Result (m) % uncert.
6.7 1.3
11.3 1.6
14.3 2.2
20.0 1.8
23.4 1.6
Table 2. Fractional Calibration Uncertainties (FCU in Reference 2) For the Two Quantitative Analyses.
Compound
HC1 "4fit"
HC1 "Meomp"
Run 2*
Run 3*
FCU(%)
4.6
1.05
3.14
Analytical Region (cm*1)
2747 - 2848
2569-2871
* Spectra of four samples from the cylinder standard (103 ppm HG in nitrogen) were used in the
"Mcomp" analysis. The spectra were measured at the same instrument configuration used in each ran.
Table 3. Summary of results comparisons in 4 runs (8 data sets).
Data Set
Run 1 Inlet
Run 1 Outlet
Run 2 Inlet
Run 2 Outlet (Figuie 2)
Run 3 Inlet
Run 3 Outlet (Figure 3)
Average "4FTT"
Results
HC1 ppm % 4 * o l
43.3 3.9
34.5 4.1
14.8 7.7
48.0 4.5
62.5 5.6
58.0 5.5
Average "Multicomp"
Result
HCl ppm
42.1
32.9
13.1
46.4
50.9
47.3
% Difference J
2.9
4.4
11.8*
3.2
18.6
18.4
No. of Results1
36
30
16
33
41
52
1 - Average percent uncertainty in the 4FTT results.
2- Equals (4FIT-Multicomp)/4Frr.
3 - Equals the number of spectra included in the average. Results from condenser and ambient air
samples were not included in the averages.
4 - Flow restriction during this run may have caused HCl losses resulting in lower measured
concentrations for this run. An average difference of 1.7 ppm corresponded to a relatively large percent
difference of 11.8 % on the smaller average concentration for this run.
-------
97-MP74.05
Table 4. Method 301 statistical analysis of "4FIT" HC1 results in Figure 3,
Unspiked
Run Average =
Statistical
Results
HC1 ppm
57.18 *
SD =
F =
RSD=
Bias =
ts
di (d,)2
9.68 52.561
2.093
0.491
3.7
-0.088
0.12
Spiked
HC1 ppm d i
62.14 * 4.74
SD • L466
SDp^rfs 1.807
Exp Cone = 5.05
CF a 1.02
(d,)2
25.784
* Represents the average result in 12 unspiked or spiked samples. Statistical variables are described in
Section 6.3 of EPA Method 301.3 Procedure for determining spiked dilution factor and expected
concentration, Exp Cone, is described in reference 10.
Table 5. Summary of Method 301 statistical analysis of "Multicomp" results in Figure 3.
Unspiked
HC1 ppm d i (d i)2
Run Average =
Statistical
Results
45.88 *
SD =
F =
RSD=
Bias =
ts
8.62 34.242
1.689
0.628
3.7
-0.070
0.11
Spiked
HC1 ppm
50.86 *
SD =
SDpoded8*
Exp Cone =
CF =
di
3.51
1.338
1.524
5.05
1.01
(d,)2
21.496
* Represents the average result in 12 unspiked or spiked samples. Statistical variables are described in
Section 6.3 of EPA Method 301.3 Procedure for determining spiked dilution factor and expected
concentration, Exp Cone, is described in reference 10.
-------
Figure 1. Extractive sampling system.
Baghout* Intel
Probe 12
I I
v**t « •«
Unhculud Llnu
Healed Una
Heated
Probe Box
1 1 .
1 1
-t*
1
i
1-
.. •—
— Baltton
Filler
H*attd bundle i
00'
Spiki ii»« 1
1 *
|§,
20'
J
20*
o
Ui
------- |