United Stales
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA-454/R-99-05I
September 1999
Air
LIME MANUFACTURING EMISSIONS TEST
E PA REPORT (FOURIER TRANSFORM INFRARED
SPECTROSCOPY)
Chemical Lime Company
(Formerly Eastern Ridge Lime Company)
Ripplemead, Virginia
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LIME MANUFACTURING EMISSION TEST REPORT
(FOURIER TRANSFORM INFRARED SPECTROSCOPY)
FINAL REPORT
Chemical Lime Company
(Formerly Eastern Ridge Lime Company)
Ripplemead, Virginia
Prepared for
Emission Measurement Center
United States Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attn: Michael L. Toney
EPA Contract NO. 68-D-98-027
Work Assignment 2-11
MRI Project No. 104951-1-011-06
September 30, 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. 2-11. Mr. Michael Toney is the EPA Work Assignment Manager (WAM).
Dr. Thomas Geyer is the MRI Work Assignment Leader (WAL). The field test was performed,
and draft and revised test reports were submitted under EPA Contract No. 68-D2-0165, Work
Assignment No. 4-01. Mr. Dennis Holzschuh and Michael Toney were the EPA WAMs for the
Emission Measurement Center (EMC) under Work Assignment 4-01.
This report presents the procedures, schedule, and test results for an emissions test
performed at Eastern Ridge Lime Company in Ripplemead, Virginia. The field test was
conducted in October, 1996. The draft and revised test reports were submitted in January and
September 1997, respectively. MRI performed FIIR emissions measurements at the inlet and
outlet of a wet scrubber control device using EPA Method 320. Method 320 has since been
promulgated in the Federal Register on May 19,1999.
This report consists of one volume (210 pages) with six sections and five appendices.
Midwest Research Institute
Andrew Trenholm
Deputy Program Manager
Approved:
^/JeffShular
\ Director, Environmental Engineering Division
September 30, 1999
-------
TABLE OF CONTENTS
Page
LIST OF FIGURES ,..,,.., vii
LIST OF TABLES vii
1.0 INTRODUCTION 1-1
1.1 BACKGROUND 1-1
1.2 PROJECT SCOPE 1-1
1.3 PROJECT PERSONNEL 1-2
2.0 TEST LOCATIONS . 2-1
2.1 NO. 2 KILN SCRUBBER INLET .2-1
2.2 SCRUBBER OUTLETS (A AND B) 2-1
2.3 HYDRATOR STACK 2-4
3.0 RESULTS 3-1
3.1 TEST SCHEDULE 3-1
3.2 FIELD TEST PROBLEMS AND CHANGES 3-1
3.3 SCRUBBER INLET , .3-3
3.4 SCRUBBER OUTLET 3-3
3.5 HYDRATOR STACK 3-3
4.0 FTIR TEST PROCEDURES 4-1
4.1 SAMPLING SYSTEM DESCRIPTION 4-1
4.1.1 Sampling System Components .4-1
4.1.2 Sample Conditioning 4-3
4.2 SAMPLING PROCEDURE 4-3
4.2.1 Testing Two Locations Simultaneously 4-3
4.2.2 Testing a Single Location 4-4
4.3 SAMPLING PROCEDURES .4-4
4.3.1 Batch Sampling 4-6
4.3.2 Flow Through Measurements 4-6
4.3.3 Dilution Samples 4-6
4.3.4 Condenser Samples 4-6
4.4 ANALYTICAL PROCEDURES 4-7
4.5 FTIR SYSTEM 4-7
4.6 ANALYTE SPIKING 4-8
4.7 SCREENING FOR HAPs 4-8
-------
TABLE OF CONTENTS (CONTINUED)
'••age
5.0 SUMMARY OF FTO. QA/QC PROCEDURES , 5-1
5.1 SAMPLING AND TEST CONDITIONS 5-1
5.2 FTIR SPECTRA 5-2
5.3 CORRECTIVE ACTIONS 5-3
6.0 REFERENCES 6-1
APPENDIX A. ADDITIONAL DATA AND CALCULATIONS
APPENDIX B. FIELD DATA RECORDS
APPENDIX C. FTIR ANALYTICAL RESULTS
APPENDIX D. PROCESS DESCRIPTION AND DATA
APPENDIX E. EPA METHOD 320
EPA FTIR PROTOCOL
VI
-------
. TABLE OF CONTENTS (CONTINUED)
LIST OF FIGURES
Pag
Figure 2-1. Test location at Eastern Ridge hydrator stack 2-2
Figure 2-2. Test location at Eastern Ridge scrubber inlet 2-3
Figure 2-3. Test locations at Eastern Ridge scrubber outlet 2-5
Figure 3-1. SO2 concentrations at Eastern Ridge scrubber inlet 3-15
Figure 3-2. CO concentrations at Eastern Ridge scrubber inlet 3-16
Figure 3-3. HC1 concentrations at Eastern Ridge scrubber inlet 3-17
Figure 3-4. SO2 concentrations at Eastern Ridge scrubber outlet 3-18
Figure 3-5. CO concentrations at Eastern Ridge scrubber outlet 3-19
Figure 3-6. HC1 concentrations at Eastern Ridge scrubber outlet 3-20
Figure 3-7. Spectra from Eastern Ridge scrubber outlet, 10/18/96 3-21
Figure 4-1. FTIR sampling system configuration for test at Eastern Ridge lime plant 4-2
Figure 4-2. FTIR instrument and sampling configuration ..' 4-5
LIST OF TABLES
Page
TABLE 3-1. SCHEDULE OF FTIR TESTING AT EASTERN RIDGE 3-2
TABLE 3-2. FTIR RESULTS FROM THE EASTRTDGE SCRUBBER
INLET, 10/18/96 3-4
TABLE 3-3. FTIR RESULTS FROM THE EASTRIDGE SCRUBBER
OUTLET, 10/18/96 3-6
TABLE 3-4. EASTERN RIDGE SCRUBBER INLET AND OUTLET
ESTIMATED UNCERTAINTIES FOR NON-DETECTS 3-8
TABLE 3-5. EASTERN RIDGE HYDRATOR. ESTIMATED UNCERTAINTIES
FOR NON-DETECTS 3-11
VII
-------
1.0 INTRODUCTION
1.1 BACKGROUND
The Emission Measurement Center (EMC) of the U. S. EPA received a request from the
Minerals and Inorganic Chemicals Group (MICG) of the U.S. EPA to perform emissions testing
at coal-fired lime kilns. In partial fulfillment of the test request, EMC issued Work
Assignments 2-11 and 4-01 under EPA Contract Nos. 68-D-98-027 and 68-D2-0165,
respectively, to Midwest Research Institute (MRI). The purpose of this project was to measure
organic and inorganic hazardous air pollutants (HAPs) using a test method based on Fourier
transform infrared (FTIR) spectroscopy. This report describes the test procedures and presents
results of the testing at Eastern Ridge Lime plant in Ripplemead, Virginia.
1.2 PROJECT SCOPE
Three locations were tested at Eastern Ridge: the inlet and outlet of a wet scrubber off of
the kiln, and the hydrator stack.
The procedures followed in this test are described in the FTIR sampling Method 320 for
hazardous air pollutants (HAPs).1 The objectives of the field test were to: (1) screen for HAPs
regulated in Title in of the 1990 Clean Air Act Amendments, (2) measure, if detected,
compounds that have been previously measured at cement kilns (e.g., formaldehyde, napthalene,
p-xylene), and (3) measure other pollutants such as SO2 and NOX.
The test request specifically identified HC1 as a target analyte. This facility uses coal as
fuel to fire the kiln and HC1 has been measured with FTIR methods at other coal-burning
facilities. Draft Method 320 (reference 1) uses an analyte spiking procedure for quality assurance
(or Method 301 validation) to verify that the sampling system is suitable for measuring target
analyte(s) at the expected concentration. In this test, analyte spiking was performed using an HC1
cylinder standard from Scott Specialty Gases.
1-1
-------
In the FTIR screening procedure, spectra of gas samples contained in a leak tight infrared
gas cell are recorded at regular intervals over a sampling run. Typically, 8 to 10 sample spectra
are recorded in an hour. These spectra are then analyzed using reference spectra in the EPA
library to identify and quantify any HAPs in sample. Unidentified spectral features are analyzed
to check for the presence of other compounds, for which there are currently no reference spectra,
1.3 PROJECT PERSONNEL
This project was administered by the EMC of the U.S. EPA. The Test Request was
initiated by the MICG of the Office of Air Quality and Standards (OAQPS), Midwest Research
was assisted in the field test by staff from Emission Testing Services, Inc. (ETS) and Envirostaff,
Inc. Dr. Grant Plummer of Rho Squared assisted in the data analysis. Key project personnel are
listed in Table 1-1.
TABLE 1-1. PROJECT PERSONNEL
Eastern Ridge Lime Company
EMC Work Assignment
Manager
MRI Work Assignment
Leader
J. Steven Castleberry
Mr. Michael Toney
Dr. Thomas Geyer
(618)465-7741
(919)541-5247
(919)851-8181
1-2
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2.0 TEST LOCATIONS
Eastern Ridge Lime Company has two coal-fired rotary kilns. Emissions from the kiln
are controlled by two parallel Ducon wet scrubbers.
The facility also operates a hydrator to convert lime to hydrated lime.
The sampling location figures were prepared by Pacific Environmental Services, Inc.
(PES). The information below was also provided by PES.
2.1 NO. 2 KILN SCRUBBER INLET
The common inlet is in a rectangular duct at a 45° angle to ground. At the kiln discharge
the duct is about 6-ft by 4-ft. The dimensions narrow to about 5-ft by 4-ft immediately before the
duct splits upstream of the two scrubbers. Insulation was placed over the duct to provide a heat
shield.
The scrubber inlet location was within 50-ft of the outlet locations and within 100-ft of
where the FTIR trailer was parked. Figure 2-1 is a schematic of this location.
2.2 SCRUBBER OUTLETS (A AND B)
The sampling locations at the outlets of both scrubbers were similar. The scrubber outlet
stacks were within 8-ft of each other and within 100-ft of the FTIR trailer location. The outlet
sampling ports were in 48-in ID, round vertical stacks. Scaffolding and a ladder provided access
to ports in the scrubber stacks.
Flow straightening vanes were lowered into each stack before testing. The vanes blocked
the original FTTR test ports so new ports were cut in each stack just above the tops of the vanes
below the manual sampling ports. Figure 2-2 is a schematic of the scrubber outlet locations.
2-1
-------
(sJ
Sample Port
6-incii ID Sample Port
To Scrubber A
To Scrubber B
To Scrubbers
Sjdo Vtcw
Figure 2-1. Scrubber inlet location.
-------
Flow
Straightening
Vanes
to
Blocked Off
Scrubber
A
4 8" ID
Cro$»-Scclion
SAMPLE TRAVERSE POINT LOCATIONS
Old Duct
Not In Use
Flow
Straightening
Vanes •
Point
Number
J
2
3
4
5
6
7
8
9
10
11
12
Fraction of Distance
Stack ID
.021
.067
.111
.177
.250
.356
.644
.750
.823
.882
.933
.979
Figure
Inches
1.00
3.19
5.69
8.50
12.00
17.06
30.94
36.00
39.50
42.31
44.81
47.00
Port Depth
Inches
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25
3.25
2-2. Scrubber outlet,,
Port Location llMMIHHflmUll
Inches 1
4.25
6.44 ) \
8.94 / \
11.75 / \
15.25 / \
20.31 / \
34.19
39.25
42.75
45.56
48.06
50.25
slacks.
Scrubber
B
-------
2.3 HYDRATOR STACK
The sampling ports were in a (23,5-in ID) round, vertical stack, 10-ft upstream and 12-ft
downstream of the nearest flow disturbances. An inside stairway provided access to the roof and
scaffolding provided access to the sampling ports. The sampling location was within 100-ft of
the FT1R trailer position.
Figure 2-3 is a schematic of the hydrator stack location. The FTIR sampling ports were
about 4-ft below the manual sampling ports shown in Figure 2-3,
2-4
-------
O
23-5'ID
SAMPLE TRAVERSE POINT LOCATIONS
Point Fraction of Distance Port Depth Port Location
Number Stack ID fetches Inches Inches
Cross Section
1
2
3
4
5
6
7
s
.032
,105
.194.
J23
.677
.806
.895
.968
0.75
2.44
4.96
736
I5.?4
13.94
21.06
22.75
3.00
3.00
3.00
3.00
3.00
3.00
3,00
3.00
I 3.75
5.44
716
IOJ6
1&94
21.94
24.06
22.75
Figure 2-3. Hydrator stack.
2-5
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3.0 RESULTS
3.1 TEST SCHEDULE
The testing was completed within a week on the test site from October 14 through
October 19, 1996. Table 3-1 summarizes the F11R sampling schedule. A complete record of all
FTIR sampling is in Appendix B.
The FTIR testing was coordinated with manual sampling and Method 25A testing
performed by Pacific Environmental Services (PES), Process conditions were monitored by
Research Triangle Institute (RTI) during the field test.
3.2 FIELD TEST PROBLEMS AND CHANGES
Initially, the FTIR instrument was not working properly because the interferometer could
not consistently hold alignment. An Analect service technician was consulted on 10/15. The
technician suggested a slower scan speed and that helped the instrument function adequately, but
a site visit was scheduled for 10/17. About one hour into Run 1 on 10/16 the instrument lost
alignment. The alignment could not be recovered so FTIR testing was stopped. On 10/17 the
Analect technician visited the site, repaired and realigned the interferometer. FTIR testing was
resumed on 10/18 to coincide with Run 3 of the manual and M25 A testing.
During the first test run, sample flow from the inlet location decreased rapidly to where it
was only about 2 1pm when the FTIR testing was stopped after about one hour. The moisture
combined with a high particulate level quickly clogged the particulate filter. Particulate did not
clog the 50-ft section of heated line upstream of the filter. The flow problem was remedied by
replacing the 3/8-in diameter sample probe with a Vi-in. probe. When sampling was resumed for
Run 3, the flow was higher and much more consistent for the run duration. Sample flow was
much better at the scrubber outlet, but that probe was also replaced with a Vi-in diameter probe.
3-1
-------
TABLE 3-1. SCHEDULE OF FTIR TESTING AT EASTERN RIDGE
Date
10/15/96
10/16/96
10/17/96
10/18/96
10/19/96
Time
(Bkg & Cals)
1700-1758
907-1318
1835-2000
947-1042
1345
1627
1633
932-1145
1240
1342-1406
1410
1609-1620
Time
(Sampling)
1455-1550
1044-1117
1122-1139
1144-1236
1237
1244-1325
1355-1612
1206-1244
1247-1314
1409
1419-1434
1436
1444-1531
Kiln No 2. Scrubber Inlet
Calibration and leak check
Background and Calibrations
Inlet to scrubber
Background after cell alignment
Background, calibration, and leak
check
Unspiked
SF6 spike
HC1 spike
Spike off to inlet
Unspiked
Background
Unspiked
Background
Calibration
Kiln No 2. Scrubber
Outlet
Unspiked
Unspiked
Unspiked
Unspiked
Unspiked
Hydrator
Background and calibrations at
hydrator stack
Hydrator stack
Background
Hydrator stack hot wet
Calibration
Started SF6 spike to probe
Calibration
Hot wet spiked W/SF6
started HC1 spike
spiked w/ HC1
Background and calibration
to
-------
3.3 SCRUBBER INLET
On October 16 limited testing was completed for about one hour before the FTIR
instrument malfunction occurred, A full test run was completed on October 18. The principal
emissions were water vapor, CO2, SO2, CO, and HC1. The HC1 was not detected in samples that
had been treated with the condenser system. The concentration results are presented in Table 3-
2, Results for SO2, CO, and HC1 are presented graphically in Figures 3-1 to 3-3. Some HC1
emissions were measured at the inlet and, in addition, three samples were spiked with the HC1
gas standard to determine if sampling system introduced any bias in the measured HC1
concentrations.
The estimated spike recovery is given in Table 3-2. Four samples spiked with HC1 were
collected (samples 208-211). It is apparent from Table 3-2 that the spiked HC] concentration
was still increasing toward the expected value. Collecting additional samples may have given a
higher percent recovery.
3.4 SCRUBBER OUTLET
Table 3-3 and Figures 3-4 to 3-7 present the results from the scrubber outlet. The west
outlet stack (B) was sampled for the first part of the run. Then the probe was moved to the east
(A) stack, which was tested for the remainder of the run.
The effluent at the outlet of both scrubber stacks was cooler and had a higher moisture
content than at the inlet location. In addition, a wet scrubber is expected to provide an effective
control for the emission of HC1, which is very soluble. The SO2 emissions were significantly
reduced compared to the inlet concentrations. The peak HC1 emission at the outlet was almost
15 ppm, about half the peak HC1 emission measured at the inlet.
3.5 HYDRATOR STACK
Moisture at the hydrator stack was about 60 percent. It was necessary to maintain flow
through the manifold at at least about 5 LPM to prevent condensation in the rotameter. The HC1
spike was observed but not recovered quantitatively.
3-3
-------
TABLE 3-2. FTIR RESULTS FROM THE EASTRIDGE SCRUBBER INLET, 10/18/96.
File name '
SCINLOOl.SPC
SCINL002.SPC
SCINL201.SPC
SCINL202.SPC
SCINL203.SPC
SCINL204.SPC
SCINS205.SPC
SCINS206.SPC
SCINS207.SPC
SCINH208.SPC
SCINH209.SPC
SCINH210.SPC
SCINH211.SPC
SCINL212.SPC
SCINL213.SPC
SCINC214.SPC
SCINC215.SPC
SCINC216.SPC
SC1NL217.SPC
SCIND218.SPC
SCINL219.SPC
SCINC220.SPC
SCIND221.SPC
SCIhO.222.SPC
Time
10/16/96 15:02
10/16/96 15:12
10:52
10:57
11:09
11:13
11:29
11:33
11:38
11:58
12:08
12:19
12:30
13:02
13:08
13:13
13:20
13:55
14:54
15:07
15:24
15:30
15:48
15:55
SO2 ppm 4*a SO2lbs/hr
235.2 7.8 74.3
243.8 7.7 77.1
268.6 8.1 84.9
265.0 8.1 83.7
175.7 12.9 60.8
156.0 12.4 54.0
174.9 11.4 60.5
167.6 16.8 58.0
202.8 14.8 70.2
151.3 14.6 52.4
184.5 11.3 63.8
261.4 8.0 82.6
312.0 8.3 98.6
201.3 5.1 63.6
179.9 5.1 56.9
211.7 4.9 66.9
245.6 7.6 77.6
100.4 4.8 31.7
191.0 10.7 60.4
168.2 9.0 53.2
106.8 4.9 33.7
204.9 7.5 64.7
SF4 ppm 4*o
0.052 0.042
0.054 0.041
0.065 0.043
0.062 0.043
0.329 0.069
0.353 0.066
0.364 0.061
0.000 0.087
0.000 0.078
0.000 0.076
0.000 0.059
0.063 0.043
0.065 0.044
0.032 0.027
0.035 0.027
0.000 0.026
0.052 0.041
0.000 0.025
0.000 0.057
0.000 0.048
0.000 0.026
0.042 0.040
CO ppm 4*o COlbs/hr
134.1 30.6 18.5
139.6 29.2 19.3
154.3 30.8 21.3
127.3 29.9 17.6
81.2 21.8 12.3
67.7 21.6 10.3
77.6 21.4 11.7
51.3 24.3 7.8
62.5 21.7 9.5
43.9 22.2 6.6
41.8 21.0 "6.3
48.2 31.2 6.7
51.9 32.1 7.2
63.0 13.6 8.7
52.1 12.4 7.2
61.0 12.5 8.4
41 :8 30.8 5.8
35.0 13.2 4.8
54.5 33.8 7.5
60.4 13.5 8.3
25.8 15.7 3.6
37.2 31.6 5.1
HCI ppm 4*o HCMbs/hr
0.00 2.56 0.0
23.86 2.29 3.7
4.56 2.16 0.8
14.43 2.01 2.6
10.75 1.93 1:9
21.92 2.01 3.9
4.45 1.29 0.9
5.91 1.24 1.2
5.44 1.15 1.1
4.36 1.30
18.53 1.53
30.92 1.65
19.11 1.41
9.32 1.93 1.7
22.31 2.09 4.0
2.06 0.49 0.4
0.90 0.48 0.2
0.68 0.49 0.1
29.17 2.02 5.2
14.32 1.07 2.6
16.69 3.02 3.0
1.37 0.54 0.2
6.29 0.80 1.1
7.61 1.62 1.4
average Ibs/hour
SF6 standard =
average SF6 =
dilution = 4.01 7.349
59.6
4.01
0.349
11.5
HCI spike-unspike =
HCI "expected" =
percent deviation - spike from unspike =
12.03
8.97
average HCI spike = 22.85
average HCI unspike = 1 0.83
25.45%
8.9
DSCFM =
% moisture =
29031
8.37
1.8
1 - File name: 'SCINL1 untreated scrubber Inlet sample; 'F1 flowing; bold, In box, spiked ('S1 with SF6, samples 208 to 211 spiked with HCI); 'D1 - dilution sample, 'C'
condenser sample.
'4'sigma1 - estimated uncertainty. •• •
-------
TABLE 3-2. (continued)
File name 1 Date
SCINL001.SPC 10/16/96
SCINL002.SPC 10/16/96
SCINL201.SPC 10/18/96
SCINL202.SPC 10/18/96
SCINL203.SPC 10/18/96
SCINL204.SPC 10/18/96
SCINS205.SPC 10/18/96
SCINS206.SPC 10/18/96
SCINS207.SPC 10/18/96
SCINH208.SPC 10/18/96
SCINH209.SPC 10/18/96
SCINH210.SPC 10/18/96
SCINH211.SPC 10/18/96
SCINL212.SPC 10/18/96
SCINL213.SPC 10/18/96
SCINC214.SPC 10/18/96
SCINC215.SPC 10/18/96
SCINC216.SPC 10/18/96
SCINL217.SPC 10/18/96
SCIND218.SPC 10/18/96
SCINL219.SPC 10/18/96
SCINC220.SPC 10/18/96
SCIND221.SPC 10/18/96
SCINL222.SPC 10/18/96
Time
15:02:00
15:12:00
10:52:00
10:57:00
:09:00
:13:00
:29:00
:33:00
:38:00
:58:00
12:08:00
12:19:00
12:30:00
13:02:00
13:08:00
13:13:00
13:20:00
13:55:00
14:54:00
15:07:00
15:24:00
15:30:00
15:48:00
15:55:00
NO ppm 4*a NO Ibs/hr
661.1 363.3 84.0
620.5 315.3 78.8
592.9 272.3 87.8
585.3 249.3 86.7
565.4 244.7 83.7
577.5 250.1 85.5
387.9 139.1 57.5
398.0 138.9 58.9
379.1 131.6 56.2
378.7 151.7 56.1
388.5 150.9 57.6
406.0 149.3 60.1
388.6 140.2 57.6
572.7 247.6 84.8
557.0 246.8 82.5
41.7.1 85.9 61.8
458.2 95.7 67.9
448.1 94.5 66.4
570.1 230.7 84.5
353.4 74.2 52.3
587.8 266.3 87.1
459.7 102.4 68.1
359.5 91.2 53.2
583.6 228.5 86.4
Time
15:02:00
15:12:00
10:52:00
10:57:00
1 :09:00
1 :13:00
1 :29:00
1 :33:00
1 :38:00
1 :58:00
12:08:00
12:19:00
12:30:00
13:02:00
13:08:00
13:13:00
. 13:20:00
13:55:00
14:54:00
15:07:00
15:24:00
15:30:00
15:48:00
15:55:00
NO2 ppm 4*a NO2 Ibs/hr
0 48.7
0 47.4
0 236.3
0 189.6
0 182.2
0 190.9
0 33.7
0 25.5
0 22.5
0 131.6
0 104.5
0 37.1
0 29.0
0 187.3
0 191.7
13.0 8.8 3.0
14.5 8.3 3.3
16.2 7.6 3.7
0 145.2
0 9.5
0 180.9
14.3 8.6 3.2
0 12.2
0 135.0
1 - File name: "SCINL" untreated scrubber inlet sample; "F" flowing; "S" spiked (bold indicates SF6or HCI); "D" - dilution sample; "C" condenser
sample.
"4*sigma" - estimated uncertainty. " •
Interference from moisture limits the NO2 analysis.
-------
TABLE 3-3. FTIR RESULTS FROM THE EASTREDGE SCRUBBER OUTLET, 10/18/96.
File name '
SCOUTOOl .SPC Wesi Slack (B)
SCOUT002.SPC
SCOUT201.SPC
SCOUT202.SPC
SCOUT203.SPC
SCOUT204.SPC
SCOUT205.SPC
SCOUT206.SPC
SCOUC207.SPC
SCOUC208.SPC
SCOUC209.SPC
SCOUT210.SPC
SCOUD211.SPC
SCOUD212.SPC
SCOUT213.SPC
Time
10/16/96 15:25
10/16/96 15:48
10:44
10:47
'11:02
11:05
11:18
11:23
11:47
11:53
12:37
12:44
12:51
12:57
13:30
SO2 ppm 4*a SO2 Ibs/hr
31.0 9.1 5.1
14.8 9.8 2.4
0.0 9.5 0.0
0.0 9.9 0.0
13.7 9.7 2.3
15.4 9.8 2.5
5.4 4.1 0.9
12.4 4.1 2.0
12.8 4.3 2.1
22.1 10.1 3.6
0.0 6.9 0.0
0.0 7.1 0.0
0.0 9.5 0.0
CO ppm 4* a CO Ibs/hr
92.2 31.2 6.6
111.0 32.3 8.0
91.0 33.4 6.5
106.4 33.4 7.6
115.4 32.8 8.3
94.8 33.5 6.8
62.6 12.0 4.5
69.9 12.5 5.0
50.7 11.6 3.6
105.3 34.2 7.5
0.0 33.5 0.0
0.0 33.7 0.0
53.1 39.3 3.8
HCI ppm 4* a HCI Ibs/hr
0 1.72 0.0
0 1.55 0.00
14.47 3.26 1.35
5.23 3.42 0.49
4.70 3.22 0.44
0.00 3.18 0.00
5.81 3.14 0.54
3.28 3.12 0.31
0.79 0.48
0.77 0.49
2.50 0.53
7.60 3.31 0.71
7.10 2.10 0.66
5.37 2.30 0.50
4.38 3.37 0.41
Average Ibs/hour =
1.6
5.3
0.5
SCOUT214.SPC East Slack (A)
SCOUC215.SPC
SCOUC216.SPC
SCOUT217.SPC
SCOUT218.SPC
SCOUC219.SPC
SCOUC220.SPC
SCOUD221.SPC
SCOUD222.SPC
SCOUD223.SPC
SCOUC224.SPC
SCOUC225.SPC
SCOUT226.SPC
SCOUD227.SPC
SCOUC228.SPC
SCOUT229.SPC
14:06
14:13
14:19
14:28
14:41
14:46
14:50
15:00
15:03
15:15
15:20
15:35
15:42
16:00
16:05
16:10
0.0 7.4 0.0
30.8 4.4 7.0
13.9 4.4 3.2
0.0 7.7 0.0
0.0 10.6 0.0
5.9 4.5 1.3
4.5 4.4 1.0
0.0 5.9 0.0
0.0 3.4 0.0
0.0 5.8 0.0
0.0 4.4 0.0
14.5 4.2 3.3
0.0 9.0 0.0
0.0 2.2 0.0
7.8 4.2 1.8
0.0 7.8 0.0
49.6 32.4 4.9
73.8 13.7 7.3
53.4 11.8 5.3
47.7 33.9 4.7
0.0 47.5 0.0
45.7 12.4 4.5
46.2 11.6 4.6
0.0 26.4 0.0
0.0 13.0 0.0
0.0 26.2 0.0
51.4 12.1 5.1
47.7 11.2 4.7
0.0 43.5 0.0
0.0 . 9.8 0.0
43.0 11.3 4.3
0.0 37.9 0.0
2.11 2.00 0.27
0.00 0.56
0.00 0.55
0.00 2.16 0.00
0.00 3.48 0.00
0.00 0.56
0.00 0.53
10.46 1.48 1.35
9.11 0.70 1.18
8.71 1.45 1.12
0.77 0.53
0.65 0.56
4.41 2.72 0.57
10.78 0.56 1.39
0.64 0.53
3.20 2.13 0.41
Average Ibs/hour =
1.10
2.84
A - DCFM =
A - % moisture =
18613
18.1
B - DSCFM =
B - % moistu
13633
17
1 - File name: 'SCOUT1 scrubber outlet sample, untreated; 'F' flowing; 'D' - dilution sample; 'C' condenser sample.
'4'sigma' - estimated uncertainty.
0.70
-------
TABLE 3-3. (continued)
?ile name date
SCOUT001 .SPC West Slack (B) 10/1 6/96
SCOUT002.SPC 10/16/96
SCOUT201.SPC 10/18/96
SCOUT202.SPC ' 10/18/96
SCOUT203.SPC 10/18/96
SCOUT204.SPC 10/18/96
SCOUT206.SPC 10/18/96
SCOUT206.SPC 10/18/96
SCOUC207.SPC 10/18/96
SCOUC208.SPC 10/18/96
SCOUC209.SPC 10/18/96
SCOUT210.SPC 10/18/96
SCOUD211.SPC 10/18/96
SCOUD212.SPC 10/18/96
SCOUT213.SPC 10/18/96
SCOUT214.SPC 10/18/96
SCOUC215.SPC 10/18/96
Average Ibs/hour =
SCOUC216.SPC East Stack (A) 10/18/96
SCOUT217.SPC 10/18/96
SCOUT218.SPC 10/18/96
SCOUC219.SPC 10/18/96
SCOUC220.SPC 10/18/96
SCOUD221.SPC 10/18/96
SCOUD222.SPC 10/18/96
SCOUD223.SPC 10/18/96
SCOUC224.SPC 10/18/96
SCOUC225.SPC 10/18/96
SCOUT226.SPC 10/18/96
SCOUD227.SPC 10/18/96
SCOUC228.SPC 10/18/96
SCOUT229.SPC 10/18/96
Time
15:25
15:48
10:44
10:47
11:02
11:05
11:18
11:23
11:47
11:53
12:37
12:44
12:51
12:57
13:30
14:06
14:13
14:19
14:28
14:41
14:46
14:50
15:00
15:03
15:15
15:20
15:35
15:42
16:00
16:05
16:10
NO ppm 4*a NO Ibs/hr
537.5 404.7 35.6
511.3 372.3 33.8
549.5 371.2 42.2
536.1 392.1 41.2
536.2 373.0 41.2
530.6 372.9 40.7
521.8 369.9 40.1
510.7 360.6 39.2
319.4 60.3 24.5
313.9 57.5 24.1
334.2 62.8 25.7
507.5 377.6 39.0
313.8 204.6 24.1
326.5 210.1 25.1
49 1. 4 356. 1 37.7
479.2 248.6 36.8
374.9 72.8 28.8
34.0
377.8 80.8 40.1
482.8 268.2 51.3
524.2 390.4 55.7
401.2 81.7 42.6
400.9 81.0 42.6
311.2 153.0 33.1
132.3 62.8 14.1
311.4 152.8 33.1
404.9 82.3 43.0
391.3 83.6 41.6
515.4 331.2 54.8
69.8 40.9 7.4
384.0 84.9 40.8
533.7 281.9 56.7
NO2 ppm 4*o NO2 Ibs/hr
0.0 18.7
0.0 28.8
0.0 365.4 .
0.0 315.2
0.0 339.5
0.0 362.8
0.0 356.4
0.0 355.7
14.0 8.0 1.6
9.9 7.7 1.2
1 3.6 8.5 1.6
0.0 341.4
0.0 197.3
0.0 198.3
0.0 351.3
0.0 239.8
13.3 8.8 1.6
1.5
15.3 7.6 2.5
0.0 290.0
0.0 284.5
14.6 9.1 2.4
14.3 8.3 2.3
0.0 133.2
0.0 9.8
0.0 131.2
14.3 8.6 2.3
14.4 7.8 2.3
0.0 359.2
0.0 7.6
17.8 8.4 2.9
0.0 271.8
Average Ibs/hour =
39.77
2.46
1 File name: "SCOUT" scrubber outlet sample, untreated; "F" flowing; "D" - dilution sample; "C" condenser sample.
"4"sigma" - estimated uncertainty.
-------
TABLE 3-4, ESTIMATED HAP UNCERTAINTIES, EASTERN RIDGE SCRUBBER INLET AND OUTLET
Compound
Acetonitrile
AcroleLn
Aciylcmitrile
Allyl Chloride
Senzeite
Jromoform
1,3-Butadiene
Carbonyl Sulfide
Chlorobenzene
athyl Benzene
Ethyl Chloride
Ethylene Dibmmide
n-Hexane
Methyl Bromide
Methyl Chloride
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
MIefliyl Methaciylate
Methylene Chloride
2-Nilropropiuie
Propylene Dichloride
Styrene
Tetrachloroethylene
Toluene
1. 1,2-Trichloroethuie
Trichloroethylene
2,2,4-Trimelhylpentaiie
Vinyl Acetate
Vinyl Bromide
Vinyl Chloride
Vinylidene Chloride
O-xylene
P-xylene
Analytical Region (cm1)
3038.97 - 3042.42
2636.11 - 2875.59
968,58 - 974.19
899.55 - 965.72
3036.88 - 3063.07
1135.9 - 1154.2
895.91 - 919.75
2026.14 - 2085.23
1069.86 - 1103.34
2850.71 - 2959.43
943.43 - 1000.16
1167.96 - 1208.92
2835.27 - 3005.43
2948.11 - 2972.53
1017.96 - 1020.72
1140.7 - 1222.63
2872.05 - 2994.95
1137.5 - 1232.04
743.96 - 769.17
831.47 - 868.5
996.86 - 1038
886.69 - 920.72
899.2 - 925.2
2862 - 2924
916.98 - 956.37
826.25 - 860.91
2861.57 - 3009.23
1201.77 - 1242.73
899.81 - 904.54
894.43 - 899.25
1059.44 - 1113.01
2859.84 - 3095.04
2854.43 - 3083.14
Scrubber Inlet
Estimated
RMSD Uncertainty (ppm)
1.1E-03 13.2
1.9E-03 2.8
7.7E-03 4.1
1.1E-02 7.5
2.7E-02 14.0
9.0E-03 1,9
3.8E-03 1.3
3.6E-01 12.8
8.0E-03 4.3
7.5E-03 10.2
l.OE-02 16.1
1.3E-02 10.5
1.2E-02 2.0
1.4E-02 17.4
3.3E-03 12.0
1.3E-02 10.9
1.3E-02 5.9
1.5E-02 1.9
1.4E-01 15.0
7.0E-03 8J
8.1E-03 10.6
3.5E-03 2.8
4.5E-03 0.5
4.1E-03 7.2
1.2E-02 9.1
7.6E-03 1.3
1.3E-02 1.8
1.8E-02 0.8
1.7E-03 0.8
1.1E-03 2.0
1.1E-02 3.2
2.4E-02 16.8
2.3E-02 14.1
Scrubber Outlet
Estimated
RMSD Uncertainty (ppm)
9.53E-03 98.63
7.83E-03 11.35
2.01E-02 10.61
4.49E-02 31.55
2.16E-01 112.30
1.20E-01 24.99
5.45E-02 18.20
4.84E-01 17.48
5.70E-02 30.89
6.56E-02 88.68
2.64E-02 40.86
1.89E-01 149.17
1.15E-01 18.54
1.05E-01 133.50
1.87E-02 67.99
1.83E-01 149.64
L09E-01 51.10
3.71E-02 20.82
2.75E-01 29.46
1.19E-01 145.47
4.00E-02 52.21
1.56E-02 21.72
5.88E-02 5.91
2.62E-02 45.90
3.71E-02 28.96
3.87E-02 8,24
1.23E-01 16.45
1.06E-01 10.42
1.35E-03 0.63
9.69E-03 18.29
7.45E-02 22.02
2.05E-01 144.20
2.01E-01 121.88
See Section 4.8, Screening For HAPs.
3-8
-------
TABLE 3-4, CONTINUED
Compound
Carbon Disulfide
Carbon Tetrachloride
Chloroform
Cumene
1,2-Epoxy Butane
Ethylene Oxide
Methanol
Methyl Chloroform
Methyl Iodide
Methyl t-Butyl Ether
Propylene Oxide
M-xykne
Acetone
Acetaldehyde
Acetophenone
Acrylic Acid
Aniline
Benzotrichloride
Benzyl Chloride
Bis(chloromethyl)ether
Chloroacetic acid
2-Chloroacteophenone
Chloiomethyl methyl ether
Chloroprene
o-Cresol
m-Cresol
p-Cresol
l,2-Dibromo-3-chloTO pro pane
1,4-Dichlorobenzene
Dichloroethyl ether
1 , 3 -Dichloropropene
Dichlorvos
N,N-Diethyl aniline
Dimethyl carbamoyl chloride
Analytical Region (cm1)
2171.64 - 2198.03
793.89 - 800.58
758.21 - 781.25
2951.21 - 2998.48
902.37 - 919.7
866.9 - 875
2807.91 - 3029.4
1057.95 - 1105.3
1250.18 - 1253.53
1195 - 1210
2875.59 - 3097.75
2910.25 - 2952.78
1182 - 1255.03
2685.41 - 2744.4
1140.4 - 1286.06
1104.89 - 1164.68
1102.9 - 1123.63
866.5 - 877.9
3027.52 - 3109.06
1068.78 - 1154.25
1094.97 - 1124.12
1274.39 - 1285.42
1111.02 - 1146.08
875.9 - 878,8
1092.8 - 1114.07
1139.68 - 1172.77
1159.1 - 1185.5
1134.26 - 1175.42
995.96 - 1031.06
1109.35 - 1155.04
768 - 791
835.77 - 876.95
2655.32 - 3156.07
389.55 - 917.52
Scrubber Inlet
Estimated
RMSD Uncertainty (ppm)
7.8E-03 8.5
3.5E-02 0.8
5.4E-02 3.0
1.8E-02 5.2
4.4E-03 3.5
3.9E-03 1.0
1.5E-02 13.5
1.1E-02 2.2
1.5E-03 1.5
8.0E-03 1.4
2.5E-02 17.8
8.8E-03 5.9
1.7E-02 8.1
1.5E-03 2.8
3.0E-02 4.3
8.5E-03 1.2
8.1E-03 2.9
3.7E-03 0.7
3.7E-02 32.1
l.OE-02 1.2
7.2E-03 1.7
1.2E-02 2.5
9.4E-03 1.5
3.6E-03 0.7
5.9E-03 2.7
6.5E-03 1.3
1.2E-02 1.4
1.2E-02 15.0
4.3E-03 2.0
8.9E-03 1.1
3.9E-02 8.6
6.8E-03 0.9
2.3E-02 14.2
3.3E-03 0.9
Scrubber Outlet
Estimated
RMSD Uncertainty (ppm)
5.19E-02 56.16
2.17E-01 4.68
1.17E-01 6.56
1.60E-01 45.11
5.85E-02 47.22
2.75E-02 7.33
1.34E-01 119.19
6.71E-02 13.06
8.99E-03 9.02
6.71E-02 12.53
2.15E-01 150.95
7.87E-02 53.09
2.52E-01 121.27
9.53E-03 17.35
3.41E-01 " 48.76
9.74E-02 13.53
9.00E-02 31.73
2.47E-02 5.00
3.06E-01 264.80
8.76E-02 10.34
8.28E-02 19.48
2.61E-01 53.08
1.04E-01 16.70
1.94E-02 3.83
7.34E-02 33.83
7.20E-02 14.25
1.89E-01 22.79
1.76E-01 218.20'
4.03E-02 19.20
1.01E-01 12.54
1.40E-01 31.04
1.88E-02 2.90
1.89E-01 119.51
6.53E-02 10.03
3-9
See Section 4.8, Screening For HAPs.
-------
TABLE 3-4, CONTINUED
Compound
Dimethyl formamide
1,1 -Dimethyl hydrazine
Dimethyl phlhalate
1,4-Dioxane
EpichJorohydrin
Ethyl Acrylate
Ethyleae Dichloride
Ethylidene dichloride
Formaldehyde
Hexachtotobutadiene
HexacMorocylcopentadiene
Hexachloroethane
Hexajnediylphosphoraniide
Maleic Anhydride
Methyl hydrazine
Naphthalene
Nitrobenzene
N-Nitrosodhnethylene
N-Nitrosomoipholine
Phenol
beta-Propiolactone
Propionaldehyde
1,2-PiDpylenirmiie
Quioline
Styrene Oxide
1,1 ,2,2-Tetrachloroethane
2,4-Taluene diisocyanate
o_Tohiidine
1,2 ,4-Tiichloro benzene
2,4,5 -Trichloiophenal
2,4,6-Trichlorophenol
Triethylamine
Ammonia
Ammonia
Analytical Region (cm"1)
2824.8 - 2873.6
2740.77 - 2914,08
1157.86 - 1254.16
2919.4 - 2921.3
943.52 - 981.73
1181.93 - 1210
1227.88 - 1241.5
1041.11 - 1080.5
2788.33 - 2842.2
976.9 - 997.7
1227.02 - 1240.42
779.26 - 797.38
949.42 - 1019.53
2817.35 - 2823,26
2681.2 - 3130.6
885.27 - 905.56
2683 - 3061.78
779.31 - 783.55
841,7 - 861.39
928 - 1085.28
892.23 - 1024.64
998.4 - 999.9
860.13 - 957.64
2546.18 - 3114.35
817,57 - 821,31
800.19 - 803.73
861.39 - 903,93
794.92 - 824.07
2254.7 - 2301.18
2858.5 - 2951.85
1086.21 - 111437
1178,04 - 1204.16
856.27 - 863,36
2756.62 - 2839.34
Scrubber Inlet
Estimated
RJV1SD Uncertainty (ppm)
2.0E-03 1.4
3.1E-03 1.5
1.6E-02 9.3
8.9E-04 0.2
1.2E-02 10.8
1.2E-02 0.7
6.4E-03 3,9
1.5E-02 6.9
1.7E-03 1.9
5.3E-03 0.8
6.4E-03 0.5
9.0E-01 20.7
8.5E-03 1.3
1.9E-03 2.1
2.3E-02 15.6
1.8E-03 0.2
1.6E-02 19.0
1.5E-02 1.6
8.2E-03 15
1.2E-02 4.0
9.3E-03 4.0
1.7E-04 0.9
8.8E-03 2.0
l.SE-02 20,9
4.3E-03 2.0
2.0E-02 3.3
3.2E-03 2,5
1.8E-02 4.4
5.3E-02 0.9
6.7E-03 6,1
6.5E-03 1.8
1.2E-02 4,1
2.5E-03 0.6
l.SE-03 0.8
Scrubber Outlet
Estimated
RMSD Uncertainty (ppm)
8.70E-03 S.98
1.62E-02 8.13
2.41E-01 138.37
8.9SE-04 0.30
3.06E-02 27.18
1.46E-01 8.08
9.00E-02 54.79
5.86E-02 27.19
6.73E-03 7,35
8.21E-03 1,25
9.26E-02 7,61
1.03E+00 23.76
3.32E-02 4.92
6.87E-03 7.30
1.86E-01 128.28
2.55E-02 2.76
1.48E-01 176.38
5.60E-02 5,95
1.40E-01 60.04
4.15E-02 13.97
4.18E-02 18.18
8.16E-03 17.59
4.76E-02 10.79
1.58E-01 184,09
3.97E-03 1,86
1.31E-01 21,21
4.49E-02 34.30
U7E-01 38.75
7.94E-02 1.30
6.37E-03 25.45
2.72E-02 9,38
1J3E-01 50.79
4.05E-02 10.47
6.16E-03 2.84
3-10
See Section 4.8, Screening For HAPs.
-------
TABLE 3-5. EASTERN RIDGE HYDRATOR ESTIMATED HAP UNCERTAINTIES
Compound
Acetonitrile
Acrolein
Acrylonitrile
AEyl Chloride
Benzene
Biomofonn
1,3-Butadiene
Carbonyl Sulfide
Chloio benzene
Ethyl Benzene
Ethyl Chloride
Ethykne Dibtomide
n-Hexane
Methyl Bromide
Methyl Chloride
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Methyl Methacrylate
Methylene Chloride
2-Nitro propane
Propylene Dichloride
Styrene
Tetrachloroethylejie
Toluene
1 , 1 , 2-Trichloroethane
Trichloroethylene
2,2,4-Trimethylpentane
Vinyl Acetate
Vinyl Bromide
Vinyl Chloride
Vinylidene Chloride
O-xylene
Analytical
1041.4
2636.11
968.58
899.55
3036.88
1135.9
895.91
2026,14
1069.86
2850,71
943.43
1167.96
2835.27
2948,11
1017.96
1140.7
2872.05
915.64
743.96
831.47
996.56
974,29
899.2
2862
916.98
919.7
2861.57
1003.83
899.81
894.43
1059.44
2859.84
Hydrator Si
Region (cm*1)
- 1042.88
- 2875.59
- 974.19
- 965.72
- 3063.07
- 1154.2
- 919.75
- 2085.23
- 1103.34
- 2959.43
- 1000.16
- 1208.92
- 3005.43
- 2972,53
- 1020.72
- 1222.63
- 2994.95
- 962.12
- 769.17
868.5
1038
- 1006.59
925.2
2924
- 956.37
- 959.88
- 3009.23
- 1041.65
- 904.54
- 899,25
- 1113.01
- 3095.04
tack
RMSD
4.2E-03
3.5E-03
6.7E-03
2.1E-02
1.5E-01
7.3E-02
2.7E-02
2.5E-01
2.8E-02
3.2E-02
l.OE-02
1.3E-01
6.6E-02
5.4E-02
8.3E-03
1.2E-01
6.3E-02
1.5E-02
1.5E-01
6.7E-02
1.7E-02
5.1E-03
2.9E-02
1.2E-02
1.6E-02
1.6E-02
7.0E-02
1.7E-02
1.4E-03
4.1E-03
4.0E-02
1.3E-01
Estimated
Uncertainty (ppm)
23.9
5.1
3.6
14.5
78.3
15.2
9.1
8.9
15.4
43.6
15.8
103.2
10.6
69.2
30,2
100.6
29.3
8.5
15.8
81.6
21.7
7.1
2.9
20.3
12.3
3.4
9.4
5.3
0.6
7.7
11.8
92.0
See Section 4.8, Screening For HAPs
3-11
-------
TABLE 3-5. CONTINUED
Compound
3-xylene
Caibon Disulfide
Carbon Tetrachloride
rhlorofonn
Cumene
1,2-Epoxy Butane
Ethylene Oxide
Methaaol
Methyl Chloroform
Methyl Iodide
Methyl t-Butyl Ether
Propylene Oxide
M-xylene
Acetone
Acetaldehyde
Acetophenone
Acrylic Acid
Aniline
Benzotriehloride
Benzyl Chloride
Bis (chloromethyl)ether
Chloroacetic acid
2-Cliloroacteophenone
Chloromettiyl methyl ether
Chloioprene
o-Cresol
m-Cresol
p-Cresol
1 , 2-Dibromo-3-chloropropajie
1,4-Dichlora benzene
Dichloroethyl ether
1,3-Dichloropropene
Dichlorvos
Hydrator Si
Analytical Region (em1)
770.61
2171.64
793.89
758,21
1015.6
902.37
866.9
2807.91
1057.95
1250.18
1070.6
2875.59
2910.25
1182
2685.41
874.88
953.62
1102.9
866.5
3027 52
1068.78
1094.97
1274.39
1111.02
875.9
1092.8
1139.68
2865.7
1134.26
995.96
1109.35
768
967.79
- 819.06
- 2198.03
- 800.58
- 781,25
- 1040.81
919.7
875
- 3029.4
- 1105.3
- 1253.53
1109
- 3097.75
- 2952.78
- 1255.03
- 2744.4
- 1126.36
- 1046.71
- 1123.63
877.9
- 3109.06
- 1154.25
- 1124.12
- 1285.42
- 1146,08
878.8
- 1114.07
- 1172.77
2893
- 1175.42
- 1031.06
- 1155.04
791
- 1000.25
acfc
RMSD
1.2E-01
3.1E-02
1.8E-01
6.6E-02
1.1E-02
3.0E-02
1.4E-02
8.0E-02
3.4E-02
5.5E-03
3.7E-02
1.4E-01
3.9E-02
1.7E-01
4.1E-03
2.7E-02
1.3E-02
5.2E-02
1.3E-02
2.0E-01
5.2E-02
4.6E-02
1.7E-01
6.5E-02
1.1E-02
4.2E-02
3.SE-02
5.6E-03
1.1E-01
1.8E-02
6.2E-02
8.3E-02
6.3E-03
Estimated
Uncertainty (ppn^>
76.5
33.2
4.0
3.7
25.6
24.0
3.8
71.7
6.6
5.5
6.9
96.6
26,4
81.5
7.5
24.5
6.5
18.2
2.6
174.2
6.1
10.9
• 35.2
10.5
2,2
19.4
7.4
11.2
140.6
8.4
7.7
18.4
1.0
See Section 4.8, Screening For HAPs
3-12
-------
TABLE 3-5. CONTINUED
Compound
N,N-Diethyl aniline
Dimethyl carbamoyl chloride
Dimethyl formamide
1, 1-Dimethy] hydrazme
Dimethyl phthalate
1,4-Dioxane
Epichlorohydria
Ethyl Acrykte
Ethylene DichJoride
Ethylidene dichloride
Formaldehyde
HexaeMorobutadiene
Hexachlorocylcopentadiene
Hexachloroe thane
Hexamethylphosphoranflide
Hydrochloric Acid
Isophorone
Maleie Anhydride
Metliyl hydrazine
Naphthalene
Nitrobenzene
N- Nitro so dimethylene
N-Nitrosomorpholine
Phenol
beta-Propiokctone
Propionaldehyde
1 ,2-Propylenimine
Quinoline
Styrene Oxide
1 , 1,2,2-Tetrdchtoroethflne
2,4-Toluene diisocyanate
o_Toluidiiie
1.2,4-Tiichloro benzene
Hydrator S
Analytical Region (cm1)
2655.32
1068.78
2824.8
2740.77
1157.86
2861.1
943.52
1181.93
712
1041.11
2788.33
976.9
1227.02
779.26
949.42
2817.35
2681.2
885.27
2683
779.31
841.7
928
892.23
1024
860.13
2546.18
817.57
800.19
861.39
794,92
2254.7
979
1028.2
- 3156.07
- 1114.47
- 2873.6
- 2914.08
- 1254.16
- 2864.8
- 981.73
1210
736
1080.5
- 2842.2
997.7
- 1240.42
- 797.38
- 1019.53
- 2823.26
- 3130.6
- 905.56
- 3061.78
- 783.55
- 861.39
- 1085.28
- 1024.64
- 1026.6
- 957.64
- 3114.35
- S21.31
- 803.73
- 903.93
- 824.07
- 2301.18
997.8
- 1048.69
,nck
RMSD
1.2E-01
3.6E-02
3.5E-03
7.4E-03
1.6E-01
2.5E-03
1.2E-02
1.1E-01
1.5E-01
2.9E-02
3.6E-03
2.5E-03
5.5E-02
9.4E-02
1.4E-02
3.5E-03
1.2E-01
1.1E-02
9.4E-02
3.5E-02
8.2E-02
1.9E-02
1.8E-02
4.6E-C4
2.1E-02
l.OE-01
6.7E-04
9.0E-02
2.0E-02
L1E-01
3.4E-02
1.8B-03
8.9E-03
Estimated
Uncertainty (ppm)
77.5
5.5
2.4
3.7
92.5
0.4
10.7
5.9
30.0
13.5
4.0
0.4
4.5
2.2
2.1
3.7
83.4
1.2
111.9
3.8
35.3
6.3
7.8
2.3
4.9
116.3
0.3
14.5
15.2
28.4
0.6
7.2
3.1
See Section 4.8, Screening For HAPs
3-13
-------
TABLE 3-5. CONTINUED
Componnd
2,4,5-TricMflrophenol
2, 4,6 -Trichlorophenol
Triethyhnrine
Ammonia
Hydrator S
Analytical Region (cm l)
1178,04 - 1204.16
856,27 - 863.36
2756,62 - 283934
893.1 - 926
ark
Estimated
RMSD Uncertainty (ppm)
1.1E-01 37.4
L9E-02 4.9
3.2E-03 1.5
2.6E-02 17,2
See Section 4.8, Screening For HAPs
3-14
-------
_c
'n
t
3
n
E
D)
T3
n
a.
Q.
350.0
300.0 •-
250.0 --
SO2 (ppm) at Eastern Ridge Scrubber Inlet
(10/18/96)
8 200.0 --
150.0 --
100.0 -•
50.0 •-
CM
d
in
o
en co
o T-
O)
co
co oo
co co
§
c\i
o
co
CO
CD
CO
8
Time of day
(not to scale)
Figure 3-1. SO2 concentrations at Eastern Ridge scrubber inlet.
-------
LtJ
(D
r
8
(0
cn
'55
ro
Q.
Q.
200.0
CO (ppm) at Eastern Ridge Scrubber Inlet
(10/18/96)
C\l
in
0
t^
LO
o
O5
O
»-
00
»-
0)
(N
•^
00
00
•^
00
00
•^
00
in
*-
CO
0
CM
0)
CVJ
0
00
CM
s
CO
§
CO
00
n
0
CM
00
m
m
m
•^•
m
•^•
r--.
0
m
•^•
CM
m
0
m
m
00
•
-------
35
HCI (ppm) at Eastern Ridge Scrubber Inlet
(10/18/96)
-5
H h
SF6 Spiked Samples
H 1 1 1 h
H 1 1 h
-+-
Condenser Samples
H 1 1 1 h
Diluted Sample
H 1 1—
CM
in
in
o
co
CM
co
co
co
co
co co
U) O
•^ c\i
O)
8
8 "
co co
o
CM
co
in
in
s
N- <*
O CM
in in
in
in
in
CM CM co
co
in in
Time of day
(not to scale)
Figure 3-3. HCI concentrations at Eastern Ridge scrubber inlet.
-------
8I-£
ppm and 4 sigma uncertainty
•
GO
S
o
o
o
o>
I
cr.
o
ce
en
<-f
a
3
.
•8
CO
O
cr
cr
0)
i-t
o
-------
>.
+•>
8
3
(0
>
XJ
C
(0
Q.
Q.
160.00
140.00
120.00:
100.00
80.00
60.00
40.00
20.00
0.00
-20.00
-40.00
-60.00
CO (ppm) at Eastern Ridge Scrubber Outlet
(10/18/96)
H 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 h
r-
o
CM
oo co r- co r--
T- CM ^ LO CO
cocooioot-cooocoinoincMOino
CM CM CM CM CO
Time ofday
(not to scale)
Figure 3-5. CO concentrations at Eastern Ridge scrubber outlet.
-------
HCI (ppm) at Eastern Ridge Scrubber Outlet
(10/18/96)
0)
o
3
(0
O)
'55
TJ
(0
CL
CL
20.00
15.00
10.00 -•
5.00 - -
0.00 -•
Condenser Samples
Condenser Samples
-5.00 -I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1-
in o
o i-
o o
Time of day
(not to scale)
Figure 3-6. HC1 concentrations at Eastern Ridge scrubber outlet.
-------
OJ
A, first sample
C>, first sample minus fourth sample
A___Jl^__yW_
\J, 10th sample minus fourth sample
Ji<, spectrum of HC1 cylinder standard
2850
2800 2750
Wavenumbers (cm-1)
2700
Figure 3-7. Spectra from Eastern Ridge scrubber outlet, 10/18/96. This figure proves the presence of HC1 in the unspiked outlet emissions and
indicates how the HC1 emissions varied during the test run. A, "scout201;" B, "scout204;" C, the result after subtracting "scout204"
from "scout201;" D, the result after subtracting "scout204" from "scout210." E, spectrum of 103 ppm HC1 cylinder standard measured at the
same path length and temperature. The "standard" spectrum has been scaled by 0.1. All spectra are plotted to the same scale, over a range
of 0.035 absorbance units. Refer to Table 3-3 for file names, times, and corresponding HC1 concentrations from the output of the
special analysis.
-------
4.0 FTIR TEST PROCEDURES
A heated sample delivery system (Figure 4-1) was used to extract flue gas through a
stainless steel probe and transport the flowing sample gas through a heated Teflon sampling line
to a heated gas distribution manifold. Valves in the manifold were used to direct the sample flow
(or a calibration standard) to the FTIR gas cell.
4.1 SAMPLING SYSTEM DESCRIPTION
This description refers to Figure 4-1.
4.1.1 Sampling System Components
The sample was extracted through a single port using 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. 1II). A Balston particulate 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 sample pump outlet was connected to the sample manifold. The sample stream
passed through a secondary Balston particulate filter immediately after entering the manifold
box. The manifold is constructed of stainless steel 3/8-in tubing and contains 4-way valves and
heated rotameters (0 to 20 LPM) to allow the operator to control sample flow to the FTIR cell. A
heated 1/4-in diameter 20-ft long Teflon jumper line connected the manifold to the inlet of the
FTIR gas cell. The manifold was maintained at 300° to 310°F.
4-1
-------
Scrubber Outlet
Prob* tl
Heated
Sample manifold
V.nt«2
Vcnttl
Heated
Probe Box
Probe #2
Scrubber
Inlet
Balston
Filters
Sampl. DIM *1
' VM*
Splk. Un.
Flow meter
Heated
bundle
100'
Sampl* Una Wl
100'
Praaura Oauga
ttl .nd*2
Unheated Line
Heated Line
20'
201
Calibration Oas Urn
Calibration
Oai Manifold
To Calibration
Gas Cylinders
Figure 4-1. FTIR extractive sampling system configuration for test at Eastern Ridge lime plant.
-------
4.1.2 Sample Conditioning
Some samples were passed through a chilled condenser system to remove moisture before
going to the FTIR cell. The condenser inlet was connected to a second outlet of the gas
distribution manifold through a another heated 1/4-in Teflon. A 4-way valve on the manifold
controlled sample flow to the condenser. The condenser outlet was connected by a Teflon line to
the inlet of the FTIR gas cell.
Since the condenser is not effective for measuring HC1 or other water-soluble
compounds, it was not used extensively. The primary benefit of the condenser is in lowering
moisture to better reveal spectral features of gas phase compounds, such NOX and SO2.
4.2 SAMPLING PROCEDURE
This test required two sampling configurations.
4.2.1 Testing Two Locations Simultaneously
The inlet and outlet to the wet scrubber were sampled with the configuration shown in
Figure 4-1. A separate sample assembly (probe, line and pump) was used for each location.
Both sampling lines were connected to the common sampling manifold. Each line had a pressure
gauge at the manifold inlet and a rotameter at the manifold outlet. A turn-valve was used to
independently control and monitor the total sample flow through either sample line. Four-way
valves, at the manifold outlets leading to the FTIR cell and condenser, could be closed or turned
to select gas from either sample.
Both sample lines were contained in the same insulated heated bundle up to scrubber
outlet location. The scrubber outlet sample probe was connected directly to the heated probe box
that contained the initial particulate filter. The scrubber inlet probe was connected to the same
probe box with a 50-ft section of heated sample line. The initial particulate filter for the inlet
location was also in the probe box at the end of the 50-ft section of line. The length of the heated
bundle from the scrubber outlet to the manifold was 100-ft.
A third, spike, line was contained in the 100-ft heated bundle from the scrubber outlet to
the manifold. The spike line carried dry gas standard from the calibration manifold through a
mass flow meter (Sierra, ± 1 percent) up to a 3-way in the heated probe box. The valve could be
turned to either allow the spike flow to enter the scrubber outlet sample line upstream of the
4-3
-------
particulate filter, or direct the spike flow to a "tee" at the back of the scrubber inlet probe. In this
way either sample line could be spiked with the HC1 standard at a controlled dilution ratio. In
this test only the inlet sample was spiked.
The total sample line length was 150-ft from the scrubber inlet location and 100-ft from
the scrubber outlet locations to the manifold in the FTIR trailer.
Downstream of the scrubber inlet location the duct divided to pass through two scrubbers,
each with its own stack. The stacks were only separated by about 8-ft and were accessible from
the same platform. To obtain measurements from both scrubber outlets, the west stack (B) was
sampled for the first portion of the sample run, then the probe was moved to the east (A) stack
where sampling at the scrubber outlet was resumed with same sample configuration described
above.
4.2.2 Testing a Single Location
The hydrator stack was sampled alone. This configuration was the same as that shown in
Figure 4-1 for the sample line connection to the scrubber outlet. The spike line and valve
configuration for line 1 in Figure 4-1 was also used.
4.3 SAMPLING PROCEDURES
Figure 4-2 is a schematic of the FTIR instrument and connections to the manifold and
condenser.
Most of the measurements were performed using a batch sampling procedure to collect a
spectrum of a static sample. Some measurements were performed with the sample flowing
through the cell. Some samples were diluted in the cell with dry nitrogen and some were passed
through a condenser.
4-4
-------
Condenser
Vent 2 Vent 1
// / X X X X / /Hat sample line (1/4")X XXX
/
Cell oven
d«Uclar
Multi-pass gas
cell
MtifwonwUf
7" g)4 waV
Optical path
Unheated
teflon line
///////////////////// / / / /// / Hot sample line (1/4") ////////////•////// / //
Heated gas
manifold
way
See Figure 4-1
for detail
— Sample loc *1
Sample loc *2
Figure 4-2. FTIR instrument and sampling configuration.
-------
4.3.1 Batch Sampling
The batch sampling procedure was used to collect samples in the FTIR cell,1 Sample gas
was kept continuously flowing through each line and out the manifold vents (Figure 4-1). The
4-way valve was turned to divert a portion of the flow to the FTIR cell. The total flow meter
before the vent was monitored to ensure that a positive flow was always directed out the vent
during sampling. The eel] was filled to above ambient pressure, which was about 720 mm Hg,
the 4-way valve was closed, and the cell outlet valve was opened to allow the cell to vent to
ambient pressure. The spectrum of the static sample was recorded and then the cell was
evacuated for the next sample.
4.3.2 Flow Through Measurements
The cell was filled as in the batch sampling procedure. The sample inlet valve was kept
open and the cell outlet valve was also opened to allow gas to pass through the cell. The sample
was maintained at ambient pressure by having the outlet valve partially open to the vacuum
pump. The inlet sample flow valve was adjusted until the pressure gauge was stable at ambient
pressure. The spectrum of the sample was recorded, and then the cell was evacuated for the next
sample.
4.3.3 Dilution Samples
Diluting the sample is a procedure for reducing spectral interference from moisture or
CO2. This procedure is only effective if the target analyte is present at a high enough
concentration to be detected after the dilution. The objective was to dilute the sample to Vi to 1/4
its original concentration,
The cell was partially filled with dry nitrogen and the cell pressure was recorded. Then
the cell was filled to ambient pressure with sample gas. The final pressure was recorded, the
spectrum of the static sample was measured and the cell was evacuated for the next sample.
4.3.4 Condenser Samples
Directing the sample through a condenser can remove much of the moisture and improve
the measurement sensitivity for analytes that pass through the condenser. Analytes that are water
soluble, such as HC1, or have low vapor pressures at 32 °F cannot be measured using a condenser
system.
4-6
-------
Sample was diverted to the condenser through a second 4-way valve on the main
manifold (Figure 4-2). The valve was turned to direct sample from either location through the
condenser. This could be done while untreated sample was sent to the FTIR cell through the
other 4-way valve. After flow passed through the condenser for about 10 minutes, a 3-way valve
at the cell inlet was turned to allow the condenser sample into the cell. The cell was filled to
ambient pressure and the spectrum recorded using the batch sampling procedure.
Before and after sampling a location dry nitrogen was passed through the condenser and
into the FTIR cell and a spectrum of the nitrogen was recorded. This was to verify that the
condenser was not contaminating the samples.
4.4 ANALYTICAL PROCEDURES
Analytical procedures in the EPA FTIR Protocol (Appendix D) were followed.2
Analytical programs were prepared after the field test was completed. The programs employed
automated routines to analyze the spectra using mathematical techniques based on a K-matrix
analysis to determine analyte concentrations and sequentially subtract scaled reference spectra
from the sample spectra. The subtracted residual baseline spectra was analyzed to estimate
uncertainties in the reported concentrations. K-matrix, and other quantitative methods, are
described in references 3 and 4. Additional description of the analytical procedures are given in
Appendix C.
4.5 FTIR SYSTEM
The FTIR system used in this field test was a KVB/Analect RFX-40 interferometer. The
gas cell was a heated variable path (D-22H) gas cell from Infrared Analysis, Inc. A path length
of 36 laser passes was used for measurements at the scrubber locations and the path length was
reduced to 16 passes for measurements at the hydrator stack, A mercury/cadmium/telluride
(MCT) liquid nitrogen detector was used with a spectral resolution of 1.0 cm"1, the highest
resolution of the RFX-40 system.
The path length was measured by shining a He/Ne laser into the cell, and adjusting the
mirror tilt until the desired number of laser passes was observed. The number of passes was
recorded on the data sheets in Appendix B. The spectrum of an ethylene gas standard was
measured before and after each run. These ethylene spectra (calibration transfer standards or
4-7
-------
CTS) were then compared to CTS spectra in the EPA FTIR reference spectrum library to
determine the path length associated with the number of passes. Details of this procedure and
path length results are given in Appendix C.
4.6 ANALYTE SPIKING
Hydrogen chloride was an important target analyte. It is reactive and water soluble.
Sample flow and temperature influence whether HC1 can quantitatively pass through the
sampling system to the analyzer. An FTIR instrument is ideally suited to measure spiked
samples because many analytes have very distinct infrared spectra and this is especially true of
HC1.
The purpose of this procedure is to measure a gas standard directly with the analyzer and
compare that measurement to one in a sample that has been spiked with a known concentration
of the analyte. Ideally, the spike will comprise about 1/10 or less of the spiked sample.
The spike procedure follows Section 9.2 of EPA Method 320.' The SF6 tracer gas was
not contained in the same cylinder as the HC1 standard. The tracer gas was first spiked from a
cylinder standard of 4 ppm SF6 in nitrogen. The total sample flow and the spike flow were
continuously monitored and recorded while three separate spiked batch samples were collected
and their spectra recorded. The SF5 spike was then turned off and the HC1 spike was turned on.
The HC1 spike flow was set at the same value as the SF6 flow. At least three batch samples
spiked with HC1 were collected and their spectra recorded while the total sample flow was
continuously monitored and recorded. The HC1 spike was then turned off and the procedure was
repeated with the SFS standard to collect three more samples.
Only the inlet location was spiked because, unless HC1 could be measured at the inlet, it
was unlikely to be emitted after passing through the wet scrubber. The sample flow from the
inlet was very consistent using the !4-in diameter probe. Since the spike flow rate was also very
consistent, the spike ratio was not changing so the procedure of spiking the analyte and the tracer
gas separately should have been effective. This is supported by the results of the SF6 spike
measurements before and after the run. These results were consistent so variations in the HC1
concentration in the (HC1) spiked samples was due to variations in the flue gas HC1
concentration.
4-8
-------
4.7 SCREENING FOR HAPs
Estimated uncertainties for undetected compounds are presented in Tables 3-12 to 3-14.
After analysis, the residual sample spectra were screened for absorbances due to
hazardous air pollutants in the EPA FTIR spectral library.
The residual spectra were produced by sequential subtractions of scaled reference spectra.
Reference spectra were scaled by a factor equal to the ratio of the calculated sample
concentration divided by the reference spectrum concentration (corrected for path length and
temperature). The estimated uncertainty is determined primarily by the moisture in the sample
gas. Higher moisture results in a higher calculated uncertainty.
The noise level in each analytical region of the residual spectra was taken as the root mean
square deviation (RMSD) of the baseline. The RMSD was multiplied by the width (in cm"1) of
the analytical region. This value was compared to the integrated area in the same region of a
reference spectrum of the compound.
The noise was calculated from the equation:
1
n
(1)
where:
RMSD = Root mean square deviation in the absorbance values within a region.
n = Number of absorbance values in the region.
Aj = Absorbance value of the i'h data point in the analytical region.
AM = Mean of all the absorbance values in the region.
The estimated uncertainty for a non-detect is given by;
(2)
RMSD x (x. - x.)
U = -JL \L x CONK
ppm Area* R
4-9
-------
where:
Uppm = Noise related uncertainty in ppm.
X2 = Upper limit, in cm"1, of the analytical region.
X, = Lower limit, in cm"1, of the analytical region.
AreaR = Total band area (corrected for path length, temperature, and pressure) in
analytical region of reference spectrum.
ConR = Reference spectrum concentration.
This procedure for estimating the uncertainty for an undetected compound usually yields a
number that is higher than the actual quantitation limit. This is because no attempt is made to
optimize the analytical regions for each compound, nor is the spectral subtraction optimized. (All
spectral subtractions are performed, even subtractions that are unnecessary for detecting a
particular compound, before the RMSD calculations are performed.) Additionally, band area
calculations give a conservative estimate of analyte quantitation limits because the analytical
program can usually detect analyte absorbances at lower concentrations than the band area
calculations indicate.
4-10
-------
5,0 SUMMARY OF FTIR QA/QC PROCEDURES
5.1 SAMPLING AND TEST CONDITIONS
Before the test, sample lines were cleaned by purging with moist air (250°F). Following
this, the lines were checked with nitrogen. This was done by heating the sampling lines to 250 °F
and then 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 (99.99 percent) that was taken directly
from a cylinder. The lines were checked again on site before sampling. After each sampling run
where HC1 was detected, the probe was pulled from the stack and ambient air samples were
measured to determine the residence time of the HC1 in the line.
The run duration for FTIR testing was concurrent with the Method 25A. More than
20 samples were collected and their spectra recorded within the sample run.
Each spectrum was assigned a unique file name and written to the hard disk and a backup
disk under that file name when the spectrum was collected. Two copies of each interferogram
were also saved under the same filename as the absorbance spectrum using a different file
extension. Absorbance spectra and interferograms were saved to different file directories. Two
copies of background and calibration interferograms and spectra were also stored on disks to
separate directories. A complete copy of all spectra and interferograms was submitted to EPA at
the completion of the test before leaving the site.
All of the spectral file names, sampling information, sampling times, sample temperatures
and pressures, and the instrument configuration were recorded in writing on data sheets. Copies
of these data sheets were submitted to EPA upon completion of the test. Copies of the data
5-1
-------
sheets (both the written and transcribed versions) are also included in Appendix B of this report.
Minor errors in the original data sheets are corrected in the transcribed version.
Effluent was allowed to flow through the entire sampling system for at least 5 minutes
before the first sample was collected. The 20-ft section from the manifold to the FTIR cell was
the only part of the sampling system that came in contact with gas from both locations. This
20-ft section of heated line was evacuated after each sample by closing the 4-way valve at the
manifold and opening the cell and line to the pump at the cell outlet. This line (and the
manifold) was also included in the pre-test leak-check procedure.
FTIR spectra were monitored and a new background spectrum was collected periodically.
The data records in Appendix B indicate when new background spectra were collected.
After each change of location, the sample lines were purged with air or nitrogen to clear
contamination from the previous run. The lines were checked for contamination by measuring
the FTIR spectrum of ambient air samples.
When the condenser was in use, sample was kept constantly flowing through it before a
sample was measured. Before switching to the other location, nitrogen was passed through the
condenser and a sample of the nitrogen was measured in the FTIR cell.
5.2 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" (Appendix D).2 A
spectrum of the calibration transfer standard (CTS) was recorded at the beginning and end of
each test run. Positive pressure and vacuum leak checks of the FTIR cell, connection line and
sample manifold were performed according to the procedures in references 1 and 2. Leak check
results are recorded in Appendix B, Two ethylene standards were used for the CTS. A 20.0 ppm
standard was used primarily for the longer path length and a 99.4 ppm standard was used for the
shorter path length. Both ethylene standards were measured at each path length. The CTS
spectrum provides a check on the operating conditions of the FTIR instrumentation, e.g., spectral
resolution and cell path length. Ambient pressure was recorded whenever CTS spectra were
collected. Atmospheric pressure measurements were also recorded by the PES test crew.
Ambient pressure was about 720 mm Hg (about 28.4 in. Hg).
5-2
-------
Two copies of all interferograms, processed backgrounds, sample spectra, and the CTS
were stored on separate computer disks. Additional copies of sample and CTS absorbance
spectra were also stored for data analysis. Sample absorbance spectra can be regenerated from
the raw interferograms, if necessary.
5.3 CORRECTIVE ACTIONS
The instrument malfunction described in Section 3.2 was corrected and testing continued.
5-3
-------
6.0 REFERENCES
1, "Measurement of Vapor Phase Organic and Inorganic Emissions by Extractive Fourier
Transform Infrared (FTIR) Spectroscppy," EPA Contract No. 68-D2-0165, Work
Assignment 3-08, July, 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. "Computer-Assisted Quantitative Infrared Spectroscopy," Gregory L. McClure (ed.),
ASTM Special Publication 934 (ASTM), 1987.
4. "Multivariate Least-Squares Methods Applied to the Quantitative Spectral Analysis of
Multicomponent Mixtures," Applied Spectroscopy, 39(10), 73-84, 1985,
5. "Method 301 - Field Validation of Pollutant Measurement Methods from Various Waste
Media," 40 CFR Part 63, Appendix A.
6-1
-------
APPENDIX A,
ADDITIONAL DATA AND CALCULATIONS
This appendix presents measurements and results from PES. Included are Method 25A
results and stack gas measurements conducted during the testing.
-------
12/13/98 15:33 ^19139410234 PES RTP XC
1^1003/000
9/4
.~7
-------
^-is/ab
ft3 KTF >C
1^004/030
October 16,1996
Eastern Ridge Lime Company
Kiln No, 2 Intet to Scrubbers
Calibration Sa«s
0.0 ppffl
30,04 ppm
48.72 ppm
Sy«Um Calibration
O.SQ
29.60
48.BO
8400
Slow
0,999823*
0.947S922
1.0869601
Sampling System Blai
asm
0.80%
2.00K
4.00%
1320
Q.a ppm
30,04 ppffl
49.72 ppm
17.86 fpw.
Syrttm CaUfiMkM
0.&0
31.20
51JQ
98.60
0.60%
1.30*
Slope
CL9999027
0.9&280M
1,1985651
CMR
120 0.40K
S1JO O.CWH
1ED8.1S.-tS
1S:15-1S30
4,1
4.1
4.5
1890.18:21
4.8
3.4
4.7
3JS
4.5
4,0
1730
PcttCal Drtl
2.40 1-60S
2^20 iOO%
*6M
0.0 ppm
30.04 ppm
49,72 ppcn
37,66 Cpm
System diferedon
2^0
29120
46 JQ
BO.OO
0.31 %
0.87%
3.S83J7SB
1738-17:45
Comdad
zs
18:00.16:15
ia:is-ia;30
43
4,1
1.B
1.7
3.S
-------
12/1S/96 15:39
©19199410234
FES RTF NC
0005/030
19:15.1930
1&3O.19M5
1945-20:00
Eastern Ridge Lime Company
Kiln No. 2 Inlet to Scrubbers
3.7
Pot) Col
1.20
45.01
0,9
1.4
1.2
Ml
1JOS
October 17,1996
0.0 ppm
30.W ppm
4471 ppni
97.86 ppm
Systam CtUtMUan
0.40
2B.40
91.60
Conation O9999313
Slow. O.B2S13S4
0.6321578
Samp.lnfl Syneni Biot
2.00*
3.6O%
S.OC%
1137
PomlCd Drift
a.4o aoo%
40.90
Cetraclad
6,1 ppcnTHC
3.4
12.-1S-1Z30
1230-12:45
12:45-13.110
13X0-13:15
13:15-1330
1332
14.00-14:15
14;15.14.-30
5.B
8.7
8.8
8.7
6.3
PoatC«l
1.60
DrtB
1.00%
15:00-15:15
15:15-15:30
1530-1836
1S-3B
O3 ppmTMC
&«
\
u^)
TT
5.3
SJJ
a.i
1&OO-1B-.15
1«:1*-16.30
17.136
S3
~
6.1
PtuiCal
1,80
4B.BO
1JCU
0.40*
-------
12/13/96 13:39
S19199-110234
PES RTF N'C
12006/030
Eastern Ridge Ume Company
Kiln No. 2 Inlet to Scrubbers
October IS, 1996
o.o ppm
30,04 ppm
49.72 ppm
97J6 ppm
%M«nn dlfiatiect
0.40
47JO
10,80
CerraWon 0.89833*7
Slap* 0,9161029
Inhxcapt 03107061
Sampling System BUa
0.00*
6,40%
10-.10-1030
10J45-11-.00
iiMO-n:ifi
11:16.1130
liao-tr.45
11;4S.1iOO
12S3
5,3
5,0
4.1
3.8
1Z-30-1Z45
1245-13:05
13SJ5-13:1S
13?30-13,-45
14:04
Pod Col
0,80
4E.OO
*.
Po«C«J
1JO
on
0.40*
1.20*
QOfTOClBfl
_ppmTHC
4.4
4.0
3,9
3,T
Prtfl
OJBOK
2.80%
6.9
s.e
1430-14:45
8.4
6.1
tS«0-iS:iS
15:15-15;30
5J
4.8
15:*S-16.-OD
3,4
3.0
2.4
2J
1K08
PtatCi
C.DO
23,60
33.20
Drift
4,80%
8.00W
-------
1." 1 a / 9 6
PE5 RT? NC
Summary of Stack Gas Parameters and Test Results
Lime Manufacturing Emission Test - Eastern Ridge Lime Company
US EPA Test Method 23 - CDD/CDF
Kiln No. 1 - Scrubber A Outlet
Page 1 of 6
(Y)
(dH)
(Pbar)
(Vm)
(Tm)
(P9)
(Ts)
(Vic)
(%CO2)
(%O2)
(%N2)
(Cp)
(dP)
(Theta)
(Dn)
(An)
(Vmstd, cf)
(Vmstd, cm)
(Qm)
(Ps>
(%H20)
(%H2Osat)
(Vwstd)
(Mfd)
(Md)
(Ms)
(Vs)
(A)
(Qa)
(Qs.cmm)
(Qs,cfm)
(I)
RUN NUMBER
RUN DATE
RUNTIME
MEASURED DATA
Meter Box Correction Factor, Y
Avg Meter Orifice Pressure, in. H20
Barometric Pressure, in, Hg
Sample Volume, ff
Average Meter Temperature, "F
Stack Static Pressure, in, H2O
Average Stack Temperature, "F
Condensate Collected, ml
Carbon Dioxide content, % by volume
Oxygen content, % by volume
Nitrogen content, % by volume
Pitot Tube Coefficient
Avg Sqrt Delta P, (in. H2O)VS
Sample Time, min
Nozzle Diameter, in.
CALCULATED DATA
Nozzle Area, ft*
Standard Meter Volume, dscf
Standard IMeter Volume, dscm
Average Sampling Rate, dscfrn
Stack Pressure, in, Hg
Moisture, % by volume
Moisture (at saturation), %
Standard Water Vapor Volume, ft"
Dry Mole Fraction
Molecular Weight-dry, Ibflb-mote
Molecular Weight-wet, Ib/lb-mole
Stack Gas Velocity, ft/s
Stack Area, fp
Stack Gas Volumetric flow, acfrn
Stack Gas Volumetric flow, dscfrn
Stack Gas Volumetric flow, dscmm
Isokinetic Sampling Ratio, %
M23-A-1
10/16/96
1510-2038
1,003
1.073
28.65
138.183
84
-0.07
138
653.3
21.1
6.6
72.3
0.84
0.583
240
0.257
0.000360
129.658
3.652
0.540
28.64
19.2
19.3
30.751
0.81
31.64
29.03
35,5
12,57
26,772
18,296
518,1
103.1
M23-A-2
10/17/96
1140-1630
1.008
0.827
28.54
121.991
90
-0.07
135
606.3
23.7
5.0
71.3
0.84
0.547
240
0.247
0.000333
112.781
3.177
0.470
28,53
20.2
18.1
28.539
0.82
3199
29,46
33,0
12.57
24,919
17,273
489.1
102.8
M23-A-3
10/18/96
1100-1543
1.008
0.984
28.32
130.841
93
-0.07
135
556.0
21.0
6.7
72.3
0.84
0.589
240
0.247
0,000333
118,347
3.334
0.493
28.31
18.1
18.1
26.171
0.82
31.63
29.17
35.9
12.57
27,049
18,613
527.1
100.1
Average
1.008
0.962
28.50
130.340
91
-0.07
136
605.2
21.9
6.1
72.0
0.84
0.573
240
0,250
0.000342
120.262
3.388
0.501
28,50
19.2
18.5
28.487
0.82
31.75
29.22
34.8 I
12.57
26,247
18,061
511.4
102.0
-------
PES RTF NC
Summary of Stack Gas Parameters and Test Results
Lime Manufacturing Emission Test • Eastern Ridge Lime Company
US EPA Test Method 29 - Metals and Paniculate Matter
KHn No. 2 - Scrubber A Outlet
Page! of 3
00
(dH)
(Pbar)
(Vm)
(Tm)
(Pg)
(Ts)
(We]
(%CO2)
(%02)
(%N2)
(Cp)
-------
12/13.-96
15:40
FES RTF NC
41010/030
Summary of Stack Gas Parameters and Test Results
Lime Manufacturing Emission Test - Eastern Ridge LJme Company
US EPA Test Method 23 - CDD/CDF
Kiln No. 2 - Scrubber B Outlet
Page 1 of 6
00
(dH)
(Pbar)
(Vm)
(Tm)
(P9)
(Ts)
(Vte)
(%CO2)
(%02)
(%N2)
(Cp)
(dP)
(Theta)
(Dn)
(An)
(Vmstd, cf)
(Vmstd, cm)
(Qm)
(Ps)
(%H2O)
(%H2Osat)
(Vwstd)
(Mfd>
(Md)
(Ms)
(Vs)
(A)
(Qa)
(Qs.cmm)
(Qs.cfrn)
(I)
RUN NUMBER
RUN DATE
RUNTIME
MEASURED DATA
Meter Box Correction Factor, Y
Avg Meter Orifice Pressure, in, H20
Barometric Pressure, in, Hg
Sample Volume, fP
Average Meter Temperature, °F
Stack Static Pressure, in. H20
Average Stack Temperature, "F
Condensate Collected, ml
Carbon Dioxide content, % by volume
Oxygen content % by volume
Nitrogen content, % by volume
Pitot Tube Coefficient
Avg Sqrt Delta P, (in. H20)1/*
Sample Time, min
Nozzle Diameter, in.
CALCULATED DATA
Nozzle Area, ft1
Standard Meter Volume, dscf
Standard Meter Volume, dscm
Average Sampling Rate, dscfm
Stack Pressure, In, Hg
Moisture, % by volume
Moisture (at saturation), %
Standard V/ater Vapor Volume, fP
Dry Mole Fraction
Molecular Weight-dry, Ib/lb-mole
Molecufar Weight-wet, Ib/lb-mole
Stack Gas Velocity, ft/s
Stack Area, ft*
Stack Gas Volumetric flow; acfm
'Stack Gas Volumetric flow, dscfm
Stack Gas Volumetric flow, dscmm
Isokinetic Sampling Ratio, %
M23-B1
10/16/96
1511-2027
1,003
2.292
28.65
187.909
94
-O.OB
135
783,0
19.0
7.8
73.2
0.34
0.363
240
0.375
0.000767
172,998
4.873
0.721
28.65
17.S
17.8
36,856
0.82
31.35
29.01
22.1
12.57
16,653
11,667
330.4
101.3
M23-B2
10/17/96
1140-1630
1.003
0,808
28.54
116.621
95
0.05
131
415.4
20.0
7.7
72.3
0.84
0.312
240
0.310
0.000524
106.346
2.996
0.443
28.S4
15.5
16.3
19.553
0.84
31.51
29.41
18.8
12.57
14,168
10,192
288.6
104.3
M23-B3
10/18/96
1100-1540
1.003
1.476
28,30
151.944
8t
0.12
134
614.4
19.7
7.6
72,7
0.84
0.425
240
0.310
0.000524
141.244
3.979
0.589
28.31
17.0
17.6
28.920
0.83
31.46
29.17
25.9
12.57
19,530
'13,633
386.0
103.5
Average
1.003
1.525
28.50
152.158
90
0.04
133
604.3
19.6
7.7
72.7
0.84
0.367
240
0.332
0.000605
140.196
3,949
0.584
28.50
16.7
17.3
28.443
0.83
31.44
29.20
22.3
12.57
16,783
11,831
335.0
103.0
-------
12/1S/36
15:40
PES RTF NC
^1011/030
Summary or Stack Gas Parameters and Test Results
Lime Manufacturing Emission Test - Eastern
(Y)
(dH)
(Pbar)
(Vm)
(Tm)
(Pg)
(Ts)
(Vic)
(%CO2)
(%02)
(%N2)
-------
12/13/96 15:40
"S1S199410234
PES RTF NC
(§012/030
Eastern Ridge Lime Company
Kiln No. 2 Outlet of Sewbbors
October 16,1996
Soubber A
Sembbere
Calibrated SUM
0.0 ppm
30.04 ppm
49.72 ppo
QI,BO ppfn
Syittm Cm&nUan
2.35
30,25
49 38
83 «6
o.ao
30,00
49.20
84.40
CMWtattofl O.StBIB?
Stojse 0,9271117
Intercept 2.5593123
Sampibj Systom Slat
0,15%
1.42K
4.34%
CamxBilan 0,599886
Slope D.9S16106
mtratfS 1.2143
-------
12/13/96 15:40
•31919941023-1
PES RTF N
^3013/030
Eastern Ridge Lime Company
Kiln No.' 2 Outlet of Scrubbers
October 17,1396
ScrutberA
SswbbtrB
CaBrMbn Gtie*
o.o ppm
30.04 ppm
43,72 ppm
97.06 ppm
System Calibration
O.BO
£9.60
48.40
8120
System Calibration
o.so
30.00
49.20
H4.4Q
Direct Coiioration
0.00
30.40
50^40
87.20
CwreMUan 0.953902B
Slap* 0.9378908
intercept 1.1976362
Sampling System Bias
0.80%
2,00*
4,00%
Cojreution OJ938B6
Slap* O.S3181M
mwrcept 1J14366S
Sampling System Bias
0.40%
1.20%
2.10%
Cwreiattsn O.S9S9
Slopa O.BB2I
Caifcraaen &w
1.37H
11:10
Pan CM OftK PofflCM Drift
110 0.40% o.ao a.oos
45.80 LflW 48.80 0.40K
0,0 ppm
30.0* ppm
49.72 ppm
87J6 ppm
system CalitoaUon
1-20
23.40
iS.SO
78.80
CaKfiiian Enw
0.47%
Slops
OJS994SS
0,8622034
1J3t0148
ir.«-iz.-oo
B.4
CoiractM
5.7
1230-13:45
1445-13:00
13X10-13:15
13:15-13:30
13:33
14330-14:15
14:15-1420
7.1
5.0
7,7
3.5
PostCal Drift PostCal
1.60 0.40% 1J20
44.00 1.60% 44.40
27.01
9.9
7.5
15:00-1 5:i S
15.15-15:30
15t30-1&45
1S;45.16;00
1&OO-1BH5
s
a.a
183B
p
-------
12/13/96 15:41
1J191S9410234
PES RTF NC
143014/030
Eastern Ridge Lime Company
Kiln No. 2 Outlet of Scrubbers
October 18,1895
Scrubber A
Scrubbers
Cslitf iton Saasa
9.0 ppm
30,04 ppm
48,72 ppm
87,86 ppnt
System CaBbfZton
1.20
29.60
48.00
92.40
System CaHbraUan
120
29.60
48.80
83.20
Dinct Cafersiion
0.40
29.60
49,60
as.60
CotrelaUan 0,989917*
Sbp« O.S239703
WOrcapJ 1.5810258
Sampling System Bias
O.aOH
O.QO«
i.so%
3.20%
Correlation QJ3S9174
Slojw 0,83454
Intercept 1J3B1022
Samplng System Btu
OJOW
D.00%
a,ac%
2.
-------
12/13/95
5:41
PES RTF NC
^016/030
Summary of Stack Gas Parameters and Test Results
Lime Manufacturing Emission Test - Eastern Ridge Lima Company
US EPA Test Method 23 - Metals and Paniculate Matter
Kiln No. 2 - Hydrator Stack
Paga 1 of 3
00
-------
APPENDIX B.
FIELD DATA RECORDS
-------
-------
Data Sheet: FTIR Background and Calibration Spectra: Eastern Ridge Lime Kiln. EPA Work Assignment 4-01.
Date
10/15/96
10/15/96
10/16/96
10/17/96
.10/18/96
10/18/96
10/19/96
10/19/96
10/19/96
Time
17:00
17:50
17:50
17:58
9:07
9:15
9:30
10:45
10:57
11:11
1 1 :42
13:18
18:35
18:58
19:10
19:21
20:00
9:47
9:53
10:03
10:12
10:17
10:27
10:32
10:42
13:45
16:27
16:33
9:32
9:50
9:55
10:55
11:02
11:13
File Name
BKG1015A
CTS1015A
BKG1016A
CTS1016A
CTS1016B
BKG1016B
CTS1016C
HCI001
HCIOOA
BKG1016C
BKG1017A
CTS1017A
BKG1017B
CTS1017B
SF6EA001
BKG1018A
CTS1018A
SF6EA002
HCIEA001
HCIEA002
SF6HCI01
SF6HCI02
BKG1018B
BKG1018C
CTS1018B
BKG1019A
CTS1019A
CTS1019B
BKG1019B
CTS1019C
CTS1019D
Path
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
16 passes
16 passes
1 6 passes
Location/Notes
# scans
Res (cm-1)
Cell temp (F)
Leak check cell & manifold under pressure of 931 torr. Held steady for one minute.
:lowing N2 - Fairly wet
Leak check (time = 0, P=4.1) at (time = 2, P=10.1)
Tempi 23 C (cell)
Ethylene 99.4 ppm in N2 AAL16529
Ethylene 20 ppm in N2 Almo 29430
3ackground/N2
20 ppm in N2 Almo 29430
HCI 103.0 ppm 1A7805
N2 in cell after purge showing HCI traces remaining
Background after cell alignment
20 ppm Ethylene
N2 dryer
20 ppm
4.01 ppm cyl #A7853
20 ppm Ethylene
SF6 @ 4.01 ppm undiluted
HCI 103.0 ppm undiluted (static in the cell)
Same fill of HCI 5 minutes later
50/50 mixture total flow = 48 through cell
Same fill static
100
100
100
100
50
50
50
200
200
50
100
50
50
100
50
50
50
50
50
2.0
2.0
2.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
'leak check through back of cal manifold (time=0, P=6.3) at (time=1, P=14.0)
100
100
50/100
1.0
1.0
1.0
Ambient
Ambient
Ambient
250F.121C
250F.121C
250F.121C
250F.121C
122C
120C
122C
122C
122C
122C
121C
121C
121C
121C
121C
122C
122C
122C
Pressure
725.4
725.4
725
726.9
726.4
725.3
724.1
722.4
722.4
722.4
720.4
716.8
716.8
716.8
716.8
716.8
715.7
715.7
715.7
'leak check cell (time=0. P=5.3torr), (time=2min, P=8.2torr), (time=0, P=798.8), (time=1, P=800.2)
Hydrator stack
20 ppm Ethylene'
20 ppm Ethylene 2nd fill
Shorter path length for 38% moisture. Using ZnSe Window
20 ppm Ethylene
20 ppm Ethylene
100
50/100
100
50/100
50/100
1.0
1.0
1.0
1.0
1.0
122C
122C
122C
122C
122C
71 7.6torr
717.6torr
717.9
717.5
717.5
BKG
1016A
1016A
A
B
B
A
A
A
A
A
A
B
B
Apod
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
C
NB/med
NB/med
NB/med
NB/med
g:\private\tjg\emb\4-01\report\tabs\LIME_DAT.XLS
-------
Data Sheet: FTIR Background and Calibration Spectra: Eastern Ridge Lime Kiln. EPA Work Assignment 4-01.
Date
10/19/96
Time
11:28
11:35
11:41
11:45
12:40
13:42
13:44
14:06
14:10
16:09
16:14
16:20
File Name
CTS1019E
CTS1019F
SF6HY001
SF6HY002
BKG1019C
CTS1019G
CTS1019H
SF6HY003
SF6HY004
BKG1019C
CTS1019I
Path
16 passes
1 6 passes
16 passes
16 passes
16 passes
16 passes
16 passes
16 passes
16 passes
16 passes
1 6 passes
Location/Notes
99.4 ppm Ethylene
99.4 ppm Ethylene
4.01 ppm SF6 cal. standard
Second sample SF6 4.01 ppm
Closed down aperature to reduce energy
99.4 ppm Ethylene
99.4 ppm Ethylene
SF6 4.01 ppm
SF6 4.01 ppm
started spike (SF6) up to probe @ 1 .OOppm total flow = 65
N2
99.4 ppm Ethylene In Nitrogen
# scans
50/100
50/100
50/100
50/100
100
50/100
50/100
50/100
50/100
100
50/100
Res (cm- 1)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Cell temp (F)
122C
122C
122C
122F
122F
122F
122F
122F
122F
122C
122C
Pressure
717.4
717.5
717
717.4
716.9
716.9
716.5
716.4
717.3
717.3
BKG
B
B
B
B
C
C
C
C
D
Apod
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
NB/med
g:\private\tjg\emb\4-01\report\tabs\LIME_DAT.XLS
-------
Data Sheet: FTIR Batch Samples: Eastern Ridge Lime Kiln. EPA Work Assignment 4-01.
Date
10/16/96
10/18/96
10/18/96
— -
Sample time
14:55-14:58
15:02-15:04
15:10-{5~:14
15:15-15:21
15:33-15:50
10:44-10:46
10:48-10:50
10:52-10:54
10:57
11.02-11:04
11:06-11:07
11:10-11:11
11:13-11:15
11:17
11:22
11:24
11:29-11:31
11:34
11:37-11:39
11:44
11:46-11:48
11:53-11:55
11:59-12:01
12:05-12:12
12:14-12:23
12:25
12:27
12:30
"12:36-12:38
12:37
12:44-12:47
12:51
12:55-12:58
13:03-13:04
13:08-13:10
13:13-13:15
13:18-13:22
13:25
File name
Ambient 1
SCINL001
SCINL002
SCOUT001
SCOUT002
SCOUT201
SCOUT202
SCINL201
SCINL202
SCOUT203
SCOUT204
SCINL203
SCINL204
SCOUT205
SCOUT205
SCINS205
SCINS206
SCINS207
HCI spike on
SCOUC207
SCOUC208
SCINH208
SCINH209
SCINH210
Empty 001
Empty 002
SCINH211
SCOUC209
SCOUT210
SCOUT211
SCOUD212
SCINL212
SCINL213
SCINC214
SCINC215
SCOUT213
Path
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
36 passes
Location/Notes
nlet probe
nlet to scrubber
nlet to scrubber
low restricted at about 30 THC approx. 2 ppm
low restricted to about 10
Scrubber outlet west (P=716.3)
Scrubber outlet west (P-716.3)
Scrubber inlet
Scrubber inlet
Scrubber outlet west
Scrubber outlet west
Scrubber inlet
Scrubber inlet
Scrubber outlet west
SF6 spike on to inlet
Scrubber outlet west
spiked w/ 1 .OOlpm SF6
spiked w/1.00lpmSF6
spiked W/SF6 at inlet
ttscans
50
50
50
50
50
50/100
HCI spike on to inlet, spike - 1.00 Ipm, total (low- 120
Condenser Sample scrubber outlet west
Condenser Sample scrubber outlet west
inlet spiked w/HCI @ 1 .051pm
inlet spiked w/HCI @ 1.041pm flow through cell
evacuate cell
new fill w/HCI spike
evacuated cell
50/100
50/100
50/100
50/100
50
50/100
1e3 (cm-1
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
HCI spike to inlet P=724.4, flow through cell -> 40, spike = 0.96
Condenser from outlet
spike oft to inlet
H/W from scrubber outlet west
fill to 360 torr with outlet sample diluted with N2, fill to 720 torr with N2
fill to 360 w/N2. fill to 720 w/outlet sample
untreated direct to cell
Condenser sample scrubber inlet, flow through t
Condenser sample scrubber inlet, flow through c
Scrubber outlet west
50/100
80/100
50/100
50/100
50/100
1.0
1.0
1.0
Cell Temp (F)
123C
123C
123C
123C
123C
122F
122F
122C
122C
122C
122C
122C
122C
Spk/Unsp
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
S(SF6)
S(SF6)
S(SF6)
S(HCI)
S(HCI)
S(HCI)
Snmple Cond.
H/W
H/W
H/W (P-722.2)
H/W
H/W
H/W
H/W
H/W
/acuated cell
U
U
U
Sample Flow
110
110
110
110
110
85
85
120
120
80
75
120
120
1 20 total 1 .00 spike
120 total 1.00 spike
totaU120, SF6=0.98lm
total flow= 120
total flow= 120
total=120, HCU1.00
total=120
BKG
C
C
C
C
C
1018A
1018A
1018A
A
A
total outlet flow = 40 (bouncing)
diluted
H/W
H/W
total inlet flow = 120
total-35
120
approx. 30
1018A
A
A
A
A
g:\private\tjg\emb\4-01Veport\tabs\LIME_DAT.XLS
-------
Data Sheet: FTIR Batch Samples: Eastern Ridge Lime Kiln. EPA Work Assignment 4-01.
Date
10/18/96
10/18/96
Sample time
13:55-13:57
13:30-14:00
14:05-14:08
14:11-14:14
14:18-14:21
14:26-14:30
14:33-14:36
14:35
14:40-14:43
14:45-14:47
14:49-14:52
14:55-14:56
15:00-15:02
15:05-15:06
15:08-15:09
15:15-15:16
15:19-15:22
15:25-15:26
15:29-15:31
15:35-15:37
15:42-15:44
15:50-15:51
15:55-15:57
15:58-15:59
16:05-16.07
16:10-16:12
3ATOR STACK
10/19/96
12.06-12:08
12:14-12:15
12:19-12:21
12:27-12:28
12:43-12:44
12:47-12:49
12:52-12:55
12:59-13:01
13:07-13:09
13:12-13:14
14:09
14:19-14:22
File name
SCINC216
SCOUT214
SCOUC215
SCOUC216
SCOUT217
CONBLNK1
SCOUT218
SCOUC219
SCOUC220
SCINL217
SCOUD221
SCOUD222
SCIND218
SCOUD223
SCOUC224
SCINL219
SCINC220
SCOUC225
SCOUT226
SCIND221
SCINL222
SCOUD227
SCOUC228
SCOUT229
HYDHW001
HYDCN002
HYDCN003
HYDDI004
HYDDI005
HYDHW006
HYDCN007
HYDHW008
HYDD1009
HYDD1010
HYDHS012
Path
36 passes
36 passes
36 passes
16 passes
1 6 passes
1 6 passes
16 passes
16 passes
1 6 passes
16 passes
Location/Notes
Condenser sample from Inlet
switch outlet probe to east stack and replaced gla
Scrubber outlet east stack
Scrubber outlet east stack
Scrubber outlet east stack
Scrubber outlet east stack
nitrogen through the condenser
Probe box back In operation
Scrubber outlet east stack
Scrubber outlet east stack
Scrubber outlet east stack
Scrubber inlet
Outlet west to 360torr w/N2, to 720torr w/sample
Outlet west to 600 w/N2, to 720 w/sample
to 360 w/N2, to 720 w/scrubber outlet
to 360 w/N2, to 720 w/scrubber outlet east
Outlet east condenser
Inlet
Inlet
Outlet east condenser
Outlet east condenser
inlet to 360 w/N2. to 720 w/sample
Inlet untreated sample
to 67.5 w/sample. to 720 w/N2
Outlet east condenser
Outlet east condenser
Sample 1 line on manifold total flow=85
from hydrator stack, some water condensed in th
through condenser
through condenser
diluted to 600 w/N2, to 718 w/sample
diluted to 600 w/N2, to 718 w/sample
Hot wet
Condenser
Hot wet
dilution @ 2:1 to 360 w/N2, to 720 w/sample
dilution @ 2:1 to 360 w/N2, to 720 w/sample
tfscans
50/100
S3 WOOl plUC
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
50/100
Started SF6 spike up to probe @ 1.04 Ipm, total How «65
Hot wet spiked W/SF6 50/1 00
Res cm-1)
1.0
Cell Temp (F)
122C
Spk/Unsp
U
to Improve flow to manifold
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
.0
.0
.0
.0
.0
1.0
1.0
1.0
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122C
122F
122F
122F
122F
122F
122F
122F
122F
122F
122F
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
Sample Cond.
Cond.
H/W
Cond.
Cond.
H/W
H/W
Cond.
Cond.
H/W
Dil
Oil
Dil
D
Cond
H/W
Cond
Cond
H/W
Dilute
H/W
Dil
Cond
H/W
H/W
Cond.
Cond.
Dil
Dil
H/W
Cond
H/W
H/W
H/W
H/W
Sample Row
total- 120
total - 75
total =. 60
total - 60
total - 60
total = 60
50
50
120
50
50
120
120
50
50
120
120
50
50
50
70 in stack
70
70
70
60
60
60
total = 60
total = 60
total » 60
total = 60
BKG
B
B
B
B
B
B
B
B"
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
C
C
C
C
C
C
C
g :\private\tjg\emb\4-01 \report\tabs\LI ME_DAT.XLS
-------
Data Sheet: FTIR Batch Samples: Eastern Ridge Lime Kiln. EPA Work Assignment 4-01.
Date
10/19/96
Sample time
14:27-14:28
14:33-14:34
14:36
14:44-14:46
14:49
14:56-14:59
15:05-15:10
15:23
15:31
File name
HYDHS013
HYDHS014
HYDHS015
HYDHS016
HYDHS017
HYDHS018
HYDHS019
HYDHS020
Path
>
16 passes
Location/Notes
Hot wet spiked W/SF6 0.98 Ipm
Hot wet spiked W/SF6 0.981pm
started HCI spike @ 1.00 Ipm
ffscans
50/100
50/100
spiked w/HCI @ 0.97- 0.98 Ipm, flow through at 717.3 torr
spiked w/HCI @ 0.99 Ipm, flow through at 719 torr
spiked w/HCI @ 1.03 Ipm, flow through at 719.2 torr
moisture condensing in rotameter cell |
Res (cm- 1)1 Cell Temp (F)
1.0 1 122F
1.0
122F
Spk/Unsp
U
U
Sample Good.
H/W
H/W"
spiked w/HCI @ 1 . 1 7 Ipm, flow through cell at about 50, rotameter to cell Is dry, manifold @ 320F, P-716.5 torr
continued purging cell as In HYOSO18
continued purging cell, rotameter to cell still dry
continued purge flow through @ about 50, P-7 1 1 .8 torr
spike flow - 1 .06 Ipm
Moisture was @ 58% at Hydrator stack
Sample Flow
total - 75
total - 75
total flow -75
total flow -=75
total Ibw -78
total flow -78
flow out vent - 25
BKG
g:\private\tjg\emb\4-01\report\tabs\LIME_DAT.XLS
-------
Datasheet: FTIR CTS and Background Spectra. Lime Kilns. EPA W.A. 3804-01.
Date
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm-1
Cell
emp.
°F
Press.
BKG
Apod
/too
T
w ^ z.
s /C.
L-
A
/OO
Ut
/o/fefl
•2-
( l
/OO
10*1
Moo(
w -,•
[0
-------
Datasheet: FTIR CTS and Background Spectra. Lime Kilns. EPA W.A. 3804-01.
Date
Time
File Name
Patli
M
Location/ Notes
# scans
Res.
cm1
Cell
Temp.
Press.
BKG
Apod
it
bit
13/7
1-ioC,
I***
W
/0
(CO
S
It
*
/o o
••(*,
10:1-7
\0\ll
\t(.(0\
MC (02-
£J_
-------
Datasheet: FTIR CTS and Background Spectra. Lime Kilns. EPA W. A. 3804-01.
Date
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm"1
Cell
Temp.
°F
Press. BKG
Apod
(0°
too
C
o ;
- /^^
/««««•
in.(<, -
/-o
-711,
H'.oL
&u
1(1
111, H
jCIi.
If- HI
-------
Datasheet: FTIR CTSr and Uackgrd!!mh5pectrat Lime Kilns. EPA W. A. 3804-01.
Date
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm"1
Cell
Temp.
°F
Press.
BKG
Apod
7/7
jC
<-
-------
ata Sheet: FTIR Batch Samples: Lime Kilns. 15PAWA. 3804-01.
To'
t»o
]
raoe o<.
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm'1
Temp.
°F
Spk/
Unsp
Sample
Cond.
Sample
Flow
BKG
>o
no
C
i /
00 2.
1*1 f
Jo
1
10^(0
loft
\}
1 1
4f<
IV '•».'/'
/,*>
5 "
-------
Datasheet: FTIR Batch Samples: Lime Kilns. EPA WA. 3804-01.
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm-'
Temp.
°F
Spk/
Unsp
Sample
Cond.
Sample
Flow
BKG
/IHY
. 00
; I
"
A ^
' £0
UCt •- Lot.
4&\
K Z (l
trv
\.(JfAJ v
^
"Torr
JX$ +o
V
-------
Datasheet: FT1R Batch Samples: Lime Kilns. EPA WA. 3804-01.
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans
Res. Temp.
-1 II or'
cm F
Spk/
Unsp
Sample
Cond.
Sample
Flow
/O
u
u;
-2-0
ft
It/u,
,>-*-—
yooi C,
HP
JJM
(I
^
-------
Datasheet: FTIR Batch Samples: Lime Kilns. EPA WA. 3804-01.
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm'1
Temp.
°F
Spk/
Unsp
Sample
Cond.
Sample
Flow
*
12-2-C
4/U
Q
jl$?
/Zo
V/u
-------
Datasheet: FT1R Batch Samples: Lime Kilns. EPA WA. 3804-01.
•A
*
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans! Res.
cm'1
Temp.
°F
Spk/
Unsp
Sample
Cond.
Sample
Flow
\
u
5*0
u»
»/
6«
\)
U
u
111
l OA.*
1 1
-------
Datasheet: FTIR Batch Samples: Lime Kilns. EPA WA. 3804-01.
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans
Res.
cm"1
Temp.
°F
Spk/
Unsp
Sample
Cond.
Sample
Flow
BK(J
-4*-
-~>
Hi
•*',<
t /
C
2
-0
d
-U
5_
((,
7'
W
-------
Data Sheet: FT1R Batch Samples: Lime Kilns. EPA WA. 3804-01.
A"
Date
Sample
Time
File Name
Path
M
Location/ Notes
# scans j Res. | Temp. 9 Spk/
| cm'1 | ° F | Unsp
Sample I Sample
Cond. I Flow
BKCi
-------
APPENDIX C.
FTIR ANALYTICAL RESULTS
-------
Draft Report
December 1996
Results of Least Squares Concentration Determinations for
FTIR Spectra Collected at Eastern Ridge Lime Kiln
Prepared by:
Grant M. Plummer, Ph.D.
Rho Squared
Prepared for:
Thomas J, Geyer, Ph.D.
Midwest Research Institute
C-l
-------
Disclaimer
This document was prepared by Rho Squared under Midwest Research Institute
Purchase Order Number D02329. This document has been reviewed neither by Midwest
Research Institute nor by the U. S. Environmental Protection Agency,
The opinions, conclusions, and recommendations expressed herein are those of the
author, and do not necessarily represent those of Midwest Research Institute or those of the
United States Environmental Protection Agency.
Mention of specific trade names or products within this report does not constitute
endorsement by the EPA, by Midwest Research Institute, or by Rho Squared,
C-2
-------
Data Collection and Analytical Method
Midwest Research Institute performed extractive FTIR source testing in October 1996 at
Eastern Ridge lime kiln and provided the spectral data to Rho Squared for preliminary
quantitative least squares analysis. Compounds of quantitative interest in the samples, referred to
below as analytes and identified in conversations with Dr. Tom Geyer of MRI, are HC1, H2CO,
CO, SO2, NO, and NO2. The spectra also contain features from the interferant compound H2O,
and SF6 was quantified in some spectra as the diluent tracer compound used for dynamic spiking.
References 1 through 5 comprise a thorough description of one technique for analyzing
FTIR absorbance spectra. Using the programming language ARRAY BASIC™ (GRAMS,™
Version 3.02, Galactic Industries Corporation, Salem, New Hampshire) Rho Squared has
prepared a computer program to perform this technique. The "classical least squares" (CLS) or
"K-Matrix" technique and the associated computer program are described in Reference 6. The
terminology and basic analytical approach employed in this work are described in the "EPA
FTIR Protocol" (Reference 7).
The program allows the analyst to select a number of analytical regions and to specify
which of the selected reference spectra will be employed in determining the corresponding
compound concentrations. Baseline parameters (linear, and quadratic in some cases) were also
determined in the calculations but are not reported here. Reference spectra for the current work
were provided by MRI or were taken from the EPA FTIR spectral library of Hazardous Air
Pollutants (hereafter, the "EPA library"). Additional information regarding the reference spectra
is listed below.
The program calculates the standard Icr uncertainty in each concentration. However, all
uncertainties quoted below are equal to four times the calculated lo values. The program also
calculates the residual spectra (the difference between the observed and least squares fit
absorbance values) for each sample spectrum and analytical region. These data are not presented
C-3
-------
here but have been submitted to MRI in digital form with this report. The GRAMS™ format
residual spectral files have DOS extensions of the form "m", where the integer n designates the
analytical region label for a particular analytical run. Although this labeling scheme does not
uniquely identify the residual spectra, the frequency ranges are unique and make identification of
the various spectra straightforward.
For each analytical region, compounds whose reference spectra are employed in the least
squares fits are characterized either as analytes or as interferants. Table 1 lists the analytical
regions and summarizes the characterizations of the six target compounds (HC1, H2CO, CO, SO2,
NO, and NO2). Note that each target compound appears as an analyte in one and only one
analytical region. The concentrations and uncertainties reported in this work correspond to the
analyte characterizations of Table 1.
TABLE 1. ANALYTICAL REGIONS AND COMPOUND
CHARACTERIZATIONS3 b
Analytical
Region
0
1
1
3
4
Lower Bound
(cm-"
900
1581.7
1898.6
2110
2747
Upper Bound
(cm-"
1200
1613.3
1904.8
2125.5
2848
HC1
.
-
.
A
H,CO
_
-
-
A
CO
_
-
A
-
SO2
A
-
.
-
NO
_
A
-
-
NO,
_
A
-
-
-
H,0
I
I
I
-
-
CO7
I
-
-
I
-
SFS
A
-
-
-
-
"1 indicates "interferant," A indicates "analyte," and the hyphen indicates that the compound was not included in the least
squares spectral analyses of the analytical region.
""Baseline slope and offset for each analytical region were also determined in the least squares concentration analyses (see
Reference 6). Quadratic baseline contributions were also determined for region 4.
MRI provided a total of 87 spectral files for analysis. After determining concentration
values and uncertainties for each compound in each analytical region of every sample spectrum,
the program rejects compounds from each analytical region if either a) the determined
concentration is negative or b) the 40 uncertainty in the concentration is greater than the
(positive) determined concentration. If a compound is rejected from a region for a particular
spectrum, the concentration is recorded as exactly zero in the output file along with the related
uncertainty from the original fit. Such uncertainty values are extremely conservative upper limits
C-4
-------
on the uncertainty of the reported zero concentration values. Concentration results and their 4o
uncertainties were recorded in Excel™ spreadsheet files and provided to MRI for inclusion in a
comprehensive report to EPA.
Pathlength Determinations
Absorption pathlengths were determined from 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 ISa.aif were de-resolved to the appropriate spectral resolution (either 1 or
2 cm"1) according to the procedures of reference 7 (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 7, Appendix H) in two regions (the FP, or
"fingerprint" region from 790 to 1139 cm"1 and the CH, or "CH-stretch region" from 2,760 to
3,326 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 Tables 2 and 3. The CH values
were used in analytical region 4; the FP values were used in all other analytical regions.
C-5
-------
TABLE 2. PATHLENGTH DETERMINATION RESULTS FOR
EASTERN RIDGE TEST DATA
CTS Conditions
# Passes Temp (K)
16 393
36 393
CH region
Result (m) % uncert.
6.1 2,8
18,9 2.4
FP region
Result (m) % uncert.
7.3 1,4
21.2 1.5
TABLES. REFERENCE SPECTRA
Compound
HC1
H,CO
CO
SO,
NO
NO2
H70
CO,
SF,
Analytical region
0
_
_
_
198.alf
-
-
194jsub.spc
I93clbsa.spc
(a)
1
.
~
-
200clbse.spc
194fsub.spc
.
2
_
„
199clbsa.spc
.
194fsub.spc
.
3
_
co20829a,spc
„
-
-
_
193clbsa,spc
-
4
097 .alf
087clasb.spcb
_
_
-
.
_
-
-
Tile sf640p_l.alf was used for spectra recorded at (nominal) forty passes in the infrared absorption cell and for
all Eastern Ridge data.
hResults of analyses excluding Ft,CO from this analytical region were also supplied to MRI,
Reference Spectra
Reference spectra for the current work were provided by MRI or were taken from the
EPA library. Table 4 lists the spectra used in the analyses for each analytical region.
C-6
-------
TABLE 4, FRACTIONAL CALIBRATION UNCERTAINTY (FCU)
Compound
S02
HCI
SF6 (20 passes)
SFS (40 passes)
FCU (%)
4,6
8,5
1.5
1.2
C-7
-------
For the compound HC1, the FTIR library spectra were de-resolved to 1 cm"1 and
normalized for absolute temperature, concentration, and absorption pathlength. The resulting
files were averaged to provide a "reduced absorptivity" (see Reference 6), which was stored in
the spectral file O97.alf and employed in all subsequent HC1 analyses. The HC1 analysis was
applied to the de-resolved EPA library HC1 spectra to determine the fractional calibration
uncertainty (FCU), which is presented in Table 5. Similar procedures were followed to
determine the reduced absorptivity and FCU values for the compounds S02 and SF6. For SO2!
1.0 cm-1 resolution spectra provided by MRI were used; the spectra used for SF6 were those
recorded on the field instrument, at two different absorption pathlengths.
References
1, 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).
2. 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).
3. 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).
4. W.C. Hamilton, Statistics in Physical Science. Ronald Press Co., New York, 1964,
Chapter 4.
5. P.R. Griffiths and J.A. DeHaseth, Fourier Transform Infrared Spectroscopv. John Wiley
and Sons, New York, 1986, ISBN 0-471-09902-3.
C-8
-------
6. G. M. Plummer and W. K. Reagen, "An Examination of a Least Squares Fit FTIR Spectral
Analysis Method," Air and Waste Management Association, Paper Number 96-WA65.03.
7. "Protocol for the Use of Extractive Fourier Transform Infrared Spectrometry for the
Analyses of Gaseous Emissions from Stationary Sources," U.S. Environmental Protection
Agency (EMTIC Bulletin Board, 1995).
C-9
-------
APPENDIX D.
PROCESS DESCRIPTION AND DATA
-------
RESEARCH TR ANGLE INSTITUTE
/RTI
Center for Environmental Analysis
MEMORANDUM
TO: Joseph Wood, ESD/MICG (MD-13)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
tf>
FROM: Cybele Brockmann, RTI
DATE: July 31, 1997
SUBJECT: Process Description for Eastern Ridge Lime
REFERENCE: Information Gathering and Analysis for the Lime
Manufacturing Industry NESHAP
EPA Contract 68-D1-0118
ESD Project 95/06
RTI Project 6750-017
Attached is the description of processes at Eastern Ridge;
processes were monitored during testing at the plant October 16-
19, 1997.
3040 Cornwallis Road • Post Office Box 12194 • Research Triangle Park, North Carolina 27709-2194 USA
Telephone 919 990-8603 • Fax 919 990-8600
-------
I. Process Description for Eastern Ridge Plant
Lime (CaO) is typically produced in the U.S. by crushing and
then heating limestone (CaCO3) in an inclined, rotating kiln.
The limestone is heated to temperatures of around 2000 degrees
Fahrenheit (deg F) which cause it to breakdown chemically into
lime and C02 . At Eastern Ridge, most of the lime is sold as CaO;
a small amount (ten percent of production) is converted into
hydra ted lime
Limestone at the Eastern Ridge plant is surface-mined from a
quarry located at the plant. The quarried limestone is crushed
and screened into several sizes and then transferred to a storage
area. Prior to entering the kiln, the sized stone is washed with
water to remove dirt.
The number two kiln is an inclined rotating kiln with a de-
sign capacity of 350 tons of lime per day (115,150 tons per
year) .2 The kiln is 392 feet long with a 'tapered diameter (11
feet in diameter at the front end of the kiln and 10 feet in
diameter the remaining length of the kiln).3 The incline of the
kiln is 1/2 inch per foot.4 Limestone enters the kiln at its
back end (the highest point of incline) and tumbles through the
kiln via gravity and the rotating motion of the kiln (typical
rotating rates are 55 to 65 revolutions per hour) . The residence
time of the feed material in the kiln is four hours. Approxi-
mately two tons of limestone are required to produce a ton of
lime.5
The combustion of fuel, which consists of pulverized coal
suspended in air, occurs at the front end of the kiln (the origin
and chemical composition of the coal at the time of testing are
unknown) . The coal is pulverized to the consistency of powder in
a bowl mill (the bowl mill is exclusive to the number two kiln) .
Air from the firing hood, located directly above the combustion
end of the kiln, is pulled into the bowl mill. The air preheats
and dries the coal. A fan on the mill blows the air and dry
pulverized coal from the mill into the kiln. Typically a
quarter to a third of a ton of coal is consumed per ton of lime.6
As the lime exits the kiln, it drops into one of ten satel-
lite coolers that are attached to the exterior of the kiln. The
coolers are long cylindrical tubes (30 feet long by 8 feet wide
in diameter) filled with chains. As the coolers rotate with the
kiln, the lime tumbles through the chains which conduct heat away
from the lime.7 Lime drops from the cooler tubes onto a conveyor
belt. The lime is conveyed to a screen, separated by particle
size, and stored. Fines from product screening are collected,
stored, and used in hydrate production.
-------
Approximately ten percent of the lime produced at Eastern
Ridge is chemically reacted with water to form a hydrated
product.8 The chemical reaction for hydration is as follows:
CaO + H2O ~ Ca(OH)2 + heat
Lime Hydrate
At Eastern Ridge, the hydration process is carried out in seven
steps. In step one, lime fines are mixed with water in a pug
mill to form a partially hydrated product. The pug mill is a
horizontal cylinder that contains a shaft fitted with short,
heavy paddles that push and mix the materials through the mill.
The source of water to the pug mill is effluent from the wet
scrubber that treats exhaust from steps two through seven (the
scrubber is discussed further under Hydrator Emissions Control).9
In steps two through seven, the partially hydrated product passes
through a series of six mixing barrels which allow the mixture to
fully react (the transfer time through all six mixing barrels is
approximately thirty minutes). After the lime is hydrated, it is
transferred to a storage bin, milled, and separated from impu-
rities (such as unreacted lime and limestone) with a whizzer
separator (similar to a cylone). Approximately 28,000 tons of
hydrate are typically produced annually.10
II. Emissions Control
Kiln Emissions Control
Exhaust from the number two kiln is routed to two, parallel
spray towers. The spray towers/scrubbers were manufactured by
Ducon and were installed at the plant in the 1970's. Each scrub-
ber is equipped with a fan which draws the kiln exhaust up
through the tower. Water is sprayed into the tower at various
points upstream of the fan and into the fan itself.11 The
exhaust from the fan exits through a stack. Effluent from the
scrubbers is directed to a series of four settling ponds where
solids are removed. Clarified water is recycled back to the
scrubbers.
Hydrator Emissions Control
The hydration process is exothermic, and part of the water
in the hydrate mixture is vaporized. Gases from the hydrator,
containing water and lime particles, are pulled by fan to a Ducon
scrubber, scrubbed with 10 gallons per minute (gpm) of water
(typical), and then vented to the atmosphere.12 (The flow rate
of scrubbing water varies somewhat with the moisture content of
-------
the lime fines in step one of the hydration process. For
example, newly processed lime fines have less moisture than fines
which have been kept in storage; thus, the former may require
more than 10 gpm while the latter may require less than 10
,gpm.)13 Effluent from the scrubber is added to the lime fines in
step one. The Ducon scrubber is the same type of spray tower
used to control the kiln exhaust.
, Refer to Figure 1 for a diagram of the kiln, hydrator and
associated emissions control. The diagram indicates the relative
locations for each unit operation, direction of flow for material
and gas, input and output of materials and gas, and approximate
locations where process parameters were measured.
III. Process Operation
Data indicating the operation of the kiln, the scrubbers
treating the kiln exhaust, and the scrubber treating the hydrator
exhaust are presented in this section. All process data for the
kiln were manually recorded by RTI every 15 minutes during the
emissions testing and taken from computer screens in the kiln
control room; the recorded data were measured with instruments
.already in place and used by the plant for process control of the
kiln.
For the scrubbers treating the kiln exhaust, PES measured
the pressure drop across each of the scrubbers and
measured/calculated the volumetric flow rates of water entering
and exiting each of the scrubbers. To measure pressure drop, PES
drilled pressure taps upstream of each scrubber tower and at the
end of each exhaust stack. The pressure drop across the upstream
tap and exhaust tap of each scrubber was measured using a U-tube
manometer. The pressure drop across each scrubber was measured
and recorded once during each run, just prior to testing.
PES measured the volumetric flow rate of water exiting the
bottom of the each scrubber by placing a container of known
volume below the water outlet and recording the time to fill the
container. The opening of the container was slightly smaller
than the water outlet, thus, the container only collected
approximately 80 percent of the exiting water. PES took two
measurements of the water flow rate exiting the bottom of each
;scrubber; the measurements were taken back-to-back during run 2
of the kiln 2 scrubber tests.
PES measured the temperature, gas flow, and moisture content
of the kiln exhaust just prior to each scrubber tower and exiting
each scrubber stack; based on these measurements, PES calculated
-------
the volumetric flow rates of water vapor entering and exiting
each scrubber. These calculated flow rates, along with the
measured flow rate of water exiting each scrubber, were entered
into a mass balance of water across the system to calculate the
flow rate of water injected into each scrubber (see Figure 2 for
a mass balance of water of the scrubber system).
During emissions testing, RTI manually recorded the water
flow rate to the scrubber treating the hydrator. The water flow
rate was measured by an instrument already in place and used by
the plant for control of the hydrator. The water flow rate was
initially recorded every 15 minutes; however, after no change was
noted during the first hour, and after the operator of the hydra-
tor stated that the flow rate would remain fairly constant, the
readings were recorded less frequently.
Table 1 is a statistical summary of the process data
collected during testing. Tables 2a, 2b, and 2c display all of
process data collected during testing.
Table 3 is a comparison of the values of the process
parameters recorded during testing to previously cited values of
these parameters. Previously cited values were extracted from
emission test reports provided by the plant {private testing was
comissioned in 1989 and 1995};14 a trip survey of the plant
written by Research Triangle Institute in 1995,-15 a questionnaire
filled out by the plant for EPA in 1995;16 and standard operating
procedures (SOP) of Eastern Ridge Lime plant.17 Values cited by
the kiln operator during testing are also included in Table 3.
Notes Pertaining to Test Data
Coal feed rate, limestone feed rate, kiln speed
Table 4 compares calculated coal feed rates with the average
coal feed rates recorded during testing. Coal feed rates were
calculated using previously cited values for tons of coal per ton
of lime and tons of lime per ton of limestone and using the
average limestone rates recorded during testing. Using the
questionnaire values for tons of coal per ton of lime and tons of
lime per ton of limestone, the calculated coal feed rates were
1.85, 2.06, and 1.89 tons of coal per hour. Using the value for
tons of coal per ton of lime cited by the kiln operator and the
1995 test data, and using the questionnaire value for tons of
lime per ton of limestone, the calculated coal feed rates were
4.36, 4.46, and 4,87 tons of coal per hour. The recorded average
coal feed rates were 3.69, 3.65 and 3.61 tons of coal per hour
(Table 4).
-------
Front end temperature, back end temperature, excess air
As shown in Table 3, the average back end temperatures
during testing were below both ranges of temperature specified in
the SOP. The front end temperature fell within the operating
range specified by the SOP. The percentage of oxygen in the kiln
exhaust exceeded the SOP ranges on two of the test days.
Despite the fact that the back end temperature and the
oxygen level were not within the ranges specified by the SOP, all
of the kiln operators stated that they were operating the kiln
under normal conditions during testing. They also stated that
the operation of the kiln varies on a day to day basis depending
on the weather, the size of the limestone, the moisture content
of the coal, the BTU value of the coal, and other factors. These
factors may explain why the average oxygen content in the kiln
exhaust varied between days 10/17 and 10/18. According to the
kiln operator, the process was operating under normal conditions
on both of these days.
Stone size
Three different sizes of calcitic limestone were fed to the
number two kiln during testing; the stone sizes were referred to
as "twos", "threes", and "fours". The sizes of these stones are
based on mesh size. "Twos" are stones that pass through a 1 and
3/8 inch mesh and are retained on a 7/8 inch mesh. "Threes" are
stones that pass through a 7/8 inch mesh and are retained on a
3/8 inch mesh. "Fours" are stones that pass through a 3/8 inch
mesh and are retained on a 3/16 inch mesh.18 During testing, the
size two stone was fed to the kiln separately while the size
three and four stones were combined and fed to the kiln as one
feed. The process data in Tables 2a through 2e indicate the
times when the different stone sizes were fed to the kiln. The
decision to use a stone size during the testing was dictated by
the existing supply of the stone. Neither size two stone nor
sizes three and four stones were available in a large enough sup-
ply to feed the number two kiln the same stone size during the
entire three days of testing.
-------
Table 1. Statistical Summary of Process Data Collected at Eastern Ridge Lime Company
Run 1 of Ki!n 2 Scrubber Tests
10/16/96; data recorded from 3:04 pm to 8:40 pm
Parameters for Kiln 2
Tons of coal per hour
Tons of limestone per hour
Front end temperature (deg F)
Back end temperature (deg F)
Kiln revolutions per hour
Percent oxygen at back end kiln
mean
3.69
25.21
1741
1010.3
59
1,2
std. dev.
0,1
2.0
48.1
14.4
4.8
0.8
mln.
3.55
21.65
1600
979.4
50
0.1
. max.
3.78
27.64
1826
1038.1
64
4.1
# recordings
21
20
21
21
21
21
Run 2 of Kiln 2 Scrubber Tests
10/17/96; data recorded from 11:42 am to 4:21 pm
Parameters for Kiln 2
Tons of coal per hour
Tons of limestone per hour
Front end temperature (deg F)
Back end temperature (deg F)
Kiin revolutions per hour
Percent oxygen at back end kiln
mean
3.65
28.16
1869
945.0
66
0.3
std. dev.
0.1
0.8
19.1
8.4
2.1
0.2
mm.
3.53
26.66
1840.00
931.2
62
0
max.
3.85
29.04
1900
965.0
68
0.7
# recordings
14
14
14
14
14
14
Run 3 of Kiln 2 Scrubber Tests
10/18/96; data recorded from 11:05 am to 3:47 pm
Parameters for Kiln 2
Tons of coal per hour
Tons of limestone per hour
Front end temperature (deg F)
Back end temperature (deg F)
Kiln revolutions per hour
Percent oxygen at back end kiln
mean
3.61
25.81
1840
1020.1
60
1.3
std. dev.
0.0
1,4
15.6
17.6
3.4
0.4
mm.
3.54
23.73
1800.00
1003.6
55
0.8
max.
3.71
29.34
1858
1054.9
68
2.5
# recordings
15
15
15
15
15
15
Run 1 of Hydrator Tests
Sat 10/19/96; data recorded from 10:00 am to 3:35 pm
[Parameters for Hydrator
Water flow rate (gal/min)
mean
9.6
std, dev.
0.1
mm.
9.4
max.
9.6
# recordings
11
Runs 2 & 3 of Hydrator Tests
Sun 10/20/96; data recorded from 8:00 am to 3:00 pm
parameters for Hydrator
(Water flow rate (gal/min)
mean
9.5
std. dev.
0.1
mm.
9.4
max.
9.6
# recordings
8
-------
Table 2a, Process Data
10/16/96; Run 1 of Kiln 2 Scrubber Tests
Day kiln operator = Tony
Night kiln operator = James
KILN PARAMETERS
Time CFR LSFR FET BET RPH % O2
2:50 PM Kiln burners turned off for approximately 5 minutes to allow sampling probes to be inserted
upstream of scrubbers; the burners were turned off to reduce the heat of the exhaust where the probes were
being inserted.
currently burning small stone
3:04 PM 3.71 21.65 1668
3:19 PM 3,77 21.74 1731
3:34 PM 3.68 25.68 1800
3:49 PM 3.74 27.08 1750
4:04 PM 3.7 27.61 1734
4: 19PM 3.74 27.48 1734
4:34 PM 3.78 27.24 1757
4:49 PM 3.66 26.95 1719
5:04 PM 3.75 27.03 1319
(*oxygen high because coal grate clogged up; coal feed
5:12 PM 3.73 27.19 1600
Break for filter change for Method 23
5:40 PM 3.72 24.22 1728
5:55 PM 3.72 24.35 1709
new operator came; changed to large size stone around
6:10 PM 3.64 24.35 1733
6:25 PM 3.72 24.59 1705
6:40 PM 3,59 24.39 1732
6:59 PM 3.62 1780
Stopped for testing change; resumed around 7:20
7:30 PM 3.7 24.58 1760
7:45 PM 3.7 27.64 1793
8:00 PM 3.7 27.01 1763
8:1 5PM 3.71 23.37 1780
8:30 PM 3.55 23.33 1755
8:40 PM 3.67 23.67 1826
979.4
1002.7
1014.5
1013.3
1007.5
1007.5
998
1001.6
989.5
turned off
979.8
1004.7
1012.9
6:00
1012.7
1017.4
1020.6
1028.2
1009.5
1008.9
1009.7
1014.3
1035.2
1038.1
50
50
60
64
63
63
64
63
63
for a few minutes to
63
56
56
56
56
56
56
64
64
63
54
54
54
1.9
1.4
1.1
1
1.1
1.1
0.1
0.7
16.5*
unclog)
4.1
1.1
1.5
1.1
1
0.7
1.5
0.6
0.9
0.6
0.7
1.6
1.4
SCRUBBER PARAMETERS
Pressure drop of exhaust
Scrubber A Scrubber B
2.9 in. H2O1.0in. H2O
CFR = coal feed rate (tons per hour)
LSFR = limestone feed rate (tons per hour)
FET = front end temperature of kiln (deg F)
BET = back end temperature of kiln (deg F)
RPH = kiln revolutions per hour
% O2 = percent oxygen at back end kiln
-------
Table 2b. Process Data
10/17/96; Run 2 of Kiln 2 Scrubber Tests
Day kiln operator = Chuck
KILN PARAMETERS
Time CFR LSFR FET BET RPH
11:42 AM
12:1 5PM
12:30 PM
12:51 PM
1:06 PM
1:27 PM
stone size
1:43 PM
2:00 PM
2: 17PM
3:06 PM
3:21 PM
3:49 PM
4:04 PM
4:21 PM
3,7
3.85
3.7
3.7
3.63
3.66
change
3.67
3.8
3.6
3.54
3.53
3.55
3.62
3.55
26.66
27.57
27.35
27.67
27.61
27.58
28.19
28.22
28.95
28.95
28.85
28.85
29.04
28.81
1860
1889
1860
1850
1900
1840
1880
1880
1850
1850
1900
1870
1860
1870
965
953.2
952.9
948.2
949.1
940.2
942.3
931.2
936.8
939.8
938,7
945.6
944.1
942.8
62
64
64
64
64
64
66
66
68
68
68
68
68
68
0.5
0.1
0.3
0.2
0.6
0.1
0.2
0
0.1
0.4
0.7
0,5
0.3
0.3
SCRUBBER PARAMETERS
Pressure drop Water Effluent
Scrubber A Scrubber B Scrubber A Scrubber B
4.9 in. H2O 0.9 in. HZO 33 gal /9 se 33 gal /15 sec
33 gal /10 s< 33 gal /15 sec
CFR = coal feed rate (tons per hour)
LSFR = limestone feed rate (tons per hour)
FET = front end temperature of kiln (deg F)
BET = back end temperature of kiln (deg F)
RPH = kiln revolutions per hour
% O2 = percent oxygen at back end kiln
-------
Table 2c, Process Data
10/18/96; Run 3 of Kiln 2 Scrubber Tests
Day kiln operator = Chuck
KILN PARAMETERS
Time
11:05 AM
1 1 :20 AM
11:40 AM
11:57 AM
12:15 PM
12:36 PM
12:56 PM
port changes
1:37 PM
1:53 PM
2:15 PM
2:35 PM
2:59 PM
3:17 PM
3:39 PM
3:47 PM
CFR
3.58
1:55 PM
3.6
3.69
3.62
3.54
2:38 PM
; resumed
3.6
3.59
3.62
3.55
3.59
3.71
3.58
3.62
LSFR
29.34
27.48
26.43
25.94
25.77
26.12
25.71
around 1 :35
26.22
25.68
23.99
23.94
23.73
26.06
25.43
25.34
FET
1855
1841
1847
1850
1845
1840
1821
1840
1831
1824
1857
1800
1850
1858
1840
BET
1005.1
1003.6
1008.5
1006.1
1007.2
1011.8
1015.3
1015.8
1017.2
1015.4
1018.3
1019.6
1054.9
1052.7
1050,5
RPH
68
64
62
60
60
60
60
60
60
55
55
55
60
60
60
%O2
1.2
0.9
0.8
1
1.9
2.5
1.2
1.3
0.9
1.3
1.5
1.2
1.3
1.5
1.3
SCRUBBER PARAMETERS
Pressure drop
Scrubber A Scrubber B
3.8 in. H2O 4.9 in. H2O
CFR = coal feed rate (tons per hour)
LSFR = limestone feed rate (tons per hour)
FET = front end temperature of kiln (deg F)
BET = back end temperature of kiln (deg F)
RPH = kiln revolutions per hour
% O2 = percent oxygen at back end kiln
-------
Table 2d. Process Data
10/19/96; Runs 1 & 2 on Hydrator*
operator = Shockey
Time HZ0 flow rate to scrubber
10:00 AM 9.6
10:35 AM 9.6
10:50 AM 9.6
11:50 AM 9.6
12:03PM 9.6
12:20 PM 9.6
12:45 PM 9.6
1:15 PM 9,6
1:27 PM 9.6
3:22 PM 9.6
3:35 PM 9.4
'Run 1 test data was discarded due to non isokinetic conditions
Table 2e. Process Data
10/20/96; Runs 3&4 on Hydrator
Operator = Dave
Time H20 flow rate to scrubber
8:00 AM 9.6
9:00 AM 9.6
10:00 AM 9.6
11:00 AM 9.6
12:OOPM 9.4
1:00 PM 9.4
2:00 PM 9.4
3:00 PM 9.4
10
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Table 3. Comparison of Values of Operating Parameters Recorded During Testing to Values of Parameters Cited from Other Sources
Operating Parameters
Tons per hour of coal
Tons per hour of limestone
Tons limestone/ton lime
Tons coal/ton of lime
Kiln speed
(revolutions per hour)
Back end temp, of kiln
(deg F)
Front end temp, of kiln
(deg F)
% O2 in exhaust
Water flow rate to hydrator
scrubber (gpm)
Average values
recorded during
testing
3.69; 3.65; 3.61
25.21; 28. 16; 25.81
59; 66; 60
1010; 945; 1020
1741; 1869; 1840
1.2; 0.3; 1.3
9.6; 9.5
1Ref2.
2Ref 1.
3Ref2
4Ref2
Values from standard operating
and procedures manual for
Eastern Ridge Lime
1050 to 1 150 (operating range)
1 100 to 1 120 (desired range)
1200 to 1950 (operating range)
1700 to 1850 (desired range)
0.1 to 1 (operating range)
0.1 - 0.3 (desired range)
Values from Values from Values Values
Values from kiln 1995 site f rom 1 995 from 1 989
questionnaire1 operator survey2 test data3 test data4
2.045 3.9-4 3.96 4 4
27.8S6 Max 27 19
1.91
0.14 0.33 0.25-0.33
55 to 65 65
1050-1200 1100 928
Avg1800 1620 1863
4.5
10
Value not specified directly in questionnaire; value calculated from reported tons coal/ton of lime (0.14) and reported tons of lime per day (350).
6Value not specified directly in questionnaire; value calculated from reported tons of limestone/ton of lime (1.91), and reported tons of lime per
day (350).
-------
Table 4. Comparison of Calculated and Recorded Coal Feed Rates
Calculated coal rate Calculated coal rate Recorded
(tons/hr) based on (tons per hour) based average coal rate
0.14 tons coal/ton of on 0.33 tons coal/ton (tons per hour)
lime1 of lime2 during testing
Run 1 of kiln 2 scrubber tests 1.85 4.36 3.69
Run 2 of kiln 2 scrubber tests 2.06 4.87 3.65
Run 3 of kiln 2 scrubber tests 1.89 4.46 3.61
1 Equation for calculating coal feed rates based on 0.14 tons of coal / tonoflime
... .- , 0.14tonscoal . . tonoflime . . average tons of limestone , , . . .
calculated coal feed rate = (questionnaire data) (questionnaire data) — (recorded data)
ton lime 1.91 tons limestone hr
calculated coal feed rate from run 1 of kiln 2 scrubber tests = 0.14* * 25.21 = 1.85 tons coal per hour
1.91
1
calciilatedcodfeediatefrcmrun2ofkita2scnibbertests = 0.14* * 28J.6 = 2.06 tons coal per hour
1.91
calculated coal feed rate from run 3 of kiln 2 scrubber tests = 0.14* * 25.81 = 1.89 tons coal per hour
1.91
2Equation for calculating coal feed rates based on 0.33 tons of coal / tonoflime:
- , , , .,, . 0.33tonscoal _., _,,««• , x tonoflime , . . , , average tons of limestone
calculated coal feed rate = (kiln operator and 1995 test data) (questionnaire data) — (recorded data)
ton lime 1.91 tons limestone hr
calculated coal feed rare from run 1 of kiln 2 scrubber tests = 0.33* * 25.21 = 4.36 tons coal per hour
1.91
calculated coal feed rate from run 2 of kiln 2 scrubber tests = 0.33* * 28J.6 = 4.87 tons coal per hour
1.91
calculated coal feed rare fromrun 3 of kiln 2 scrubber tests = 0.33* * 25.81 = 4.46 tons coal per hour
1.91
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u>
Limestone Feed
Exhaust / , \ Scrubber B
{ fan )•
Stack V
Water
Exhaust
T-V^T
Stack
fan
Water
f
Scrubber A
e
Water
a: Location of coal feed measurement
b: Location of limestone feed measurement
c: Location of front end temperature measurement
d: Location of back end temperature and % oxygen measurement
Gas Flow
Cooled Lime
Screening
Fines
Water
Material Flow
Hydrator
Hydrated Product
Figure 1. Process Diagram of Kiln # 2, Hydrator, and Associated Emission Control System at Eastern Ridge Lime.
-------
22 gpm water
vapor2
A
10 gpm water
vapor in
exhaust from
kiln2
Scrubber A
water in = 273 gpm (by difference)
water out = 261 gpm1
18 gpm water
vapor2
A
Scrubber B
6 gpm water
vapor in
exhaust from
kiln2
water in = 177 gpm (by difference)
water out =165 gpm1
Average of two measurements taken during run 2 of kiln 2 scrubber tests
2Calcuated from air flow, temperature, and moisture measurements at this location during run 2
of kiln 2 scrubber tests
Figure 2. Mass Balance of Water Across Kiln 2 Scrubbers
14
-------
REFERENCES
1. Heath, Elizabeth, Research Triangle Institute. "Site Survey
of Eastern Ridge Lime, Inc., Ripplemead, Virginia."
February 1, 1996.
2. Eastern Ridge response to questionnaire sent out in 1995 by
the National Lime Association as part of a voluntary effort
with the Environmental Protection Agency to obtain
data/information for the MACT program.
3. Ref 1
4. Ref 1
5. Ref 2
6. Ref 1
7. Telecommunication between Cybele Brockmann of Research
Triangle Institute and John Collins, Safety & Enviornmental
director of Eastern Ridge Lime, November 21, 1996.
8. Ref 1
9. Ref 7
11. Ref 1
12. Ref 7
13. Ref 2
14. Ref 7
15. Ref 2
16. Ref 1
17. Standard Operating and Procedures Manual of Eastern Ridge
Lime Plant
18. Ref 7
15
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APPENDIX E,
EPA METHOD 320
EPA FTIR PROTOCOL
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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 INTRARED (Fill) SPECTHOSCOPY
1.0 Introduction.
Persons unfamiliar with basic elements of FTIR
spectroscopy should not attempt to use this method. This
method describes sampling and analytical procedures for
extractive emission measurements using Fourier transform
infrared (FTIR) spectroscopy. Detailed analytical
procedures for interpreting infrared spectra are described
in the "Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous
Emissions from Stationary Sources," hereafter referred to as
the "Protocol." Definitions not' given in this method are
given in appendix A of the Protocol. References to specific
sections in the Protocol are made throughout this Method.
For additional information refer to references 1 and 2, and
other EPA reports, which describe the use of FTIR
spectrometry in specific field measurement applications and
validation tests. The sampling procedure described here is
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2
extractive. Flue gas is extracted through a heated gas
transport and handling system. For some sources, sample
conditioning systems may be applicable. Some examples are
given in this method. Note: sample conditioning systems
may be used providing the method validation requirements in
Sections 9.2 and 13.0 of this method are met.
1.1 Scope and Applicability.
1.1.1 Analytes. Analytes include hazardous air pollutants
(HAPs) for which EPA reference spectra have been developed.
Other compounds can also be measured with this method if
reference spectra are prepared according to section 4.6 of
the protocol.
1.1.2 Applicability. This method applies to the analysis
of vapor phase organic or inorganic compounds which absorb
energy in the mid-infrared spectral region, about 400 to
4000 cm"1 (25 to 2.5 um) . This method is used to determine
compound-specific concentrations in a multi-component vapor
phase sample, which is contained in a closed-path gas cell.
Spectra of samples are collected using double beam infrared
absorption spectroscopy. A computer program is used to
analyze spectra and report compound concentrations.
1.2 Method Range and Sensitivity. Analytical range and
sensitivity depend on the frequency-dependent analyte
absorptivity, instrument configuration, data collection
parameters, and gas stream composition. Instrument factors
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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 (RM5D) 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
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4
may be increased by increasing the cell path length or (to
some extent) using a higher resolution. Both modifications
also cause a corresponding increased absorbance for all
compounds in the sample, and a decrease in the signal
throughput. For this reason the practical lower detection
range (quantitation limit) usually depends on sample
characteristics such as moisture content of the gas, the
presence of other interferants, and losses in the sampling
system.
1.3 Sensitivity. The limit of sensitivity for an optical
configuration and integration time is determined using
appendix D of the Protocol: Minimum Analyte Uncertainty,
(MAU). The MAU depends on the RMSD noise in an analytical
region, and on the absorptivity of the analyte in the same
region.
1.4 Data Quality. Data quality shall be determined by
executing Protocol pre-test procedures in appendices B to H
of the protocol and post-test procedures in appendices I and
J of the protocol.
1.4.1 Measurement objectives shall be established by the
choice of detection limit (DLJ and analytical uncertainty
(Atfi) 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
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5
gathered in a pre-test site survey. Spectral interferants
shall be identified using the selected DL, and AUt 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 noi^e 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 AUi can be maintained; if the measured analyte
concentration is less than MAUi, 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
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6
path (background).
2.1.2 Most molecules absorb infrared radiation and the
absorbance occurs in a characteristic and reproducible
pattern. The infrared spectrum measures fundamental
molecular properties and a compound can be identified from
its infrared spectrum alone.
2.1.3 Within constraints, there is a linear relationship
between infrared absorption and compound concentration. If
this frequency dependent relationship (absorptivity) is
known (measured), it can be used to determine compound
concentration in a sample mixture.
2.1.4 Absorptivity is measured by preparing, in the
laboratory, standard samples of compounds at known
concentrations and measuring the FTIR "reference spectra" of
these standard samples. These "reference spectra" are then
used in sample analysis: (1) compounds are detected by
matching sample absorbance bands with bands in reference
spectra, and (2) concentrations are measured by comparing
sample band intensities with reference band intensities.
2.1.5 This method is self-validating provided that the
results meet the performance requirement of the QA spike in
sections 8.6.2 and 9.0 of this method, and results from a
previous method validation study support the use of this
method in the application.
2.2 Sampling and Analysis/ In extractive sampling a probe
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7
assembly and pump are used to extract gas from the exhaust
of the affected source and transport the sample to the FTIR
gas cell. Typically, the sampling apparatus is similar to
that used for single-component continuous emission monitor
(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.
aL = absorption coefficient (absorptivity) of the ith
sample component.
b = path length of the cell.
Ci = concentration of the ith sample component.
2.2.2 Analyte spiking is used for quality assurance (QA).
In this procedure (section 8.6.2 of this method) an analyte
is spiked into the gas stream at the back end of the sample
probe. Analyte concentrations in the spiked samples are
compared to analyte concentrations in unspiked samples.
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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.
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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
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10
configurations or sampling temperatures.
3.5 Interferant. A compound in the sample matrix whose
infrared spectrum overlaps with part of an analyte spectrum.
The most accurate analyte measurements are achieved when
reference spectra of interferants are used in the
quantitative analysis with the analyte reference spectra.
The presence of an interferant can increase the analytical
uncertainty in the measured analyte concentration.
3,6 Gas Cell. A gas containment cell that can be
evacuated. It is equipped with the optical components to
pass the infrared beam through the sample to the detector.
Important cell features include: path length (or range if
variable), temperature range, materials of construction, and
total gas volume.
3.7 Sampling System. Equipment used to extract the sample
from the test location and transport the sample gas to the
FTIR analyzer. This includes sample conditioning systems.
3.8 Sample Analysis. The process of interpreting the
infrared spectra to obtain sample analyte concentrations.
This process is usually automated using a software routine
employing a classical least squares (els), partial least
squares (pis), or K- or P- matrix method.
3.9 One hundred percent line. A double beam transmittance
spectrum obtained by combining two background single beam
spectra. Ideally, this line is equal to 100 percent
-------
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 i's .
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 reference CTS.
3.18 Test CTS. CTS spectra collected at the sampling
resolution using the same optical configuration as for
sample spectra. Test spectra help verify the resolution,
temperature and path length of the 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 ETIR system configuration. This is
estimated by the MAU. It depends on the RMSD in an
analytical region of a zero absorbance line.
3.21 Quantitation Limit. The lower limit of detection for
the FTIR system configuration in the sample spectra. This
is estimated by mathematically subtracting scaled reference
spectra of analytes and interferences from sample spectra,
then measuring the RMSD in an analytical region of the
subtracted spectrum. Since the noise in subtracted sample
spectra, may be much greater than in a zero absorbance
spectrum, the quantitation limit is generally much higher
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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 is used to verify the test procedures for
measuring specific analytes at a source. Validation
provides proof that the method works under certain test
conditions.
3.26 Validation Run. A validation run consists of at least
24 measurements of independent samples. Half of the samples
are spiked and half are not spiked. The length of the run
is determined by the interval between independent samples.
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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: (I) deposits on
reflective surfaces or transmitting windows, (2) changes in
detector sensitivity, !3) a change in the infrared source
output,, or (4) failure in the instrument electronics. In
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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 C02 are common spectral
interferants. Both of these compounds have strong infrared
spectra and are present in many sample matrices at high
concentrations relative to analytes. The extent of
interference depends on the (1) interferant concentration,
(2) analyte concentration, and (3) the degree of band
overlap. Choosing an alternate analytical region can
minimize or avoid the spectral interference. For example,
C02 interferes with the analysis of the 670 cm*1 benzene
band. However, benzene can also be measured near 3000 cm"1
(with less sensitivity).
4.2 Sampling System Interferences. These prevent analytes
from reaching the instrument. The analyte spike procedure
is designed to measure sampling system interference, if any.
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17
4.2.1 Temperature, A temperature that is too lew 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.
Not e: ^Mention of rtradenames or specific eroducts does
not constitute endorsement, bv the Environmental
Protection Agency.
The equipment and supplies are based on the schematic
of a sampling system shown in Figure 1. Either the batch or
continuous sampling procedures may be used with this
sampling system. Alternative sampling configurations may
also be used, provided that the data quality objectives are
met as determined in the post-analysis evaluation. Other
equipment or supplies may be necessary, depending on the
design of the sampling system or the specific target
analytes.
6.1 Sampling Probe. Glass, stainless steel, or other
appropriate material of sufficient length and physical
integrity to sustain heating, prevent adsorption of
analytes, and to transport analytes to the infrared gas
cell. Special materials or configurations may be required
in some applications. For instance, high stack sample
temperatures may require special steel or cooling the probe.
-------
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 FTIR system or through sample conditioning
systems. Usually includes heated flow meter, heated valve
for selecting and sending sample to the analyzer, and a by-
pass vent. This is typically constructed of stainless steel
tubing and fittings, and high-temperature valves.
6.5 Stainless Steel Tubing. Type 316, appropriate diameter
(e.g., 3/8 in.) and length for heated connections. Higher
grade stainless may be desirable in some applications.
6.6 Calibration/Analyte Spike Assembly. A three way valve
assembly (or equivalent) to introduce analyte or surrogate
spikes into the sampling system at the outlet of the probe
upstream of the out-of-stack particulate filter and the FTIR
-------
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/rain and be accurate to ± 2 percent (or better)
of the flow meter span.
6.8 Gas Regulators. Appropriate for individual gas
standards.
6.9 Polytetrafluoroethane Tubing. Diameter (e.g., 3/8 in.)
and length suitable to connect cylinder regulators to gas
standard manifold.
6.10 Sample Pump. A leak-free pump (e.g., KNF") , with by-
pass valve, capable of producing a sample flow rate of at
least 10 L/min through 100 ft of sample line. If the pump
is positioned upstream of the distribution manifold and FTIR
system, use a heated pump that is constructed from materials
non-reactive to the analytes. If the pump is located
downstream of the FTIR system, the gas cell sample pressure
will be lower than ambient pressure and it must be recorded
at regular intervals.
6.11 Gas Sample Manifold. Secondary manifold to control
sample flow at the inlet to the FTIR manifold. This is
optional, but includes a by-pass vent and heated rotameter.
6.12 Rotameter. A 0 to 20 L/min rotameter. This meter
need not be calibrated.
6.13 'FTIR Analytical System. Spectrometer and detector,
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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
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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 FTIR system by decreasing
the ceil path length, or to use a short-path cell in
conjunction with a long path cell to measure more than one
concentration range.
7.0 Reagents and Standards,
7.1 Analyte(s) and Tracer Gas. Obtain a certified gas
cylinder mixture containing all of the analyte(s) at
concentrations within ± 2 percent of the emission source
levels (expressed in ppm-meter/K). If practical, the
analyte standard cylinder shall also contain the tracer gas
at a concentration which gives a measurable absorbance at a
dilution factor of at least 10; 1. Two ppm SFS is sufficient
for a path length of 22 meters at 250 °F.
7.2 Calibration Transfer Standard(s). Select the
calibration transfer standards (CTS) according to section
4.5 of the FTIR Protocol. Obtain a National Institute of
Standards and Technology (NIST) traceable gravimetric
standard of the CTS (± 2 percent).
7.3 Reference Spectra. Obtain reference spectra for each
analyte, interferant, surrogate, CTS, and tracer. If EPA
reference spectra are not available, use reference spectra
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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) AU4, DLt, overall
fractional uncertainty, OFUt, maximum expected concentration
(CMAXt) , and tw for each, (b) potential interferants, (c)
sampling system factors, e.g., minimum absolute cell
pressure, (PmlJ , 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, FCm, and upper wavenumber
position, FUm, plus interferants, upper wavenumber position
of the CTS absorption band, FFUm, lower wavenumber position
of the CTS absorption band, FFLm, wavenumber range FNU to
FNL. If necessary, sample and acquire an initial spectrum.
From analysis of this preliminary spectrum determine a
suitable operational path length. Set up the sampling train
as shown in Figure 1 or use an appropriate alternative
configuration. Sections 8.1 through 8.11 of this method
provide guidance on pre-test calculations in the EPA
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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 (DLt)
and the maximum permissible analytical uncertainty (AUj) for
each analyte (labeled from 1 to i). Estimate, if possible,
the maximum expected concentration for each analyte, CMAXt.
The expected measurement range is fixed by DLi and CMAX, for
each analyte (i).
8.1.2 Potential Interferants. List the potential
interferants. This usually includes water vapor and C02,
but may also include some analytes and other compounds.
3.1.3. Optical Configuration. Choose an optical
configuration that can measure all of the analytes within
the absorbance range of .01 to 1.0 (this may require more
than one path length). Use Protocol sections 4.3 to 4.8 for
guidance in choosing a configuration and measuring CTS.
8.1.4. Fractional Reproducibility Uncertainty (FRUt) . The
FRU is determined for each analyte by comparing CTS spectra
taken before and after the reference spectra were measured.
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The EPA para-xylene reference spectra were collected on
10/31/91 and 11/01/91 with corresponding CTS spectra
"ctslGSla," and "ctsllOlb." The CTS spectra are used to
estimate the reproducibility (FRU) in the system that was
used to collect the references. The FRU must be < AU,
Appendix E of the protocol is used to calculate the FRU from
CTS spectra. Figure 2 plots results for 0.25 cm"1 CTS
spectra in EPA reference library: S3 (ctsllOlb - cts!031a),
and S< [(ctsllOlb + cts!031a)/2]. The RMSD (SRMS) is
calculated in the subtracted baseline, S3, in the
corresponding CTS region from 850 to 1065 cm'1. The area
(BAV) is calculated in the same region of the averaged CTS
spectrum, S4.
3.1.5 Known Interferants. Use appendix B of the EPA FTIR
Protocol.
3.1.6 Calculate the Minimum Analyte Uncertainty, MAU
(section 1.3 of this method discusses MAU and protocol
appendix D gives the MAU procedure). The MAU for each
analyte, i, and each analytical region, m, depends on the
RMS noise.
8.1.7 Analytical Program. See FTIR Protocol, section 4.10.
Prepare computer program based on the chosen analytical
technique. Use as input reference spectra of all target
analytes and expected interferants. Reference spectra of
additional compounds shall also be included in the program
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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, ?R,
and the conditions used for collecting the sample spectra.
If sampling is performed at ambient pressure, then any
pressure correction is usually small relative to corrections
for path length and temperature, and may be neglected.
8.2 Leak-check.
8.2.1 Sampling System. A typical ETIR extractive sampling
train is shown in Figure 1. Leak check from the probe tip
to pump outlet as follows: Connect a 0- to 250-mL/min rate
meter (rotameter or bubble meter) to the outlet of the pump.
Close off the inlet to the probe, and record the leak rate.
The leak rate shall be 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 APV after 2 minutes.
8.2,2.2 For both the evacuated sample and purging
techniques, pressurize the system to about 100 mmHg above
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27
atmospheric pressure. Isolate the pump and determine the
change in pressure APp after 2 minutes.
8.2.2.3 Measure the barometric pressure, Pb in mmHg.
8.2.2-4 Determine the percent leak volume %VL for the
signal integration time tss and for APmax, i.e., the larger of
APV or APP, as follows:
AP
%VL = 50 t
ss
where 50 = 100% divided by the leak-check time of 2 minutes.
8.2.2.5 Leak volumes in excess of 4 percent of the FTIR
system volume Vss are unacceptable.
8.3 Detector Linearity. Once an optical configuration is
chosen, use one of the procedures of sections 8.3.1 through
8.3.3 to verify that the detector response is linear. If
the detector response is not linear, decrease the aperture,
or attenuate the infrared beam. After a change in the
instrument configuration perform a linearity check until it
is demonstrated that the detector response is linear.
8.3.1 Vary the power incident on the detector by modifying
the aperture setting. Measure the background and GTS at
three instrument aperture settings: (1) at the aperture
setting to be used in the testing, (2) at one half this
aperture and (3) at twice the proposed testing aperture.
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28
Compare the three CTS spectra. CTS band areas shall agree
to within the uncertainty of the cylinder standard and the
RMSD noise in the system. If test aperture is the maximum
aperture, collect CTS spectrum at maximum aperture, then
close the aperture to reduce the IR throughput by half.
Collect a second background and CTS at the smaller aperture
setting and compare the spectra again.
8.3.2 Use neutral density filters to attenuate the infrared
beam. Set up the FTIR system as it will be used in the test
measurements. Collect a CTS spectrum. Use a neutral
density filter to attenuate the infrared beam (either
immediately after the source or the interferometer) to
approximately 1/2 its original intensity. Collect a second
CTS spectrum. Use another filter to attenuate the infrared
beam to approximately 1/4 its original intensity. Collect a
third background and CTS spectrum. Compare the CTS spectra.
CTS band areas shall agree to within the uncertainty of the
cylinder standard and the RMSD noise in the system.
8.3.3 Observe the single beam instrument response in a
frequency region where the detector response is known to be
zero. Verify that the detector response is "flat" and equal
to zero in these regions.
8.4 Data Storage Requirements. All field test spectra
shall be stored on a computer disk and a second backup copy
must stored on a separate disk. The stored information
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29
includes sample interferograms, processed absorbance
spectra, background interferograms, CIS sample
interferograms and CIS absorbance spectra. Additionally,
documentation of all sample conditions, instrument settings,
and test records must be recorded on hard copy or on
computer medium. Table 1 gives a sample presentation of
documentation.
8.5 Background Spectrum. Evacuate the gas cell to s 5
mmHg, and fill with dry nitrogen gas to ambient pressure (or
purge the cell with 10 volumes of dry nitrogen). Verify
that no significant amounts of absorbing species (for
example water vapor and C02) are present. Collect a
background spectrum, using a signal averaging period equal
to or greater than the averaging period for the sample
spectra. Assign a unique file name to the background
spectrum. Store two copies of the background interferogram
and processed single-beam spectrum on separate computer
disks (one copy is the back-up).
8.5.1 Interference Spectra. If possible, collect spectra
of known and suspected major interferences using the same
optical system that will be used in the field measurements.
This can be done on-site or earlier. A number of gases,
e.g. C02, S02, CO, NH3, are readily available from cylinder
gas suppliers.
8.5.2 Water vapor spectra can be prepared by the following
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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 dilate 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 £ 5 mmHg absolute pressure, and fill the FTIR ceil 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.
3.6.2 QA Spike. This procedure assumes that the method has
been validated for at least some of the target analytes at
the source. For emissions testing perform a QA spike. Use
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31
a certified standard, if possible, of an analyte, which has
been validated at the source. One analyte standard can
serve as a QA surrogate for other analytes which are less
reactive or less soluble than the standard. Perform the
spike procedure of section 9.2 of this method. Record
spectra of at least three independent (section 3.22 of this
method) spiked samples. Calculate the spiked component of
the analyte concentration. If the average spiked
concentration is within 0.7 to 1.3 times the expected
concentration, then proceed with the testing. If
applicable, apply the correction factor from the Method 301
of this appendix validation test (not the result from the QA
spike).
8.7 Sampling. If analyte concentrations vary rapidly with
time, continuous sampling is preferable using the smallest
cell volume, fastest sampling rate and fastest spectra
collection rate possible. Continuous sampling requires the
least operator intervention even without an automated
sampling system. For continuous monitoring at one location
over long periods, Continuous sampling is preferred. Batch
sampling and continuous static sampling are used for
screening and performing test runs of finite duration.
Either technique is preferred for sampling several locations
in a matter of days. Batch sampling gives reasonably good
time resolution and ensures that each spectrum measures a
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32
discreet (and unique) sample volume. Continuous static (and
continuous) sampling provide a very stable background over
long periods. Like batch sampling, continuous static
sampling also ensures that each spectrum measures a unique
sample volume. It is essential that the leak check
procedure under vacuum (section 8.2 of this method) is
passed if the batch sampling procedure is used. It is
essential that the leak check procedure under positive
pressure is passed if the continuous static or continuous
sampling procedures are used. The sampling techniques are
described in sections 8.7.1 through 8.7.2 of this method.
8.7.1 Batch Sampling. Evacuate the absorbance cell to
s 5 rranHg absolute pressure. Fill the cell with exhaust gas
to ambient pressure, isolate the cell, and record the
spectrum. Before taking the next sample, evacuate the cell
until no spectral evidence of sample absorption remains.
Repeat this procedure to collect eight spectra of separate
samples in 1 hour.
8.7.2 Continuous Static Sampling. Purge the FTIR cell with
10 cell volumes of sample gas. Isolate the cell, collect
the spectrum of the static sample and record the pressure.
Before measuring the next sample, purge the cell with 10
more cell volumes of sample gas.
8.8 Sampling QA and Reporting.
8.8.1 Sample integration times shall be sufficient to
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33
achieve the required signal-to-noise ratio. Obtain an
absorbance spectrum by filling the cell with K2. 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.
3,8,2 Assign a unique file name to each spectrum.
3,8.3 Store two copies of sample interferograms and
processed spectra on separate computer disks.
3.8.4 For each sample spectrum, document the sampling
conditions, the sampling time (while the cell was being
filled), the time the spectrum was recorded, the
instrumental conditions (path length, temperature, pressure,
resolution, signal integration time), and the spectral file
name. Keep a hard copy of these data sheets.
8.9 Signal Transmittance. While sampling, monitor the
signal transmittance. If signal transmittance (relative to
the background) changes by 5 percent or more (absorbance =
-.02 to .02) in any analytical spectral region, obtain a new
background spectrum.
8.10 Post-test CTS. After the sampling run, record another
CTS spectrum.
8.11 Post-test QA.
8.11.1 Inspect the sample spectra immediately after the run
to verify that the gas matrix composition was close to the
expected (assumed) gas matrix.
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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 C7S spectra. The
peak absorbance in pre- and pos.t-test CTS must be ± 5
percent of the mean value. See appendix E of the FTIR
Protocol.
9.0 Quality Control.
Use analyte spiking (sections 8.6.2, 9.2 and 13.0 of
this method) to verify that the sampling system can
transport the analytes from the probe to the FTIR system.
9.1 Spike Materials. Use a certified standard (accurate to
± 2 percent) of the target analyte, if one can be obtained.
If a certified standard cannot be obtained, follow the
procedures in section 4.6.2.2 of the FTIR Protocol.
9.2 Spiking Procedure. QA spiking (section 8.6.2 of this
method) is a calibration procedure used before testing. QA
spiking involves following the spike procedure of sections
9.2.1 through 9.2.3 of this method to obtain at least three
spiked samples. The analyte concentrations in the spiked
samples shall be compared to the expected spike
concentration to verify that the sampling/analytical system
is working properly. Usually, when QA spiking is used, the
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35
method has already been validated at a similar source for
the analyte in question. The QA spike demonstrates that the
validated sampling/analytical conditions are being
duplicated. If the QA spike fails then the
sampling/analytical system shall be repaired before testing
proceeds. The method validation procedure (section 13.0 of
this method) involves a more extensive use of the analyte
spike procedure of sections 9.2.1 through 9.2.3 of this
method. Spectra of at least 12 independent spiked and 12
independent unspiked samples are recorded. The
concentration results are analyzed statistically to
determine if there is a systematic bias in the method for
measuring a particular analyte. If there is a systematic
bias, within the limits allowed by Method 301 of this
appendix, then a correction factor shall be applied to the
analytical results. If the systematic bias is greater than
the allowed limits, this method is not valid and cannot be
used.
9.2.1 Introduce the spike/tracer gas at a constant flow
rate of s 10 percent of the total sample flow, when
possible. (Note: Use the rotameter at the end of the
sampling train to estimate the required spike/tracer gas
flow rate.) Use a flow device, e.g., mass flow meter {± 2
percent), to monitor the spike flow rate. Record the spike
flow rate every 10 minutes.
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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 = DF+Spike^ + Unspike(l-DF) (4)
DF = Dilution factor of the spike gas; this value
shall be alO.
SfsidiD = SFs (o;c tracer gas) concentration measured
directly in undiluted spike gas.
SF6(splc, = Diluted SF6 (or tracer gas) concentration
measured in a spiked sample.
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37
SpikedlJ. = 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.G 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
s 0.001.
10.2 Absorbance Path length. Verify the absorbance path
length by comparing reference CTS 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
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38
apodization function that was used in transforming the
reference spectra.
10.5 FTIR Cell Volume. Evacuate the cell to s 5 mmHg.
Measure the initial absolute temperature (Tt) and absolute
pressure (Pi) . Connect a wet test meter (or a calibrated
dry gas meter), and slowly draw room air into the cell.
Measure the meter volume (VJ , meter absolute temperature
jTm) , and meter absolute pressure (Pm); and the cell final
absolute temperature (Tf) and absolute pressure (Pf).
Calculate the FTIR cell volume Vss, including that of the
connecting tubing, as follows:
v m
m >T*
i/ _ m
(5)
T, r,
11.0 Data Analysis and Calculations.
Analyte concentrations shall be measured using
reference spectra from the EPA FTIR spectral library. When
EPA library spectra are not available, the procedures in
section 4.6 of the Protocol shall be followed to prepare
reference spectra of all the target analytes.
11.1 Spectral De-resolution. Reference spectra can be
converted to lower resolution standard spectra (section 3.3
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39
of this method) by truncating the original reference sample
and background interferograms. Appendix K of the FTIR
Protocol gives specific deresolution procedures, Deresolved
spectra shall be transformed using the same apodization
function and level of zero filling as the sample spectra.
Additionally, pre-test FTIR protocol calculations (e.g.,
FRCJ, MAU, FCU) shall be performed using the de-resolved
standard spectra.
11.2 Data Analysis. Various analytical programs are
available for relating sample absorbance to a concentration
standard. Calculated concentrations shall be verified by
analyzing residual baselines after mathematically
subtracting scaled reference spectra from the sample
spectra. A full description of the data analysis and
calculations is contained in the FTIR Protocol (sections
4.0, 5.0, 6.0 and appendices). Correct the calculated
concentrations in the sample spectra for differences in
absorption path length and temperature between the reference
and sample spectra using equation 6,
con-
(6)
where:
Ccocr = Concentration, corrected for path length.
Ccaic = Concentration, initial calculation (output of the
analytical program designed for the compound).
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40
Lr = Reference spectra path length.
L, = Sample spectra path length.
Ts = Absolute temperature of the sample gas, K.
Tr = Absolute gas temperature of reference spectra, K.
Ps = Sample cell pressure.
Pr = Reference spectrum sample pressure.
12.0 Method Performance.
12.1 Spectral Quality. Refer to the FTIR Protocol
appendices for analytical requirements, evaluation of data
quality, and analysis of uncertainty.
12.2 Sampling QA/QC. The analyte spike procedure of
section 9 of this method, the QA spike of section 8.6.2 of
this method, and the validation procedure of section 13 of
this method are used to evaluate the performance of the
sampling system and to quantify sampling system effects, if
any, on the measured concentrations. This method is self-
validating provided that the results meet the performance
requirement of the QA spike in sections 9.0 and 8.6.2 of
this method and results from a previous method validation
study support the use of this method in the application.
Several factors can contribute to uncertainty in the
measurement of spiked samples. Factors which can be
controlled to provide better accuracy in the spiking
procedure are listed in sections 12.2.1 through 12.2.4 of
this method.
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41
12.2.1 Flow meter. An accurate mass flow meter is accurate
to ± 1 percent of its span. If a flow of 1 L/min is
monitored with such a MFM, which is calibrated in the range
of 0-5 L/min, the flow measurement has an uncertainty of 5
percent. This may be improved by re-calibrating the meter
at the specific flow rate to be used.
12.2.2 Calibration gas. Usually the calibration standard
is certified to within ± 2 percent. With reactive analytes,
such as HC1, the certified accuracy in a commercially
available standard may be no better than ± 5 percent.
12.2.3 Temperature. Temperature measurements of the cell
shall be quite accurate. If practical, it is preferable to
measure sample temperature directly, by inserting a
thermocouple into the cell chamber instead of monitoring the
cell outer wall temperature.
12.2.4 Pressure. Accuracy depends on the accuracy of the
barometer, but fluctuations in pressure throughout a day may
be as much as 2.5 percent due to,weather variations.
13.0 Method Validation Procedure.
This validation procedure, which is based on EPA Method
301 (40 CFR part 63, appendix A), may be used to validate
this method for the analytes in a gas matrix. Validation at
one source may also apply to another type of source, if it
can be shown that the exhaust gas characteristics are
similar at both sources.
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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
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43
13.2.3 shall be used.
13.2.1 With a single FTIR instrument and sampling system,
begin by collecting spectra of two unspiked samples.
Introduce the spike flow into the sampling system and allow
10 cell volumes to purge the sampling system and FTIR cell.
Collect spectra of two spiked samples. Turn off the spike
and allow 10 cell volumes of unspiked sample to purge the
FTIR cell. Repeat this procedure until the 24 (or more)
samples are collected,
13.2.2 In batch sampling, collect spectra of 24 distinct
samples. (Each distinct sample consists of filling the cell
to ambient pressure after the cell has been evacuated.)
13.2.3 Alternatively, a separate probe assembly, line, and
sample pump can be used for spiked sample. Verify and
document that sampling conditions are the same in both the
spiked and the unspiked sampling systems. This can be done
by wrapping both sample lines in the same heated bundle.
Keep the same flow rate in both sample lines. Measure
samples in sequence in pairs. After two spiked samples are
measured, evacuate the FTIR cell, and turn the manifold
valve so that spiked sample flows to the FTIR cell. Allow
the connecting line from the manifold to the FTIR cell to
purge thoroughly (the time depends on the line length and
flow rate). Collect a pair of spiked samples. Repeat the
procedure until at least 24 measurements are completed.
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13,3 Simultaneous Measurements With Two FTIR Systems. If
•anspiked effluent concentrations of the target analyte(s)
vary significantly with time, it may be desirable to perform
synchronized measurements of spiked and unspiked sample.
Use two FTIR systems, each with its own cell and sampling
system to perform simultaneous spiked and unspiked
measurements. The optical configurations shall be similar,
if possible. The sampling configurations shall be the same.
One sampling system and FTIR analyzer shall be used to
measure spiked effluent. The other sampling system and FTIR
analyzer shall be used to measure unspiked flue gas. Both
systems shall use the same sampling procedure (i.e., batch
or continuous),
13.3,1 If batch sampling is used, synchronize the cell
evacuation, cell filling, and collection of spectra. Fill
both cells at the same rate (in cell volumes per unit time)»
13.3.2 If continuous sampling is used, adjust the sample
flow through each gas cell so that the same number of cell
volumes pass through each cell in a given time (i.e. TCj =
TC2) ,
13.4 Statistical Treatment. The statistical procedure of
EPA"Method 301 of this appendix, section 6.3 is used to
evaluate the bias and precision. For FTIR testing a
validation "run" is defined as spectra of 24 independent
samples, 12 of 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 (7)
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 * 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.
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46
14.0 Pollution Prevention.
The extracted sample gas is vented outside the
enclosure containing the FTIR system and gas manifold after
the analysis. In typical method applications the vented
sample volume is a small fraction of the source volumetric
flow and its composition is identical to that emitted from
the source. When analyte spiking is used, spiked pollutants
are vented with the extracted sample gas. Approximately 1.6
x 10"4 to 3.2 x 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 gr 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 CF1 part 63, appendix
A.
4. "Molecular Vibrations; The Theory of Infrared and Raman
Vibrational Spectra," E. Bright Wilson, J. C. Decius, and P.
C. Cross, Dover Publications, Inc., 1980. For a less
intensive treatment of molecular rotational-vibrational
spectra see, for example, "Physical Chemistry," G. M.
Barrow, chapters 12, 13, and 14, McGraw Hill, Inc., 1979.
5. "Fourier Transform Infrared Spectrometry," Peter R.
Griffiths and James de Haseth, Cheaical Analysis, 83, 16-
25, (1986), P. J. Elving, J. D. Winefordner and I. M.
Kolthoff (ed.), John Wiley and Sons.
6. "Computer-Assisted Quantitative Infrared Spectroscopy,"
Gregory L. McClure (ed.J, 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 I. EXAMPLE PRESENTATION OF SAMPLING DOCUMENTATION.
Smrnflm TIM
Spvctrw Pll* IBM
l*ckftra«Bd File IBM
Supl« cM^tl loatag
rrvcnaa cnwlltlaa
TUe
File
Se
£•!•
CIS Spectrum
-------
49
SampU Ga* D»fcv«ry Manifold
Calibration Gas Ling
Mace Flow Calbration Gas Manifold
4J
To CaJfcralion
Gas Cylinder*
Pump #2
Figure 1. Extractive FTIR sampling system.
-------
50
-8H
FRU = SRMS(FU-FL)/BAV
SRMS = .00147
BAV = 3.662
FM = FRU = .086
1050
1000
950 900
Wavenumbers
850
800
750
Figure 2. Fractional Reproducibility. Top: average of cts!031a and
ctsllOlb. Bottom: Reference spectrum of p-xylene.
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Page l
PROTOCOL FOR THE USE OP EXTRACTIVE FOURIER TRANSFORM
INFRARED (FTIR) SPECTROMETRY FOR THE ANALYSES OF GASEOUS
EMISSIONS FROM STATIONARY SOURCES
INTRODUCTION
The purpose of this document is to set general guidelines
for the use of modern FTIR spectroscopic methods for the analysis
of gas samples extracted from the effluent of stationary emission
sources. This document outlines techniques for developing and
evaluating such methods and sets basic requirements for reporting
and quality assurance procedures.
1.0 NOMENCLATURE
1.1 Appendix A lists definitions of the symbols and terms
used in this Protocol, many of which have been taken directly
from American Society for Testing and Materials (ASTM)
publication E 131-90a, entitled "Terminology Relating to
Molecular Spectroscopy."
1.2 Except in the case of background spectra or where
otherwise noted, the term "spectrum" refers to a double-beam
spectrum in units of absorbance vs. wavenumber (cm"1).
1.3 The term "Study" in this document refers to a
publication that has been subjected to EPA- or peer-review.
2.0 APPLICABILITY AND ANALYTICAL PRINCIPLE
2.1 Applicability. This Protocol applies to the
determination of compound-specific concentrations in single- and
multiple-component gas phase samples using double-beam absorption
spectroscopy in the mid-infrared band. It does not specifically
address other FTIR applications, such as single-beam
spectroscopy, analysis of open-path (non-enclosed) samples, and
continuous measurement techniques. If multiple spectrometers,
absorption cells, or instrumental linewidths are used in such
analyses, each distinct operational configuration of the system
must be evaluated separately according to this Protocol.
2.2 Analytical Principle.
2.2.1 In the mid-infrared band, most molecules exhibit
characteristic gas phase absorption spectra that may be recorded
by FTIR systems. Such systems consist of a source of mid-
infrared radiation, an interferometer, an enclosed sample cell of
known absorption pathlength, an infrared detector, optical
elements for the transfer of infrared radiation between
components, and gas flow control and measurement components.
Adjunct and integral computer systems are used for controlling
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EPA PTIR Protocol - . 0=™= ->
^
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 Che absorption spectrum of the sample gaa. 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 OF PROTOCOL REQUIREMENTS
The characteristics that distinguish FTIR systems from gas
analyzers used in instrumental gas analysis methods (e.g.,
EPA Methods SC and 7E) are: (I) 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 thia 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: ,
3.3.1 Sample -Independent Factors. Examples ^re^ system
configuration and performance (e.g., detector sensitivity and
infrared source output) , quality and applicability of reference
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EPA, FTIR 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 PRB-TEST PREPARATIONS AND 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 (AUj). The AUA is the
maximum permissible fractional uncertainty of analysis for the
i"1 analyte concentration, expressed as a fraction of the analyte
concentration in the sample.
4.1.3 Required detection limit for each analyte (DL^, 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
i, ppm).
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SPA FTIH PrOtOCOl
14,
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
Nj, 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 (vsS' liter) . Select the
techniques and/or equipment for the measurement of sample
pressures and temperatures.
4.4 Select Spectroscopic System. Select a spectroscopic
configuration for the application. Approximate the absorption
pathlength (Ls' , meter), sample pressure (Pg'- kpa' ' absolute
sample temperature TS' , and signal integration period (tgg,
seconds) for the analysis. Specify the nominal minimum
instrumental linewidth (MIL) of the system. Verify that the
fractional error at the approximate values Ps' and TS' is less
than one half the smallest value AU
e v<3.j. ues fg CLH.U A g
i (see Section 4.1.2).
4.5 Select Calibration Transfer Standards (CTS's). Select
CTS's that meet the criteria listed in Sections 4.5.1, 4.5.2, and
4.5.3.
Note; It may be necessary to choose preliminary analytical
regions (see Section 4.7), identify the minimum analyte
linewidthB, or estimate the system noise level (see
Section 4.12) before selecting the CTS. More than one
compound may be needed to meet the criteria; if so, obtain
separate cylinders for each compound,
4.5.1 The central wavenumber position of each analytical
region lies within 25 percent of the wavenumber position of at
least one CTS absorption band.
4.5.2 The absorption bands in 4.5.1 exhibit peak
absorbances greater than ten times the value RMSEST (see
Sectioh 4.12) but less than 1.5 absorbance units.
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BPA PTIR Protocol
4.5.3 At least one absorption CTS band within the operating
range _ of the FTIR instrument haa 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 (FFU_ and FFL^, respectively) that
bracket the CTS absorption band or bands for the associated
analytical region. Specify the wavenumber range, FNU to FNL,
containing the absorption band that meets the criterion of
Section 4.5.3.
4.5.5 Associate, whenever possible, a single set of CTS gas
cylinders with a set of reference spectra. Replacement CTS gas
cylinders shall contain the same compounds at concentrations
within 5 percent of that of the original CTS cylinders; the
entire absorption spectra {not individual spectral segments) of
the replacement gas shall be scaled by a factor between 0.95 and
1.05 to match the original CTS spectra.
4.6 Prepare Reference Spectra.
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 l (see
Reference D) or shall be traceable to NIST standards. Obtain
from the supplier an estimate of the stability of the analyte
concentration; obtain and follow all the supplier's
recommendations for recertifying the analyte concentration.
4.6.2.2 Self -Prepared Chemical Standards. Chemical
standards may be prepared as follows: Dilute certified
commercially prepared chemical gases or pure analytes with ultra -
pure carrier (UPC) grade nitrogen according to the barometric and
volumetric techniques generally described in Reference A,
Section A4.6.
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EPA PTIR Protocol Paae> fi
-*- 1A 1QOg a
4.6.3 Record a set of the absorption spectra of the GTS
{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. €.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 concent rat ion- 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
concent rat ion- pathlength product of that analyte at its required
detection limit.
4.6.4 Permanently store the background and interferograms
in digitized form. Document details of the mathematical process
for generating the spectra from these interferograms . Record the
sample pressure (PR) , sample temperature (TR) , reference
absorption pathlength (LR) , and interferogram signal integration
period (tgR3 . Signal integration periods for the background
interferograms shall be *tgp. Values of Pp, LR, and tSR shall
not deviate by more than ±1 percent from the time of recording
{Rl} to that of recording {R2}.
4.6.5 If self -prepared chemical standards are employed and
spectra of only two concentrations are recorded for one or more
compounds, verify the accuracy of the dilution technique by
analyzing the prepared standards for those compounds with a
secondary (non-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 AU-i, the dilution technique is not sufficiently
accurate and the reference spectra prepared are not valid for the
analysis.
4.7 Select Analytical Regions. Using the general
considerations in Section 7 of Reference A and the spectral
characteristics of the analytes and interferants, select the
analytical regions for the application. Label them m = 1 to M.
Specify the lower, center and upper wavenumber positions of each
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EPA PTIR Protocol
analytical region (FI^, FC^,, and FUm, respectively) . Specify the
analytes and interferants which exhibit absorption in each
region.
4.8 Determine Fractional Reproducibility Uncertainties.
Using Appendix E, calculate the fractional reproducibility
uncertainty for each analyte (FRU^ from a comparison of {Ri} and
{R2}. If FRUj_ > AUA for any analyte, the reference spectra
generated in Section 4.6 are not valid for the application.
4.9 Identify Known Interferants. Using Appendix B,
determine which potential interferant affects the analyte
concentration determinations. If it does, relabel the potential
interferant as "known" interferant, and designate these compounds
from k - 1 to K. Appendix B also provides criteria for
determining whether the selected analytical regions are suitable.
4.10 Prepare Computerized Analytical Programs.
4.10.1 Choose or devise mathematical techniques (e.g,
classical least squares, inverse least squares, cross-
correlation, and factor analysis) based on Equation 4 of
Reference A that are appropriate for analyzing spectral data by
comparison with reference spectra.
4.10.2 Following the general recommendations of Reference
A, prepare a computer program or set of programs that analyzes
all the analytes and known interferants, based on the selected
analytical regions (4.7) and the prepared reference spectra
(4.6). Specify the baseline correction technique (e.g.,
determining the slope and intercept of a linear baseline
contribution in each analytical region) for each analytical
region, including all relevant wavenumber positions.
4.10.3 Use programs that provide as output [at the
reference absorption pathlength (LR) , reference gas temperature
(TR) , and reference gas pressure (pR)J the 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,
TR, and PR| use a program or set of programs that applies
multiplicative corrections to the derived concentrations to
account for these variations, and that provides as output both
the corrected and uncorrected values . Include in the report of
the analysis (see Section 7.0) the details of any transformations
applied to the original reference spectra (e.g.,
differentiation) , in such a fashion that all analytical results
may be verified by an independent agent from the reference
spectra and data spectra alone.
4.11 Determine the Fractional Calibration Uncertainty.
Calculate the fractional calibration uncertainty for each analyte
) according to Appendix F, and compare these values to the
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SPA PTIR Protocol D _ ..
14, IQ^fi _ °e
fractional uncertainty limits (AU^ see Section 4.1), if
FCUi > KU±) , either the reference spectra or analytical programs
for that analyte are unsuitable.
4.12 Verify System Configuration Suitability. Using
Appendix C, measure or obtain estimates of the noise level
(RMSEST, absorbance) of the FTIR system; alternatively, construct
the complete spectrometer system and determine the values RMS-
using Appendix G. Estimate the minimum measurement uncertainty
for each analyte (MAUj, ppm) and known interferant (MIUV, ppm)
using Appendix D. --- +- -- .-..__-
and FCUj_ < AU^ foi eaun ctnaJ-yte ana. cna.
the requirements listed in Section 4.5.
Verify that (a) MAUt < (Al^) (DL^) , FRU4 < AU,,
and FCU,- < AU4 for each analyte and that (b) the CTS chosen meets
5.0 SAMPLING AMD ANALYSIS PROCEDURE
5.1 Analysis System Assembly and Leak-Test. Assemble the
analysis system. Allow sufficient time for all system components
to reach the desired temperature. Then determine the leak-rate
(LR) and leak volume (VL) , where VL - LR tss. Leak volumes shall
be s4 percent of Vgs.
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 Ls shall
not differ from the approximated sample pathlength Ls' (see
Section 4.4) by more than 5 percent.
5.4 Record Sample Spectrum. Connect the sample line to the
source. Either evacuate the absorption cell to an absolute
pressure below 5 mmHg before extracting a sample from the
effluent stream into the absorption cell, or pump at least ten
cell volumes of sample through the cell before obtaining a
sample. Record the sample pressure Ps. Generate the absorbance
spectrum of the sample. Store the background and sample single
beam interferograms, and document the process by 'which the
absorbance spectra are generated from these data. (If necessary,
apply the spectral transformations developed in Section 5.6.2),
The resulting sample spectrum is referred to below as Sg.
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EPA FTIR Protocol
No_£e.: Multiple sample spectra may be recorded according to
the procedures of Section 5.4 before performing Sections 5.5
and 5.6.
5.5 Quantify Analyte Concentrations. Calculate the
unsealed analyte concentrations RUAi and unsealed interferant
concentrations RUIv 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 * ^RPRTs^^S^R1 • Calculate the final analyte and
interferant concentrations RSAj_ - Ri,PSRUAi and RSIk = RLPSRUIk-
5.6 Determine Fractional Analysis Uncertainty. Pill the
absorption cell with CTS at the pressure Ps. Record a set of CTS
spectra {R4}. Store the background and CTS single beam
interferograms. Using Appendix H, calculate the fractional
analysis uncertainty (FAU) for each analytical region. If the
FAU indicated for any analytical region is larger than the
required accuracy requirements determined in Section 4.1, then
comparisons to previously recorded reference spectra are invalid
in that analytical region, and the analyst shall perform one or
both of the following procedures:
5.6.1 Perform instrumental checks and adjust the instrument
to restore its performance to acceptable levels. If adjustments
are made, repeat Sections 5.3, 5.4 (except for the recording of a
sample spectrum), and 5.5 to demonstrate that acceptable
uncertainties are obtained in all analytical regions.
5.6.2 Apply appropriate mathematical transformations (e.g.,
frequency shifting, zero- filling, apodization, smoothing) to the
spectra (or to the interferograms upon which the spectra are
based) generated during the performance of the procedures of
Section 5.3. Document these transformations and their
reproducibility. Do not apply multiplicative scaling of the
spectra, or any set of transformations that is mathematically
equivalent to multiplicative scaling. Different transformations
may be applied to different analytical regions. Frequency shifts
shall be smaller than one-half the minimum instrumental
linewidth, and must be applied to all spectral data points in an
analytical region. The mathematical transformations may be
retained for the analysis if they are also applied to the
appropriate analytical regions of all sample spectra recorded,
and if all original sample spectra are digitally stored. Repeat
Sections 5.3, 5.4 (except the recording of a sample spectrum),
and 5.5 to demonstrate that these transformations lead to
acceptable calculated concentration uncertainties in all
analytical regions.
6.0 POST -ANALYSIS EVALUATIONS
Estimate the overall accuracy of the analyses performed in
Section 5 as follows:
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EPA PTIR Protocol
p=oo
g^
6.1 Qualitatively Confirm the Assumed Matrix. Examine each
analytical region of the sample spectrum for spectral evidence of
unexpected or unidentified interferants. If found, identify the
interfering compounds (see Reference C for guidance) and add them
to the list of known interferants. Repeat the procedures of
Section 4 to include the interferants in the uncertainty
calculations and analysis procedures. Verify that the MAU and
FCU values do not increase beyond acceptable levels for the
application requirements. Re-calculate the analyte
concentrations (Section 5.5} in the affected analytical regions.
6.2 Quantitatively Evaluate Fractional Model Uncertainty
(FMU) . Perform the procedures of either Section 6.2.1 or 6.2.2:
6.2.1 Using Appendix I, determine the fractional model
error (FMU) for each analyte.
6.2.2 Provide statistically determined uncertainties FMU
for each analyte which are equivalent to two standard deviations
at the 95% confidence level. Such determinations, if employed,
must be based on mathematical examinations of the pertinent
sample spectra (not the reference spectra alone) . Include in the
report of the analysis (see Section 7.0) a complete description
of the determination of the concentration uncertainties.
6.3 Estimate Overall Concentration Uncertainty (QCU) .
Using Appendix J, determine the overall concentration uncertainty
(OCU) for each analyte. If the OCU is larger than the required
accuracy for any analyte, repeat Sections 4 and 6.
7.0 REPORTING REQUIREMENTS
[Documentation pertaining to virtually all the procedures of
Sections 4, 5f and 6 will be required. Software copies of
reference spectra and sample spectra will be retained for some
minimum time following the actual testing.]
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EPA PTIR Protocol Paqe 11
- ^
8.0 REFERENCES
A) Standard Practices for General Techniques of Infrared
Quantitative Analysis (American Society for Testing and
Materials, Designation E 168-88) ,
B) The Coblentz Society Specifications for Evaluation of
Research Quality Analytical Infrared Reference Spectra
(Class II); Anal. Chemistry £7, 945A (1975); Appl.
Spectroscopy 444 . pp. 211-215, 1990.
C) Standard Practices for General Techniques for Qualitative
Infrared Analysis, American Society for Testing and
Materials, Designation E 1252-88.
D) "Traceability Protocol for Establishing True Concentrations
of Gases Used for Calibration and Audits of Continuous
Emissions Monitors (Protocol Number 1)," June 1978, Quality
Assurance Handbook for Air Pollution Measurement Systems,
Volume III, Stationary Source Specific Methods, EPA- 600/4-
77-027b, August 1977.
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EPA PTIR Protocol
1*, mag
APPENDIX A
DEFINITIONS OF TERMS AND SYMBOLS
A.I Definitions of Terms
absorption band - a contiguous wavenumber region of a spectrum
( equivalent ly, 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,
Note: The quantitative result for a single analyte may be
based on data from more than one analytical region.
apodization - modification of the IL3 function by multiplying the
interferogram by a weighing function whose magnitude varies
with retardation.
background spectrum - the single beam spectrum obtained with all
system components without sample present.
baseline - any line drawn on an absorption spectrum to establish
a reference point that represents a function of the radiant
power incident on a sample at a given wavelength.
Beers' a law - the direct proportionality of the absorbance of a
compound in a homogeneous sample to its concentration.
calibration transfer standard (CTS) gas - a gas standard of a
compound used to achieve and/or demonstrate suitable
quantitative agreement between sample spectra and the
reference spectra; see Section 4.5.1.
compound - a substance possessing a distinct, unique molecular
structure.
concentration (c) - the quantity of a compound contained in a
unit quantity of sample. The unit "ppm" (number, or mole,
basis) is recommended.
concentration -pathlength product - the mathematical product of
concentration of the species and absorption pathlength. For
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EPA FTIR Protocol
_^___ _
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 interf erograms
are collected simultaneously " along physically distinct
absorption paths. Here, the term denotes a spectrum in
which the sample and background interf erograms are collected
at different times along the same absorption path.
fast Fourier transform (PPT) - 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/PTIR; HPCL/PTIR, 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 (
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EPA FT1R Protocol _
ingiint- 14, mfi _ __ _ Page 14
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 ia varied.
linewidth - the full width at half maximum of an absorption band
in units of wavenumbers (cm"1) .
mid- infrared - the region of the electromagnetic spectrum from
approximately 400 to 5000 cm"1.
pathlength - see "absorption pathlength."
reference spectra - absorption spectra of gases with known
chemical compositions, recorded at a known absorption
pathlength, which are used in the quantitative analysis of
gas samples.
retardation,
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BPA PTIR Protocol _ _ _
1A- 1Q
-------
BPA PTIR Protocol
CPOTj - estimated concentration of the jth potential interferant.
, re
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EPA PTIR Protocol
Isci or k' indicated standard concentration - the concentration
from the computerized analytical program for a a ingle -
compound reference spectrum for the itn analyte or kfc" known
inter ferant .
kPa - kilo-Pascal (see Pascal) .
LS' - estimated sample absorption pathlength.
LR - reference absorption pathlength.
LS - actual sample absorption pathlength.
- mean of the MAUim over the appropriate analytical regions.
minimum analyte uncertainty - the calculated minimum
concentration for which the analytical uncertainty limit
(AUjJ in the measurement of the itn analyte, based on
spectral data in the m*-" analytical region, can be
maintained.
- mean of the MIUjm over the appropriate analytical regions.
MXUjm, minimum interferant uncertainty - the calculated minimum
concentration for which the analytical uncertainty limit
CPOTj/20 in the measurement pf the jtn interferant, based on
spectral data in the mtn analytical region, can be
maintained.
HIIi, minimum instrumental linewidth - the minimum linewidth from
the FTIR system, in wavenumbers.
Note ; The MIL of a system may be determined by observing an
absorption band known (through higher resolution
examinations) to be narrower than indicated by the system.
The MIL is fundamentally limited by the retardation of the
interferometer, but is also affected by other operational
parameters (e.g., the choice of apodization) .
HA - number of analytes.
HJ - number of potential interf erants .
NV - number of known interf erants.
N an - the number of scans averaged to obtain an interferogram.
OFUj - the overall fractional uncertainty in an analyte
concentration determined in the analysis (OFU^ -
FCUi , FAUj_ , FMUi } ) .
Pascal (Pa) •• metric unit of static pressure, equal to one Newton
per square meter; one atmosphere is equal to 101,325 Pa;
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BPA PTIR Protocol
6
1/760 atmosphere (one Torr, or one millimeter Hg) is eoual
to 133.322 Pa.
pnin " minimum pressure of the sampling system during the
sampling procedure.
PS' - estimated sample pressure.
PR - reference pressure.
Pg - actual sample pressure.
BMSsa " measured noise level of the FTIR system in the mth
analytical region.
RMSD, root mean square difference - a measure of accuracy
determined by the following equation:
RMSD *
(i) £ '
(2)
where
n - the number of observations for which the accuracy is
determined.
&j_ =« the difference between a measured value of a property
and its mean value over the n observations.
Ng te: The RMSD value "between a set of n contiguous
absorbance values (A^) and the mean of the values" (f^) is
defined as
RMSD »
N
(3)
RSA± - the (calculated) final concentration of the ith analyte.
RSIk - the (calculated) final concentration of the ktn known
interferant.
tflca_, scan time - time used to acquire a single scan, not
including flyback.
tg, signal integration period - the period of time over which an
interferogram is averaged by addition and scaling of
individual scans. In terms of the number of scans Ngcan and
scan time tgcan, ts = Ngcantgcan.
tSR - signal integration period used in recording reference
spectra.
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EPA FTIR Protocol Paqe 19
• a
tgg - signal integration period used in recording sample spectra.
TR - absolute temperature of gases used in recording reference
spectra.
TS - 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.
VSS " v0*111116 of tne infrared absorption cell, including parts of
attached tubing.
wifc " weight used to average over analytical regions k for
quantities related to the analyte i; see Appendix D.
Note that some terms are missing, e.g., BAVm, OCU, RMSSm/ SUBgr
SICif SACif Ss
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HPA FTIE Protocol p
*nj»««- 1*S 109 f :_ ra3'= ^u
APPENDIX B
IDENTIFYING SPECTRAL INTERFERANTS
B.I General
B.l.l Assume a fixed absorption pathlength equal to the
value Ls'.
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.1.3 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^_) (AU^) , where DLj_ is the required
detection limit and AU^ is the maximum permissible analytical
uncertainty. For the nr-11 analytical region, calculate the band
area (AAIj_m) and average absorbance (AAVim) from these scaled
analyte spectra.
B.2.2 Prepare spectral representations of each potential
interferant at its expected concentration (CPOTj). For the mth
analytical region, calculate the band area (lAIjjJ and average
absorbance (IAVjm) 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., lAl^- > 0.5 AAIim for any pair ij and any m) ,
classify the potential interferant as known interferant. Label
the known interferants k - 1 to K. Record the results in matrix
form as indicated in Figure B.2.
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EPA PTIR PrOtOCOl Darre. 1 1
21
B.2.5 Calculate the average total absorbance (AVTm) for
each analytical region and record the values in the last row of
the matrix described in Figure B.2. Any analytical region where
AVTm >2.0 is unsuitable.
FIGURE B.I Presentation of Potential Interferant Calculations
Analytical Regions
1 .... M
Analyte Labels
. AAI1M
AAIZ1
Potential Interferant
Labels
! . . . IAI1M
IAIJ1 • • • IAIJM
FIGURE B.2 Presentation of Known Interferant Calculations
Analytical Regions
1 .... M
Analyte Labels
AAIIM
Known Interferant
Labels
IAI1M
IAIK1 .
Total Average
Absorbance AVT, AVTM
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3PA FTIR Protocol
ingint 14.
Page 22
APPENDIX C
ESTIMATING NOISE LEVELS
C.I General
C.I.I The root -mean -square (RMS) noise level is the
standard measure of noise in this Protocol. The RMS noise level
of a contiguous segment of a spectrum is defined as the RMS
difference (RMSD) between the absorbance values which form the
segment and the mean value of that segment (see Appendix A) .
C.I. 2 The RMS noise value in double -beam absorbance
spectra is assumed to be inversely proportional to: (a) the
square root of the signal integration period of the sample single
beam spectra from which it is formed, and (b) to the total
infrared power transmitted through the interferometer and
absorption cell.
C.I. 3 Practically, the assumption of C.I. 2 allow the RMS
noise level of a complete system to be estimated from the
following four quantities:
(a) RMSj^kjj - the noise level of the system (in absorbance
unitsT, without the absorption cell and transfer optics,
under those conditions necegsa_ry_.to yield the specified
minimum instrumental llnewidth . e.g., Jacquinot stop
size.
(b) tj^mjg - the manufacturer's signal integration time used
todet ermine RMSMAN.
(c) tss - the signal integration time for the analyses.
(d) TP - the manufacturer's estimate of the fraction of the
total infrared power transmitted by the absorption cell
and transfer optics from the interferometer to the
detector.
C.2 Calculations
C.2.1 Obtain the values of RMS
MAN'
-MAN'
and TP from the
manufacturers of the equipment, or determine the noise level by
direct measurements with the completely constructed system
proposed in Section 4.
C.2.2 Calculate the noise value of the system (RMSEST) as
follows:
RMS
BST
TP
\
(4)
"MAN
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EPA PTIR Protocol Paae 2 ^
iiiGPiat- 1*. THfi - , _ • _ *
APPENDIX D
ESTIMATING MINIMUM CONCENTRATION MEASUREMENT
UNCERTAINTIES (MALI and MIU)
D . 1 General
Estimate the minimum concentration measurement uncertainties
for the itn analyte (MAUj_) and jth interferant (MIU-j ) based on
the spectral data in the mtjl analytical region by comparing the
analyte band area in the analytical region (AAI^m) and estimating
or measuring the noise level of the system (RMSES^, or RMSSm) .
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 - KMSsm if
measured (Appendix G) , or set RMS = RMSEST if estimated (Appendix
C) .
D.2. 2 For each analyte associated with the analytical
region, calculate
(RMS) (DLi ) (AU, ) (5)
D.2. 3 If only the mth analytical region is used to
calculate the concentration of the itn analyte, set MAU.j_
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
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EPA PTIR Protocol
x-ii-ii.t- i a ,
Page 24
J
Ice to')
where the weight
is defined for each term in the sum as
p e [m' }
D.2.5 Repeat Sections D.2.1 through D.2.4 to calculate the
analogous values MIU-i for the interferants j = 1 to J. Replace
the value (AU^) (DL/1 in the above equations with CPOTj/20;
replace the value AAlim in the above equations with iAljm.
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EPA FTIR Protocol
IA. mos
APPENDIX S
DETERMINING FRACTIONAL REPRODUCIBILITY UNCERTAINTIES (FRU)
E.I General
To estimate the reproducibility of the apectroscopic 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} conaiat of N spectra, denoted by
S1j_, i-1, N. Similarly, the CTS spectra {R2} consist of N
spectra, denoted by S2i, i»l, N. Each Ski is the spectrum of a
single compound, where i denotes the compound and k denotes
the set {R)c} of which SJH is a member. Form the spectra S3
according to 83 ^ - ^2i"*li ^or eacl1 i- Form the spectra S4
according to S4^ - [S2j_+S1j_f/2 for each i.
E.2. 2 Each analytical region m is associated with a portion
of the CTS spectra Sji and S,^, for a particular 1, with lower
and upper wavenumber limits FFL-^ and FFUm, respectively.
E.2. 3 For each m and the associated i, calculate the band
area of S4^ in the wavenumber range PPU^ to FFL-j. Follow the
guidelines of Section B.I. 2 for this cand area calculation.
Denote the result by BAVm.
E.2. 4 For each m and the associated i, calculate the RMSD
of S3i 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
FM-, = SRMSm(FFUm-FFLm)/BAVm
E.2. 6 If only the mtn analytical region is used to
calculate the concentration of the itn analyte, set
E.2. 7 If a number p^ of analytical regions are used to
calculate the concentration of the ittl analyte, set FRU^ equal to
the weighted mean of the appropriate FM_ values calculated above.
Mathematically, if the set of analytical regions employed is
{m1 } , then
where the W are calculated as described in Appendix D.
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EPA FTIR Protocol
APPENDIX F
DETERMINING FRACTIONAL CALIBRATION UNCERTAINTIES (FCU)
F . 1 General
F.l.l The concentrations yielded by the computerized
analytical program applied to each single -compound reference
spectrum are defined as the indicated standard concentrations
(ISC's). The ISC values for a single compound spectrum should
ideally equal the accepted standard concentration (ASC) for one
analyte or interferant, and should ideally be zero for all other
compounds. Variations from these results are caused by errors in
the ASC values, variations from the Beer's law (or modified
Beer's law) model used to determine the concentrations, and noise
in the spectra. When the first two effects dominate, the
systematic nature of the errors is often apparent; take steps to
correct them.
F.I. 2 When the calibration error appears non- systematic,
apply the following method to estimate the fractional calibration
uncertainty (FCU) for each compound. The FCU is defined as the
mean fractional error between the ASC and the ISC for all
reference spectra with non- zero ASC for that compound. The FCU
for each compound shall be less than the required fractional
uncertainty specified in Section 4.1.
F.I. 3 The computerized analytical programs shall also be
required to yield acceptably low concentrations for compounds
with ISC=0 when applied to the reference spectra. The limits
chosen in this Protocol are that the ISC of each reference
spectrum for each analyte or interferant shall not exceed that
compound's minimum measurement uncertainty (MAU or MIU) .
F.2 Calculations
F.2.1 Apply each analytical program to each reference
spectrum. Prepare a similar table as that in Figure F.I to
present the ISC and ASC values for each analyte and interferant
in each reference spectrum. Maintain the order of reference file
names and compounds employed in preparing Figure F.I.
F.2. 2 For all reference spectra in Figure F.I, verify that
the absolute value of the ISC's are less than the compound's MAU
(for analytes) or MIU (for interferant s) .
F.2. 3 For each analyte reference spectrum, calculate the
quantity (ASC- ISC) /ASC. For each analyte, calculate the mean of
these values (the FCU-^ for the it]1 analyte) over all reference
spectra. Prepare a similar table as that in Figure F.2 to
present the FCUj_ and analytical uncertainty limit (AUj_) for each
analyte.
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EPA PTIR Protocol
Page 27
FIGURE F.l
Presentation of Accepted Standard Concentrations (ASC's)
and Indicated Standard Concentrations (ISC's)
Compound
Name
Reference
Spectrum
File Name
ASC
(ppm)
ISC(ppm)
Analytes Interferants
1-1
J=
]
= !„„. ;
E
J
FIGURE F.2
Presentation of Fractional Calibration Uncertainties (FCU's)
and Analytical Uncertainties (AU's)
Aaalyte
Name
FCU
! («>
AU
(*>
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EPA PTIR Protocol Paae 28
a.igf.jj. 11 j i«tgg _ 3
APPENDIX G
MEASURING NOISE LEVELS
G.1 General
The root-mean-square (RMS) noise level is the standard
measure of noise. The RMS noise level of a contiguous segment of
a spectrum is the RMSD between the absorbance values that form
the segment and the mean value of the segment (see Appendix A) .
G.2 Calculations
G.2.1 Evacuate the absorption cell or fill it with UPC
grade nitrogen at approximately one atmosphere total pressure.
G.2.2 Record two single beam spectra of signal integration
period tsg.
G.2.3 Form the double beam absorption spectrum from these
two single beam spectra, and calculate the noise level RMSSm in
the M analytical regions.
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EPA FTIR Protocol 0=,,^ -,n
iiigiiqt i*r isifi . __ . yage 29
APPENDIX E
DETERMINING SAMPLE ABSORPTION PATHLENGTH (LQ) AND
FRACTIONAL ANALYTICAL UNCERTAINTY (FAUJ
H.I General
Reference spectra recorded at absorption pathlength
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EPA PTIR Protocol
Iiig-I1«t- Id
Page 30
and
TA - -'
IAAV s -L, Asi
/T\/T\/P\
4.1*11 311*311
* Y" T T Ri
\T3ALRAPR;
(10)
The fractional analytical uncertainty is defined as
FAU =
NRMS,
IA
(11)
AV
-------
EPA FTIR Protocol
I*
APPENDIX I
DETERMINING FRACTIONAL MODEL UNCERTAINTIES (FMU)
I.I 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 RSAi) ,
select a reference spectrum SAj_ with indicated standard
concentration ISC^. Calculate the scaling factors
= TB Ls P3 j
Tg La PR ISC,
and form the spectra SAC^ by scaling each SA.j_ by the factor RAi.
1.2.2 For each interferant, select a reference spectrum SIk
with indicated standard concentration ISCk. Calculate the
scaling factors
_ — — -
" Ts LR PR ISCk
and form the spectra SlCk by scaling each SIk by the factor RI^.
1.2.3 'For each ' analytical region, determine by visual
inspection which of the spectra SA^ and SIC^ exhibit absorbance
bands within the analytical region. Subtract each spectrum
-------
EPA PTIR Protocol Paae 32
14, ^
and SICj^ exhibiting absorbance from the sample spectrum So to
form the spectrum SUBg. To save analysis time and to avoia the
introduction of unwanted noise into the subtracted spectrum, it
is recommended that the calculation be made (1) only for those
spectral data points within the analytical regions, and (2) for
each analytical region separately using the original spectrum Sg .
1.2.4 For each analytical region m, calculate the RMSD of
SUBg between the absorbance values and their mean in the region
FFUm to FFLjjj. Denote the result by RMSSm.
1.2.5 For each analyte i, calculate the quantity
FM - mma,
^ AAI
for each analytical region associated with the analyte.
1.2.6 If only the mtn analytical region is used to
calculate the concentration of the itn analyte, set FMU£=FMm.
1.2.7 If a number of analytical regions are used to
calculate the concentration of the ith analyte, set FM.^ equal to
the weighted mean of the appropriate FM_ values calculated above.
Mathematically, if the set of analytical regions employed is
{m' } , then
Wik FMk
where W is calculated as described in Appendix D.
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EPA PTIR Protocol Page 33
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, FCU,
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 OFUi = MAX{FRUj_, FCUj_, FAU.j_, FMU.j_} and
= MAX{RSAi*OPUi,
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EPA FTIR Protocol
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 game 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) decamp cts0305a.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 0305dres,0305dres.aif ,1
"Compose" transforms truncated interferograms back to spectral
format .
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EPA PTIR Protocol n , _
IA iggp _ . ge 5
(iii) IG2SP 0305drea.aif,0305dres.dsf,3,i,low cm"1, high caT1
"IG2SP" converts inter ferogram to a single beam spectrum
using Norton- Beer medium apodization, 3, and no zero filling, i.
De- resolved interferograma 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 inter ferogram in the same way.
(iv) DVDR 0305dres.dsffblcg0305a.dflf, 0305dres.dlf
"DVDR" ratios the transformed sample spectrum against the
background .
(v) ABSB 0305dres.dlf,0305drea.dl£
"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, 03 OSdres .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.I.
K.2.3 Grams™ Software Procedure - Grains™ is a software
package that displays and manipulates spectra from a variety of
instrument manufacturers. It^-3 procedure assumes familiarity
with basic functions of Grams™.
This procedure is specifically for using Grams to truncate
and transform reference interferograms that have been imported
into Grams from the KVB/Analect format. Table K-i 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.
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SPA PT1R Protocol Page 36
J
Desired Nominal Spectral
Resolution (cm"1)
0.25
O.SO
1.0
2.0
Data File Name
Z00250.sav
ZOOSOO.sav
Z01000 .aav
Z02000 .sav
Parameter "N"
Value
65537
32769
16385
8193
(i) Import using "File/Import" the desired *.aif file. Clear
all open data slots.
(ii) Open the resulting *.spc interferogram as file #1.
(iii) 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-#s(#0,#N)+50
(iv) Run ICOKPUTS.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
"IT":)
First: N Last: 0 Type: Single Beam
Zero Fill: Nona Apodization: (as desired)
Phasing; User
Points: 1024 Interpolation: Linear Phase :
Calculate
(v) As in step (iii), in the "Arithmetic/Calc" menu item
enter and then run the following commands (refer to Table 1 for
appropriate "PILE," which may be in a directory other than
"c:\mdgrama.")
setffp 7898.8805, 0 » loadspe «c:\mdgrams\ PILE" t #2»#s+#2
(vi) Use "Page Up" to activate file #2, and then use the
"Pile/Save As" menu item with an appropriate file name to save
the result.
K.3 Verification of New Resolution
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SPA PTIR Protocol Page 37
"
K.3.1 Obtain interferograms of reference sample and
background spectra. Truncate interferograms and convert to
abaorbance apectra 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 (a) of the
CTS band(s). Use the following equation to compare this RMSD to
the test CTS band area. The ratio in equation 7 must be no
greater than 5 percent (0.05).
RMSS, x n(FFUi -
RMSS=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.
FFUA &-The upper and lower limits (cm"1) , respectively, of the
analytical region.
Atest-CTS'band area in the ith analvt:ica:L region of the test CTS.
-------
TECHNICAL REPORT DATA
fPIeau read Inttmetions on the revtnt before compitttnf/
1. REPORT NO,
EPA-454/R-99-051
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
.ime Manufacturing Emission Test Report
ourier Transform Infrared Spectroscopy
(Chemical Lime
formerly Eastern
Ridge)
9. REPORT DATE
September 1999
8, PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
EMAD
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO, •
Midwest Research Institute
EPA Cont. # 68-D-98-027
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND P*KIOD COVERED
Final EmissionTest Report
14. SPONSORING AGENCY COOK
EPA/200/04
IS, SUPPLEMENTARY NOTES
16. ABSTRACT
The purpose of this project was to measure organic and inorganic hazardous air
Dollutants (HAPs) using a test method based on Fourier Transform Infrared Spectroscopy.
This report describes the test procedures and presents results of the testing at Eastern
3'idge Lime plant in Ripplemead, Virginia.
HACT Rule Support
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.tOENTIFIERS/OPEN ENDED TERMS C. COSATI
Mact Support for the
Lime Manufacturing
Industry
18. DISTRIBUTION STATEMENT
Release Unlimited
EPA Form 2220-1 (R«». 4-77) PREVIOUS EDITION is OBSOLETE
19. SECURITY CLASS iThtsReponi
20. SECURITY CLASS (Tins pagei
21. NO, Of
195
22. PRICE
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