United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park. NC27711
EPA - 454/R-00-008
March 2000
Air
&EPA
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Austin White Lime Company
Austin, Texas
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Lime Kiln Source Characterization
Final Report
Contract No. 68-D7-0001
Work Assignment 2-03
Austin White Lime Company
Austin, Texas
Prepared for:
Michael L. Toney
Emission Measurement Center
Emission, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
January 2000
U.S. Environmental Protection Agency
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Table of Contents
Page
1.0 INTRODUCTION 1-1
1.1 Objectives 1-1
1.2 Brief Site Discussion 1-2
1.3 Emissions Measurements Program 1-2
1.3.1 Test Matrix 1-2
1.3.2 Test Schedule 1-3
1.4 Test Report 1-4
2.0 SUMMARY OF RESULTS 2-1
2.1 Emissions Test Log 2-1
2.2 FTIR Results 2-2
2.2.1 Overview 2-2
2.2.2 FTIR Emission Results 2-3
3.0 SAMPLING AND ANALYTICAL PROCEDURE 3-1
3.1 Determination of Gaseous Organic HAPs, HC1, and Criteria Pollutants by Fourier
Transform Infrared Spectroscopy (FTIR) 3-1
3.1.1 FTIR Sampling Equipment 3-1
3.1.2 Preparation for Sampling 3-5
3.1.3 Sampling and Analysis 3-7
3.1.4 FTIR Method Data Review Procedures 3-10
3.1.5 FTIR QA/QC Procedures 3-13
4.0 QUALITY ASSURANCE/QUALITY CONTROL 4-1
4.1 FTIR Analytical Quality Control 4-1
Appendix A FTIR Data Spreadsheet Calculation QA/QC Sheets
Appendix B Gas Cylinder Certification Sheets
Appendix C Raw FTIR Data
Appendix D FTIR Field Data Sheets
Appendix E Pre-test Calculations
Appendix F Post-test Calculations
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List of Figures
Page
2-1. HC1 Inlet Run - Austin White Baghouse - Kiln #3 2-5
2-2. HC1 Outlet Run - Austin White Baghouse - Kiln #3 2-6
2-3. HC1 Inlet Run - Austin White Wet Scrubber - Kiln #2 2-7
2-4. HC1 Outlet Run - Austin White Wet Scrubber - Kiln #2 2-8
3-1. FTIR Sampling and Measurement System 3-3
List of Tables
Page
2-1. Emissions Test Log 2-1
2-2. Wet Scrubber Kiln #2, FTIR HC1 Results, ppmv 2-4
2-3. Baghouse Kiln #3, FTIR HC1 Results, ppmv 2-4
2-4 Other Species Detected by FTIR - Wet Scrubber - Kiln #2, Inlet 2-10
2-5. Other Species Detected by FTIR - Wet Scrubber - Kiln #2, Outlet 2-11
2-6. Other Species Detected by FTIR - Baghouse - Kiln #3, Inlet 2-12
2-7. Other Species Detected by FTIR - Baghouse - Kiln #3, Outlet 2-13
3-1. Typical FTIR Operating Parameters 3-6
3-2. Compounds for Which Reference FTIR Spectra Are Available in the ERG
Spectral Library 3-10
4-1. QC Spiking Results 4-3
4-2. Gas Standard Analysis Results 4-4
4-3. HC1 QA Spike Run 1 Results - Baghouse 4-5
4-4 HC1 QA Spike Run 2 Results - Baghouse 4-6
4-5 Gas Standard Analysis 4-7
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1.0 INTRODUCTION
The purpose of this testing program is to: (1) quantify hydrogen chloride (HC1) emission
levels; and (2) gather screening data on other hazardous air pollutants (HAP) emissions from
lime production plants to support a national emission standard for hazardous air pollutants
(NESHAP).
Three measurement methods were conducted at this facility:
• Fourier Transform Infrared Spectroscopy (FTIR) (EPA Draft Method 320);
Gas Filter Correlation - Infrared (GFC-IR) (EPA Method 322); and
• Dioxin/furan manual trains (EPA Method 23).
This report presents data from the FTIR measurements performed by Eastern Research Group.
The EPA Method 23, 25A, and 322 measurements were conducted by Pacific Environmental
Services, Inc. (PES), and Air Pollution Characterization and Control, Ltd. (APCC), under
subcontract to PES, respectively. Process data was collected by Research Triangle Institute, Inc.
(RTI), under contract to EPA. Please refer to the report prepared by PES for information and
results of the Method 23, 25A, and 322 testing. For this test, screening means a measurement to
determine approximate levels of species other than HO.
The lime kiln facility and sampling locations tested in this program are detailed in the
report prepared by PES.
1.1 Objectives
The objective of the FTIR testing of the lime facility was to quantify HCl and perform
screening of other HAPs detectable by FTIR, using EPA Draft Method 320.
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1.2 Brief Site Discussion
Testing was conducted at the Austin White Lime Company located in Austin, Texas.
Testing was performed on the inlet and outlet on Kiln #2 and #3, wet scrubber and a baghouse,
respectively. Detailed site information can be found in the report prepared by PES.
1.3 Emissions Measurements Program
This section provides an overview of the emissions measurement program conducted at
the Austin White Lime Company, located in Austin, Texas. Included in this section are
summaries of the test matrix, test schedule, and authorized deviations from the test plan.
Additional detail on these topics are provided in the sections that follow.
1.3.1 Test Matrix
The complete sampling and analytical matrix that was performed is presented in the
report prepared by PES. In this report, only FTIR-related test matrix will be provided. FTIR
spectroscopy was used, in accordance with EPA Draft Method 320, to quantify HCl and also, in
a screening capacity, to measure other HAPs that can be detected by FTIR.
FTER measurements were conducted in two sets:
• Unconditioned; and
• Conditioned.
Unconditioned sampling was conducted during the extent of the EPA Method 23 dioxin
manual train runs. These runs were approximately 3 hours in duration. After completion of a
dioxin run, the FTIR measured conditioned sample gas for a one-hour period to screen for
aromatic species such as benzene, toluene, etc.
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During each run (i.e., unconditioned or conditioned) the FTIR analysis time was divided
equally between inlet and outlet samples. Each location was monitored for no less than a total of
90 minutes. Some data points (typically, 5 minutes) were discarded for each set due to
inlet/outlet sample mixing in the FTIR analysis cell. The actual amount of data points discarded
is given later in this report. This procedure ensures the remaining data points were data truly
representing the location being tested in that set.
1.3.2 Test Schedule
The test schedule for EPA Methods 23, 25A, and 322 measurements is given by the
report prepared by PES. Section 2.1 gives the test log for the FTIR testing at this site.
7.3.3 Deviations from Test Plan/Schedule
Deviations from the original FTIR Site-Specific Test Plan (SSTP) are listed below:
Testing was originally planned for 15 minute intervals between the inlet and
outlet. The measurements consisted of collecting 20 at the outlet, then 30 minute
intervals alternating from the inlet and the outlet, in order to synchronize with the
GFC-IR measurements performed by APCC.
The EPA Work Assignment Manager authorized one hour total sample collection
of the conditioned samples, l/2 hour each on inlet and outlet. If detection of other
HAPs was determined, then the run would extend to the full 2 hours, as originally
planned. In this case, no additional HAPs were detected in the conditioned
samples.
Some indicated sampling system temperatures were below the 350°F target that
was stated in the test plan. These temperatures are the highest attainable with
these sampling system components. It was determined after completion of the test
program that the measured temperature of some of the sampling system
components was a sensitive function of thermocouple location. When test
thermocouples were inserted in the sample-wetted regions of the sampling system,
they indicated temperatures above 350°F in all cases.
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1.4 Test Report
This final report, presenting all data collected and the results of the analyses, has been
prepared in four sections, and an appendix as described below:
• Section I provides an introduction to the testing effort and includes a brief
description of the test site and an overview of the emissions measurements
program;
• Section 2 gives a summary of the test results for the FTIR results for HCl and
other detected species;
• Section 3 presents detailed descriptions of the sampling and analysis procedures;
and;
• Section 4 provides details of the QA/QC procedures used on this program and the
QC results.
A detailed description of the site, sampling locations, process and plant operation during the field
test is provided in the PES-prepared report. Copies of the field data sheets and FTIR
concentration data are contained in the appendices.
Six appendices are found in this report. They are organized as follows:
• Appendix A contains spreadsheet QA/QC review sheets;
• Appendix B contains QC gas cylinder certification sheets;
• Appendix C contains raw FTIR data;
• Appendix D contains FTIR field data sheets;
• Appendix E contains pre-test calculations; and
• Appendix F contains post-test calculations.
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2.0 SUMMARY OF RESULTS
This section provides the FTIR results of the emissions test program conducted at the
Austin White Lime Company in Austin, Texas from June 30 to July 1, 1998. Results for the
extractive FTIR test conducted for HC1 and screening for selected HAPs are provided in this
section. Other (non-HAP) species detected are also reported. Testing was performed at the inlet
and outlet of the wet scrubber from Kiln #2 and the Baghouse from Kiln #3.
2.1 Emissions Test Log
ERG performed extractive FTIR measurements for HCl and other HAPs. Table 2-1
presents the emissions test log that shows the test date, location, run number, test type and run
times for each method.
Table 2-1. Emissions Test Log
Date
6/30/98
6/30/98
6/30/98
7/0 1 /98
7/01/98
7/01/98
Location
Baghouse Kiln #3
(inlet/outlet)
Baghouse Kiln #3
(inlet/outlet)
Baghouse Kiln #3
(inlet/outlet)
Wet Scrubber Kiln #2
(inlet/outlet)
Wet Scrubber Kiln #2
(inlet/outlet)
Wet Scrubber Kiln #2
(inlet/outlet)
Run
Number
Spike 1
Run 1
Spike 2
Spike 1
Run 1
Spike 2
Test Type
FTIR HCl Spike (inlet)/
System QC (outlet)
FTIR (Unconditioned)
FTIR (Conditioned)
FTIR HCl Spike (inlet)/
System QC (outlet)
FTIR HCl Spike (inlet)/
System QC (outlet)
FTIR (Unconditioned)
FTIR (Conditioned)
FTIR HCl Spike (inlet)/
System QC (outlet)
Run Time
10:15- 11:56
12:45-16:22
17:36- 18:31
16:27- 17:21
11:51 - 13:57
14:15- 17:35
19:26-20:26
17:58- 19:04
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2.2 FTIR Results
2.2.1 Overview
FTER data for HCI and other species were collected at the inlet and outlet of the wet
scrubber and baghouse. FTIR data collection of unconditioned samples was synchronized with
EPA Method 23 manual dioxin/furan testing and EPA Method 322 GFC-ER HCI measurements.
Conditioned samples were measured by FTIR for other HAP species.
FTER data were collected by alternating sample analysis between inlet and outlet every
30 minutes for Kiln #2 and every 35 minutes for Kiln #3. Inlet and outlet samples were drawn
on a continuous basis; only the FTER sample analysis was alternated between inlet and outlet.
The first five data points from each 30 (Kiln #2) and 35 (Kiln #3) minute inlet/outlet
measurement period were discarded to eliminate data for samples containing both inlet and outlet
sample gas. Five data points correspond to the measured response time of the complete FTER
sampling and analysis system (details on measurement of system response time are given below).
The measurement run contained a total of 74 (Kiln #2) and 79 (Kiln #3) 1-minute average data
points for both inlet and outlet measurements, after discarding the transient data points. A
1-minute average data point is generated by analysis of a composite spectrum consisting of an
average of 43 FTER spectra collected over the 1 minute period.
Section 2.1 gives the schedule of the tests performed at the Austin White Lime Company
in Austin, Texas. Both unconditioned and conditioned samples were analyzed. Conditioned
samples were generated by passing the raw sample gas through a water vapor/carbon dioxide
scrubbing system (see Section 3.1.1 for details). Conditioned samples extracted from the wet
scrubber were measured after unconditioned sample extraction for the next hour. One minute
average data points were generated by analysis of the composite spectrum consisting of an
average of 43 FTER spectra collected over the 1-minute period. These results are reported in
Section 2.2.2.2.
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The west scrubber and baghouse removal efficiency for HC1 was measured from the
inlet/outlet data from each location and is reported in Section 2.2.2.1.
2.2.2 FTIR Emission Results
This section contains the FTIR HC1 test results for the wet scrubber and baghouse inlet
and outlet.
2.2.2.1 FTIR HCI Test Results. The estimated FTIR HCl detection limit for this
study was between 0.13 and 0.14 ppmv. Approximately half the FTIR instrument analysis time
was split equally between inlet and outlet. Results given below are organized by location. HCl
removal efficiency was also calculated for each run. Raw data is presented in Appendix C listing
each compounds run values every minute. All HCl emission runs were collected during the
unconditioned tests.
Wet Scrubber - Kiln #2, Outlet/Inlet HCl Results—Table 2-2 gives a summary of
the wet scrubber outlet/inlet FTIR HCl results. Appendix C provides 1-minute averages for all
target species. The measured HCl removal efficiency due to the baghouse was not statistically
significant, assuming that the sample gas composition to the inlet of the scrubber did not change
significantly during the outlet testing. Figures 2-1 and 2-2 show a real-time graph for the inlet
and outlet runs, respectively.
Baghouse - Kiln #3, Outlet/Inlet HCl Results—Table 2-3 gives a summary of the
Baghouse outlet/inlet FTIR HCl results. The measured HCl removal efficiency due to the
Baghouse was 71.0 percent, assuming that the sample gas composition to the inlet of the scrubber
did not change significantly during the outlet testing. Figures 2-3 and 2-4 show a real-time graph
for the inlet and outlet runs, respectively.
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Table 2-2. Wet Scrubber
Kiln #2, FTIR HCI Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Runl
7/01/98
14:15 - 17:35
Inlet
3.30
2.14
9.53
0.83
74
Outlet
5.19
4.23
17.07
0.90
89
NC
SD = Standard Deviation
NDP = Number of data points measured
RE = Removal Efficiency in percent: 100 X (Avg. inlet-Avg. outlet)/Avg. inlet
NC = Not Calculated due to the outlet being greater than the inlet value, however inlet and outlet
levels are statistically equivalent, due to the level of standard deviation.
Note: = Raw data presented in Appendix C.
Table 2-3. Baghouse
Kiln #3, FTIR HCI Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Run 1
6/30/98
12:45 - 16:22
Inlet
1.76
3.97
15.08
<0.15
80
Outlet
0.51
1.27
6.86
<0.15
110
71.0
SD = Standard Deviation
NDP = Number of data points measured
RE = Removal Efficiency in percent: 100 X (Avg. inlet-Avg. outlet)/Avg. inlet
Note = Raw data presented in Appendix C.
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12.00
Figure 2-1. HCI Inlet Run - Austin White Wet Scrubber - Kiln #2
10.00
8.00
6.00
4.00
I
o
o
O
2.00
0.00
Time
-------
Figure 2-2. HCI Outlet Run - Austin White Wet Scrubber - Kiln #2
18.00
16.00
0.00 r—i—i i i i i i i i i i i i i—i i i i i i i i i i—i i i i i i i i i i—i
Time
-------
Figure 2-3. HCI Inlet Run - Austin White Baghouse - Kiln #3
16.00
14.00
12.00
_ 10.00
g; 8.00
o
o
0 6.00
0.00 I i i i i i i i i i—i i i—i i i i i—i
Time
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Figure 2-4. HCI Outlet Run - Austin White Baghouse - Kiln #3
8.00
7.00
6.00
^ 5.00
•**
o
^ g. 4.00
oo o.
o
O
O
3.00
2.00
1.00
0.00
co co o> CM m oo
in m in o o o
i- - CM m
O T- T-
CO
Time
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2.2.2.2 Other Species Detected by FTIR. Other species were detected during the
unconditioned and conditioned FTIR test runs. Species in Table 2-4 thorugh 2-7 indicated with a
"U" were measured concurrently with HC1. Species in Table 2-4 through 2-7 indicated with a
"C" were measured during the conditioned sample test run. Results given below were are
organized by location.
Wet Scrubber - Kiln #2, Outlet/Inlet for Other Species Results—Table 2-4 and
2-5 gives the summary of the wet scrubber for the inlet and outlet FTIR results for other species
found during the standard Draft Method 320 extractive analysis, respectively.
Baghouse - Kiln #3, Outlet/Inlet for Other Species Results—Table 2-6 and 2-7
respectively gives the summary of the baghouse for the inlet and outlet FTIR results for other
species found during the standard Draft Method 320 extractive analysis.
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Table 2-4. Other Species Detected by FTIR - Wet Scrubber - Kiln #2, Inlet
(all values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C.H,
C
0.89
0.07
1.09
0.76
25
0.16
C2H4
C
2.68
0.12
2.85
2.27
25
0.11
C3HA
C
1.66
0.24
2.07
1.05
25
0.32
C02
u
13.3
1.65
16.0
11.7
89
0.057
NH,
U
2.17
2.22
7.04
<0.32
89
0.32
CO
U
131
5.79
141
119
89
0.66
NO
U
133
14.4
159
104
89
7.6
H2CO
U
2.03
0.13
2.39
1.66
89
0.10
C *
*~4
U
1.73
0.11
1.91
1.46
89
0.30
H2O
U
21.5
2.46
25.6
19.3
89
0.13
to
o
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points; the total number for the inlet was 7 5-minute intervals, not the standard 1-minute intervals used during the unconditioned sampling.
EDL - Estimated detection limit for spectral region used for analysis
Stcl. Dev. - Standard Deviation
Max. - Maximum
Min. = Minimum
Note: Raw data presented in Appendix C.
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Table 2-5. Other Species Detected by FTIR - Wet Scrubber - Kiln #2, Outlet
(All values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C6H6
C
0.44
0.09
0.63
0.31
25
0.16
C2H4
C
1.64
0.07
1.82
1.46
25
0.11
C3H6
C
0.94
0.22
1.43
0.56
25
0.32
CO2
u
12.4
1.31
14.3
11.0
89
0.085
CO
u
66.1
2.78
71.0
62.2
89
0.79
NO
U
125
15.7
152
95.3
89
7.2
NH3
U
0.59
1.05
4.72
<0.47
89
0.47
H2O
U
35.1
3.73
39.6
30.7
89
0.22
N>
U/C - Unconditioned (U) or Conditioned (C) Sample
NDP - Number of data points; the total number for the inlet was 7 5-minute intervals, not the standard 1-minute intervals used during
the unconditioned sampling.
EDL - Estimated detection limit for spectral region used for analysis
Std. Dev. = Standard Deviation
Max. = Maximum
Min. = Minimum
Note: Raw data presented in Appendix C.
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Table 2-6. Other Species Detected by FTIR - Baghouse - Kiln #3, Inlet
(All values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C.H4
C
0.77
0.07
0.94
0.65
20
0.14
C2H4
C
2.05
0.11
2.22
1.79
20
0.12
QH2
C
023
0.03
0.27
0.16
20
0.07
CO,
u
14.8
1.85
15.8
5.86
80
0.0657
NH3
U
7.40
5.28
13.4
<0.36
80
0.36
CO
U
<9.36
0.02
0.21
< 9.36
80
9.36
NO
U
243
66.6
400
114
80
2.52
H,CO
U
118
20.5
148
42.8
80
8.64
C 4
*-4
U
1.54
0.31
1.87
< 0.96
80
0.96
H2O
U
4.23
0.54
4.88
<2.06
80
2.06
to
U/C - Unconditioned (U) or Conditioned (C) Sample
C,+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hcxane equivalent)
NDP - Number of data points; the total number for the inlet was 7 5-minutc intervals, not the standard I-minute intervals used during the unconditioned sampling.
EDL - Estimated detection limit for spectral region used for analysis
Std. Dev. = Standard Deviation
Max. = Maximum
Min. = Minimum
Note: Raw data presented in Appendix C.
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Table 2-7. Other Species Detected by FTIR - Baghouse - Kiln #3, Outlet
All values are ppmv, except CO2 and H,O in percent
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C6H4
C
0.72
0.12
0.97
0.48
25
0.14
C2H4
C
1.69
0.28
2.04
1.08
25
0.12
C2H2
C
0.22
0.04
0.26
0.13
25
0.07
CO,
u
<0.59
0.13
0.64
<0.59
25
0.59
CO
u
<0.36
0.17
0.67
<0.36
25
0.36
NO
U
3.37
040
4.26
2.77
25
0.64
NH,
U
1.06
0.18
1.55
0.77
25
0.51
H2CO
U
148
1.86
16.1
5.48
110
0.0658
C *
*-4
U
<9.36
4.72
34.4
<9.36
no
9.36
H2O
U
218
97.4
468
52.6
110
2.52
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points; the total number for the inlet was 7 5-minute intervals, not the standard 1-minute intervals used during the unconditioned sampling.
EDL - Estimated detection limit for spectral region used lor analysis
Std. Dev. = Standard Deviation
Max. = Maximum
Min. = Minimum
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3.0 SAMPLING AND ANALYTICAL PROCEDURE
The sampling and analytical procedure used by ERG for the lime plant test program is
extractive FTIR spectroscopy, conducted in accordance with EPA Draft Method 320. In this
section, description of the FTIR method used is provided.
3.1 Determination of Gaseous Organic HAPs, HCI, and Criteria Pollutants by
Fourier Transform Infrared Spectroscopy (FTIR)
The extractive FTIR measurement method is based on continuous extraction of sample
gas from the stack, transporting the sample to the FTIR spectrometer and performing real-time
spectral measurement of the sample gas. The sample gas spectra are analyzed in real time for
target analytes, archived and possibly re-analyzed at a later date for other target analytes. This
section provides details on the FTIR sampling and measurement system.
3.1.1 FTIR Sampling Equipment
The FTIR measurement system meets the sampling and analysis requirements set forth in
EPA Draft Method 320, "Measurement of Vapor Phase Organic and Inorganic Emissions By
Extractive Fourier Transform Infrared Spectroscopy." This system has been used with complete
success with many source categories, and can also be adapted to switch quickly between two
sources (i.e., inlet and outlet) with a single FTIR spectrometer.
The sampling and measurement system consists of the following components:
• Heated probe;
• Heated filter;
• Heat-traced Teflon® sample line;
• Teflon® diaphragm, heated-head sample pump;
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• FTIR spectrometer;
• FTIR sample conditioning system; and
• QA/QC apparatus.
Figure 3-1 illustrates the extractive unconditioned FTIR sampling and measurement
system. In operation at a stationary source, the sample is continuously extracted from the stack
through the heated probe. Sample gas is then sent into a heated filter assembly that will remove
any paniculate matter from the sample stream to protect the remainder of the sampling and
analysis system. The probe liner and filter body consist of glass, and the filter element is
polytetrafluoroethylene (PTFE or Teflon®). In addition to providing an inert surface, the glass
filter holder allows the operator to observe the filter loading during sampling operations. The
probe and filter are contained in a heated box mounted on the stack and maintained at a
temperature of 177° C (350° F). A second probe/filter, heat-traced sample line, and heated head
pump used are not shown in Figure 3-1.
After passing through the filter assembly, a primary heat-traced PTFE sample line
transports the sample gas to the FTIR spectrometer maintained at approximately 177° C (350° F)
driven by a heated- head PTFE diaphragm sample pump maintained at approximately 204° C
(400° F). The sampling flow rate through the probe, filter, and sampling line is a nominal
20 standard liters per minute (LPM). Sample gas then enters an atmospheric pressure heated
PTFE distribution manifold where it is sent to the FTIR spectrometer via a slipstream flowing at
9 LPM. Other slipstreams can be sent to other instruments, if necessary. Excess sample gas not
used by instruments is vented to atmosphere.
A secondary heated-head PTFE diaphragm sample pump takes FTIR spectrometer sample
gas from the distribution manifold maintained at approximately 204° C (400° F) and directed
into the FTIR sample cell maintained at 185° C (365° F) for real-time analysis. The cell consists
of nickel-plated aluminum, with gold-plated glass substrate mirrors and potassium chloride
windows. Exhaust gas from the cell is vented to the atmosphere.
K \0091 -02\002W).i\WHrrEUM\WHTUME RPT
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Heat-traced line
Sample
Gas In
Spike or QA/QC Gas
-L
Vaporization
block
Main Sample Pump
QA/QC Gas Standard Manifold
Heat-traced line
(up to 100 feet)
QA/QC Gas Standards
Spiking Solution
OJ
Heated Flow Meter
Legend
Bold text and lines = Heated
Normal text and lines = Unheated
Sample Distribution Manifold
FTIR
Sample
Pump/
Flowmeter
I I \
To Other Instruments
FTIR Sample Cell
Excess sample to
atmosphere
Exhaust to atmosphere
Figure 3-1. FTIR Sampling and Measurement System
-------
Sample conditioning (when required) is achieved by passing raw sample gas through a
PermaPure® dryer and a series of impingers filled with sodium (or lithium) hydroxide pellets.
The PermaPure® drier selectively removes water vapor and the sodium hydroxide pellets remove
CO; and other acid gases. The sample conditioning apparatus is switched into the FTIR sample
path by a valving system. Lower detection limits for some compounds can be achieved with a
conditioned sample.
3.1.2 Preparation for Sampling
Before commencement of daily sampling operations, the following tasks were carried out:
• System leak check;
• Measurement of FTIR background spectrum;
• Instrumental QC; and
• Sampling and measurement system QC spike run.
Detailed descriptions of these tasks are described in the paragraphs below.
The heated sampling lines, probes, and a heated filter were positioned at the inlet and
outlet locations. All heated components were brought to operating temperature, and a leak check
of both inlet and outlet sampling systems were performed. The leak check was performed by
plugging the end of the probe and watching the main sample rotameter to observe the reading.
Positive leak check was confirmed when the rotameter reading was zero.
A background spectrum was measured using zero nitrogen through the cell. Next the QC
gases were measured. They agreed to within ±6 percent (±10 percent for HC1) of target value.
The QC gases used for this program include:
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Halocarbon 22 (H22), used to calibrate the pathlength. Halocarbon 22 is used for
its highly linear response due to the lack of sharp spectral features, and is an
extremely stable compound.
Carbon monoxide (CO) used for frequency calibration. Carbon monoxide is
directly injected into the sample cell to measure photometric accuracy, validity of
the non-linear correction algorithm and serve as a frequency (i.e., wavelength)
calibration. Acceptable limits for CO standard analysis are ±6 percent of certified
concentration;
Methane/nitric oxide/carbon dioxide mixture, used for overall system
performance check (calibration transfer standard) (acceptance limits are
±6 percent of the certified concentration); and
Hydrogen chloride standard, analyzed to verify the instrumental response of HC1,
a key target analyte (acceptance limits are ±10 percent of certified concentration).
The sampling and measurement system spike test was done to perform validation and
directly challenge the complete system and provide information on system accuracy and bias.
This test is conducted to satisfy the requirements set in EPA Draft Method 320 entitled
"Measurement of Vapor Phase Organic and Inorganic Emissions By Extractive Fourier
Transform Infrared Spectroscopy." Section B. 1 .C of Draft Method 320 gives a description of the
dynamic spiking apparatus.
The following FTIR spiking procedure was used:
• Measured native stack gas until system equilibrates - took two measurements (i.e.,
two, 1 minute samples);
• Started spike gas flow into sample stream, upstream of the heated filter;
• Let system equilibrate;
• Measured spiked sample stream for 2 minutes (i.e., two, 1 minute samples);
• Turned off spike gas flow;
• Let system equilibrate with native stack gas; and
K \009I-02\002\003\WHITELIM\WHTLIMERPT 3-5
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• Repeated cycle, two more times.
The above procedure produced six spiked/unspiked sample pairs. Spike recovery for six
spiked/unspiked sample pairs were computed from the procedure given in Section 8.6.2 of EPA
Draft Method 320. The recovery was between 70-130 percent and allowed the system to be
considered acceptable for testing.
3.1.3 Sampling and Analysis
FTIR unconditioned sampling was performed simultaneously with the manual testing.
The start and stop times of the manual methods were coordinated with the FTIR operator, so that
FTIR data files can be coordinated with manual method start and stop times. FTIR inlet/outlet
sampling was accomplished using two heated transfer lines, and a valving system to switch from
inlet to outlet and vice versa.
Table 3-1 gives typical FTIR operating conditions. These parameters provide detection
limits of 0.1-1 ppm for typical FTIR analytes, while providing adequate dynamic range
(nominally 1-1,000 ppm). Some of these parameters are sample matrix dependent.
Table 3-1. Typical FTIR Operating Parameters
Parameter
Spectral Range (cm'1)
Spectral Resolution (cm"1)
Optical Cell Pathlength (m)
Optical Cell Temperature (° C)
Sample Flow Rate (liters/minute)
Integration Time (minutes)
Value
400 - 4,000
0.5
3.4
185
9 (3.0 optical cell volumes/minute)
1 (Average of 43 spectra)
Sample flow rate was determined by the data averaging interval and FTIR spectrometer
sample cell volume. A minimum of three sample cell volumes of gas must flow through the
K WWI-02>002\00:i\WHITELIM\WHTUME RPT
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system to provide a representative sample during a single integration period. Typically, a
1 minute averaging period with a 3 liter volume sample cell gives a minimum flow rate of
9 LPM. Typically a flow rate of 20 standard LPM is used to accommodate the FTIR and other
instrumentation on-site, and to minimize sample residence time in the sampling system.
The temperature of all sampling system components were at a minimum of 177°C
(350 °F) to prevent condensation of water vapor or other analytes in the sampling system. Actual
sampling system operating temperatures were determined before the start of testing. The FTIR
sample cell temperature was maintained at 365° F (185° C) to minimize condensation of high-
boiling point analytes on the cell optics.
FTIR sample cell pressure was monitored in real-time to calculate analyte concentration
in parts-per-million. The cell was normally operated near atmospheric pressure with the cell
pressure continuously monitored.
Sampling probe location was determined by the requirements set in EPA Method 1 in
terms of duct diameters upstream and downstream of disturbances. Concurrent EPA Method 2
velocity measurements were not carried out at the same process stream location as the FTIR
sampling point to provide mass emission rate determination. The stack gas velocity and flow
rate were determined by the applicable manual test methods performed by PES. Velocity
information can be found from the report prepared by PES.
Sampling and analysis procedures are straightforward for a single-source measurement.
Once QA/QC procedures were completed at the beginning of the test day, the sample was
allowed to flow continuously through the FTIR spectrometer cell and the software was instructed
to start spectral data collection. The spectrometer collected one interferogram per second and
averaged a number of interferograms to form a time-integrated interferogram. The typical
averaging times range was approximately 1 minute. The interferogram was converted into a
spectrum and analyzed for the target analytes. After spectral analysis, the spectrum was stored
on the computer and later permanently archived. Spectral data collection was stopped after a
K:\009I-02\002\OCH\WH1TELIM\WHTLIME RPT 3-7
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predetermined time, corresponding to a "run." Typical runs were approximately 3 hours long,
giving approximately 180 1-minute average data points for each target analyte. The figure of
180 points were reduced by approximately 120 points due to elimination of data points per
switch between inlet/outlet samples and vice versa. At the end of the test day, the end-of-day
QA/QC procedures were conducted.
Before any testing was started at a given site, an initial "snapshot" of the stack gas was
taken with the FTER measurement and analysis system to determine the true sample matrix.
Because sample conditioning was required for certain analytes, the FTIR spectrometer analyzed
these compounds after the unconditioned analysis. The order used during this program is shown
in the table below.
Sampling
Conditions
Unconditioned
Conditioned
Sampling Time
Synchronized
with dioxin
sampling
1 hour (after
completion of
dioxin run)
Inlet
5 minute cell purge and 25
minute sample collection
2 minute cell purge and 28
minute sample collection
Outlet
5 minute cell purge and 15
or 25 minute sample
collection
2 minute cell purge and 28
minute sample collection
The sample being delivered to the FTIR cell alternated between the inlet and the outlet.
The switching valve, located just upstream of the common manifold, was manually activated
periodically to provide alternating inlet and outlet sample collections during each three-hour
period (the estimated dioxin run duration). This procedure resulted in a set of data points
collected for the inlet and outlet, respectively. Five data points per set are discarded to eliminate
analysis results with combined inlet and outlet samples.
FTIR method performance was gauged from the results of the QA/QC procedures given
in Section B5 of EPA Draft Method 320. Acceptable spiking tests met acceptance for accuracy
within ± 30 percent. The acceptable instrument diagnostic and system response checked
K «09l-02\002V003\WHrrELIM\WHTLIME RPT
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accuracy to be within ± 6 percent of target for all gas standards, and ± 10 percent for the HC1
standards. Acceptable system response check precision was 6 percent RSD.
Quantitative analysis was performed by a mathematical method called multi-variate least
squares (commonly known as Classical Least Squares or CLS). CLS constructs an optimized
linear combination (or 'fit') of the reference spectra to duplicate the sample spectrum, utilizing
the Beer-Lambert Law. The Beer-Lambert Law states that the absorbance of a particular spectral
feature due to a single analyte is proportional to its concentration. This relationship is the basis
of FTIR quantitative analysis. The coefficients of each compound in the linear fit yield the
concentration of that compound. If it is found that the quantitative analysis of a given compound
responds non-linearly to concentration, a calibration curve is developed by measuring a series of
reference spectra with differing optical depths (concentration times pathlength) and using them
in the linear fit. Low molecular weight species such as water vapor and carbon monoxide
require nonlinear correction, possibly even at levels as low as 100 ppm-meters (concentration
times pathlength). Analytes greater than 50-60 amu molecular weight usually does not require
nonlinear corrections. An experienced spectroscopist can determine whether nonlinear
corrections are necessary for an analyte in a given source testing scenario.
The ERG validated spectral database includes the compounds shown in Table 3-2. These
spectra were validated in the laboratory at a cell temperature of 185° C against certified gaseous
standards. Any compounds identified in the stack gas and not included in the ERG database can
be quantified if necessary after subsequent laboratory reference spectrum generation.
3.1.4 FTIR Method Data Review Procedures
The following procedure was conducted to review and validate the FTIR data.
K ro9!.02\002\00.1\WHITEL!M\WHTLIME RPT 3-9
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Table 3-2. Compounds for Which Reference FTIR Spectra Are
Available in the ERG Spectral Library"
1-butene
1,3-butadiene
2-methylpropane
2-propanol
2-methoxyethanol
2-methyl-2-propanol
2-methylbutane
4-vinylcyclohexane
acetaldehyde
acetic acid
acetone
acetylene
acrolein
ammonia
benzene
carbon monoxide
carbon dioxide
carbonyl sulfide
chlorobenzene
c/.s-2-butene
cyclohexane
cyclopentane
cyclopropane
ethane
ethylbenzene
ethylene
formaldehyde
hydrogen fluoride
hydrogen chloride
isobutylene
m-xylene
/rz-cresol
methane
methanol
methyl ethyl ketone
methylene chloride
n-butanol
/i-butane
n-pentane
nitric oxide
nitrogen dioxide
nitrous oxide
o-cresol
o-xylene
p-cresol
p-xylene
phenol
propane
propylene
styrene
sulfur dioxide
toluene
rrart.y-2-butene
water vapor
Spectra were collected at a cell temperature of 185° C.
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A. Post-test Data Review procedure (on-site)
1. Examine the concentration vs. time series plot for each compound of interest, and
identify regions with the following characteristics:
• sudden change in concentration;
• unrealistic concentration values;
• significant changes in 95 percent confidence intervals reported by
software; and
• sudden increase of noise in data.
2. Select representative spectra from the time periods indicated from Step 1.
3. Subtract from each representative spectrum chosen in Step 2 a spectrum taken
immediately prior in time to the indicated time region.
4. Manually quantitate (including any nonlinear corrections) for the species in
question and compare the result with the difference m software-computed
concentrations for respective spectra.
5. If concentration values in Step 4 do not agree to within 5 percent, determine
whether the difference is due to a recoverable or non-recoverable error.
6 (i). If the error is non-recoverable, the spectra in the indicated time region are
declared invalid.
7 (ii). If the error is recoverable, and time permits, determine possible source(s) of error
and attempt to correct. If time is critical, proceed with measurement. If
correction is achieved, conduct QA/QC checks before continuing.
8. Determine the peak-to-peak scatter or the root mean square (RMS) noise-
equivalent-absorbance (NEA) for the representative spectra.
9. If the NEA exceeds the limits required for acceptable detection limits, the spectra
in the time region are declared invalid (due to non-recoverable error).
10. Data found invalid are subject to re-measurement.
K.\DOT|.02V002\003\WHITEUM\WHTLIMERPT 3-1 1
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B. Final Data Review (off-site)
The procedures for final data review include those given above; however, if a non-
recoverable error was found during this phase, the data are considered invalid. In addition, the
following procedures are carried out by the spectroscopist to perform a final data validation:
1. If any recoverable data errors are detected from the procedure, determine the
cause and perform any necessary corrections.
2. For analytes that were not detected or detected at low levels:
• estimate detection limits from validated data;
• check for measurement bias.
3. Verify spreadsheet calculations by independent calculation (results in
Appendix A).
3.1.5 FTIR QA/QC Procedures
The FTIR QA/QC apparatus will be used to perform two functions:
• Dynamic analyte spiking; and
• Instrumental performance checks.
Dynamic analyte spiking was used for quality control/quality assurance of the complete
sampling and analysis system. Dynamic spiking is continuous spiking of the sample gas to
provide information on system response, sample matrix effects, and potential sampling system
biases. Spiking is accomplished by either:
• Direct introduction of a certified gas standard; or
• Volatilization of a spiking solution.
K \009l.02\002\003\WHrrEUMWHTLIME RPT
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Certified gas standards are preferred due to simplicity of use, but many target analytes
cannot be obtained as certified gas standards, and must be spiked using standards generated by
volatilized solutions.
Gaseous spiking is carried out by metering the spike gas into the sample stream at a
known rate. Spike levels are calculated from mass balance principles. When certified gas
standards are used, a dilution tracer, such as sulfur hexafluoride, is used to directly measure the
fraction of spike gas spiked into the sample. This technique can be used instead of mass balance
calculations.
FTIR method performance is gauged from the results of the QA/QC. Acceptable spiking
tests will meet Draft Method 320 criteria (i.e., accuracy of within ± 30 percent) or a statistical
equivalent when less than 12 spiked/unspiked pairs are collected. The EPA Draft Method 320
instructs the user to determine the percent spike recovery of three pairs of spiked/unspiked
samples. The EPA Draft Method 320 acceptance criterion is 70 to 130 percent recovery for the
three pa;.rs of samples. The acceptable instrument diagnostic and system response check
accuracy were within ± 6 percent of target (±10 percent for HC1 standards). Acceptable system
response check precision was 6 percent RSD.
K W}(»-02\00:\OOWVHITELIM\WHTLIME RPT
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4.0 QUALITY ASSURANCE/QUALITY CONTROL
Specific QA/QC procedures were strictly followed during this test program to ensure the
production of useful and valid data throughout the course of the project. A detailed presentation
of QC procedures for all sampling and analysis activities can be found in the Site Specific Test
Plan and Quality Assurance Project Plan for this project. This section reports all QC results so
that the data quality can be ascertained.
In summary, a high degree of data quality was maintained throughout the project. All
sampling system leak checks met the QC criteria as specified in Draft Method 320. Acceptable
spike recoveries and close agreement between duplicate analyses were shown for the sample
analyses. The data completeness was 100 percent, based on changes authorized by the Work
Assignment Manager.
4.1 FTIR Analytical Quality Control
Dynamic analyte spiking was used for quality control/quality assurance of the complete
sampling and analysis system. Dynamic spiking is continuous spiking of the sample gas to
provide information on system response, sample matrix effects, and potential sampling system
biases. Spiking was accomplished by direct introduction of a certified gas standard.
Gaseous spiking was carried out by metering the spike gas into the sample stream at a
known rate. A sulfur hexafluoride dilution tracer was used to directly measure the fraction of
spike gas spiked into the sample. The EPA Draft Method 320 limits the dilution of the sample
gas to 10 percent.
Before any testing was started at a given site, an initial "snapshot" of the stack gas is
taken with the FTER measurement and analysis system to determine the true sample matrix. If
any target analytes are present at significantly higher levels than expected, adjustments were
K «»1-02VX)2\00.1\WHITELIM\WHTLIME RPT 4- 1
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made to the cell pathlength and/or the spectral analysis regions used for quantitative analysis.
These adjustments minimized interferences due to unexpectedly high levels of detected analytes.
FTIR method performance is gauged from the results of the QA/QC. All spiking tests
met Draft Method 320 criteria. The acceptable instrument diagnostic and system response check
accuracy should be within ± 6 percent of target for all gas standards except HC1. The accuracy
for the HC1 standard should be within ±10 percent.
Analytical QC checks for the FTIR system consisted of the following:
• Dynamic spiking of HC1;
• Direct measurement of a HC1 gas standard;
• Direct measurement of a CO gas standard;
• Direct measurement of a methane (CH4), nitrous oxide (NO:), and carbon
dioxides (CO2) standard; and
• Pathlength calibration using halocarbon 22 (H22).
Dynamic spiking runs were conducted twice daily: before and after testing. Six spiked/unspiked
data points were collected. Statistical calculations consistent with EPA Method 301 were
performed on the data. Recovery of 70-130 percent was the acceptance criteria. Table 4-1
through 4-4 summarize the dynamic spiking results. All dynamic spiking tests met the above
acceptance criteria. In all runs, sample gas was diluted 10 percent or less.
Direct instrumental measurement of HC1, CO, H22, and a CH4, NO2 and CO2 mixture
was conducted before and after daily testing activities. Acceptance criteria are normally ±6
percent of target, using EPA protocol gases. However, since the HC1 standard was obtained at a
±5 percent analytical tolerance, the acceptance criteria was set at ±10 percent. FTIR NOX is
measured as NO + NO:. Examination of Table 4-5 shows that all QC checks met the above
criteria.
K \009I -OiWCmiWHITELIMWHTUME RPT
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Table 4-1. HCI QA Spike Run 1 Results - Wet Scrubber
Austin White Lime Company
Outlet
Spike Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
6.54
6.4 1
6.37
6.40
6.60
6.94
6.54
Spiked
(ppmv)
153.63
164.74
167.84
176.16
214.76
172.64
174.96
Corrected
Difference
(ppmv)
147.74
158.97
162.11
170.40
208.82
166.39
169.07
Spike
Level
(ppmv)
149.00
149.00
149.00
149.00
149.00
149.00
149.00
% Recovery
WMMi.
113.47
SF6
Cone.
(ppmv)
0.048
0.048
0.048
0.048
0.048
0.048
0.048
Dilution
Ratio
0.100
0.100
0.100
0.100
0.100
0.100
0.100
Inlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
64.44
58.23
53.16
48.44
54.97
71.11
58.39
Spiked
(ppmv)
180.38
183.70
185.71
188.18
229.33
164.38
188.61
Corrected
Difference
(ppmv)
121.42
130.42
137.07
143.86
179.03
99.31
135.18
Spike
Level
(ppmv)
126.65
126.65
126.65
126.65
126.65
126.65
126.65
%
Recovery
'WMKs
106.74
SF6
Cone.
(ppmv)
0.041
0.041
0.041
0.041
0.041
0.041
0.041
Dilution
Ratio
0.085
0.085
0.085
0.085
0.085
0.085
0.085
NOTE: The spike runs were conducted before and after the test runs, therefore the minimum and
maximum values listed here may be different than those listed in the test runs. Section 2. Sample gas
dilution was held to 10 percent or less in all runs. Percent recovery is defined in Draft Method 320.
(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv. respectively).
% Recovery = 100 x
Corrected Difference
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
K \0091-O:\002\00.1\WHITELIM\WHTL1ME RPT
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Table 4-2. HCI QA Spike Run 2 Results - Wet Scrubber
Austin White Lime Company
Spike Run
Number
1
2
3
4
5
6
Average
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
3.15
3.00
3.03
3.04
2.87
3.38
3.08
Lowest
Unspiked
Value (ppmv)
163.62
164.47
144.88
145.78
140.24
150.37
151.61
Spiked
(ppmv)
140.24
150.37
154.83
159.17
164.67
165.42
155.78
Spiked
(ppmv)
203.47
207.26
223.18
223.95
170.32
169.33
199.59
Outlet
Corrected
Difference
(ppmv)
137.41
147.67
152.10
156.43
162.09
162.38
153.01
Inlet
Corrected
Difference
(ppmv)
46.11
49.37
84.10
84.00
35.69
24.97
54.04
Spike
Level
(ppmv)
148.00
148.00
148.00
148.00
148.00
148.00
148.00
Spike
Level
(ppmv)
59.20
59.20
59.20
59.20
59.20
59.20
59.20
% Recovery
'9%^
WK^/
103.39
%
Recovery
W^&
91.28
SF6
Cone.
(ppmv)
0.209
0.209
0.209
0.209
0.209
0.209
0.209
SF6
Cone.
(ppmv)
0.084
0.084
0.084
0.084
0.084
0.084
0.084
Dilution
Ratio
0.100
0.100
0.100
0.100
0.100
0.100
0.100
Dilution
Ratio
0.040
0.040
0.040
0.040
0.040
0.040
0.040
NOTE: The spike runs were conducted before and after the test runs, therefore the minimum and
maximum values listed here may be different than those listed in the test runs. Section 2. Sample gas
dilution was held to 10 percent or less in all runs. Percent recovery is defined in Draft Method 320.
(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv, respectively).
Recovery = 100 x
Corrected Difference
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
K \Q09I-02\002\OO.WHITELIM\WHTLIME RPT
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Table 4-3. HCI QA Spike Run 1 Results - Baghouse
Austin White Lime Company
Outlet
Spike Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
6.53
6.56
6.32
5.88
5.55
5.27
6.02
Spiked
(ppmv)
35.90
39.89
42.64
43.45
45.12
45.70
42.12
Corrected
Difference
(ppmv)
29.75
33.72
36.69
37.92
39.90
40.74
36.45
Spike
Level
(ppmv)
30.41
30.41
30.41
30.41
30.41
30.41
30.41
% Recovery
WM9,.
119.86
SF6
Cone.
(ppmv)
0.300
0.340
0.350
0.360
0.370
0.370
0.348
Dilution
Ratio
0.059
0.059
0.059
0.059
0.059
0.059
0.059
Inlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
9.56
9.07
9.29
8.50
7.88
7.29
8.60
Spiked
(ppmv)
14.46
15.63
17.93
19.60
20.95
21.02
18.27
Corrected
Difference
(ppmv)
6.96
8.51
10.64
12.93
14.77
15.30
11.52
Spike
Level
(ppmv)
11.69
11.69
11.69
11.69
11.69
11.69
11.69
%
Recovery
'WM^/s
98.52
SF6
Cone.
(ppmv)
0.450
0.450
0.440
0.440
0.430
0.430
0.440
Dilution
Ratio
0.215
0.215
0.215
0.215
0.215
0.215
0.215
NOTE: The spike runs were conducted before and after the test runs, therefore the minimum and
maximum values listed here may be different than those listed in the test runs. Section 2. Sample gas
dilution was held to 10 percent or less in all runs. Percent recovery is defined in Draft Method 320.
(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv, respectively).
% Recovery = 100 x
Corrected Difference
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
-02<002\00.1\WHrrEUM\WHTUME RPT
4-5
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Table 4-4. HCI QA Spike Run 2 Results - Baghouse
Austin White Lime Company
Spike Run
Number
1
2
3
4
5
6
Average
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
4.24
4.27
4.23
4.39
4.03
4.73
4.32
Lowest
Unspiked
Value (ppmv)
17.50
18.79
19.81
20.59
21.24
21.12
19.84
Spiked
(ppmv)
17.34
17.97
18.06
18.25
18.31
18.59
18.09
Spiked
(ppmv)
40.32
43.54
45.06
46.50
46.98
48.13
45.09
Outlet
Corrected
Difference
(ppmv)
13.37
13.97
14.10
14.14
14.53
14.16
14.04
Inlet
Corrected
Difference
(ppmv)
24.58
26.64
27.24
27.98
27.87
29.13
27.24
Spike
Level
(ppmv)
15.94
15.94
15.94
15.94
15.94
15.94
15.94
Spike
Level
(ppmv)
25.40
25.40
25.40
25.40
25.40
25.40
25.40
% Recovery
WMX.
88.12
%
Recovery
WMS',
107.24
SF6
Cone.
(ppmv)
0.320
0.320
0.320
0.310
0.310
0.310
0.315
SF6
Cone.
(ppmv)
0.510
0.510
0.520
0.520
0.520
0.520
0.517
Dilution
Ratio
0.063
0.063
0.063
0.063
0.063
0.063
0.063
Dilution
Ratio
0.100
0.100
0.100
0.100
0.100
0.100
0.100
NOTE: The spike runs were conducted before and after the test runs, therefore the minimum and
maximum values listed here may be different than those listed in the test runs, Section 2. Sample gas
dilution was held to 10 percent or less in all runs. Percent recovery is defined in Draft Method 320.
(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv, respectively).
% Recovery = 100 x
Corrected Difference
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
K \0091-02\002\CXWWHrTELIM\WHTLIME RPT
4-6
-------
Table 4-5. Gas Standard Analysis Results
Date
6/30/98
6/30/98
7/01/98
7/01/98
Time
08:35 AM
06:36 PM
08:28 AM
08:33 PM
Compound
HC1
CO
CH4
NO
C02
H22
HC1
CO
CH4
NO
CO,
H22
HC1
CO
CH4
NO
CO:
HC1
CO
CH4
NO
CO,
H22
True
(ppm)*
253
102.3
491
503
4.99 %
253
102.3
491
503
4.99 %
253
102.3
491
503
4.99 %
3.40m
253
102.3
491
503
4.99 %
Result
(ppm)*
248.2
102.3
489.4
501.9
4.95 %
3.40m
245.4
102.4
491.2
503.2
4.97 %
3.38m
251.1
100.2
490.4
505.4
5.07 %
3.41 m
249.1
100.4
493.3
493.2
4.99 %
3.28m
%
Recovery
98.1
100
99.7
99.8
99.2
97.0
100.1
100
100
99.6
99.2
100.2
99.9
100.5
101.6
98.4
98.1
100.5
98.0
100
HC1 Gas Standard Accuracy: ±5 percent; Acceptance Criteria: ±10 percent of target.
CO Gas Standard Accuracy: ±1 percent; Acceptance Criteria: ±6 percent of target.
CH4 NO, and CO2 Gas Standard Accuracy; ±1 percent; Acceptance Criteria: ±6 percent of target.
* All compounds are recorded in ppm except for CO, in percent (%), and H22 in meters (m).
The Halocarbon 22 (H22) is used to calibrate the pathlength.
K \009l-02\002\001\WHrTELIM\WHTLIME RPT
4-7
-------
APPENDIX A
FTIR DATA SPREADSHEET CALCULATION
QA/QC SHEETS
K \0091-02V002V003WHITELIM\WHTLIME RPT
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
1. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
Facility Name:
DATE:
Source Location (INLET or OUTLET)
0/acr
TIME:
Run Description
Reviewer:
Date:
entnes match, referencesvafut
''---s^
e
1. Pollutants matches pollutants in both the
original and QA/QC data
I/
2. Times for Inlet/Outlet samples match.
3. Number of data points match.
4. Column statistics match (i.e., Average.
Standard Deviation, Maximum, Minimum)
5. Verily that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
^Check that calculations are cor
l/
2. No errors in the data macro
Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
• For each facility tested, the reviewer will have:
1. Excel QA/'QC workbook
2. Inlet and Outlet QA/QC information
Facilit Name:
DATE:
Source Location (INLET or OUTLET
ET) ,
TIME:
Run Description
Reviewer:
entries match references valu
jrSJir-*-- «*~- «-!*«'i •''•-.-i- -^i*1*-'
me following by comparing tficprm
1. Pollutants matches pollutants in both the
original and QA/QC data
I. Times for Inlet/Outlet samples match.
3. Number of data points match.
4. Column statistics match (i.e., Average,
Standard Deviation, Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
. QA/QC values are identical.
!. No mathematical errors
fo errors in the data macro
Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
I. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
Facilit Name:
UU*.
DATE:
Source Location (INLET or OUTLET!
'•amgf^g-ofttfT
TIME:
Run Description
M
Reviewer:
Date:
)A/QC entries match references valui
K>«^»^;i-.i---.->i^'V—-••-<• -•"--'.•"••'•%j*j»*v '•
: the following by comparing thepnnf
1. Pollutants matches pollutants in both the
original and QA/'QC data
2. Times for Inlet/Outlet samples match.
3. Number of data points match.
4. Column statistics match (i.e., Average.
Standard Deviation, Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
Check that calculations are co
!. No mathematical errors
2. No errors in the data macro
* Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
1. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
Facility Name:
DATE:
Source Location (INLET or OUTLET)
TIME:
Run Description
Reviewer:
Date:
A/QC entriesjnafch references values?
'' •- t'.vS'«v»iV'4
comparmg the.
1. Pollutants matches pollutants in both the
original and QA/QC data
t/
2. Times for Inlet/Outlet samples match.
v/
3. Number of data points match.
4. Column statistics match (i.e., Average.
Standard Deviation. Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
t. No mathematical errors
2. No errors in the data macro
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
1. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
Facility Name:
i ,/ *\
LAMK
DATE:
Source Location (INLET or OUTLET)
^^
TIME:
Run Description
Review
Date:
iecklist
£&QA/QC entries match, references values
^W*f«<^>«l->'ti?5^i'*'-i'-tJ"/-'< ••^'•"••i./'^-V'Wajn'i. i»-'
me iollowmg by comparing the prmtourof tne
I. Pollutants matches pollutants in both the
original and QA/QC data
2. Times for Inlet/Outlet samples match.
3. Number of data points match.
4. Column statistics match (i.e., Average.
Standard Deviation, Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
!. No mathematical errors
2. No errors in the data macro
Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
• For each facility tested, the reviewer will have:
I. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
FadlityName:
DATE:
Source Location (INLET or OUTLET)
TIME:
Reviwer:
Date:
1. Pollutants matches pollutants in both the
original and QA/QC data
J
2. Times for Inlet/Outlet samples match.
I/
3. Number of data points match.
4. Column statistics match (i.e., Average.
Standard Deviation, Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
._ QA/QC values are identical.
ChecK that calculations'are co
M'M.* » +^Jrt--\*M ~ '—-'• J^.* -^.-- -^.->—
i. No mathematical errors
2. No errors in the data macro
l\>^Mc is
-------
APPENDIX B
GAS CYLINDER CERTIFICATION SHEETS
K «09l-02\002\OOWVHITELiM\WHTL!ME RPT
-------
REC'O AUG 141998
SPECTRR GHSES
^^J 3434 Route 22 West • Branchburg, NJ 08876 USA Tel: (908) 252-9300 • (800) 932-0624 • Fax: (908) 252-0811
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville . NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 134942
ITEM*: 1
CERTIFICATION DATE: 8/10/98
P.O.#: 9101008011-R132
BLEND TYPE: CERTIFIED
CYLINDER # : 1689487Y
CYLINDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
COMPONENT
ANALYTICAL ACCURACY: + / - 5%
REQUESTED GAS
CONC
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluoride
50 0 ppm
2.00 ppm
54.3 ppm
2.01 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluoride is +/- 2%
ANALYST:
Tefd Neeme
DATE:
8/10/98
USA • United Kingdom • Germany • Japan
130 3003
-------
SPECTBfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-8551
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Momsville , NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER # : 126876
ITEM*: 1
CERTIFICATION DATE: 8/29/97
BLEND TYPE: CERTIFIED
CYLINDER # : 1852209Y
CYLINDER PRES: 2000 PSIG
P.OJ: 7904004005-R562
ANALYTICAL ACCURACY:
+/- 5 %
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONG
200 ppm
20.0 ppm
Balance
ANALYSIS
210 ppm
20.2 ppm
Balance
ANALYST:
Ted Neeme
DATE:
8/29/97
USA • United Kingdom • Germany • Japan
isa a a a s
-------
SPECTRfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-8551
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 128118
ITEM*: 1
CERTIFICATION DATE: 10/16/97
BLEND TYPE: CERTIFIED
CYLINDER # : 1757972Y
CYLINDER PRES: 2000 psig
P.O.*: 7904004005-R690
ANALYTICAL ACCURACY:
+/- 2%
COMPONENT
Hydrogen Chloride-
Sulfur Hexafluoride
REQUESTED GAS
CONC
200 ppm
20.0 ppm
ANALYSIS
220 ppm
20.0 ppm
Nitrogen
Balance
Balance
' Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
Ted Neeme
DATE:
10/16/97
USA • United Kingdom • Germany • Japan
-------
1^1998
SPECTRfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-855 •
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER*: 132874
ITEM*: 2
CERTIFICATION DATE: 5/11/98
BLEND TYPE: CERTIFIED
CYLINDER*: 1370597Y
CYLINDER PRES: 2000 psig
P.O.*: 9101008004-R986
ANALYTICAL ACCURACY:
/- 2%*
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONC
250 ppm
5.00 ppm
Balance
ANALYSIS
253 ppm
5.08 ppm
Balance
•Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
DATE:
5/11/98
Mike Deyle
USA • United Kingdom • Germany • Japan
ISO 9002
-------
SPECTRfl GflSES
3434 Route 22 West • Branchburg, NJ 08876 USA Tel: (908) 252-9300 • (800) 932-0624 • Fax: (908) 252-0811
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville , NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER # :
ITEM# :
CERTIFICATION DATE:
P.O.*:
BLEND TYPE:
134942
2
8/10/98
9101008011-R132
CERTIFIED
CYLINDER #: 1015632Y
CYLINDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
ANALYTICAL ACCURACY: + / - 5%
COMPONENT
REQUESTED GAS
CONC
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluoride
250 ppm
2.00 ppm
260 ppm
2.00 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluoride is +/- 2%
ANALYST:
DATE: 8/10/98
Ted Neeme
USA • United Kinnrlnm • ftarmanu • .lanan
-------
SPECTRfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-855<
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 132874
ITEMS: 1
CERTIFICATION DATE: 5/11/98
BLEND TYPE: CERTIFIED
CYLINDER #: 1757934Y
CYLINDER PRES: 2000 psig
P.OJ: 9101008004-R986
ANALYTICAL ACCURACY:
/- 2%*
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONC
500 ppm
5.00 ppm
Balance
ANALYSIS
516 ppm
5.09 ppm
Balance
* Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
DATE: 5/11/98
USA • United Kingdom • Germany • Japan
iso s o a a
-------
SPECTBfl GflSES
3434 Route 22 West • Branchburg, NJ 08876 USA Tel: (908) 252-9300 • (800) 932-0624 • Fax: (908) 252-0811
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Momsville , NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER # : 134942
ITEM*: 3
CERTIFICATION DATE: 8/10/98
P.OJ: 9101008011-R132
BLEND TYPE: CERTIFIED
CYLINDER # : 982153Y
CYLINDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
ANALYTICAL ACCURACY: + / - 5%
COMPONENT
REQUESTED GAS
CONC
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluonde
1,000 ppm
2.00 ppm
1,030 ppm
2.02 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluonde is +/- 2%
ANALYST:
H-
DATE:
8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
iso Baas
-------
SPECTRA GASES
277 Coit St. • Irvington, NJ 07111 USA Tel.: (201) 372-2060 • (800) 932-0624 • Fax: (201) 372-8551
Shipped From: 80 Industrial Drive • Alpha, N.J. 08865
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE #: G1
CUSTOMER:
SGI ORDER #
ITEM*:
P.O.*:
Eastern Research Group Inc.
126876
3
7904004005-R562
CERTIFICATION DATE: 8/26/97
EXPIRATION DATE: 8/26/2000
CYLINDER # :
CYLINDER PRES:
CGA OUTLET:
CC80890
2000 PSIG
350
CERTIFICATION HISTORY
COMPONENT
Carbon Monoxide
DATE OF
ASSAY
8/19/97
8/26/97
MEAN
CONCENTRATION
102.1 ppm
102.6 ppm
CERTIFIED
CONCENTRATION
102.3 ppm
ANALYTICAL
ACCURACY
+/- 1%
BALANCE
Nitrogen
REFERENCE STANDARDS
COMPONENT
Carbon Monoxide
SRM/NTRM#
SRM-1680b
CYLINDER*
CLM010013
CONCENTRATION
490.4 ppm
INSTRUMENTATION
COMPONENT
Carbon Monoxide
MAKE/MODEL
Honba-VIA-510
SERIAL *
570423011
DETECTOR
NDIR
CALIBRATION
DATE(S)
8/26/97
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 160 PSIG.
ANALYST:
-Pol
DATE:
8/26/97
TED NEEME
-------
SPECTRfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-8551
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER*: 128118
ITEM*: 2
CERTIFICATION DATE: 10/16/97
BLEND TYPE: CERTIFIED
CYLINDER #: CC82244
CYLINDER PRES: 2000 psig
P.O.*: 7904004005-R690
ANALYTICAL ACCURACY: +/- 2%
COMPONENT
Chlorodifluoromethane
REQUESTED GAS
CONG
40.0 ppm
ANALYSIS
40.3 ppm
Nitrogen
Balance
Balance
ANALYST:
Ted Neeme
DATE:
10/16/97
USA • United Kingdom • Germany • Japan
ISO 3002
-------
55
SPECTRA GASES
277 Coit St. • Irvington, NJ 07111 USA Tel.: (201) 372-2060 • (800) 932-0624 • Fax: (201) 372-8551
Shipped From: 80 Industrial Drive • Alpha, NJ. 08865
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE #: G1
CUSTOMER:
SGI ORDER #:
ITEM*:
P.O.*:
Eastern Research Group Inc.
126876
5
7904004005-R562
CYLINDER #: CC79878
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 660
CERTIFICATION DATE: 8/27/97
EXPIRATION DATE: 8/19/99
CERTIFICATION HISTORY
COMPONENT
Methane
Nitric Oxide
NOx
Carbon Dioxide
DATE OF
ASSAY
8/21/97
8/20/97
8/27/97
8/19/97
MEAN
CONCENTRATION
491 ppm
502.1 ppm
504.6 ppm
4.99 %
CERTIFIED
CONCENTRATION
491 ppm
503 ppm
503 ppm
4.99 %
ANALYTICAL
ACCURACY
+/- 1%
+/- 1%
Reference Value Only
+/-1%
BALANCE
Nitrogen
REFERENCE STANDARDS
COMPONENT
Methane
Nitric Oxide
Carbon Dioxide
SRM/NTRM*
SRM-2751
NTRM-81687
SRM-1674b
CYLINDER*
CAL013479
CC57165
CLM007273
CONCENTRATION
98.6 ppm
1009 ppm
6.98%
INSTRUMENTATION
COMPONENT
Methane
Nitric Oxide
Carbon Dioxide
MAKE/MODEL
H. Packard-6890
Nicolet-760
Horiba-VIA-510
SERIAL *
US00001434
ADM9600121
571417045
DETECTOR
GC - FID
FTIR
NDIR
CALIBRATION
DATE(S)
8/21/97
8/27/97
7/25/97
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
DATE:
TED NEEME
8/27/97
-------
APPENDIX C
RAW FTIR DATA
K \009I -02\00:\OOWVHITELIM\WHTUME RPT
-------
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Inlet
All data in ppmv wet basis 1
rule conditioned outlet/Intel kin 2
Description Austin White
Method line Sac Al cond |
Starting Dale/Time- Wed Jul 01 19 26.02 1998
Time
2001:57
20:0257
2003.56
200456
20.05.56
2006.57
20-07 57
2008.57
20-09 57
201057
201158
20.12 58
20-1358
20.14.58
20:15-59
201659
20:17:58
20:18:58
20.19.58
2020.58
20:21:58
2022:59
2023:59
20.24:59
20-25.58
Average
Standard deviation
Maximum value
Minimum value
C6H6
0.76
082
084
0.82
088
091
093
090
091
096
096
0.87
091
099
090
089
083
085
065
076
0.85
093
0.93
093
109
089
007
109
0.76
(«-)C6H6
033
032
041
043
045
052
053
059
0.56
055
055
062
058
0.59
0.59
058
057
056
0<1
0.63
061
0.66
0.68
071
0.78
0.56
Oil
0.78
0.32
C7H8
000
0.00
0.00
000
000
000
ooc
000
000
0.00
000
000
0.00
000
000
000
000
000
0.00
000
0.00
000
000
0.00
000
0.00
000
000
000
[+OC7H8
105
101
128
1.36
141
164
167
187
178
1 75
1 74
195
183
185
1.87
184
1.79
1.77
194
198
193
207
2.15
223
247
1 77
034
247
101
OXYL
0.00
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
o.oo
0.00
000
000
000
000
000
000
000
000
000
000
000
[»-)OXYL
067
OSS'
082
087
090
1.05
107
120
1.14
12
.11
25
17
.18
20
18
1.15
1 13
124
127
124
133
137
143
158
1 13
022
158
065
MXYL
000
000
000
000
000
000
000
000
000
000
000
0.00
000
000
000
000
000
000
0.00
0.00
000
000
0.00
000
000
000
000
000
000
[*-)MXYL
1 41
136
1 72
183
189
220
225
251
239
235
234
262
245
248
251
247
2.41
237
260
266
260
278
288
300
331
238
045
331
136
PXYL
198
184
211
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
024
066
211
000
[*-)PXYL
153
1 47
1 87
199
205
239"
I 244
273
259
255
254
285
266
270
273
269
262
258
282
290
282
303
313
3.26
360
258
050
360
1 47
STYR
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
ooo
000
000
000
- - --
Bt-)STYR
r 1 22
1 18
150
1 59
1 64
191
|_ 195
2 18
207
204
203
228
213
216
2 18
215
209
206
226
231
226
242
250
260
288
206
040
288
1 18
13BUT
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
018
018
0 18
000
034
000
000
028
000
000
005
010
034
000
(+-J13BU1
020
019
019
018
018
018
018
017
0 18
018
017
016
019
020
018
017
017
016
015
015
016
017
018
019
021
018
001
021
015
CO2
000
000
000
000
000
000
000
ooo
000
000
000
000
000
000
000
r 000
000
000
000
000
000
000
000
000
000
000
ooo"
1 000
000
(+-£02
059
057
072
076
079
092
094
1 05
1 00
098
097
109
102
104
1 05
1 03
101
099
108
1 11
1 08
1 16
120
125
138
099
0 19
1 38
057
H2O
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
(»-)H20
12696
12204
15498
16491
17012
19839
20244
22603
21477
211 51
21027
23612
22066
22363
22621
22249
21698
21374
233.95
23988
23378
25066
25963
26970
29809
21392
4098
298 09
12204
C2H4
227
249
253
261
262
256
272
271
271
275
271
265
278
271
274
278
265
273
272
264
268
2.69
282
269
277
268
012
285
227
(«-fC2H4
012
011
Oil
Oil
010
011
Oil
010
011
011
010
oto
Oil
012
010
010
010
009
009
009
010
010
010
011
012
010
001
012
009
C2H2
018
020
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
0.00
0.00
000
000
000
000
000
002
005
020
000
(+-E2H2
018
0.17
022
023
024
028
029
032
031
030
030
034
031
032
032
032
0.31
030
033
0.34
033
036
037
038
042
030
0.08
042
017
C3H6
1 54
105
1 73
1 41
1 74
1 51
131
1 57
1 55
1 70
153
165
1.75
1.75
1.78
164
1.68
1.88
1.29
174
197
2.07
2.02
200
191
1.66
0.24
207
105
[+-JC3H6
035
032
032
031
030
031
031
030
031
0.31
030
030
033
034
030
030
029
027
026
026
0.28
030
030
032
0.36
031
002
036
026
CH3OH
000
000
0.00
000
000
000
000
000
000
000
000
000
000
000
000
000
0.00
0.00
000
000
000
000
000
000
0.00
000
000
0.00
000
»CH3OK
014
013
013
012
012
012
012
012
012
012
012
012
0.13
013
012
012
012
0.11
010
010
011
0.12
012
0.13
014
0.12
001
0.14
oto
-------
Outlet
AH data m ppmv wet basts
Title- conditioned outlet/Mel kiln 2
Description. Austin White
Method title- Sec Al.cond
Starting Date/Time Wed Jul 01 19 26-02 199f
Time
193156
193256
193357
193455
193556
19-36-56
193756
193856
193957
19*055
19.41:56
19-42.56
19-.43.S6
1944.S6
19:4558
19-4657
19 47.57
19.48 57
19 49.57
19 50:57
19:51 57
1952.58
19.53.58
195457
19.55 57
Average
Standard deviation
Maximum value
Minimum value
C6H6
043
049
046
035
054
0.43
052
047
0.44
033
041
036
039
039
036
040
031
031
040
044
049
059
059
063
054
0.44
009
063
031
<«-)C6H6
Oil
013
012
012
015
012
013
015
021
017
0.17
019
017
0.19
018
018
0.15
010
011
013
0.14
0.17
021
0.25
026
016
0.04
026
010
C7H6
O.OC
000
000
000
000
000
000
000
0.00
0.00
0.00
000
000
0.00
0.00
0.00
000
0.00
000
000
000
000
000
0.00
000
000
000
000
0.00
(*-)C7H>
036
040
038
039
047
037
041
049
065
055
055
080
052
061
056
058
046
030
0.35
0.42
044
055
065
0.80
084
051
014
084
030
OXYL
000
000
000
000
0.00
000
000
000
000
000
000
000
0.00
000
000
000
000
000
000
0.00
000
000
000
000
000
000
000
000
000
(+-JOXYL
023
026
024
025
030
024
026
031
042
035
0.35
039
0.33
039
036
037
0.29
0.19
022
027
028
035
042
051
053
032
009
053
019
MXYL
000
000
ooo
000
000
000
000
000
000
000
0.00
0.00
000
000
000
000
0.00
000
000
000
000
000
000
000
000
000
000
0.00
0.00
[+JMXYL
048
054
051
052
064
050
055
065
088
073
074
081
0.70
082
076
077
062
0.41
047
057
060
074
087
108
1 12
068
018
1 12
041
PXYL
122
1 42
1 50
144
1 44
126
1 58
147
145
137
1.22
1 39
1 18
137
1 10
136
1 02
107
128
167
194
1 75
188
188
219
146
029
219
102
[+JPXYL
052
058
056
057
069
055
059
071
095
0.80
081
088
076
089
082
084
067
044
051
062
065
080
095
1 17
1.22
074
020
1 22
044
STYR
000
000
ooo
000
000
000
ooo
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
[tJSTYB
042
0.47
045
045
055
044
047
057
1,76
064
064
n'o
061
071
066
067
054
035
041
049
052
064
076
094
097
059
0 16
097
035
13BUT
000
000
000
000
000
000
000
000
000
000
000
0.00
000
000
000
000
000
000
000
000
ooo
000
000
000
000
000
000
000
000
(tJISBUT
0 18
6 18
019
019
019
020
018
019
0 19
019
019
018
018
018
018
019
016
016
017
018
018
019
019
020
020
018
001
020
016
CO2
' 000
000
1 42
1 51
351
000
000
^_ 329
579
425
481
498
529
528
625
574
312
000
000
000
000
000
000
000
000
221
244
625
000
(+-JC02
020
022
021
022
027
021
023
027
037
031
031
034
029
034
032
032
026
017
020
024
025
031
036
045
047
029
008
047
017
H2O
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
;+-|H2O
4329
4836
4617
4697
5732
4524
4916
5869
7879
6588
6673
7306
6298
7397
6822
6964
5563
3677
4239
5098
5368
6665
7869
9710
10096
61 49
1642
10096
3677
C2H4
146
163
1 54
163
1.58
165
1 55
1 61
162
166
1 73
180
160
182
161
164
163
160
174
162
1 72
166
171
168
159
164
007
182
1 46
>-)C2H«
010
010
Oil
011
Oil
012
Oil
011
011
Oil
Oil
Oil
Oil
Oil
011
Oil
009
0.09
010
0.11
Oil
O.tl
Ott
012
0.12
Oil
001
012
009
C2H2
0.19
017
017
019
0.13
016
017
018
016
0.15
0.18
01«
020
015
0.18
017
019
014
018
017
0.16
018
020
018
016
017
002
020
013
(t-)C2H2
006
007
007
007
OOB
006
007
008
Oil
009
0.10
0.10
009
Oil
010
010
008
005
006
0.07
008
009
Oil
0.14
014
009
002
0.14
0.05
C3H6
124
076
082
078
124
076
056
105
063
1.27
069
1.12
106
074
086
103
1 12
079
082
1.43
0.79
077
too
104
109
094
022
143
056
VJC3H6
031
030
032
032
033
034
031
033
033
033
0.32
031
031
031
031
0.32
027
027
030
031
031
032
033
034
035
032
0.02
0.35
027
CH3OH
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
0.00
000
000
000
V)CH3OH
012
012
013
013
013
013
012
013
013
0.13
013
0.12
0.12
012
012
013
Oil
011
0.12
012
012
013
0.13
013
0.14
0.12
001
0.14
0.11
-------
APPENDIX D
FTIR FIELD DATA SHEETS
K 'O»1-0:\002\OOWHITEUM\WHTLIME RPT
-------
Facility
Stack ID
KlU
FTIR Temperature Readout Sheet
Outlet Stack
\10
'3(7
3)
Inlet Probe
33?
77 ^
Outlet Probe
3V2
Inlet Filter
Outlet Filter
Inlet HT
3/2.
Outlet HT
Inlet Pump
266
7.70
10
Outlet Pump
516
3/2.
11
FTIR Pump
'7
Z??
12
Pump Box
\-L~l
/ze
/Z5"
I'M
13
Extra HT
14
FTIR Jumper
72?
120
77
7/7
15
Pump Jumper
'321
16
Hot Box
35" /
17
Hot Box
18
Extra HT
32.7
311
30?
7*2.
19
Electronics Box
9
9$
20
Al
-------
Facility
Stack ID
Date
Run Number
FTIR Temperature Readout Sheet
Channel
Description
\yx'\l'»
Ml 5
Inlet Stack
42.?
Outlet Stack
Inlet Probe
3*8
Outlet Probe
Inlet Filter
Outlet Filter
S2
3VV
Inlet HT
Outlet HT
7V
3V7
g~7*f
Inlet Pump
^77
27
•25^
2.11
10
Outlet Pump
33*
11
FTIR Pump
•Z7/
27
30*
12
Pump Box
/t
13
Extra HT
zee
2-1*2-
2.7?
27?
27V
277
17*7
14
FTIR Jumper
717
3/7
721
15
Pump Jumper
3*
12. V
lit
16
Hot Box
3^7
17
Hot Box
2,5"
18
Extra HT
1*7
19
20
Electronics Box
99
-------
Facility
Stack ID
Date
Run Number
FTIR Temperature Readout Sheet
Recorded By
Channel
Description
Inlet Stack
Outlet Stack
Inlet Probe
Outlet Probe
Inlet Filter
Outlet Filter
Inlet HT
Outlet HT
V}!
Inlet Pump
10
Outlet Pump
11
FTIR Pump
12
Pump Box
IX
13
Extra HT
14
FTIR Jumper
15
Pump Jumper
16
Hot Box
17
Hot Box
18
Extra HT
19
20
Electronics Box
-------
FTIR Temperature Readout Sheet
-------
APPENDIX E
PRE-TEST CALCULATIONS
K 'ttW|.02\00:\001\WHITELiM\WHTLIME RPT
-------
Below are the results of the Draft Method 320 pre-test calculations for this test program. The
calculations are organized by appendix as found in the FTIR Protocol. These calculations were
originally taken from the Secondary Aluminum HCI program from late 1997.
Appendix B
Potential Interferant Calculations:
These calculations determine potential spectral interferants for the analytes of interest (i.e., HCI).
The results for HCI are given in the table below. The analysis region for HCI is not given since it
is considered proprietary information.
TABLE 1. INTERFERANT CALCULATIONS
Analyte
Concentration Band area IAI/AAI Average absorbance
HCI (target)
0.1 ppmv
0.0005436
0.00000322
H,O (potential interferant)
20%
0.2213
407
0.00131
CO-, (potential interferant)
20%
0.000002
0.0036
H,CO (potential interferant)
1 ppmv
0.0002100
0.386
CH, (potential interferant)
0.0105
Note: Compounds in bold are known interferants. AVT is computed from target and known
interferants.
Known interferant criteria is IAI/AAI > 0.5
From the Table, two potential interferants are identified: H2O and CH4.
Appendix C
Noise Level
This calculation determines instrumental noise level in the spectral analysis region for HCI. For
a 1 minute integration time, the RMS noise is found to be 0.00022 (absorbance units) in the HCI
spectral analysis region by the procedure given in Appendix G.
Appendix D
Estimating Minimum Concentration Measurement Uncertainties (MAU)
The result for HCI is:
MAU (HCi) = 0.4 ppmv.
K \OWI-02\00:\(XHWHITEL!M\WHTLIME RPT
E-l
-------
This value is computed using the formula given in Appendix D. However, this value is derived
using band area calculations. The FTER spectral data in this field study are analyzed by classical
least squares (CLS), not band areas. CLS derived minimum measurement uncertainties for HC1
are on the order of 0.1-0.2 ppmv for this test program.
Appendix E
Determining Fractional Reproducibility Uncertainties (FRU1
This calculation estimates the uncertainty in analysis, using band areas, of two sequentially
measured CTS spectra collected immediately before and after the HC1 reference spectrum. The
calculation is performed in the analysis region used for HC1. The result is:
FRU(HC1 region) = 0.093.
The corresponding value using CLS is somewhat lower. For most analytes of interest, FRU
usually falls between 0.001 and 0.04 using CLS.
Appendix F
Determining Fractional Calibration Uncertainties (FCU)
This section determines the fractional calibration uncertainties when analyzing each reference
spectrum. These results will be applied to the compounds analyzed in the HC1 analysis region.
The table below gives the results.
TABLE 2. FCU DETERMINATION
Analyte
H,O
HC1
CH,
ASC (ppm)
113000
253
491
ISC (H2O)
115000
-22.5
-23.0
ISC (HC1)
0.000
254
0.000
ISC (CH4)
0.000
0.000
493
FCU
-1.7%
-0.4%
-0.2%
AU
-
30%
-
Appendix G
Measuring Noise Levels
The result of this calculation is given under the Appendix C heading.
K.\0091-02\002\001\WHITELIM\WHTLIME RFT
E-2
-------
Appendix H
Determining Sample Absorption Pathlength CLst and Fractional Analytical Uncertainty
Since the HCI reference spectrum used in this program were measured at the same pathlength to
be used during testing, these calculations are not required.
K \009I-0:\002V001\WHITELIM\WHTLIME RPT
E-3
-------
APPENDIX F
POST-TEST CALCULATIONS
K \009l.02\002\001\WHITELIM\WHTLIME RPT
-------
Below are the results of the Method 320 post-test calculations for this test program. The
calculations are organized by appendix as found in the FTDR Protocol. Since classical-least-
squares (CLS) is used for analysis, the CLS-equivalent calculations are used, since in some cases,
the FMU values using band-areas can differ as much as an order of magnitude compared to CLS-
derived results.
Appendix I
Determining Fractional Model Uncertain!
These calculations determine the fraction
HC1). The results for HC1 are given in th
outlet test. In order to achieve results that
equivalent of the calculation was perform
by the HC1 concentration.
TABLE 1. FMU CALCU
1 error in the analysis for the analytes of interest (i.e..
table below for 1 spectrum selected from the inlet and
are consistent with the CLS analysis approach, the CLS
. This is simply the reported analysis error divided
ATION FOR HCL -AUSTIN WHITE
Spectral File Name
RN010007.spa
RN010042.spa
RN010007.spa
RN010042.spa
Inlet/Outlet
Outlet (#3)
Inlet (#3)
Outlet (#2)
Inlet (#2)
irror (ppm)
0.23
0.17
0.16
0.15
Concentration (ppm)
17.1
9.53
6.86
4.78
FMU
0.013
0.018
0.023
0.031
Error is 95% confidence interval reported by CLS software.
Appendix J
Overall Concentration Uncertainty
The CLS equivalent of overall concentrat
software. The results for this test program
on uncertainty is simply the error reported by the CLS
are found in Table 1, above.
i ">•>,.» • >••/ . : . 1^'-. ... ,
f, . . .,.* ;• :
r%.; 1 .v*. v n<, •• - . - .*,
K \OOTI-02VX)2\001\WHrrELIM\WHTLIME RPT
F-l
-------
TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing)
1. REPORT NO. 2.
EPA- 454/R-00-008
4. TITLE AND SUBTITLE
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Austin White Lime Company, Austin Texas
7. AUTHOR®
EMAD
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, NC 2771 1
12. SPONSORING AGENCY NAME AND ADDRESS
Director
Office of Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
May 2000
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1 1 . CONTRACT/GRANT NO.
68-D7-0001
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The United States Environmental nrotectinn Apenr.v i«t invpRtioatina thp limp munnfartiirinff
industry source category to identify and quantify emissions of hazardous air pollutants (HAPs)
from rotary kilns. The primary objective of this test program was to obtain data on controlled and
uncontrolled emissions of hydrogen chloride (HCL) and gather screening data on other hazardous air
pollutants from lime production plants. EPA test Method 320 was used to collect the emission data.
KEY WORDS AND DOCUMENT ANALYSIS
! a. DESCRIPTORS
Hydrogen Chloride (HCL)
Hazardous Air Pollutants
18. DISTRIBUTION STATEMENT
. Release Unlimited
-« -•". *.*•••.' f •
b IDENTIFIERS/OPEN ENDED TERMS
Air Pollution control
Fabric Filter Baghouse
Wet Scrubber
19. SECURITY CLASS (Report)
Unclassified
20. SECURITY CLASS fPage)
Unclassified
c. COSATI Field/Group
21. NO. OF PAGES
120 t
22: PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
------- |