United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park. NC 27711
EPA - 454/R-00-007'
March 2000
Air
&EPA
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Martin Marietta Magnesia Specialties
Woodville, Ohio
Air
da**
Mr
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Lime Kiln Source Characterization
Final Report
Contract No. 68-D7-0001
Work Assignment 2-03
Martin Marietta Magnesia Specialties
Woodville, Ohio
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 Aienc,
Region 5, Library (PL-12J)
77 West Jackson Bpulevard, IZUi rio
Chicago.lt 60604-3590
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Table of Contents
Page
1.0 INTRODUCTION 1-1
1.1 Objectives 1-1
1.2 Brief Site Discussion -2
1.3 Emissions Measurements Program -2
1.3.1 Test Matrix -2
1.3.2 Test Schedule -3
1.3.3 Deviations from Test Plan/Schedule -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 3-4
3.1.3 Sampling and Analysis 3-6
3.1.4 FTIR Method Data Review Procedures 3-9
3.1.5 FTIR QA/QC Procedures 3-12
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. HCI Inlet Run - Kiln #1 2-4
2-2. HCI Outlet Run - Kiln #1 2-5
2-3. HCI Inlet Run - Kiln #2 2-7
2-4. HCI Outlet Run - 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. Kiln #1 ESP FnR~HCl Results, ppmv 2-6
2-3. Kiln #2 Baghouse FTIR HCI Results, ppmv 2-6
2-4. Other Species Detected by FTIR - Kiln #1 ESP Inlet 2-10
2-5 Other Species Detected by FTIR - Kiln #1 ESP Outlet 2-11
2-6. Other Species Detected by FTER - Kiln #2 Baghouse Inlet 2-12
2-7. Other Species Detected by FTIR - Kiln #2 Baghouse Outlet 2-13
2-8. Other Species Detected by FTIR - Pre-analysis Day, Kiln #2 Baghouse Outlet 2-14
2-9. Other Species Detected by FTIR - Pre-analysis Day, Kiln #2 Baghouse Inlet 2-15
3-1. Typical FTER Operating Parameters 3-6
3-2. Compounds for Which Reference FTER Spectra Are Available in the ERG Spectral
Library 3-10
4-1. HCI QA Spike Run 1 Results - Kiln #1 4-3
4-2. HCI QA Spike Run 2 Results - Kiln #1 4-4
4-3. HCI QA Spike Run 1 Results - Kiln #2 4-5
4-4. HCI QA Spike Run 2 Results - Kiln #2 4-6
4-5. Gas Standard Analysis Results 4-7
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1.0 INTRODUCTION
The purpose of this testing program is to: (I) quantify hydrogen chloride (HCl)
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 (FTIPO (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 HCl.
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 Martin Marietta Magnesia Specialties facility located in
Woodville, Ohio. Testing was performed on the inlet and outlet of two kilns: Kiln # I, which was
outfitted with an Electrostatic Precipitator (ESP), and Kiln #2, which utilizes a baghouse.
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 Martin Marietta Magnesia Specialties facility in Woodville, Ohio. Included in this section
are summaries of the test matrix, test schedule, and authorized deviations from the test plan.
Additional details on these topics is provided in the sections that follow.
1.3.1 Test Matrix
This report shows only the FTIR-related test matrix performed by Eastern Research
Group (ERG). 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. The complete sampling and analytical matrix that was performed is presented in the report
prepared by PES.
FTIR measurements were performed on both the unconditioned and conditioned source
matrix. Unconditioned sampling was conducted for the duration of the EPA Method 23 dioxin
manual train runs, approximately 3 hours. 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.
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 at least a total of
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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. The procedure of discarding the first 5 minutes of data ensures the
remaining data points were truly representative of 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 FTER testing at this site.
1.3.3 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. In order to synchronize FTIR data collection with the GFC-ER instrument,
the inlet/outlet sampling interval times were changed to 30 minutes on Kiln #1,
and 35 minutes at Kiln #2.
• The EPA Work Assignment Manager authorized 1 hour total sample collection of
the conditioned samples, Vz hour each on inlet and outlet. If other HAPs were
detected, 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 at Kiln #2.
• The Martin Marietta Magnesia Specialties company representative expressed
concern over FTIR testing of conditioned samples on Kiln #1. As a result, EPA
canceled the conditioned sampling run on Kiln #1.
• 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 FTIR 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 measurement
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 quality assurance/quality control (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 FTIR 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.
1-4
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2.0
SUMMARY OF RESULTS
This section provides a summary of the FTIR results for the emissions test program
conducted at the Martin Marietta Magnesia Specialties Lime Facility in Woodville, Ohio, from
August 26 to August 28, 1998. Results for the extractive FTIR test conducted for HC1 and
screening for selected HAPs are provided in this section. Other (non-HAP) species which were
detected are also reported. Testing was performed at the inlet and outlet of the Kiln #2 baghouse
and Kiln #1 ESP.
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
8/26/98
8/26/98
8/27/98
8/27/98
8/28/98
8/28/98
8/28/98
Location
Bahouse Kiln #2
(inlet/outlet)
Baghouse Kiln #2
(inlet/outlet)
Baghouse Kiln #2
(inlet/outlet)
Baghouse Kiln #2
(inlet/outlet)
ESP Kiln #l
• (inlet/outlet)
ESP Kiln #l
(inlet/outlet)
ESP Kiln #1
(inlet/outlet)
Run Number
Pre-Test
Spike 1
Run 1
Spike 2
Spike 1
Run 1
Spike 2
Test Type
Sample Matrix Check
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
8:55-20:10
20:10-20:45
10:25 - 15:05
16:08 - 17:08
14:49- 15:51
15:58 - 16:56
17:00-20:00
Sample not taken
19:54-20:58
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2-1
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2.2 FTIR Results
2.2. 1 Overview
FTIR data for HCl and other species in unconditional sample gas were collected at the
inlet and outlet of the kiln #1 ESP and the kiln #2 baghouse. FTIR data collection of
unconditioned samples was synchronized with EPA Method 23 manual dioxin/furan testing and
EPA Method 322 GFC-ER HCl measurements. Conditioned samples were measured by FTIR
for other HAP species. Raw data is presented in Appendix C listing each compound run values
every minute. All HCl emission runs were collected during the unconditoned tests.
FTIR data were collected by alternating sample analysis between inlet and outlet every
30 minutes for Kiln #1 and every 35 minutes for Kiln #2. Inlet and outlet samples were drawn
on a continuous basis; only the FTIR sample analysis was alternated between inlet and outlet.
The first five data points from each 30 (Kiln #1) and 35 (Kiln #2) 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 apparent response time of the complete FTIR
sampling and analysis system (details on measurement of system response time are given below).
The measurement run contained a total of 84 (Kiln #1) and 120 (Kiln #2) 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 FTIR spectra collected over the 1 minute time period.
Section 2.1 gives the schedule of the tests performed at the Martin Marietta Magnesia
Specialties facility. 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 Kiln #2
baghouse were measured for 1 hour upon completion of the unconditioned sample run. These
results are reported in Section 2.2.2.2. Conditioned samples were not extracted from the Kiln #1
ESP by request of the Martin Marietta Magnesia Specialties company representative.
7-7
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ESP 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 FT//? Emission Results
This section contains the FTIR HC1 test results for the Kiln #1 ESP and Kiln #2
baghouse inlet and outlet.
2.2.2.1 FTIR HCI Test Results The estimated FTIR HCl detection limit for the
sample matrices measured was in the range 0.12 to 0.28 pounds per million by volume (ppmv).
Approximately half of 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.
Kiln #1 ESP Outlet/Inlet HCl Results—Table 2-2 gives a summary of the Kiln #1
ESP outlet/inlet FTIR HCl results. The measured HCl removal efficiency due to the ESP was
28.0 percent. Figures 2-1 and 2-2 show graphs depicting concentration versus time for the inlet
and outlet runs, respectively.
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Figure 2-1. HCI Inlet Run - Martin Marietta Magnesia Specialties - Kiln #1
130.00
125.00 -
100.00
95.00
Time
-------
Figure 2-2. HCL Outlet Run - Martin Marietta Magnesia Specialties - Kiln #1
95.00
70.00
v v \
.
•O V \
>>- »>
Time
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Table 2-2. Kiln #1 ESP FTIR HCI Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Run 1
8/28/98
17:00 - 20:00
Inlet
117
4.61
125
107
84
Outlet
84.2
4.55
93.1
77.8
84
28.0
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.
Kiln #2 Baghouse Outlet/Inlet HCI Results—Table 2-3 gives the FTIR HCI results
for Kiln #2 baghouse inlet and outlet FTER HCI results. The measured HCI removal efficiency
due to the baghouse was 3.4 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 graphs
depicting concentration versus time for the inlet and outlet runs, respectively.
Table 2-3. Kiln #2 Baghouse FTIR HCI Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Run 1
8/27/98
10:25- 15:05
Inlet
61.1
3.91
68.7
55.6
120
Outlet
59.0
2.21
64.6
53.7
120
3.44
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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Figure 2-3. HCI Inlet Run - Martin Marietta Magnesia - Kiln #2
0)
80.00
70.00
60.00
50.00
40.00
u
o
0 30.00
20.00
10.00
0.00
r n r
^
\3 N-
Time
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Figure 2-4. HCI Outlet Run - Martin Marietta Magnesia - Kiln #2
70.00
60.00
50.00
u
3 40.00
oo .
c 30.00
o
o
20.00
10.00 -
0.00
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. These species were measured concurrently with
HC1. Results are given in Tables 2-4, 2-5, 2-6, and 2-7, organized by location. No additional
HAPs were detected in the conditioned runs.
It was determined during the Kiln #2 testing that the effluent composition during the
test had changed significantly from the pre-test sample matrix check conducted the prior day.
The pre-test sample matrix check is stated in Section 3.1.3 of the SSTP. Tables 2-8 and 2-9 give
the results for the pre-spike sample matrix check. It is clear from comparison of Table 2-8 with
Table 2-7 (outlet) and Table 2-9 with Table 2-6 (inlet) that there are significant changes in some
of the species, especially carbon monoxide (CO) and nitrogen oxide (NO). This possibly
indicates a change in combustion characteristics between the pre-test and the test times. An
unexpected HAP, carbonyl sulfide, was detected in the Kiln #2 runs. This compound is usually
detected at the levels of CO and SO2 measured in these tests due to the chemical equilibrium
which exists between CO, SO-,, and OCS.
2-9
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Table 2-4. Other Species Detected by FTIR - Kiln #1 ESP Inlet
(All values arc ppmv, except CO, and M,O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C02
U
1 5. 4
O.I 62
1 5.6
1 5.0
84
0.08
CO
U
1 327
65!
3050
1 52
84
0.37
NO
U
52!
37.3
57!
434
84
7.4
NO2
U
6.52
3.38
17.7
3.54
84
0.79
H2CO
U
0.42
0.08
0.58
0.27
84
0.23
CH4
U
3.74
0.93
5.63
<2.6
84
2.6
C +
t-4
U
0.68
0.04
0.76
0.59
84
O.I7
SO2
U
U92
92.3
1418
1 036
84
9.0
H2O
U
8.80
0.2 1 2
9.15
8.30
84
0.12
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points
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 2-5. Other Species Detected by FTIR - Kiln #1 ESP Outlet
(All values are ppmv, except CO, and H,O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO2
U
I4.7
0.0603
14.8
14.5
84
0.08
CO
U
1 370
466
2718
364
84
0.58
NO
U
500
27.0
536
435
84
6.9
NO2
U
7.20
0.98
10.7
4.69
84
0.84
H2CO
U
0.23
0.12
0.42
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Table 2-6. Other Species Detected by FTIR - Kiln #2 Baghouse Inlet
(All values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C02
U
10.2
0.281
10.6
9.74
120
0.055
CO
U
1994
1146
3918
46.3
120
0.23
NO
U
490
62.6
606
385
120
5.9
NO2
U
5.39
1.84
9.52
2.91
120
1.1
H2CO
U
0.31
0.08
0.52
0.15
120
0.11
COS
U
1.72
1.24
4.31
<0.09
120
0.09
CH4
U
4.60
1.56
7.47
<1.83
120
1.8
C +
*^4
U
0.48
0.08
0.64
0.33
120
0.12
S02
U
804
120
974
544
120
5.8
H2O
U
6.48
0.141
6.76
6.18
120
0.089
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points
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 - Kiln #2 Baghouse Outlet
(All values arc ppniv, except CO, and lf,O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO,
U
9.25
0.069
9.40
9.09
120
0.05 1
CO
U
2645
930
4641
467
120
0.56
N02
U
3.37
1.25
6.44
<6.02
120
6.02
NO
U
411
40.1
506
305
120
5.8
H2CO
U
0.29
0.08
0.5 1
<0.ll
120
0.11
COS
U
2.57
1.26
5.32
<0.18
120
0.18
CH4
U
5.30
0.99
7.50
2.67
120
1.8
C +
^•t
U
0.44
0.09
0.64
0.27
120
0.13
S02
U
808
90.9
986
563
120
5.4
H,
O
U
6.0
4
0.0
87
6.2
2
5.8
5
120
0.0
82
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points
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 2-8. Other Species Detected by FTIR - Pre-test Sample Matrix Check, Kiln #2 Baghouse Inlet
(All values are ppmv, except CO, and ]\,O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C02
U
8.15
0.140
8.39
7.96
28
0.050
CO
U
4670
762
5633
3545
28
24
NO
U
246
67.0
334
156
28
6.3
NO2
U
8.90
4.37
15.9
4.45
28
0.94
HCI
U
41.4
9.16
57.0
27.9
28
0.27
COS
U
6.35
1.77
9.15
3.94
28
0.36
CH4
U
2.95
2.02
4.65
<2.9
28
2.9
C +
^4
U
0.69
0.06
0.79
0.60
28
0.19
SO2
U
788
16.8
817
764
28
4.9
H2O
U
6.10
0.0667
6.23
5.94
28
0.081
U/C - Unconditioned (U) or Conditioned (C) Sample
C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points
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 2-9. Other Species Detected by FTIR - Pre-test Sample Matrix Check, Kiln #2 Baghouse Outlet
(All values are ppniv, except CO, and II ,O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO2
U
8.76
0.320
8.98
7.48
42
0.045
CO
U
5363
327
5842
4615
42
34
NO
U
225
34.8
295
154
42
6.1
NO2
U
1.04
3.20
15.7
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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 FTER 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 describes 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 FTER 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 which 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 are made 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 which is mounted on the stack and maintained at a
nominal 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, the sample gas is transported to the FTER
spectrometer by a primary heat-traced PTFE sample line 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.
FTIR spectrometer sample gas is taken from the distribution manifold by a secondary
heated-head PTFE diaphragm sample pump 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
is made of nickel-plated aluminum, with gold-plated glass substrate mirrors and potassium
chloride windows. Exhaust gas from the cell is vented to the atmosphere.
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Heat-traced line
Sample
Gas In
Spike or QA/QC Cas
Vaporization
block
QA/QC Gas Standard Manifold
Main Sample Pump
Heated Flow Meter
Legend
Bold text and lines = Heated
Normal lexl and lines - Unheatecl
Heat-traced line
( up to 100 feet)
FTIR
Sample
Pump/
Flowmeter^
QA/QC Gas Standards
Sample Distribution Manifold
To Otlicr Instruments
FTIR Sample Cell
Spiking Solution
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
carbon dioxide (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 provided 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 was 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 grade 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:
•3.4
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• Halocarbon 22 (H22), used to calibrate the pathlength. Halocarbon 22 has a
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 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 validate and directly
challenge the complete system and provide information on system accuracy and bias. This test is
conducted to satisfy the requirements of 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 FTER spiking procedures were 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
• Repeated cycle, two more times.
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The above procedure produced six spiked/unspiked sample pairs. Spike recovery for
six spiked/unspiked sample pairs was computed from the procedure given in Section 8.6.2 of
EPA Draft Method 320. The recovery was between 70-130 percent, so the system was
considered acceptable for testing.
3.1.3 Sampling and Analysis
Unconditioned FTIR 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'')
Spectral Resolution (cm"')
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
system to provide a representative sample during a single integration period. Typically, a
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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 was 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 ensure that condensation of high-
boiling analytes on the cell optics was minimized.
FTIR sample cell pressure was monitored in real-time in order 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 in 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 FTER 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 time 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 pre-
determined time, corresponding to a "run". Typical runs were approximately 3 hours long,
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giving a minimum of 180 1-minute averaged points for each target analyte. The figure of
180 points was reduced by 30 points due to elimination of 5 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 FTIR 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
Kiln#l - 5 minute cell
purge and 30 minute
sample collection
Kiln #2 - 5 minute cell
purge and 35 minutes
sample collection
For both Kiln #1 and Kiln
#2-2 minute cell purge
and 28 minute sample
collection
Outlet
Kiln #1-5 minute cell
purge and 30 minute
sample collection
Kiln #2 - 5 minute cell
purge and 35 minutes
sample collection
For both Kiln #1 and
Kiln #2 - 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 3-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.
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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
of within ± 30 percent. The acceptable instrument diagnostic and system response checked
accuracy to be within ± 6 percent of target for all gas standards, and ± 10 percent for the HC1
standards. Acceptable system response check for 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 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 non-
linear correction, possibly even at levels as low as 100 ppm-meters (concentration times
pathlength). Analytes greater than 50-60 amu molecular weight usually do not require non-linear
corrections. An experienced spectroscopist can determine whether non-linear 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 (365 °F) 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.
KA0091 -02\002\003\M ARTIN\MARTIN RPT ^ -9
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Table 3-2 . Compounds for Which Reference FTIR Spectra Are
Available in the ERG Spectral Library9
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
carbonvl sulfide
chlorobenzene
c/.y-2-butene
cyclohexane
cyclopentane
cyclopropane
ethane
ethylbenzene
ethylene
formaldehyde
hydrogen fluoride
hydrogen chloride
isobutylene
m-xylene
m-cresol
methane
methanol
methyl ethyl ketone
methylene chloride
rc-butanol
/i-butane
/i-pentane
nitric oxide
nitrogen dioxide
nitrous oxide
o-cresol
o-xylene
p-cresol
p-xylene
phenol
propane
propylene
styrene
sulfur dioxide
toluene
rra/z.y-2-butene
water vapor
J Spectra were collected at a cell temperature of 185° C (365 °F).
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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 in 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.
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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.
3-12
K\009l-0:\002\CX)3\MARTIN\MARTiNRPT J l ^
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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 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 3 pairs of
spiked/unspiked samples. The EPA Draft Method 320 acceptance criterion is 70 to 130 percent
recovery for the three pairs 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.
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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 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 is started at a given site, an initial "snapshot" of the stack gas is
taken with the FTIR measurement and analysis system to determine the true sample matrix. If
any target analytes are present at significantly higher levels than expected, adjustments are made
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to the cell pathlength and/or the spectral analysis regions used for quantitative analysis. These
adjustments minimize 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 CO2 standard;
and
• Pathlength calibration using 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 criterion. Tables 4-1
through 4-4 summarizes the dynamic spiking results. All dynamic spiking tests met the above
acceptance criterion. In all runs, sample gas was diluted 10 percent or less.
Direct instrumental measurement of HC1, CO, H22. and a CH4, NO: and CO; 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 criterion was set at ±10 percent. FTIR NO, is
measured as NO + NO2. Examination of Table 4-5 shows that all QC checks met the above
criteria.
4-2
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Table 4-1. HCI QA Spike Run 1 Results - Kiln 1 (ESP)
Martin Marietta Magnesia Specialities
Outlet
Spike
Run
Number
I
i
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
87.96
88.53
8943
90.54
90.01
90.77
89.54
Spiked
(ppmv)
119.83
120.05
119.75
117.67
118.33
115.85
118.58
Corrected
Difference
(ppmv)
37.51
37.18
36.09
32.84
33.95
30.75
34.72
Spike
Level
(ppmv)
33.10
33.00
33.27
32.59
32.30
32.24
32.75
%
Recovery
W%M^.
'ii^wM,
'"/^/Z/^/^
WiSfa
'wi^i^/,
W^Mt/
106.01
SF6
Cone.
(ppmv)
0.327
0.326
0.328
0.322
0.319
.0318
0.323
Dilution
Ratio
0.064
0.064
0.064
0.063
0.063
0.062
0.063
Inlet
Spike
Run
Number
1
t
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
98.01
98.29
96.57
98.79
100.10
101.31
98.84
Spiked
(ppmv)
129.62
130.55
131.09
131.26
133.26
132.85
131.44
Corrected
Difference
(ppmv)
38.53
39.18
41.25
39.41
40.26
3886
39.58
Spike
Level
(ppmv)
36.39
36.33
35.95
36.25
36.55
37.26
36.45
%
Recovery
^iiii
WM^s,
y^H^/.
108.57
SF6
Cone.
(ppmv)
0.359
0.358
0.355
0.358
0.361
0.368
0.360
Dilution
Ratio
0.071
0.070
0.070
0.070
0.071
0.072
0.071
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\003\MARTIN\MARTIN RPT
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Table 4-2. HCI QA Spike Run 2 Results - Kiln 1 (ESP)
Martin Marietta Magnesia Specialities
Outlet
Spike
Run
Number
I
•>
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
8080
82.29
81.99
83.53
82.13
81 06
81.97
Spiked
(ppmv)
124.45
120.96
119.92
120.73
119.86
118.99
120.82
Corrected
Difference
(ppmv)
50.99
45.46
44.77
44.19
44.52
44.65
45.77
Spike
Level
(ppmv)
46.92
42.63
43.07
43.20
42.64
42.81
43.54
%
Recovery
'W///M'/6
w//y/////////'/,-
WM^#/,
w^%^
y^0M^
105.11
SF6
Cone.
(ppmv)
0.463
0.421
0.425
0.426
0.421
0.422
0.430
Dilution
Ratio
0.091
0.083
0.083
0.084
0.083
0.083
0.084
Inlet
Spike
Run
Number
I
i
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
125.64
125.28
125.85
124.88
12546
125.43
125.42
Spiked
(ppmv)
158.37
158.95
157.29
157.45
155.88
159.44
157.90
Corrected
Difference
(ppmv)
43.76
44.45
42.31
43.39
41.16
45.60
43.45
Spike
Level
(ppmv)
45.26
44.40
44.58
44.72
44.19
47.66
45.14
%
Recovery
^^fPlf
'99%fc.
991$
y/////"Y//s/'/f/
96.26
SF6
Cone.
(ppmv)
0.447
0.438
0.440
0441
0436
0.470
0.445
Dilution
Ratio
0.088
0.086
0.086
0.087
0.086
0.092
0.087
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.NQ091-O:\003\001\MARTtN\MARTINRPT
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Table 4-3. HCI QA Spike Run 1 Results - Kiln 2
Martin Marietta Magnesia Specialities
Outlet
Spike
Run
Number
I
2
->
j
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
59.94
63.47
63.89
6353
62.93
61.25
62.50
Spiked
(ppmv)
97.26
96.98
9645
95.85
95.52
97.47
96.59
Corrected
Difference
(ppmv)
42.62
39.07
38.16
37.91
38.11
41 60
39.58
Spike
Level
(ppmv)
45.61
45.17
45.21
45.41
45.27
45.29
45.33
%
Recovery
iiiiii
HiHH
i^MMfr.
W%9%
W^M^
87.32
SF6
Cone.
(ppmv)
0.450
0.446
0.446
0.448
0.447
0.447
0.447
Dilution
Ratio
0.088
0.088
0.088
0.088
0.088
0.088
0.088
Inlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
51.12
51.79
5293
52.45
52.01
51.80
52.02
Spiked
(ppmv)
88.69
89.47
91.09
92.27
91.33
92.38
90.87
Corrected
Difference
(ppmv)
43.14
43.33
43.90
4548
4489
46.24
44.50
Spike
Level
(ppmv)
56.15
56.28
56.02
55.67
55.23
56.30
55.94
%
Recovery
W^M^/.
79.54
SF6
Cone.
(ppmv)
0.554
0.555
0.553
0.549
0.545
0.555
0.552
Dilution
Ratio
0.109
0.109
0.109
0.108
0.107
0.109
0.108
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 \(XWI-02\002\003VMARTIN\MART1N RPT
4-5
-------
Table 4-4. HCI QA Spike Run 2 Results - Kiln 2
Martin Marietta Magnesia Specialities
Outlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
63.86
64.10
6487
64.40
64.48
6469
64.40
Spiked
(ppmv)
110.141
111.903
111.867
110.757
109.533
110.316
110.75
Corrected
Difference
(ppmv)
52.52
54.03
53.28
52.51
51.16
51.79
52.55
Spike
Level
(ppmv)
50.39
50.11
4999
49.36
48.83
49.23
49.65
%
Recovery
W^MM
'w^i^/,
105.83
SF6
Cone.
(ppmv)
0.497
0.494
0.493
0.487
0.482
0.486
0.490
Dilution
Ratio
0.098
0.097
0.097
0.096
0.095
0.095
0.096
Inlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
5975
59.15
58.35
59.02
58.26
57.16
58.62
Spiked
(ppmv)
102.81
102.41
102.67
101.60
101.72
102.97
102.36
Corrected
Difference
(ppmv)
48.65
48.81
4978
4806
48.83
51.18
49.22
Spike
Level
(ppmv)
48.36
48.46
48.25
4795
47.54
48.56
48.19
%
Recovery
'fMM^
'ijj^jjfr,
W^^M
iiiilit
'^M^M.
102.14
SF6
Cone.
(ppmv)
0477
0.478
0.476
0.473
0.469
0.479
0.475
Dilution
Ratio
0.094
0.094
0.094
0.093
0.092
0.094
0.093
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.\(X)9I-02\002\003\MARTIN\MARTIN RPT
4-6
-------
Table 4-5. Gas Standard Analysis Results
Date
8/26/98
8/27/98
8/27/98
8/28/98
8/28/98
Time
9:08 PM
08:41 AM
5: 13PM
3:08 PM
9: 10PM
Compound
HC1
CO
CH4
NO
CO,
H22
HC1
CO
CH4
NO
C02
H22
HC1
CO
CH4
NO
CO:
H22
HC1
CO
CH4
NO
co:
H22
HC1
CO
CH4
NO
C0:
H22
True
(ppm)*
54.3
102.3
491
503
4.99 %
54.3
102.3
491
503
4.99 %
54.3
102.3
491
503
4.99 %
54.3
102.3
491
503
4.99 %
54.3
102.3
491
503
4.99 %
Result
(ppm)*
52.3
104.1
491.4
498.4
5.10%
3.40m
56.1
102.4
493.3
499.5
4.93 %
3.38m
55.5
102.3
490.7
499.4
4.84 %
3.42m
53.0
102.4
491.9
495.1
4.79 %
3.40m
58.2
101.4
493.5
493.4
4.90 %
3.43m
%
Recovery
96.3
101.8
100.1
99.1
102.2
103.3
100.1
100.5
99.3
98.8
102.2
100.0
99.9
99.3
97.0
97.6
102.4
100.2
98.4
96.0
107.2
99.1
100.5
98.1
98.2
Comments
FTIR quantitation
software did not
have non-linear
corrections
originally enabled
for CO:. 8/26/98
CO: result is
shown with
correction enabled.
HC1 Gas Standard Accuracy: ±5 percent; Acceptance Criterion: ±10 percent of target.
CO Gas Standard Accuracy: ±1 percent; Acceptance Criterion: ±6 percent of target.
CH4 NO; and CO: Gas Standard Accuracy: ±1 percent; Acceptance Criterion: ±6 percent of target.
* All compounds are recorded in ppm except for CO2 in percent (%) and H22 in meters (m). The H22 is
used to calibrate the pathlength.
KA009I-02\002\OW\MARTIN\MARTIN RPT
4-7
-------
APPENDIX A
FTIR DATA SPREADSHEET CALCULATION
QA/QC SHEETS
-------
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)
.
TI
Run Description
Review,
wmg. bycompanng-'the pnntout,q
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)
L/
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
I/
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:
DATE:
Source Location (INLET or OUTLET)
TIME:
Run Description
Reviewer:
fo.Q.
Date:
1. Pollutants matches pollutants in both the
original and QA'QC data
\J
2. Times for Inlet/Outlet samples match.
Number of data points match.
4. Column statistics match (i.e., Average,
Standard Deviation, Maximum, Minimum)
I/
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
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
Facilit Name:
Source Location (INLET or OUTLET)
Run Description
Reviewer:
te:
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.
that'calculations ar& correctii
1. 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
Facie:
DATE:
Source Location (INLET or OUTLET)
Run Description
Reviewer:
entnes,ma
-.-j^c^v^^»,
following By companng-t&e
1. Pollutants matches pollutants in both the
original and QA/QC data
LX
2. Times for Inlet/Outlet samples match.
3. Number of data points match.
T7
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.
1. 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
DATE:
Source Location (INLET or OUJLET)
Run Description
Reviewer:
&
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.
\J
. No mathematica 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
FaciU. Nao-e:
DATE:
Source Location (INLET or OUTLET)
nn-w
TI
Run Description
Reviewer:
references^
^foliovfmg bjTcJ>mparmg tfagprmfiy
1. Pollutants matches pollutants in both the
original and QA/QC data
V//
2. Times for Inlet/Outlet samples match.
l/Z
3. Number of data points match.
4. Column statistics match (i.e.. Average,
Standard Deviation. Maximum, Minimum)
I//
5. Verify that the QAQC value is zero. This
indicated that both the original and the
QA/QC values are identical.
2. No errors in the data macro
-------
APPENDIX B
GAS CYLINDER CERTIFICATION SHEETS
-------
REC'O AUG 141998
SPECTBfl GflSES
^^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
Momsville , NO 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER # :
ITEM#:
CERTIFICATION DATE:
P.O.* :
BLEND TYPE:
134942
1
8/10/98
9101008011-R132
CERTIFIED
CYLINDER # : 1689487Y
CYLINDER PRES: 2000 ps.g
CYLINDER VALVE: CGA 330
ANALYTICAL ACCURACY: + / - 5%
COMPONENT
REQUESTED GAS
CONG
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluonde
50 0 ppm
2 00 ppm
54.3 ppm
2.01 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluonde is +/- 2%
ANALYST:
A.
DATE:
8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
130 s a o 2
-------
5PECTRH 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.O.*: 7904004005-R562
ANALYTICAL ACCURACY: +/- 5 %
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONC
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
iso s a o a
-------
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:
COMPONENT
Hydrogen Chloride"
Sulfur Hexafluoride
REQUESTED GAS
CONG
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
ISO 3 O O 2
-------
SPECTBfl GflSES
ECU M2Y 1 5 1998
^^M 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
Momsville , 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
USA • United Kingdom • Germany • Japan
ISO 3 O O 2
-------
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
910100801 1-R132
CERTIFIED
CYLINDER # : 1015632Y
CYLJNDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
ANALYTICAL ACCURACY; + / - 5%
COMPONENT
REQUESTED GAS
CONC
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluonde
250 ppm
2 00 ppm
260 ppm
2.00 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluonde is +/- 2%
ANALYST:
DATE: 8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
-------
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*: 1
CERTIFICATION DATE: 5/11/98
BLEND TYPE: CERTIFIED
CYLINDER #: 1757934Y
CYLINDER PRES: 2000 psig
P.O.#: 9101008004-R986
ANALYTICAL ACCURACY:
/- 2%*
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONG
500 ppm
5.00 ppm
Balance
ANALYSIS
516 ppm
5.09 ppm
Balance
* Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
Milje-boyie
DATE: 5/11/98
USA • United Kingdom • Germany • Japan
-------
55
SPECTRfl ERSES
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*: 3
CERTIFICATION DATE: 8/10/98
P.O.#: 9101008011-R132
BLEND TYPE: CERTIFIED
CYLINDER*: 982153Y
CYLINDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
COMPONENT
ANALYTICAL ACCURACY: + / - 5%
REQUESTED GAS
CONC
ANALYSIS
Hydrogen Chloride
Sulfur Hexafluoride
1,000 ppm
2.00 ppm
1,030 ppm
2.02 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluoride is +/- 2%
ANALYST:
Ted Neeme
DATE: 8/10/98
USA • United Kingdom • Germany • Japan
-------
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.OJ:
Eastern Research Group Inc.
126876
3
7904004005-R562
CYLINDER # : CC80890
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 8/26/97
EXPIRATION DATE: 8/26/2000
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
Horiba-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 CYUNDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
DATE:
TED NEEME
8/26/97
-------
SPECTRR GRSES
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 # : 126876
ITEM*: 2
CERTIFICATION DATE: 8/29/97
BLEND TYPE: CERTIFIED
CYLINDER # : CC80877
CYLINDER PRES: 2000 PSIG
P.O.#: 7904004005-R562
ANALYTICAL ACCURACY: +/- 2 %
COMPONENT
Halocarbon 22
Nitrogen
REQUESTED GAS
CONG
40.0 ppm
Balance
ANALYSIS
40.3 ppm
Balance
ANALYST:
Ted Neeme
DATE:
8/29/97
USA • United Kingdom • Germany • Japan
-------
SPECTRA GASES
'pl
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
CERTIFICATION DATE: 8/27/97
EXPIRATION DATE: 8/19/99
CYLINDER #: CC79878
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 660
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
Nrtnc 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
-------
1111
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IS S 2 2552 32,Si— 33™ 3 S 5li £ JS — SSbiK!uui3iu2S5r35,S«2lmoI2 S*S2r— ^
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APPENDIX D
FTIR FIELD DATA SHEETS
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FTIR Temperature Readout Sheet
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Facility
Stack ID
Date
Run Number
FTIR Temperature Readout Sheet
Outlel Filter
5^1
3-n
3-n
Inlet HT
2bl
2SS
Z5Z
Outlet HT
ZSM
211
21 I
Inlet Pump
257.
"2-13
b|
2 M Co
Z52
2C.O
10
Outlet Pump
i'So
Z1S
21 Z
11
FTIR Pump
'ioo
5o^
Uo
'3\3
12
13
Pump Box
\o-J-
\07-
\ O (J
14
FTIR Jumper
3H3
"5M3
15
Pump Jumper
•ioc
3 GO
'600
So
16
Hot Box
Sue
359
17
Hot Box
33T
534
33T-
331-
331-
,33 T
18
SJM
295
21
213
"2.T-0
19
Electronics Box
SCr.
b^
20
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APPENDIX E
PRE-TEST CALCULATIONS
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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
0.0013
CO2 (potential interferant)
20%
0.000002
0.0036
H2CO (potential interferant)
pprm
0.0002100
0.386
CH, (potential interferant)
20 ppmv
0.0105
19.3
0.00006213
AVT
0.00137
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: H:O 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
E-l
-------
Estimating Minimum Concentration Measurement Uncertainties (MALT)
The result for HC1 is:
MAU (HC1) = 0.4 ppmv.
This value is computed using the formula given in Appendix D. However, this value is derived
using band area calculations. The FTIR 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 (FRU)
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.
E-2
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TABLE 2. FCU DETERMINATION
Analyte
H,O
HCI
CH,
ASC (ppm)
113000
253
491
ISC (H20)
115000
-22.5
• -23.0
ISC (HCI)
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.
Appendix H
Determining Sample Absorption Pathlength CLs) 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.
E-3
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APPENDIX F
POST-TEST CALCULATIONS
-------
Below are the results of the Draft Method 320 post-test calculations for this test program. The
calculations are organized by appendix as found in the FTIR 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 Uncertainties:
These calculations determine the fractional error in the analysis for the analytes of interest (i.e.,
HC1). The results for HC1 are given in the table below for 1 spectrum selected from the inlet and
outlet test. In order to achieve results that are consistent with the CLS analysis approach, the CLS
equivalent of the calculation was performed. This is simply the reported analysis error divided
by the HC1 concentration.
TABLE 1. FMU CALCULATION FOR HCL
MARTIN-MARIETTA MAGNESIA SPECIALTIES
Spectral File Name
RN010006.spa
RN010042.spa
RNO 10005. spa
RN010035.spa
Inlet/Outlet
Outlet (#2)
Inlet (#2)
Outlet (#1)
Inlet (#1)
Error (ppm)
0.13
0.15
0.22
0.27
Concentration (ppm)
55.31
62.09
93.14
109.47
FMU
0.002
0.002
0.002
0.002
Error is 95rr confidence mien a] reported by CLS software
Appendix J
Overall Concentration Uncertainty
The CLS equivalent of overall concentration uncertainty is simply the error reported by the CLS
software. The results for this test program are found in Table 1, above.
-------
TECHNICAL REPCST !>ATA
(Please read Instructions on reverse before completing)
1. REPORT NO.
EPA- 454/R-00-007
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Martin Marietta Magnesia Specialties, Woodville Ohio
5. REPORT DATE
May 2000
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
EMAD
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D7-0001
'2. SPONSORING AGENCY NAME AND ADDRESS
i. rector
Office of Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
EPA/200/04
?LEMENTARY NOTES
Ifi 1STRACT
The United States Environmental protection Agency is investigating the lime manufacturing
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.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Hyurogen Chloride (HCL)
Hazardous Air Pollutants
Air Pollution control
Fabric Filter Baghouse
Electro Static Precipitator (ESP)
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (Report)
Unclassified
21. NO. OF PAGES
116
20. SECURITY CLASS (Page)
~ Unclassified
22.' PRICE J
•>A Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
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