United States
Environmental Protection
Aeencv
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA - 454/R-00-006
March 2000
Air
&EPA
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Huron Lime Company
Huron, Ohio
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Lime Kiln Source Characterization
Final Report
Contract iNo. 68-D7-0001
Work Assignment 2-03
Huron Lime Company
Huron, 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
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Table of Contents
Page
1.0 INTRODUCTION -1
1.1 Objectives -2
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 2-1
2.2.1 Overview 2-1
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. HCL Inlet Run - Huron Lime - Kiln #3 2-4
2-2. HCL Outlet Run - Huron Lime - Kiln #3 2-5
3-1. FTIR Sampling and Measurement System 3-3
List of Tables
Page
2-1. Emissions Test Log 2-1
2-2. Wet Scrubber FTIR HC1 Results, ppmv 2-3
2-3. Other Species Detected by FTIR - Wet Scrubber Inlet 2-6
2-4. Other Species Detected by FTIR - Wet Scrubber Outlet 2-7
4-3. Gas Standard Analysis Results 4-6
111
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1.0 INTRODUCTION
The purpose of this testing program is to: (1) quantify hydrogen chloride (HCI) 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 HCI.
The lime kiln facility and sampling locations tested in the program are detailed in the
report prepared by PES.
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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.
1.2 Brief Site Discussion
Testing was conducted at the Huron Lime Company facility in Huron, Ohio. Testing was
performed on the inlet and outlet of a wet scrubber on Kiln #3, a coal-fired rotary kiln. 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 Huron Lime Company in Huron, 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 are 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 conducted in two sets:
• Unconditioned; and
• Conditioned.
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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 1-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 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.
7.3.2 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.
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. The measurements consisted of the following collection sequence:
75 minutes at the outlet; 15 minutes on the inlet; 15 minutes on the outlet; and
60 minutes on the inlet.
• The EPA Work Assignment Manager authorized one hour total sample collection
of the conditioned samples, ¥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
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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.
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 measurement
program;
• Section 2 gives a summary of the test results for the FTIR results for HC1 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 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 pretest 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
Huron Lime Company in Huron, Ohio on August 31, 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 wet scrubber at Kiln #3. No HAPs were detected in the conditioned samples.
2.1 Emissions Test Log
ERG performed extractive FTIR measurements for HCl and other HAPs. Table 2-1
presents the emissions test log which shows the test date, location, run number, test type and run
times for each method.
Table 2-1. Emissions Test Log
Date
8/31/98
8/31/98
9/01/98
8/31/98
Location
Kiln #3
Wet Scrubber (inlet/outlet)
Kiln #3
Wet Scrubber (inlet/outlet)
Kiln #3
Wet Scrubber (inlet/outlet)
Run
Number
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)
Run Time
08:42-10:00
17:49-22:10
00:45-01:45
22:04 - 00:30
Note: Time between spike 1 and run 1 was due to site-specific problems.
2.2 FTIR Results
2.2.1 Overview
FTIR data for HCl and other species in unconditioned sample gas were collected at the
inlet and outlet of the wet scrubber. FTIR data collection of unconditioned samples was
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synchronized with EPA Method 23 manual dioxin/furan testing and EPA Method 322 GFC-IR
HC1 measurements. Conditioned samples were measured by FTIR for other HAP species.
FTIR data were collected by alternating sample analysis between inlet and outlet every
30 to 60 minutes. Inlet and outlet samples were drawn on a continuous basis; only the FTIR
sample analysis was alternated between inlet and outlet. The first 36 data points were discarded
to eliminate data for samples containing both inlet and outlet sample gas, therefore, obtaining a
steady baseline before data collection. Twenty-four points before the inlet, then 55 points before
the next outlet, then 6 points before the final inlet points were deleted to obtain steady
observations for all detectable compounds. These data points correspond to the measured
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 77 and 66
1-minute average data points for both inlet and outlet measurements, after discarding the
appropriate data points per set. 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 Huron facility. Both
unconditioned samples 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 were measured after unconditioned sample
extraction for the next hour. Conditioned sample analysis time was 30 minutes each on the inlet
and outlet. These results are reported in Section 2.2.2.2.
The wet scrubber removal efficiency for HC1 was measured from the inlet/outlet data
from each location and is reported in Section 2.2.2.1.
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2.2.2 FTIR Emission Results
This section contains the FTIR HC1 test results for the wet scrubber inlet and outlet. No
HAPs were detected in the conditioned samples.
2.2.2.1 FTIR HCI Test Results. The estimated FTIR HCl detection limit for this
study was between 0.14 and 0.17 parts per million by volume (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 the run. Raw data are
presented in Appendix C listing each measured species 1-minute average concentration. All HCl
emission runs were collected during the unconditioned tests.
Wet Scrubber - 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 wet scrubber was 96.7 percent,
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.
Table 2-2. Wet Scrubber FTIR HCl Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Run 1
9/02/98
17:49-22:10
Inlet
181
33.8
338
136
77
Outlet
5.94
0.88
7.96
4.06
66
96 7
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 2-1. HCI Inlet Run - Huron Lime - Kiln #3
400.00
350.00
0.00
Jp'
-' N
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Figure 2-2. HCI Outet Run - Huron Lime - Kiln #3
0)
>
10
9.00
8.00
7.00
6.00
5.00
d 4.00
o
O
3.00
2.00
1.00
0.00
^
' ' ' ' ' ' ' '
Time
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2.2.2.2 Other Species Detected by FTIR. Other species were detected during the
unconditioned FTIR test runs. Results given below are organized by location.
Wet Scrubber Outlet/Inlet for Other Species Results—Table 2-3 and 2-4 respectively
gives the summary of wet scrubber for the inlet and outlet FTIR results for other species detected
during the FTIR test run.
Table 2-3. Other Species Detected by FTIR - Wet Scrubber Inlet
(All values are ppmv, except CO; and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO2
U
22.3
0.593
22.8
20.6
77
0.16
CO
U
48.9
9.13
103
41.4
77
0.52
NO
U
517
28.1
551
451
77
9.3
H,CO
U
1.09
0.57
3.43
0.58
77
0.50
H2O
U
14.2
3.41
23.5
11.7
77
0.23
U/C - Unconditioned (U) or Conditioned (C) Sample
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 2-4. Other Species Detected by FTIR - Wet Scrubber Outlet
(All values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Avg.
Std. Dev.
Max.
Min.
NDP
EDL
CO,
U
13.6
0.398
16.6
13.3
66
0.21
CO
U
30.4
3.84
38.6
22.7
66
1.2
NO
U
378
14.0
455
348
66
10.0
H,O
U
47.3
1.64
49.8
36.3
66
0.40
U/C - Unconditioned (U) or Conditioned (C) Sample
NDP - Number of data points
EDL - Estimated detection limit for spectral region used for analysis
Std. Dev. = Standard Deviation
Max. = Maximum
Mm. = Minimum
Note: Raw data presented in Appendix C.
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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 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 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, 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.
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Heat-traced line
Spike or QA/QC Gas
Sample
Gas In
Vaporization
block
Main Sample Pump
QA/QC Gas Standard Manifold
Heat-traced line
( up to 100 Feet)
QA/QC Gas Standards
Spiking Solution
Heated Flow Meter
Legend
Bold text and lines = Heated
Normal text and lines = Unheated
Sample Distribution Manifold
FTIR JL ¥ ¥ ¥
Sample O T * "
Pump/ T
FlowmeterT
To Other Instruments
FTIR Sample Cell
Excess sample to
atmosphere
Exhaust to atmosphere
Figure 3-1. FTIR Sampling and Measurement System
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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
CO2 and other acid gases. The sample conditioning apparatus is switched into the FTER 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 canned 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 leaJc 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 a frequency calibration. Carbon monoxide is
directly injected into the sample cell to measure photometric accuracy, validity of
the nonlinear 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.I .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
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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"')
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
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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
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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 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
5 minute cell purge and 15
minutes; then 60 minutes
2 minute cell purge and 28
minute sample collection
Outlet
5 minute cell purge and 90
minutes; then 15 minutes
2 minute cell p urge 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.
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
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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 ««IMI-l)2M«i:\(«n\HURON\HURON RPT
3-9
-------
Table 3-2. Compounds for Which Reference FTIR Spectra Are
Available in the ERG Spectral Library8
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/j-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
n-butanol
rt-butane
n-pentane
nitric oxide
nitrogen dioxide
nitrous oxide
o-cresol
o-xylene
p-cresol
p-xylene
phenol
propane
propylene
styrene
sulfur dioxide
toluene
rrans-2-butene
water vapor
Spectra were collected at a cell temperature of 185° C.
K \l»w|.li:M«l2\(»l.l\HL'ROS\HURON RPT
3-10
-------
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.
K \I>WI-II2\III)2\III).1\HURON\HURON RPT
3-11
-------
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 M«WI-n:\(»l2\i«i.1\Hi;RON\HURON RPT
3-12
-------
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.
FITR 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 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.
K M««)l-(i:\l»i:M«)3\HL'RON\HURON RPT
3-13
-------
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. 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 \(«NI-ii:\(«i:\i»].1\HUROS\HURON RPT
4-1
-------
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 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 methane (CH4), nitrous oxide (NO2), and carbon dioxide
(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 criteria. Tables 4-1 and
4-2 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.
Dynamic analyte spiking was attempted on the outlet at four spike levels: 25, 50, 100 and
150 ppm HC1. However, due to the reactivity of the sample gas towards HC1, unacceptable
recoveries (near zero in all cases) were found. To quantitatively prove that the sampling and
analysis system did transmit HC1 from the probe to the FTIR for analysis, a system QC check for
HC1 was performed. The system QC check was performed by injection of a HC1 standard
(nominally 5 ppm) downstream of the probe, but before the paniculate removal apparatus
K uiNMi2\i«i:\iinmuRON\HURON RPT
4-2
-------
Table 4-1. HCI QA Spike 1 Results - Huron Lime Company
Outlet*
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Spiked
(ppmv)
5.54
5.54
5.54
5.54
5.54
5.54
5.54
Corrected
Difference
(ppmv)
5.54
5.54
5.54
5.54
5.54
5.54
5.54
Spike
Level
(ppmv)
5.98
5.98
5.98
5.98
5.98
5.98
5.98
%
Recovery
WX%^/,
92.71
SF6
Cone.
(ppmv)
0.230
0.230
0.230
0.230
0.230
0.230
0.230
Dilution
Ratio
0.110
0.110
0.110
0.110
0.110
0.110
0.110
Inlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
177.10
176.80
178.60
181.10
179.00
179.60
178.70
Spiked
(ppmv)
278.20
280.30
282.90
286.40
285.90
287.30
283.50
Corrected
Difference
(ppmv)
120.91
123.28
124.28
125.56
126.93
127.79
124.79
Spike
Level
(ppmv)
115.24
115.24
115.24
115.24
115.24
115.24
115.24
%
Recovery
"WM^
108.29
SF6
Cone.
(ppmv)
0.2:.6
0.228
0.229
0.226
0.226
0.224
0.227
Dilution
Ratio
0.112
0.112
0.112
0.112
0.112
0.112
0.112
*System QC check - description on page 4-2 and 4-3.
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).
Corrected Difference
% Recovery = 100 x
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
4-3
-------
Table 4-2. HCI QA Spike 2 Results - Huron Lime Company
Outlet*
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Spiked
(ppmv)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Corrected
Difference
(ppmv)
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Spike
Level
(ppmv)
4.68
4.68
4.68
4.68
4.68
4.68
4.68
%
Recovery
^WMMi,
0.00
SF6
Cone.
(ppmv)
0.180
0.180
0.180
0.180
0.180
0.180
0.180
Dilution
Ratio
0.086
0.086
0.086
0.086
0.086
0.086
0.086
Inlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
166.20
164.60
162.80
161.70
160.80
156.40
162.08
Spiked
(ppmv)
238.00
243.20
243.70
244.00
247.30
248.30
244.08
Corrected
Difference
(ppmv)
89.74
96.36
98.47
99.75
103.85
108.78
99.49
Spike
Level
(ppmv)
111.16
111.16
111.16
111.16
111.16
111.16
111.16
%
Recovery
W^Sk
89.50
SF6
Cone.
(ppmv)
0.218
0.214
0.214
0.219
0.217
0.216
0.216
Dilution
Ratio
0.108
0.108
0.108
0.108
0.108
0.108
0.108
*System QC check - description on page 4-2 and 4-3.
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).
Corrected Difference
% Recovery = 100 x
Spike level
Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
K\l«W|.(i:\(«C\(«mHL'RON\HURONRPT
4-4
-------
(i.e., cyclone and paniculate filter). The recovery for this particular system QC check was
92.7 percent. Due to the high standard gas flow rate (- 1 scfm) required to perform this
measurement, only the pre-test QC check was completed. The post-test system QC took over
30 minutes to reach 20 percent recovery, which was due to the large amount of caustic material
captured on the paniculate filter during the run. The pre-test system QC check tested the system
before it had time to collect a significant amount of particulate matter. The expected time to
reach acceptable recovery (2.0 hours) during the post-test system QC check would have
consumed all of the HC1 gas standard required for the remainder of this program. The SF6 tracer
gas present in the HC1 calibration standard was detected at the expected concentration within
2 minutes of starting the post-test system QC check. This indicates proper operation of the
sampling and analysis system.
Spike gas reactions with the sample gas have been observed in other lime and cement
kilns, and is independent of analysis method. It is simply due to the reaction of caustic material
present in the sample gas with the HC1 spike gas. Introduction of HC1 spike gas into the sample
upsets the chemical equilibrium of the sample gas, causing consumption of the HC1 spike to
restore the system to chemical equilibrium (i.e., LeChatlier's principle). The caustic materials
that may present in the sample gas which cause the HC1 spike gas reaction in lime kilns are:
ammonia, calcium oxide, or calcium hydroxide. The chemistry between HC1 and these species is
well known and can be found in the chemical literature.
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. FHR NOX is
measured as NO + NO:. Examination of Table 4-3 shows that all QC checks met the above
criteria.
4-5
-------
Table 4-3. Gas Standard Analysis Results
Date
8/31/98
9/01/98
Time
07:56 AM
02:02 AM
Compound
HC1
CO
CH,
NO
CO,
H22
HC1
CO
CH4
NO
co:
H22
True
(ppm)*
54.3
102.3
491
503
4.99 %
54.3
102.3
491
503
4.99 %
Result
(ppm)*
52.0
101.4
492.2
494.0
5.15 %
3.30m
53.6
100.8
489.0
491.0
5.07 %
3.29m
%
Recovery
95.8
99.1
100.2
98.2
103.2
98.7
98.5
99.6
97.6
101.6
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 CO, Gas Standard Accuracy; ±1%; Acceptance Criteria: ±6 percent of target.
* All compounds are recorded in ppm except for CO, in percent (%), and H22 in meters (m).
Halocarbon 22 (H22) is used to calibrate the pathlength.
K «»Nl.ll2\(l
-------
APPENDIX A
FTIR DATA SPREADSHEET CALCULATION
QA/QC SHEETS
K «K»|.02VX)2\0
-------
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 OUTL
E^D
Run Description
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.
1. No mathematical errors
vv \
2. No errors in the data macro
3.
s
-------
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
: \\
n
DATE:
Source Location (INLET or OUTLET)
Run Description
Reviewer:
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.
1. No mathematical errors
2. No errors in the data macro
-------
APPENDIX B
GAS CYLINDER CERTIFICATION SHEETS
-------
REC'D AUG 141993
SPECTRfl GflSES
^^M 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
ANALYTICAL ACCURACY: + / - 5%
COMPONENT
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:
—^
DATE: 8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
-------
SPECTBfl BflSES
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*: 1
CERTIFICATION DATE: 8/29/97
BLEND TYPE: CERTIFIED
CYLINDER # : 1852209Y
CYLINDER PRES: 2000 PSIG
P.O J : 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
ISO BOOS
-------
SPECTBfl GflSES
277 Coit Street • Iryirfoon, 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
! !
-------
5b
RECTJ MAY 15 1998
SPECTRR EflSES
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, NO 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
CONG
250 ppm
5.00 ppm
Balance
ANALYSIS
253 ppm
5.08 ppm
Balance
* Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
Mike Detfe A
DATE: 5/11/98
USA • United Kingdom • Germany • Janan
-------
SPECTRfl GBSES
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*: 2
CERTIFICATION DATE: 8/10/98
P.OJ: 9101008011-R132
BLEND TYPE: 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 Kinadom • fiermsmv • .lanan
-------
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 # : 132874
ITEM*: 1
CERTIFICATION DATE: 5/11/98
BLEND TYPE: CERTIFIED
CYLINDER*: 1757934Y
CYLINDER PRES: 2000 psig
P.O J: 9101008004-R986
ANALYTICAL ACCURACY:
/- 2%*
COMPONENT
Hydrogen Chloride
Sulfur Hexaftuoride
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:
MHseHDoyle
DATE:
5/11/98
-------
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
Morrisville , 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 Hexafluoride is +/- 2%
ANALYST:
DATE: 8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
-------
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.OJ :
Eastern Research Group Inc.
126876
5
7904004005-R562
CERTIFICATION DATE: 8/27/97
EXPIRATION DATE: 8/19/99
CYUNDER #: CC79878
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 660
CERTIFICATION HISTORY
COMPONENT
Methane
Nitnc 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
Nk»let-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
-------
5PECTRB CBSES
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 J : 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 Kinadom • Germanv • -lanan
-------
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 M :
Eastern Research Group Inc.
126876
3
7904004005-R562
CYUNDER # : 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:
8/26/97
TED NEEME
-------
APPENDIX C
RAW FTIR DATA
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-------
APPENDIX D
FTIR FIELD DATA SHEETS
K WWI-02\IX>2MX»\HURON\HURON RPT
-------
Facility
Stack ID
Date
Run Number
Recorded By
W
LA
me.
VJ
FTIR Temperature Readout Sheet
Channel
Description
our
cxcr
IM
ai vo
3 \QQ
2.I5S
Inlet Stack
10 \
HiZL
112-
JII
J63_
Outlet Stack
VbT-
Inlet Probe
\OO
ilO_
Outlet Probe
112_
"5H4
*i£.
^13_
JiMS.
Inlet Filter
151
342.
3M\
\°|0
Outlet Filter
3MM
3^3
3H3
Inlet HT
ZXofc
Outlet HT
3 10
308
^Q5_
3o>
Inlet Pump
7.15
Z.-JO
Z.8"
10
Outlet Pump
£•=»!
2,13
11
FTIR Pump
3)0
Sou
-2^5
12
Pump Box
\os
Vox
lol
13
14
FTIR Jumper
3M5
3MS
15
Pump Jumper
3o5
16
Hot Box
353
5S1
35=1
35^
35?
17
Hot Box
331-
537-
33T-
33^
33?
18
19
Electronics Box
20
Spits, inkb
-------
Facility
Stack ID
Date
Run Number
FTIR Temperature Readout Sheet
Recorded By
Channel
Description
.iu.'rt',/ii^ii
&!*SiS»i» jMi -i«u,.rir.-.i*;ltUilW;JiJ - KU.
;'TlmW
Inlet Stack
261
Outlet Stack
Inlet Probe
/ t/x-
Outlet Probe
Inlet Filter
Outlet Filter
Inlet HT
2^7
Outlet HT
Inlet Pump
172-
10
Outlet Pump
Tff'-t
11
FTIR Pump
12
Pump Box
13
14
FTIR Jumper
15
Pump Jumper
16
Hot Box
17
Hot Box
33?
37
18
19
Electronics Box
20
/^^
-------
APPENDIX E
PRE-TEST CALCULATIONS
KA(Xiyi.<>2\
-------
Below are the results of the 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 lAI/AAI Average absorbance
HCI (target)
0.1 ppmv
0.0005436
0.00000322
H3O (potential interferant)
20%
0.2213
0.00131
CO, (potential interferant)
20%
0.000002
H^CO (potential interferant)
1 ppmv
0.0002100
CH4 (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:\I>WI-02VX>2\3\HURON\HURONRPT
E-l
-------
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)
Tl is 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
H2O
HC1
CHa
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 \IKiyl-()2\(«m(»)3\HURON\HURON RPT
E-2
-------
Appendix H
Determining Sample Absorption Pathlength (Ls) 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.«XNUI2WI2\IXI3\HURON\HURON RPT
E-3
-------
APPENDIX F
POST-TEST CALCULATIONS
K'WX)91-(I2V(«)2«)I)3\HURON\HURON 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 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 -HURON
Spectral File Name
RNO 10001. spa
RNlbOOOl.spa
Inlet/Outlet
Outlet
Inlet
Error (ppm)
0.25
0.97
Concentration (ppm)
11.9
179
FMU
0.021
0.005
Error is 95% confidence interval 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.
K \IXNUC\IXI2\M3\HURON\HURONRPT
F-l
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TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing)
1. REPORT NO.
EPA- 454/R-00-006
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Huron Lime Company, Huron 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 Ah* Quality Planning and Standards
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D7-0001
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
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 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. COS ATI Field/Group
Hydrogen Chloride (HCL)
Hazardous Air Pollutants
Air Pollution control
Fabric Filter Baghouse
Electro Static Preciptator (ESP)
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (Report)
Unclassified
21. NO. OF PAGES
92
20. SECURITY CLASS (Page)
"Unclassified
z. PRICE J
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
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