United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA - 454/R-99-030
July 1999
Air
&EPA
Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
Chemical Lime
Marble Falls, Texas
-------
Lime Kiln Source Characterization
Final Report
Contract No. 68-D7-0007
Work Assignment 1-08
Chemical Lime Company
Marble Falls, Texas
Prepared for:
Michael L. Toney
Emission Measurement Center
Emission, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
July 1999 , p,
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Table of Contents
1.0
Page
INTRODUCTION 1-1
1.1 Objectives 1-2
1.2 Brief Site Discussion 1-2
1.3 Emissions Measurements Program 1-2
1.3.1 Test Matrix 1-2
1.3.2 Test Schedule , : 1-3
1.3.3 Deviations from Test Plan/Schedule 1-3
1.4 Test Report 1-4
2.0 SUMMARY OF RESULTS 2-1
2.1 Emissions Test Log 2-1
2.2 FTIR Results 2-2
2.2.1 Overview 2-2
2.2.2 FTIR Emission Results 2-3
3.0 SAMPLING AND ANALYTICAL PROCEDURE 3-1
3.1 Determination of Gaseous Organic HAPs, HC1, and Criteria Pollutants by
Fourier Transform Infrared Spectroscopy (FTIR) 3-1
3.1.1 FTIR Sampling Equipment 3-1
3.1.2 Preparation for Sampling 3-4
3.1.3 Sampling and Analysis 3-6
3.1.4 FTIR Method Data Review Procedures 3-11
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
11
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List of Figures
Page
Figure 2-1. HC1 Inlet Run - Chemical Lime Company 2-5
Figure 2-2. HC1 Outlet Run - Chemical Lime Company 2-6
Figure 3-1. FTIR Sampling and Measurement System 3-3
List of Tables
Page
Table 2-1. Emissions Test Log 2-1
Table 2-2. Baghouse FTIR HC1 Results, ppmv 2-4
Table 2-3. Other Species Detected by FTIR - Baghouse Inlet 2-7
Table 2-4. Other Species Detected by FTIR - Baghouse Outlet 2-8
Table 3-1. Typical FTIR Operating Parameters 3-7
Table 3-2. Compounds for Which Reference FTIR Spectra Are Available in the ERG
Spectral Library 3-10
Table 4-1. HC1 QC Pre-test Spike Results - Chemical Lime Company 4-3
Table 4-2. HC1 QC Post-test Spike Results - Chemical Lime Company 4-4
Table 4-3. Gas Standard Analysis Results 4-5
in
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1.0 INTRODUCTION
The purpose of this testing program is to obtain uncontrolled and controlled hydrogen
chloride (HC1) and speciated hydrocarbon Hazardous Air Pollutants (HAPs) emissions data 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. 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.
FTIR source testing was conducted for the following purposes:
• Quantify HCl emission levels; and
• Gather screening (i.e., qualitative) data on other HAP emissions.
The lime kiln facility and sampling locations that were tested in the program are detailed
in the report prepared by PES.
1-1
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1.1 Objectives
The objective of the FTIR testing of the lime facility was to perform quantitative
measurement of hydrogen chloride (HC1) and screening of other HAPs detectable by FTIR, using
EPA Draft Method 320.
1.2 Brief Site Discussion
Testing was conducted at the Chemical Lime Company located in Marble Falls, Texas.
Testing was performed on the inlet and outlet of a fabric-filter baghouse on Kiln #1, a double-
shaft vertical 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 Chemical Lime Company, located in Marble Falls, Texas. Included in this section are
summaries of the test matrix, test schedule, and authorized deviations from the test plan.
Additional detail on these topics are provided in the sections that follow.
1.3.1 Test Matrix
The complete sampling and analytical matrix that was performed is presented in the
report prepared by PES. In this report, only FTIR-related test matrix will be provided. FTIR
spectroscopy was used, in accordance with EPA Draft Method 320, to quantify HC1 and also, in
a screening capacity, to measure other HAPs that can be detected by FTIR.
FTIR measurements were conducted in two sets:
• Unconditioned; and
• Conditioned.
1-2
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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 one-hour period to screen for
aromatic species such as benzene, toluene, etc. At this particular site, the conditioned run was
conducted prior to the unconditioned run.
During each run (i.e., unconditioned or conditioned) the FTIR analysis time was divided
equally between inlet and outlet samples. Each location was monitored for no less than a total of
90 minutes. Some data points (typically, 5 minutes) were discarded for each set due to
inlet/outlet sample mixing in the FTIR analysis cell. The actual amount of data points discarded
is given later in this report. This procedure ensures the remaining data points were data truly
representing the location being tested in that set.
1.3.2 Test Schedule
The test schedule for EPA Method 23 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 collecting 24 minute intervals at the outlet
and inlet, in order to synchronize with the process cycle time and GFC-IR
measurements performed by APCC.
The EPA Work Assignment Manager authorized one hour total sample collection
of the conditioned samples, '/z hour each on inlet and outlet. If detection of other
HAPs was determined, then the run would extend to the full two hours, as
originally planned. In this case, no additional HAPs were detected in the
conditioned samples.
1-3
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1.4 Test Report
This final report, presenting all data collected and the results of the analyses, has been
prepared in four sections, and six appendices as described below:
• Section I provides an introduction to the testing effort and includes a brief
description of the test site and an overview of the emissions measurements
program;
• Section 2 gives a summary of the test results for the FTIR results for 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 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 raw FTIR
concentration data are contained in the appendices.
Seven 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 the FTIR results of the emissions test program conducted at the
Chemical Lime Company in Marble Falls, Texas on June 25, 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 baghouse.
2.1 Emissions Test Log
ERG performed extractive FTIR measurements for HC1 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
6/25/98
6/25/98
6/25/98
Location
Baghouse
(inlet/outlet)
Baghouse
(inlet/outlet)
Baghouse
(inlet/outlet)
Run
Number
Spike 1
Run 1
Spike 2
Test Type
FTIR HC1 Spike (inlet/
outlet)
FTIR (Unconditioned)
FTIR (Conditioned)
FTIR HC1 Spike (inlet/
outlet)
Run Time
09:53-11:53
15:18- 18:54
12:25- 13:45
19:32-20:19
2-1
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2.2 FTIR Results
2.2.1 Overview
FTIR data for HCl and other species were collected at the inlet and outlet of the
baghouse. FTIR data collection of unconditioned samples was synchronized with EPA Method
23 manual dioxin/furan testing and EPA Method 322 GFC-IR HCl measurements. Conditioned
samples were measured by FTIR for other HAP species.
FTIR data were collected by alternating sample analysis between inlet and outlet every
24 minutes. 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 24 minute
inlet/outlet measurement period were discarded to eliminate data for samples containing both
inlet and outlet sample gas. Five data points correspond to the measured response time of the
complete FTIR sampling and analysis system (details on measurement of system response time
are given below). The measurement run contained a total of 76 and 95 1-minute average data
points for both inlet and outlet measurements, after discarding the first five 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 Chemical Lime Company in
Marble Falls, Texas. Both unconditioned samples and conditioned samples were analyzed.
Conditioned samples were generated by passing the raw sample gas through a sample
conditioning system (See Section 3.1.1 for details). Conditioned samples extracted from the
baghouse were measured prior to unconditioned sample extraction for one hour. Five minute
average data points were generated by analysis of the composite spectrum consisting of an
average of 215 FTIR spectra collected over the 5 minute time period. These results are reported
in Section 2.2.2.2.
2-2
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The baghouse removal efficiency for HC1 was measured from the inlet/outlet data from
each location and is reported in Section 2.2.2.1.
No attempt was made at correcting measurement data to a standard level of oxygen
(e.g., 15%). Oxygen data were not collected by ERG.
2.2.2 FTIR Emission Results
This section contains the FTIR HC1 test results for the baghouse inlet and outlet.
2.2.2.1 FTIR HCI Test Results
The estimated FTIR HCI detection limit for this study was in the range of 0.18 to
0.19 ppmv. Half of the FTIR instrument analysis time was split equally between inlet and outlet.
Results given below are organized by location. HCI removal efficiency was also calculated for
each run. Appendix C contains the raw 1-minute FTIR concentration data for all monitored
species. All HCI emission tests were collected during the unconditioned runs.
Baghouse Outlet/Inlet HCI Results—Table 2-2 gives a summary of the baghouse
outlet/inlet FTIR HCI results. The measured HCI removal efficiency due to the baghouse was
39.98 percent. Figures 2-1 and 2-2 show a real-time graph for the inlet and outlet runs,
respectively. Due to the splitting of FTIR analysis time between inlet and outlet, the time axis in
the graphs is not continuous.
2.2.2.2 Other Species Detected by FTIR
Other species were detected during the unconditioned FTIR test runs. The compounds
were collected concurrently during the collection of the HCI test results. Results given below are
organized by location. No additional HAP species were detected during the conditioned run.
Appendix C contains a listing of 1-minute average values for all monitored analytes.
2-3
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Table 2-2. Baghouse FTIR HCI Results, ppmv
Date
Time
Location
Average
SD
Maximum
Minimum
NDP
RE
Runl
6/25/98
15:18 - 18:54
Inlet
38.72
13.13
62.53
16.79
76
Outlet
23.24
8.46
. 51.19
13.24
95
39.98
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 are presented in Appendix C.
Baghouse Outlet/Inlet for Other Species Results—Table 2-3 and 2-4 respectively gives
the summary of the baghouse for the inlet and outlet FTIR results for other species found during
the standard Draft Method 320 extractive sampling and analysis.
2-4
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HCI Inlet Run - Chemical Lime Company
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O
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70.00 -,
60.00
50.00
40.00
30.00
20.00
10.00
0.00
Time
Figure 2-1. HCI Inlet Run - Chemical Lime Company
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50.00
0.00
HCI Outlet Run - Chemical Lime Company
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Figure 2-2. HCI Outlet Run - Chemical Lime Company
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Table 2-3. Other Species Detected by FTIR - Baghouse Inlet
All values are ppmv, except CO2 and H2O in percent
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO2
U
17.8
1.75
20.1
9.96
76
0.035
CO
U
15.1
4.55
37.3
11.5
76
0.28
NO
U
26.4
3.82
31.1
10.3
76
6.5
CH4
U
24.7
52.9
237.3
<3.5
76
3.5
H2O
U
16.2
2.71
18.1
5.63
76
0.072
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
2-7
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Table 2-4. Other Species Detected by FTIR - Baghouse Outlet
All values are ppmv, except CO2 and H2O in percent
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CO2
U
17.5
1.34
18.4
10.9
95
0.038
CO
U
15.7
4.89
39.7
12.2
95
0.30
NO
U
25.7
2.76
28.6
12.8
95
7.0
CH4
U
26.6
57.6
256
<3.9
95
3.9
H2O
U
15.9
2.49
17.6
6.81
95
0.081
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
2-8
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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 Draft EPA Method 320. In this
section, description of the FTIR method used is provided.
3.1 Determination of Gaseous Organic HAPs, HCI, and Criteria Pollutants by
Fourier Transform Infrared Spectroscopy (FTIR)
The extractive FTIR measurement method is based on continuous extraction of sample
gas from the stack, transporting the sample to the FTIR spectrometer and performing real-time
spectral measurement of the sample gas. The sample gas spectra are analyzed in real time for
target analytes, archived and possibly re-analyzed at a later date for other target analytes. This
section provides details on the FTIR sampling and measurement system.
3.1.1 FTIR Sampling Equipment
The FTIR measurement system meets the sampling and analysis requirements set forth in
EPA Draft Method 320, "Measurement of Vapor Phase Organic and Inorganic Emissions By
Extractive Fourier Transform Infrared Spectroscopy". This system has been used with complete
success with many source categories, and can also be adapted to switch quickly between two
sources (i.e., inlet and outlet) with a single FTIR spectrometer.
The sampling and measurement system consists of the following components:
• Heated probe;
• Heated filter;
• Heat-traced Teflon® sample line;
• Teflon® diaphragm, heated-head sample pump;
• FTIR spectrometer;
3-1
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• 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 particulate 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
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 FTIR
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 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.
3-2
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Heat-traced line
Sample
Gas In
Spike or QA/QC Gas
Vaporization
block
I
QA/QC Gas Standard Manifold
Main Sample Pump
Heated Flow Meter
Legend
Bold text and lines = Heated
Normal text and lines = Unheated
Heat-traced line
(up to 100 feet)
QA/QC Gas Standards
Sample Distribution Manifold
FTIR
Sample
Pump/
Flowmeter
r
To Other Instruments
FTIR Sample Cell
Spiking Solution
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 FTIR sample
path by a valving system. Lower detection limits for some compounds can be achieved with a
conditioned sample.
3.1.2 Preparation for Sampling
Before commencement of daily sampling operations, the following tasks were carried out:
• System leak check;
• Measurement of FTIR background spectrum;
• Instrumental QC; and
• Sampling and measurement system QC spike run.
Detailed descriptions of these tasks are described in the paragraphs below.
The heated sampling lines, probes, and a heated filter were positioned at the inlet and
outlet locations. All heated components were brought to operating temperature, and a leak check
of both inlet and outlet sampling systems were performed. The leak check was performed by
plugging the end of the probe and watching the main sample rotameter to observe the reading.
Positive leak check was confirmed when the rotameter reading was zero.
A background spectrum was measured using zero nitrogen through the cell. Next the QC
gases were measured. They agreed to within ±6% (±10% for HC1) of target value. The QC gases
used for this program include:
3-4
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Halocarbon 22, used to calibrate the pathlength. Halocarbon 22 is used for its
highly linear response due to the lack of sharp spectral features, and is an
extremely stable compound.
Carbon monoxide (CO) used for frequency calibration. Carbon monoxide is
directly injected into the sample cell to measure photometric accuracy, validity of
the non-linear correction algorithm and serve as a frequency (i.e., wavelength)
calibration. Acceptable limits for CO standard analysis are ±6 percent of certified
concentration;
Methane/nitric oxide/carbon dioxide mixture, used for overall system
performance check (calibration transfer standard) (acceptance limits are ±6% of
the certified concentration); and
Hydrogen chloride standard, analyzed to verify the instrumental response of HC1,
a key target analyte (acceptance limits are ±10% of certified concentration).
The sampling and measurement system spike test was done to perform validation and
directly challenge the complete system and provide information on system accuracy and bias.
This test is conducted to satisfy the requirements set in EPA Draft Method 320 entitled
"Measurement of Vapor Phase Organic and Inorganic Emissions By Extractive Fourier
Transform Infrared Spectroscopy". Section B. 1 .C of Method 320 gives a description of the
dynamic spiking apparatus.
The FT1R spiking procedure used the following:
• Measured native stack gas until system equilibrates - took 2 measurements
(i.e., 2-1 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., 2- 1 minute samples);
• Turned off spike gas flow;
• Let system equilibrate with native stack gas; and
3-5
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• Repeated cycle, two more times.
The above procedure produced 6 spiked/unspiked sample pairs. Spike recovery for
6 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% 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 1-1000 ppm). Some of these parameters are sample matrix dependent.
Sample flow rate was determined by the data averaging interval and FTIR spectrometer
sample cell volume. A minimum of 3 sample cell volumes of gas must flow through the 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.
3-6
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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 - 4000
0.5
3.4
185
9 (3.0 optical cell
1 (Average of 43
volumes/minute)
spectra)
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 ensure that condensation of high-
boiling point 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 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
3-7
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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 pre-
determined time, corresponding to a "run". Typical runs were approximately 3 hours long,
giving a minimum of 180 one-minute averaged points for each target analyte. The figure of 180
points were reduced by 30 points due to elimination of five 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 19
minute sample collection
2 minute cell purge and 28
minute sample collection
Outlet
5 minute cell purge 19
minute sample collection
2 minute cell purge and 28
minute sample collection
The sample being delivered to the FTIR cell alternated between the inlet and the outlet.
The switching valve, located just upstream of the common manifold, was manually activated
periodically to provide alternating inlet and outlet sample collections during each three-hour
period (the estimated dioxin run duration). This procedure resulted in a set of data points
3-8
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collected for the inlet and outlet, respectively. Five data points per set are discarded to eliminate
analysis results with combined inlet and outlet samples.
FTER method performance was .gauged from the results of the QA/QC procedures given
in Section B5 of Draft EPA 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% 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 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 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.
3-9
-------
Table 3-2. Compounds for Which Reference FTIR Spectra Are Available in the
ERG Spectral Library3
1-butene
1,3-hmtadiene
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
ds-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
«-butane
«-pentane
nitric oxide
nitrogen dioxide
nitrous oxide
o-cresol
o-xylene
p-cresol
p-xylene
phenol
propane
propylene
styrene
sulfur dioxide
toluene
trans-2-butene
water vapor
Spectra were collected at a cell temperature of 185° C.
3-10
-------
3.1.4 FTIR Method Data Review Procedures
The following procedure was conducted to review and validate the FTIR data.
A. Post-test Data Review procedure (on-site)
I. 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 which
was taken immediately prior in time to the indicated time region.
4. Manually quantitate (including any non-linear corrections) for the species in
question and compare the result to 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).
3-11
-------
10. Data found invalid are subject to re-measurement.
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 which were not detected or detected at low levels:
a) estimate detection limits from validated data;
b) check for measurement bias.
3. Verify spreadsheet calculations by independent calculation (results in
Appendix A).
5.7.5 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
-------
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 Method 320 criteria (i.e., accuracy of within ± 30 percent) or a statistical
equivalent when less than 12 spiked/unspiked pairs are collected. Draft EPA Method 320
instructs the user to determine the percent spike recovery of 3 pairs of spiked/unspiked samples.
The Draft EPA 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.
3-13
-------
4.0 QUALITY ASSURANCE/QUALITY CONTROL
Specific Quality Assurance/Quality Control (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 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 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 FTIR measurement and analysis system to determine the true sample matrix. If
any target analytes are present at significantly higher levels than expected, adjustments were
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; and
• Direct measurement of a CH4, NO, and GO2 standard.
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.
Direct instrumental measurement of HC1, CO, H22, and a CH4, NO2 and CO2 mixture
was conducted before and after daily testing activities. Acceptance criteria are normally ±6
percent of target, using EPA protocol gases. However, since the HC1 standard was obtained at a
±5 percent analytical tolerance, the acceptance criteria was set at ±10 percent. FTIR NOX is
measured as NO + NO2. Examination of Table 4-3 shows that all QC checks met the above
criteria.
4-2
-------
Table 4-1. HCI QC Pre-test Spike Results - Chemical Lime Company
Outlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
10.16
16.26
10.44
14.28
7.68
9.30
11.35
Spiked
(ppmv)
41.26
49.40
33.68
41.83
25.21
29.35
36.79
Corrected
Difference
(ppmv)
32.00
34.55
24.08
28.70
18.10
20.75
26.36
Spike
Level
(ppmv)
22.41
21.91
20.42
20.42
18.93
18.93
20.50
%
Recovery
|f||||f|
128.55
SF6
Cone.
(ppmv)
0.450
0.440
0.410
0.410
0.380
0.380
0.412
Dilution
Ratio
0.089
0.087
0.081
0.081
0.075
0.075
0.081
Inlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
44.92
48.20
47.41
50.27
40.32
46.91
46.34
Spiked
(ppmv)
67.72
68.28
60.27
69.44
59.97
58.64
64.05
Corrected
Difference
(ppmv)
26.69
24.25
16.78
23.23
22.90
15.61
21.58
Spike
Level
(ppmv)
21.91
21.91
20.92
20.42
20.42
20.92
21.08
%
Recovery .
102.34
SF6
Cone.
(ppmv)
0.440
0.440
0.420
0.410
0.410
0.420
0.423
Dilution
Ratio
0.087
0.087
0.083
0.081
0.081
0.083
0.083
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).
4-3
-------
Table 4-2. HCI QC Post-test Spike Results - Chemical Lime Company
Spike
Run
Number
1
2
3
4
5
6
Average
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
18.01
16.48
16.42
18.58
22.71
29.98
20.36
Lowest
Unspiked
Value (ppmv)
41.09
49.65
53.18
56.64
60.27
63.10
53.99
Spiked
(ppmv)
39.43
40.37
43.68
49.17
56.48
63.10
48.54
Spiked
(ppmv)
51.31
56.36
66.38
74.24
76.06
78.46
67.14
Outle
Corrected
Difference
(ppmv)
22.12
25.45
28.81
32.35
35.92
35.95
30.10
Inlet
Corrected
Difference
(ppmv)
13.70
10.91
17.70
22.39
20.89
20.70
17.72
t
Spike
Level
(ppmv)
23.91
23.91
23.91
23.91
23.91
23.91
23.91
Spike
Level
(ppmv)
21.42
21.42
21.42
21.42
21.42
21.42
21.42
%
Recovery
WMMfc,
Illlllll
125.91
%
Recovery
82.73'
SF6
Cone.
(ppmv)
0.480
0.480
0.480
0.480
0.480
0.480
0.482
SF6
Cone.
(ppmv)
0.430
0.430
0.430
0.430
0.430
0.430
0.430
Dilution
Ratio
0.094
0.094
0.094
0.094
0.094
0.094
0.094
Dilution
Ratio
0.085
0.085
0.085
0.085
0.085
0.085
0.085
NOTE: The spike runs were conducted before and after the test runs, therefore the minimum and
maximum values listed here may be different than those listed in the test runs, Section 2. Sample
gas dilution was held to 10 percent or less in all runs. Percent recovery is defined in Draft
Method 320.
(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv, respectively).
4-4
-------
Table 4-3. Gas Standard Analysis Results
Date
6/25/98
6/25/98
Time
08:31 AM
08:40 PM
Compound
HC1
CO
CH4
NO
C02
H22
HC1
CO
CH4
NO
CO2
H22
True
(ppm)*
253
102.3
491
503
4.99 %
253
102.3
491
503
4.99 %
Result
(ppm)*
249.8
102.1
487.9
502.7
4.95 %
3.35m
249.9
101.7
489.6
500.6
4.96 %
3.36m
%
Recovery
98.7
99.8
99.4
99.9
99.2
98.8
99.4
99.7
99.5
99.4
Comments
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 NO2 and CO2 Gas Standard Accuracy; ±1 percent; Acceptance Criteria: ±6 percent of target.
•* All compounds are recorded in ppm except for CO2 in percent (%), and H22 in meters (m).
The Halocarbon 22 (H22) is used to calibrate the pathlength.
4-5
-------
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)
TIME:
Run Description
Reviewer:
Date:
^.Checklist
,
Resolution
jS*. QA/QC entries match references values ^ "^*v^ ^V*"*.^CM' ^4^ ^ f^ Cfc.*5- A
IjSheck^lhe following by comparing Ifie printout of the QA/QC run to th£bngihal ran mfoimation^ ^-h. **-» "
1 . Pollutants matches pollutants in both the
original and QA/QC data
V/
2. Times for Inlet/Outlet samples match.
%
3. Number of data points match.
4. Column statistics match (i.e., Average,
Standard Deviation, Maximum, Minimum)
I
S
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
i
i. No mathematical errors
I/
2. No errors in the data macro
Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
1. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
'"oQ
Facility Name
l-VL
DATE:
Source Location
LET or OUTLET)
UTLtT
TIME:
Run Description
. .
OrO 0\
Reviewer:
Dale:
^Checklist NI^V ,-' , * ,-» 'U*
?» •> >».,•, » „,. fi* , ,v> • t v» ""; .
c^-?C•> **\ ~ np^-J"
jfe.,' i "X' ^-S" 1-*- " - vA'L
"Y«^
^ * $•!
No Y*
^ ^s^«
N(A *
* * ^S* ^»J
, rs:fe
Not r
'det*.
- Resolution "N ' - * >"* " ^*}i-N ,
' >" "\ ^ X' -/*" -».!^i^^Kt
" -s --," r C/l h- 1 V
;,A^QA/QC entries match references values* _~ *\*;ff^ x ',:>;•», C^ - - '> ^ *, ^, >^-: •%"'''*' •"*.'^': :* , '
HS3ieclc,the fblTowiiig by comparing: ffie printout of the Q^QC ruatatneoriginatrBn. informations >;r* ""•v-'-C*. *--'
1. Pollutants matches pollutants in both the
original and QA/QC data
2. Times for Inlet/Outlet samples match.
3. Number of data points match. f"t~fr\
4. Column statistics match (i.e., Average,
Standard Deviation, Maximum, Minimum)
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
^
^/
/
v/
v/
I/
r
^-
X
i*B. 'Check that calculations are correct „•*. ? ' : ,. J->V & ^^^^^^'^^vfe5^^ <- - «• - ~+ ' ff,{^^^t$&f&'f^' . \-
Lt „», ,-,*. ^T«>^*. *• - 'ti^ir. ••-^Jg^pJgfc«^iHt;>^-»»; J-- " V T W" r^^^XW^,"^,
^^ •*»****'* *5. J^^St t* **T "* t."***^^" *«• t r "«a**^ sA. *f i^wvPV A*l-f**^S iHh"* PS •«"-^..i *; "^ •• V> •* ) ' f -. tr* ** \*4^-
w 'Vj- « s\— «r>i «•'* «. > v - - P^ «^Afv> •. SjRa.sV^H^sSflw.J wv;"« - ~~ » ^^ — — • *fcw— - .*ij ?;,* jv< *^
1 . No mathematical errors
2. No errors in the data macro
I/
v/
^»
- • ."-> >*•.-'• > ^^r--: ^A;-; v -'%•>•:
'•pAcUu-.JLA^l
/
-------
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
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)
i/
5. Verify that the QA/QC value is zero. This
indicated that both the original and the
QA/QC values are identical.
i. No mathematical errors
2. No errors in the data macro
* Not able to determine
-------
FTIR QA/QC REVIEW
Calculation and Methodology QA/QC Checklist
For each facility tested, the reviewer will have:
1. Excel QA/QC workbook
2. Inlet and Outlet QA/QC information
Facility Name:
DATE:
Source Location (INLET or OUTLET)
TIME
Run Description
Reviewer:
Date:
;i«*i\£rt/V\L, CU fclijra-.UKI ll,U\ I. «1« J CU V^d^ r _.l-^^,> ^,,":
p!^*"i^.-^:.^^-;VH-""^~'*i5v^j'' -^^"" V "'*"" *"'^-r*->> -"-'""•"•'' • -.:f 7^t^'-r-r^
|@ecK.tfr&doU6^g^
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.
Column statistics match (i.e., Average,
Standard Deviation, Maximum. Minimum)
Verify that the QA/QC value is zero. This
indicated that both the original and the
.QA/QC values are identical.
No mathematical errors
2. No errors in the data macro
\7
s -ii~>.
1 *
KiU
OK.
I/
* Not able to determine
-------
APPENDIX B
GAS CYLINDER CERTIFICATION SHEETS
-------
REC'O AUG 14 1998
SPECTRH 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
CONG
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
i 3 a 3 a a 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 # : 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
isa a a a a
-------
SPECTRH GHSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-8551
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 128118
ITEM*: 1
CERTIFICATION DATE: 10/16/97
BLEND TYPE: CERTIFIED
CYLINDER # : 1757972Y
CYLINDER PRES: 2000 psig
P.O.*: 7904004005-R690
ANALYTICAL ACCURACY:
+/- 2%
COMPONENT
Hydrogen Chloride**
Sulfur Hexafluoride
REQUESTED GAS
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 s o a s
-------
SPECTRR GflSES
JET) MAY 15 1998
^^M 277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-355 •
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 132874
ITEM#: 2
CERTIFICATION DATE: 5/11/98
BLEND TYPE: CERTIFIED
CYLINDER*: 1370597Y
CYLINDER PRES: 2000 psig
P.O.#: 9101008004-R986
ANALYTICAL ACCURACY:
/- 2%*
COMPONENT
Hydrogen Chloride
Sulfur Hexafluoride
Nitrogen
REQUESTED GAS
CONG
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 s a o a
-------
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 # : 134942
ITEM*: 2
CERTIFICATION DATE: 8/10/98
P.O.#: 9101008011-R132
BLEND TYPE: CERTIFIED
CYLINDER*: 1015632Y
CYLINDER PRES: 2000 psig
CYLINDER VALVE: CGA 330
ANALYTICAL ACCURACY: + / - 5%
COMPONENT
REQUESTED GAS
CONG
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 Kingdom • Germany • Japan
iso so a a
-------
SPECTBfl 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 # : 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:
MikeHDoyle
DATE:
5/11/98
USA • United Kingdom • Germany • Japan
iso a a a s
-------
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.O.#: 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 Hexafluoride
1,000 ppm
2.00 ppm
1,030 ppm
2.02 ppm
Nitrogen
Balance
Balance
Sulfur Hexafluoride is +/- 2%
ANALYST:
H-
DATE:
8/10/98
Ted Neeme
USA • United Kingdom • Germany • Japan
iso s a a a
-------
5b
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
Cf
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE # : G1
CUSTOMER:
SGI ORDER #:
ITEM*:
P.O.#:
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 CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
DATE:
TED NEEME
8/26/97
-------
SPECTBfl GflSES
277 Coit Street • Irvington, NJ 07111 USA Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-8551
SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Morrisville, NC 27560
CERTIFICATE
OF
ANALYSIS
SGI ORDER #: 128118
ITEM#: 2
CERTIFICATION DATE: 10/16/97
BLEND TYPE: CERTIFIED
CYLINDER # : CC82244
CYLINDER PRES: 2000 psig
P.O.*: 7904004005-R690
ANALYTICAL ACCURACY: +/- 2%
COMPONENT
Chlorodifluoromethane
REQUESTED GAS
CONG
40.0 ppm
ANALYSIS
40.3 ppm
Nitrogen
Balance
Balance
ANALYST:
Ted Neeme
DATE:
10/16/97
USA • United Kingdom • Germany • Japan
iso s a a a
-------
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, N.J. 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
Nitric Oxide
Carbon Dioxide
SRM/NTRM*
SRM-2751
NTRM-81687
SRM-1674b
CYLINDER*
CAL013479
CC57165
CLM007273
CONCENTRATION
98.6 ppm
1009 ppm
6.98 %
INSTRUMENTATION
COMPONENT
Methane
Nitric Oxide
Carbon Dioxide
MAKE/MODEL
H. Packard-6890
Nicolet-760
Horiba-VIA-510
SERIAL #
US00001434
ADM9600121
571417045
DETECTOR
GC - FID
FTIR
NDIR
CALIBRATION
DATE(S)
8/21/97
8/27/97
7/25/97
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
DATE:
TED NEEME
8/27/97
-------
APPENDIX C
RAW FTIR DATA
-------
iMMMpprnvweV^^M
••oSM/hMai
Description: Chemlime time kiln
Method title: Lime Uncond
Starting Datefl"ime: Thu Jun 25 15
Time
15:24:35
15:26:35
15:27:35
15:28:36
15:29:35
15:30:35
15:31:35
15:32:35
15:33:35
15:34:35
15:35:36
15:36:35
15:37:35
15:38:36
15:39:37
15:40:36
15:41:36
15:42:37
16:12:38
16:13:37
18:14:38
16:15:37
16:16:38
16:17:37
16:18:37
6:19:38
6:20:37
6:21:38
6:22:37
6:24:37
6:25:37
6:26:38
6:27:37
6:28:38
6:2938
6:30:38
7:00:39
17:02:39
7:03:38
7:05:48
7:06:45
7:08:45
7:09:45
7:10:45
7:11:45
7:12:44
7:13:45
7:14:45
7:15:46
7:16:45
7:17:45
7:18:45
7:48:45
7:49:45
7:51:47
7:53:47
17:54:46
17:56:47
17:57:46
17:58:47
17:59:46
18:00:47
18:01:46
18:02:46
18:03:47
18:04:46
18:05:47
18:06:47
18:36:49
18:38:49
18:39:49
18:40:49
18:41:49
18:42:48
18:43:49
18:44:49
18:45:49
18:46:49
18-47:50
18:48:49
18-49-50
Filename
rn020007
m020009
rn020010
rn020011
rn020012
m020013
rn020014
m02001S
m020016
m020017
rn020018
m020019
m020020
m020021
m020022
rn020023
m020024
rn020025
rn020055
m020056
rn020057
m020058
rn020059
rn020060
rn020061
rn020062
rn020063
rn020064
rn020065
fn020067
rn020068
rn020069
rn020070
rn020071
rn020072
rn020073
rn020103
m020105
rn020106
m02Q108
fn020109
rn020111
rn020112
rn020113
rn020114
rn020115
rn0201 16
rn020117
rn020118
rn020119
rn020120
rn020121
rn020151
fn020152
rn020154
rn020156
rn020157
m020159
m020160
rn020l61
m020162
rn020163
rn020164
rn020165
rn020166
r 0020167
rn020168
m020169
m020199
rn020201
m020202
rn020203
m020204
rn020205
m020206
rnQ20207
m020208
m020209
m020210
rn020211
rn020212
H2O
163619.84
168371.27
170600.28
173343.91
174200.95
174840.13
155678.38
68734.70
124502.04
157047.25
159901.83
161612.03
162998.38
166125.84
169818.59
172188.23
174335.75
174774.98
162360.83
165298.31
167620.13
170728.16
172724.53
174344.33
174256.94
167172.97
75471.93
104926.76
154868.09
161431.27
164482.42
167722.56
170229.89
172423.41
173806.52
174079.52
160609.72
165990.53
169304.50
173272.08
174772.02
85713.42
98144.73
155159.50
160376.83
161735.19
163983.06
166650.97
168250.84
171178.08
172924.41
174334.08
163052.68
164951.55
170514.55
174293.97
175888.27
95742.05
76870.84
151313.89
160470.34
159888.31
163945.34
166184.50
170055.08
172800.13
173699.00
175445.42
161720.27
163302.63
168656.06
170828.56
172892.13
174468.33
175094.69
115336.30
68060.90
145316.03
157839.36
161371.81
163080 39
=•
~
F-
18:361998
(.-)H20
2032.88
2099.06
2150.65
2161.15
2205.69
2230.75
194272
1004.00
203763
1925.68
1966.96
2031.42
2036.04
2060.70
2055.66
2148.41
2165.56
2145.30
2000.01
2066.96
2118.14
2151.78
2193.74
2202.50
2207.83
2130.78
808.99
2013.61
1957.35
2062.13
2054.68
2104.97
2120.77
2171.95
2208.90
2184.38
2076.06
2077.33
2125.03
2217.41
2238.17
928.63
1995.08
2008.03
1996.34
2060.93
2090.41
2130.86
2137.32
2183.02
2173.22
2216.97
2019.00
2043.43
2099.06
223355
2250.68
1090.63
172901
1964.77
1963.21
2051.00
2072.37
2110.57
2175.81
2197.77
2250.94
2245.21
2067.00
2127.02
2216.18
2227.05
2216.38
225475
2240.28
1384.69
1456.23
1966.62
1971.18
203508
2061 49
C02
175601.75
179074.91
180183.00
181739.73
182510.23
183456.13
17239863
125198.12
161022.47
174025.95
174647.63
176281.67
177547.25
178378.16
179334.66
160163.26
181021.30
181555.23
175498.97
177022.66
176587.67
179908.47
161231.28
182290.42
182694.81
179353.80
109330.31
183658.23
173918.94
176168.92
177849.83
179061.83
179894.33
180678.56
161266.13
181688.13
174795.36
176495.03
180218.22
182274.17
183219.36
114463,87
163594.56
173922.78
174321.91
176392.02
178071.80
17944330
179589.89
180827.17
181056.36
181644.52
175031.47
176484.14
179952.39
18222323
183606.16
124319.28
168841.00
174076.45
173518.61
175645.13
177424.09
178604.64
179739.83
18070964
161675.97
182254.39
173918.92
177977.80
179363.27
17998309
181071.36
181925.00
182530.25
140897.64
150593.34
173667.50
172273.52
174127.05
176038 13
mmm
«•
(.-)C02
863.32
908.15
92860
930.83
949.29
959.52
850.34
479.80
918.82
841.61
857.60
884.31
885.20
693.37
888.37
926.30
931.90
922.82
87004
696.77
917.03
928.98
945.39
947.79
950.16
922.87
383.76
925.98
857.38
897.83
892.09
911.24
916.00
936.25
951.00
940.22
904.58
900.69
916.61
955.13
962.77
435.69
923.89
879.35
670.03
897.06
90802
92335
92480
942.06
936.38
954.03
877.75
886.83
906.39
961.20
967.27
506.32
817.18
663.49
655.51
894.25
900.21
914.94
939.92
947.07
969.20
965.22
699.71
924.50
956.57
961.39
955.87
970.17
963.40
630.09
696.44
869.16
861.07
886.10
904.89
trt
CO
13.07
14.14
14.69
15.13
15.53
16.36
21.07
31.13
14.67
13.11
12.76
13.02
13.41
14.06
14.70
15.64
16.30
16.88
13.01
13.38
13.99
14.50
15.14
15.67
16.42
17.70
39.53
5.77
3.10
2.99
352
4.07
4.85
5.42
5.96
6.40
3.00
3.81
4.19
5.56
8.05
39.71
16.36
12.81
2.46
2.88
3.35
4.09
5.08
8.01
8.71
0.39
3.08
3.43
4.51
16.10
16.61
32.03
17.56
12.79
1225
12.38
12.62
12.95
13.61
14.04
14.65
15.16
12.37
13.29
13.75
14.27
14.73
15.35
15.83
29.29
20.09
12.81
12.41
12.36
1263
C-ICO
0.49
0.49
0.51
0.53
0.53
050
0.50
0.30
0.44
0.49
0.52
0.52
0.50
0.50
0.52
0.53
0.54
0.54
0.50
050
0.50
0.49
0.53
0.54
0.51
0.53
0.32
0.41
0.45
0.51
0.50
0.53
052
0.51
0.55
0.51
0.47
050
0.51
0.52
0.53
0.34
0.41
0.49
0.46
0.48
0.51
0.47
0.47
0.49
0.51
0.52
0.48
0.49
0.51
0.49
0.51
0.36
0.35
0.45
0.47
0.47
0.46
0.49
0.51
0.50
0.48
0.50
0.45
0.45
0.47
0.52
0.51
0.51
0.52
0.42
0.33
0.45
0.46
0.46
0.46
=Y=
NO
26.22
26.29
26.83
27.49
26.06
26.60
25.73
15.50
26.91
27.46
26.89
27.14
27.56
27.95
28.00
27.16
27.48
28.62
2523
25.56
25.74
26.27
26.35
26.60
26.55
25.58
12.80
26.12
26.24
25.60
26.20
26.37
26.74
26.67
26.29
27.51
24.39
25.79
26.75
27.12
27.59
14.65
26.29
25.52
26.43
2624
27.14
28.63
26.94
27.13
27.08
27.44
25.27
25.80
26.48
25.97
26.61
15.70
2241
25.28
26.37
25.94
26.30
27.38
26.60
27.43
27.97
27.62
24.94
25.47
25.36
25.53
25.94
25.99
26.97
17.83
18.91
25.22
25.62
2555
25.98
(.-)NO
1052
10.66
11.04
11.12
11.17
11.12
10.35
7.64
10.54
10.22
10.47
10.65
10.78
10.70
10.99
10.96
11.11
11.21
10.55
10.59
10.77
11.03
11.12
1127
11.17
10.91
7.02
10.55
10.33
10.55
10.65
10.87
10.91
10.96
11.07
11.16
10.37
10.72
11.00
11.19
11.25
7.39
10.43
10.26
10.35
10.48
10.74
10.77
10.83
10.95
10.96
11.17
10.53
10.58
11.01
11.10
11.33
7.85
9.72
10.33
10.47
10.54
10.66
10.73
10.94
11.00
11.02
11.06
10.32
10.63
10.75
10.92
11.06
11.07
11.20
6.50
872
10.20
10.24
10.45
10.59
•
NO2
0.00
0.00
0.00
0.00
0.18
0.07
0.00
0.00
0.00
0.00
0.00
0.11
0.00
0.00
0.21
0.00
0.00
0.00
0.06
0.06
0.10
0.17
0.11
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.13
0.00
0.17
0.01
0.00
0.00
0.10
0,02
0.00
0.00
0.00
0.00
0.24
0.08
0.06
0.13
0.02
0.00
0.00
0.05
0.02
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.19
000
0.10
0.33
0.00
0.03
0.00
0.28
0.00
0.09
0.15
0.08
0.03
0.00
0.00
0.00
0.00
0.04
0.00
0.02
•
•— 1
(+-JN02
2.33
2.29
2.14
2.18
2.36
2.17
224
1.58
2.00
2.19
2.33
2.12
2.32
2.25
2.22
2.15
2.10
2.34
2.17
2.15
2.23
2.24
2.28
2.21
2.22
2.26
1.62
1.84
2.16
2.20
2.20
2.28
2.35
2.38
2.18
2.29
1.96
2.24
2.20
2.27
2.15
1.89
1.76
2.20
2.23
2.21
2.24
2.14
2.17
2.32
2.19
2,06
2.26
2.11
2.22
2.23
2.22
1.76
1.53
2.20
2.28
2.20
2.08
2.19
2.21
2.05
2.20
2.07
1.94
2.02
1.98
2.10
2.10
2.08
2.12
1.77
1.42
205
2.02
2.08
2.15
™
N2O
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
\
_L*JN?°
1.08
1.17
1.12
1.12
1.06
1.08
1.11
0.86
1.03
1.12
1.23
1.14
1.20
1.20
1.10
1.12
1.09
1.13
1.13
1.08
1.07
1.15
1.13
1.15
1.11
1.13
0.89
0.97
1.09
1.12
1.14
1.18
1.15
1.11
1.07
1.10
1.01
1.17
1.08
1.13
1.12
0.98
0.98
1.08
1.04
1.06
1.09
1.07
1.04
1.03
1.06
1.06
1.06
1.08
1.09
1.11
1.09
0.90
0.88
1.09
1.13
1.07
1.09
1.11
1.04
1.07
1.04
1.05
0.99
1.01
0.97
1.04
1.06
1.03
1.06
0.88
0.75
1.01
1.05
1.06
1.02
NH3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
=^t
C-INH3
0.49
0.51
0.52
0.52
053
0.54
0.48
0.27
0.51
0.47
0.48
0.49
0.50
0.50
0.50
0.52
0.52
0.52
0.49
0.50
0.51
0.52
0.53
0.53
0.53
0.52
0.21
0.52
0.48
0.50
0.50
0.51
0.52
0.53
0.53
0.51
0.50
0.53
0.54
0.24
0.52
0.49
0.49
0.50
0.51
0.52
0.52
0.53
0.52
0.53
0.49
0.50
0.51
0.54
0.54
0.28
0.46-
0.48
0.46
0.50
0.50
0.51
0.53
0.53
0.54
0.54
0.50
0.52
0.54
0.54
0.53
0.54
0.54
0.35
0.39
0.49
0.43
050
0.51
CH4
5.42
3.93
3.91
4.14
4.21
228
38.36
240.77
102.65
3826
15.51
7.39
4.22
3.11
3.88
3.78
2.43
3.29
8.91
5.76
4.05
4.02
4.11
3.51
4.21
4.79
265.60
123.80
46.96
7.64
5.04
3.25
2.76
3.59
2.67
10.08
3.03
3.33
262.01
139.48
48.62
18.25
8.75
4.82
3.02
5.04
4.63
4.40
4.13
8.71
5.74
3.16
3.30
3.39
196.34
159.37
60.75
19.23
7.41
3.47
2.59
3.43
3.61
3.44
3.93
11.49
3.44
2.71
4.10
3.46
2.88
2.75
145.49
177.84
75.02
22.99
6.40
329
^W
|.-|CH4
7.78
7.88
7.92
8.01
7.96
8.10
7.87
4.05
5.95
7.56
7.87
7.44
7.71
8.10
7.81
7.69
7.97
6.53
7.64
7.65
7.71
7.92
8.15
8.09
8.26
7.99
4.39
5.29
7.27
7.45
7.76
8.08
8.05
8.04
8.36
6.63
8.13
8.49
5.14
5.20
7.43
7.65
7.53
7.89
7-60
7.72
7.65
7.82
8.27
7.44
7.64
7.88
7.94
8.23
5.25
4.43
7.05
7.61
7.51
7.63
7.93
7.70
7,66
7.98
7.64
7.27
7.26
7.54
7.78
7.68
7.68
8.47
5.76
3.89
6.82
7.42
7.46
7.61
C2H6
3.30
3.41
3.14
3.14
2.98
2.53
4.45
12.06
6.75
4.54
3.79
3.07
3.06
3.23
300
2.61
2.93
330
3.11
2.76
2.86
3.32
3.34
303
3.13
2.73
13.34
7.20
4.72
2.99
3.21
3.08
2.84
269
3.04
262
3.08
2.79
13.73
8.30
4.77
3.52
2.79
3.16
2.74
3.15
3.13
3.14
3.14
2.80
3.00
3.07
2.98
2.86
10.75
8.56
5.06
3.67
2.86
2.89
2.93
2.81
3.20
3.13
2.95
3.13
2.81
2.85
2.92
300
2.61
2.87
8.51
9.26
5.81
368
306
294
(.-)C2H6
2.13
2. 5
2. 6
2. 9
2. 8
2.21
2.15
1.11
1.63
207
2.15
2.04
2.11
2.21
2.14
2.10
2.16
2.33
2.09
209
2.11
2.17
2.23
2.21
2.26
2.18
1.20
1.45
1.99
2.04
2.12
2.21
2.20
2.20
2.28
1.87
2.22
232
1.41
1.42
2.03
2.09
2.06
2.16
2.08
2.11
2.15
2.14
2.26
2.03
2.09
2.15
217
2.25
1.43
1.21
1.93
2.13
2.05
2.09
2.17
2.10
2.15
2.18
2.14
1.99
1.98
2.06
2.13
2.16
2.15
2.31
.56
.06
.87
.03
04
2.08
=•*•=
C2H4
0.36
0.33
0.41
0.53
0.27
0.60
1.08
3.64
0.49
0.48
0.37
0.41
0.31
0.25
0.52
0.50
061
0.46
032
0.43
0.41
0.35
0.46
0.46
032
0.46
5.16
071
0.53
0.33
0.38
0.43
0.51
0.45
0.49
0.54
0.38
0.49
5.17
0.71
0.35
0.39
0.27
0.32
0.27
0.35
0.39
0.54
0.53
0.51
0.35
0.45
0.56
0.36
3.51
1.12
0.24
0.13
036
0.32
0.36
0.46
0.25
0.53
0.60
0.28
0.40
0.63
0.59
0.58
0.46
0.44
3.17
1.70
0.45
0.42
0.27
0.36
(.-)C2H4
0.80
0.83
0.85
0.65
0.86
0.87
0.77
0.44
084
077
0.78
0.61
0.81
081
0.81
0.84
0.85
0.84
0.79
082
0.63
0.85
066
0.86
0.86
084
0.35
0.84
0.78
082
0.81
0.83
0.83
0.85
0.87
0.86
0.82
0.82
0.87
0.88
0.40
0.84
0.80
0.79
0.62
0.83
0.64
0.84
0.86
0.85
0.87
0.80
0.81
0.83
0.68
0.66
0.46
0.74
0.79
0.78
0.81
0.82
0.63
0.86
0.66
0.88
0.68
0.82
0.64
0.87
0.88
0.87
0.68
0.66
0.57
0.63
0.79
0.78
0.81
0.62
*+=
H2CO
0.22
02;
0.24
0.26
O.K
0.17
0.33
0.42
0.13
0.02
0.14
0.16
022
027
0.19
0.1!
0.24
0.26
0.22
0.18
0.21
0.32
0.25
0.24
0.18
0.36
0.73
0.10
0.05
0.13
0.09
0.08
025
0.24
022
0.16
0.05
0.10
0.16
0.08
0.53
012
0.06
0.11
0.10
0.15
0.20
0.29
0.25
0.38
0.32
0.16
0.11
0.18
0.15
018
0.59
0.10
0.00
0.07
0.00
0.06
0.09
0.13
0.13
0.16
0.16
003
0.15
0.24
017
0.24
0.19
0.18
0.52
012
0.00
0.09
0.09
002
(•-)H2CC
0.1!
O.K
0.15
0.17
02t
0.24
0.26
0.1G
0.17
0.15
0.13
0.13
0.13
0.13
0.14
0.16
0.1!
0.22
O.K
014
0.12
0.12
013
0.15
0.11
022
0.1C
0.16
015
0.13
0.12
0.13
O.K
0.17
021
0.24
0.16
0.15
0.21
0.25
0.23
0.19
0.18
0.16
0.14
0.14
0.15
0.17
0.17
0.16
0.19
0.14
014
0.13
0.17
0.20
022
0.17
0.16
0.15
0.14
0.13
0.13
0.13
0.14
016
0.19
0.13
0.14
0.14
0.15
0.17
0.19
022
0.23
017
017
0.14
0.14
0.13
^=1
ACTLD
0.71
0.84
1.02
1.4C
1.12
0,67
1.77
1.05
1.05
0.9S
1.17
0.65
1.19
0.73
0.83
1.0C
0.7C
0.6C
1.06
057
1.04
1.7C
1.01
1.17
1.4G
1.5G
1.44
1.42
1.50
1.11
0.9G
1.07
1.1£
121
1.31
i.se
1.34
1.61
1.05
1.36
1.34
1.48
0.91
1.36
0.78
1.26
1.35
0.91
1.20
1.51
1.33
1.15
1.09
1.05
1.32
1.42
1.31
1.09
1.32
1.20
0.90
0.87
0.97
124
0.95
1.33
1.15
1.20
1.62
1.33
1.64
1.70
0.93
1.29
1.32
1.35
1.36
1.30
1.45
2.09
•-JACTLD
0.71
0.71
0.7!
0.8!
1.CK
1.25
1.3!
0.9G
OK
0.7«
0.66
0.7C
0.66
0.7C
0.73
0.84
0.96
1.17
0.72
0.71
0.65
0.65
069
0.7!
0.95
1.16
0.96
0.66
0.79
0.66
0.65
0.70
0.75
0.89
1.09
125
082
078
083
1.11
1.30
1.22
1.02
0.93
0.83
0.75
0.76
0.80
087
091
0.66
1.01
0.75
0.71
0.70
0.68
1.04
1.13
0.69
0.66
077
0.74
0.66
0.69
0.68
0.74
0.85
1.01
0.70
0.76
0.76
0.78
0.87
1.01
1.17
1.23
0.87
0.88
074
0.72
0.70
•F
C4*
061
0.75
084
0.64
o.8<
0.93
0.96
1.67
1.31
1.04
0.64
0.73
0.7C
0.8C
0.84
0.91
OB:
0.79
0.85
0.83
0.8C
082
0.91
0.8!
0.92
086
2.01
1.4!
1.06
0.81
0.8!
0.83
0.8!
098
0.99
0.92
0,66
0.85
0.81
0.92
0.90
171
1.57
1.14
0.95
0.91
068
0.67
0.66
092
0.93
1.00
0.87
0.64
0.88
0.93
0.94
1.64
1.55
1.13
0.86
0.76
0.78
0.74
0.82
0.76
0.77
0.63
067
0.73
0.79
0.84
0.85
0.60
0.85
1.44
1.63
1.16
0.91
0.81
0.75
=HB=
i
C-IC4'
052
0.53
0.53
0.54
0.53
05.
053
0.27
0.4C
0.51
0.5:
OSi
0.52
05<
0.52
0.52
os:
0.57
0.51
0.51
0.52
o.s:
0.55
0.5-
055
0.5<
0.2!
0.35
049
0.50
0.5:
0.5;
0.5J
054
0.54
05!
0.4!
0.54
0.55
0.57
0.57
0.34
0.35
0.5C
0.51
0.5C
0.53
0.51
0.52
0.53
0.52
055
050
0.51
0.53
053
0.55
0.35
0.30
047
0.52
0.50
0.51
0.53
0.52
0.53
0.53
052
0.49
0.49
050
0.52
053
0.53
0.57
0.39
0.26
0.46
0.50
0.50
051
CH3O>
1.6!
1.6,
1.9<
2.0.
2.0;
2.15
2.02
1.3:
2.15
1.7:
1.81
1.6!
1.92
1.81
1.91
1.«
1.9]
1.67
1.71
1.8]
1.8:
1.95
1.9:
2.«
2.11
2.15
0.81
2.19
1.72
1.71
1.81
1.72
206
20(
2.05
2 Of
1.9;
1.80
1.8C
1.93
1.98
0.83
2.15
17!
1.77
1.89
1.96
1.98
1.8G
2.24
229
2.12
1.76
1.83
1.95
2.12
1.88
1.04
1.93
1.76
1.75
1.68
1.89
1.89
1.86
2.00
1.97
1.95
1.87
1.86
1.78
1.94
1.92
1.96
201
1.33
1.70
1.75
1.64
1.79
182
""f1^"!
r i i
•-1CH3OH
1.3S
13!
1.41
1.44
1.4E
1.46
1.30
0.72
1.43
1.30
1.31
1.36
1.36
138
1.39
1.42
1.44
1.43
1.32
1.35
1.3E
1.41
1.43
1.44
1.43
1.40
0.53
145
1.32
1.34
130
1.38
1.39
1.42
1.42
1.44
1.37
1.37
1.40
1.43
1.46
0.60
1.46
131
1.32
1.34
1.36
1.40
1.39
1.44
1.44
1.43
1.32
1.35
1.39
1.45
1.45
0.72
1.26
1.33
129
132
1.35
1.37
1.41
1.43
1.44
1.46
1.34
1.39
1.42
1.41
1.44
146
1.44
0.92
1.07
1.33
1.28
1.31
1.35
HO.
16.1!
1544
18.5!
24. 12
31.65
39.35
45.69
30.75
26.00
19.93
16.34
14.29
1393
15.43
17.66
22.26
26.92
37.23
16.92
14.65
13.24
13.3C
15.01
19.66
27.57
35.40
29.1C
24.02
20.60
15.14
14.3!
15.41
16.61
24.66
31.95
40.18
20.92
19.57
22.33
34.31
42.42
40.68
30.22
2634
21.71
1923
1622
16.98
23.98
24.22
23.58
27.64
17.86
15.75
15.60
24.68
31.57
36.33
25.46
23.31
1694
16.85
15.35
14.68
15.40
17.66
22.79
29.94
1667
16.85
17.27
18.96
23.91
30.96
38.31
39.12
25.42
24.10
19.31
1666
15.66
C-1HCI
0.1!
0.1!
0.21
0.24
02!
0.34
0.37
027
0.24
0.21
0.18
0.19
0.18
015
0.20
023
0.26
0.32
0.2C
0.1G
0.11
0.16
0.1G
021
0.26
0.31
0.26
0.23
0.21
0.1G
0.1!
0.1G
0.20
0.24
0.2G
034
0.22
0.21
0.22
0.30
0.35
0.33
0.28
0.25
0.22
0.20
0.20
0.22
023
0.25
023
0.27
0.20
0.19
0.19
0.24
0.2G
031
0.24
0.23
021
0.20
0.18
0.19
0.16
020
0.23
027
0.19
0.20
020
0.21
0.23
0.27
0.32
0.33
024
0.24
0.20
0.19
0.19
-------
18:50-50
18:51:49
18:52:50
18:54-50
rn020213
rn020214
m020215
m020217
Average
Sid, dev.
Maximum
64089.89
69748.16
71664.14
74348.27
5943920
24925.55
17588827
2078.72
2152.40
2199.44
2238.57
2047.50
268.46
2254.75
77529.67
79019.36
014608
1658.83
5532.26
3424.49
83658.23
09330.31
902.86
930.07
948.75
963.31
891.32
105.67
970.17
363.76
3.20
3.80
4.40
5.47
5.66
4.89
: 9.71
2.25
0.49
0.481
0.48
0.50
049
0.05
0.55
030
26.74
26.55
2667
27.57
25.72
2.76
2862
12.80
D.75
0.80
0.96
1.13
D.61
0.80
11.33
7.02
0.00
oTTv
0.03
(Too
0.05
0.07
0.33
0.00
1.99
2.06
27l3
2.12
0.18
2.38
1.42
0.00
0.00
0.00
0.00
0.00
0.00
000
.07
.06
/U>
.07
0.08
1.23
0.75
OOO1
0.00
0.00
0.00
0.00
0.00
0.00
O521
0.53
O54~
0.50
0.06
0.54
0.21
2.81
2.78
754
26.64
57.61
265.60
2.28
7.67
7.59
7.77
8^26
7.51
0.97
8.53
3.89
3.03
3.10
3.12
3~10
3.86
2.26
13.73
2.45
2.10
2TT01
2.13
726
2.05
0.27
2.33
1.06
0.49
0.52 '
0.52
O32
0.65
0.87
5.17
0.13
0.82
085
O8B
0.81
0.86
035
cTT
0. 5
0. 8
0. 8
0. 2
0.73
0.00
0.14
0.14
0.14
020
0.16
0.04
0.29
0.12
.14
.56
!eo
.23
0.29
2-08
0.57
0.71
07?
0.73
1.03
0.66
0.19
1.50
0.65
066
0.86
~ 0.80
0.95
0.25
2.01
0.70
0.51
0.52
0.52
O55
0.50
0.07
0.57
026
1.82
2.02
2.13
1.93
1.67
0.24
2.29
0.63
.40
.42
.43
.35
0.17
1.46
0.53
16.05
16.44
18.17
30.09
2324
8.46
51.19
13.24
0.20
0.2G
0.28
023
0.05
0.41
0.18
-------
/UgMuptn^wetjMJB^^H
yf^ffftAbtfcMg^ff^
Description: Chemfime fane kiln
Method title: lime Uncond
Stalling Date/Time: Thu Jun 25 15
Time
15:48:36
15:49:36
15:50:36
15:51:35
15:53:35
15:54:36
15:55:35
15:56:36
15:57:35
15:58:35
15:59:37
16:00:37
16:01:36
16:02:36
16:03:37
16:05:37
16:36:37
16:37:38
16:38:38
16:39:37
16:40:38
16:41:39
16:42:39
16:43:38
16:44:39
16:45:38
16:47:39
16:48:39
16:49:39
16:50:39
16:51:38
16:52:40
16:54:39
17:24:45
17:26:46
17:27:45
17:28:45
17:29:46
17:30:45
17:31:45
17:32:45
17:33:46
17:34:45
17:35:45
17:36:45
17:38:45
17:40:46
17:42:45
18:13:49
18:14:48
18:15:48
18:16:49
18:17:48
18:16:49
18:19:48
18:20:49
18:21:48
18:22:49
18:23:49
18:24:49
18:25:49
18:26:48
18:27:49
18:29:49
"'30'4'
Filename
m020031
m020032
m020033
m020034
m020036
m020037
m020038
m020039
m020040
TO020041
m020042
m020043
m020044
m020045
m020046
rn020048
rn020079
rn020080
m02D061
in020062
m020083
m020064
m020085
m020066
m020087
rn020088
m020090
rn020091
rn020092
rn020093
rn020094
rn020095
rn020097
rn020127
rn020129
rn020130
rn020131
rn020132
rn020133
rn020134
rn020135
rn020136
rn020137
m020138
m020139
m020141
rn020143
rn020145
m020176
m020177
m020178
tn020179
m020180
m020181
rn020182
m020183
m020184
H1020185
rn020186
m020187
rn020186
m020189
rn020190
rn020192
Average
Std. dev.
Maximum
Minimum
H20
168011.38
169163.98
173001.52
174676.61
177458.08
177399.64
137532.78
61599.17
150319.36
165055.97
165561.16
167747.14
169576.70
171539.91
176670.91
176956.53
168432.09
170637.75
173102.56
174982.33
177152.08
177846.09
177938.58
154182.96
56308.09
135373.66
166365.25
166595.95
168485.97
171263.11
173558.27
175867.11
177469.16
154603.64
158341.06
161219.25
161518.61
162613.56
162530.61
161338.27
84163.10
93358.73
146531.98
162521.08
166516.58
172112.28
179488.06
181180.91
169905.73
173617.69
176017.56
176056.60
178818.50
179275.66
169052.73
59993.44
1 12088.63
163525.91
165709.27
1 67260. 27
168039.72
170787.31
176954.66
178722.96
162246.05
27115.30
181160.91
56308.09
=+=\
I
16:38 1998
(.-)H20
2170.55
2174.37
2260.15
2276.37
2336.40
2380.14
1690.79
1652.37
217355
2119.09
2168.70
2191.12
2204.89
2196.71
2269.87
2298.25
2180.43
2248.39
2283.39
2303.65
2331.39
2379.53
2365.90
2069.67
1216.43
2258.24
2149.62
2206.45
2228.76
2264.97
224527
2303.66
2351.43
1891.63
1872.59
1878.08
1866.45
1896.80
1667.33
1866.23
876.17
1797.51
1671.69
2102.03
2112.82
2231.88
2314.61
2317.57
2252.74
2333.15
2346.82
2400.35
2401.62
2406.75
2339.38
723.06
2569.55
2165.85
2202.15
2237.77
2248.15
2292.16
2337.95
2360.61
214608
312.92
2569.55
72306
CO2
181712.64
18329900
165106.09
186012.59
167941.94
18856297
156792.84
156237.92
183560.31
179340.59
181022.81
183067.50
184068.22
185165.08
185875.30
166815.58
181797.02
183348.47
184891.06
185692.75
187198.56
187727.55
188278.27
176380.50
131246.70
186660.73
180600.06
18271427
164372.95
185205.66
185305.33
186744.97
167402.61
154473.05
157366.56
158392.11
159545.17
159972.06
160451.91
160026.41
99613.05
166719.31
153117.76
176101.03
181912.80
165175.20
166994.42
188353.72
183027.11
165181.59
186161.97
187509.06
188320.08
188967.45
186006.72
101014.08
201081.45
176788.30
180201.44
182348.23
183841.53
185119.00
165749.73
16731323
177891.39
17470.28
201061.45
99613.05
="t=
(.-XC02
939.38
940.06
97377
979.29
1002.62
1021.44
752.83
795.95
956.13
919.58
940.66
948.51
952.90
947.68
974.75
964.93
943.30
970.76
983.69
990.75
1000.74
1020.77
1014.84
907.25
569.47
1007.58
931.72
956.15
964.17
977.37
966.68
989.97
1009.04
826.60
817.63
817.85
612.57
824.95
812.20
612.61
411.76
836.56
737.99
914.29
915.64
962.36
991.48
991.26
973.29
1004.67
1009.24
1029.51
1029.45
1031.14
1011.50
346.93
1173.08
941.18
955.05
969.14
972.94
989.53
1003.74
1020.44
93164
125.00
1173.08
348.93
CO
12.49
12.82
1327
14.02
14.98
1565
32.83
20.26
12.61
12.01
12.19
12.46
12.97
14.43
16.19
18.15
12.75
13.11
13.67
14.21
14.68
15.45
15.86
2253
27.52
13.15
11.71
11.94
12.43
13.32
13.67
14.57
16.30
11.46
12.10
12.66
13.36
1470
16.05
15.86
29.22
15.04
11.47
11.77
11.96
12.68
14.10
15.15
12.95
13.64
14.47
15.30
15.62
16.02
16.73
37.33
15.57
12.40
12.10
12.16
12.55
13.01
1371
17.39
15.12
4.55
37.33
11.46
<*-)CO
0.54
0.52
0.51
0.53
053
0.50
048
032
0.43
0.50
0.46
0.46
0.52
052
0.56
0.53
0.49
0.51
0.52
0.49
0.53
0.54
052
0.49
0.31
0.43
0.49
0.51
0.51
0.52
0.50
0.52
0.52
0.45
0.47
0,47
0.47
050
0.51
0.49
0.36
0.39
0.42
0.47
0.51
0.48
0.49
0.51
0.49
0.51
0.52
0.50
0.54
0.51
0.57
0.28
0.43
0.49
0.49
0.53
051
0.50
0.55
0.54
0.49
0.05
0.59
0.28
1
NO
27.55
28.12
26.42
27.67
27.94
27.14
22.12
21.25
25.92
27.34
26.65
28.53
29.03
28.87
2960
29.21
26.96
26.98
27.28
27.45
27.50
27.55
28.30
25.91
16.96
25.69
27.43
27.65
28.27
28.64
29.19
29.00
28.97
20.38
21.37
22.28
22.56
21.27
21.57
21.14
10.27
23.03
22.01
27.64
28.42
28.79
29.37
29.35
26.43
26.98
28.19
27.01
27.70
27.89
26.42
10.99
29.05
27.58
26.70
27.71
27.88
29.17
29.29
28.43
26.45
3.82
31.09
10.27
C-INO
11.08
11.22
1.26
1.33
1.63
1.61
9.39
9.20
0.77
0.80
0.79
0.98
1.22
1.37
1.63
1.57
0.90
1.16
1.32
1.32
1.47
1.54
1.64
0.57
7.76
1.04
0.86
1.06
1.15
1.33
1.36
1.43
1.46
9.08
9.40
9.51
9.56
9.64
9.66
9.59
6.66
9.56
9.06
10.66
11.04
11.34
11.58
11.69
11.03
11.25
11.42
11.58
11.75
11.73
11.29
6.50
11.74
10.66
10.64
10.97
11.10
11.27
11.43
11.57
1062
1.08
11.91
6.50
•
N02
0.06
0.00
0.00
0.14
0.01
0.00
0.00
0.00
0.00
0.05
0.04
0.00
0.00
0.00
0.00
0.00
0.02
0.28
0.03
0.12
0.00
0.08
021
0.06
0.00
0.18
000
0.00
0.11
0.00
0.00
0.04
0.08
0.08
0.00
0.00
0.07
0.08
0.00
0.00
0.00
0.00
0.00
0.03
0.17
0.05
0.45
0.28
0.03
0.18
0.24
0.15
0.00
0.27
0.00
0.00
007
0.19
0.05
0.00
0.16
0.22
0.08
0.18
0.09
0.10
0.00
I"
(.-)N02
226
2.33
2.12
2.21
2.24
2.10
1.97
1.39
2.03
2.09
218
2.21
2.14
2.20
206
218
2.04
2.18
227
217
214
213
222
2.14
1.20
202
2.20
2.32
2.28
2.14
2.24
218
2.12
206
2.09
219
2.30
2.01
2.03
2.03
1.73
1.63
2.15
1.92
2.16
210
229
2.31
1.96
2.08
2.09
2.07
2.05
2.33
1.30
1.81
2.08
2.04
2.06
2.18
213
2.14
221
2.10
021
1.20
•1
TOO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0:00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0,00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
f=^:
<+-)N20
1.16
1.26
1.17
1.15
1.15
1.09
1.09
0.77
1.12
1.01
1.01
1.08
1.20
1.09
1.15
1.18
1.05
1.10
1.10
1.08
.1.06
1.07
1.15
1.05
0.63
1.00
1.09
1.08
1.14
1.13
1.13
1.06
1.06
1.07
1.14
1.20
1.31
1.17
1.16
1.12
0.04
0.94
1.10
1.05
1.06
1.04
1.00
1.06
1.01
1.05
1.10
1.10
1.08
1.11
0.75
0.99
1.07
1.06
1.06
1.11
1.13
1.14
1.09
1.06
0.10
0.63
NH3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
=^=
(.-)NH3
0.53
0.53
0.54
0.55
0.56
0.57
0.42
045
0.54
0.51
0.53
0.53
053
0.53
0.55
0.55
0.53
0.54
0.55
0.55
0.56
0.57
0.57
0.51
0.33
0.56
0.52
0.54
0.54
0.55
0.54
0.55
0.56
0.46
0.46
0.46
0.45
0.46
0.45
0.45
0.23
0.47
0.41
0.51
0.51
0.54
0.55
0.55
0.54
0.56
0.58
0.56
0.58
0.57
0.20
0.66
0.53
0.53
0.54
0.54
0.55
0.56
0.57
0.52
0.07
0.20
CH4
3.43
3.30
2.46
2.75
1.96
2.39
148.75
170.93
69.53
31.79
13.39
5.04
322
1.94
2.72
2.69
7.70
4.95
2.80
323
2.56
2.17
2.87
39.53
212.65
105.15
15.88
5.42
3.12
2.44
1.95
2.37
2.66
10.89
3.35
3.67
3.67
2.98
363
2.42
160.99
137.01
46.87
9.64
2.97
1.70
2.56
2.64
3.69
2.67
3.92
2.59
2.74
237.33
153.92
41.94
14.10
4.32
1.65
2.10
2.42
2471
52.94
237.33
1.57
=•*=«=**
(«-)CH4
8.11
8.59
8.22
8.77
8.90
8.60
7.36
3.55
7.00
7.33
7.24
7.82
8.08
8.41
6.73
8.94
7.76
7.93
8.24
6.40
8.54
8.62
882
7.77
3.48
6.26
7.77
8.10
8.12
8.39
8.76
6.50
8.53
6.93
7.63
7.97
6.33
7.92
6.21
7.84
4.68
5.04
7.03
7.75
7.93
7.97
8.39
8.84
7.72
6.63
8.73
8.76
8.39
3.75
5.45
7.77
7.60
7.64
6.16
8.61
8.78
7.86
1.20
9.42
3.48
C2H6
2.77
3.08
2.52
2.65
255
2.55
9.50
8.43
6.45
3.76
293
2.83
2.76
2.56
290
3.25
3.21
2.83
276
2.39
2.60
254
267
4.32
1030
690
3.49
3.13
2.82
2.75
2.78
251
237
260
2.66
291
2.98
247
2.50
2.41
9.62
7.76
4.35
3.01
2.72
252
2.76
2.55
2.93
2.72
• 2.63
2.74
2.40
2.28
12.03
6.85
4.46
3.14
2.79
2.66
2.93
2.59
3.58
2.08
12.03
2.28
(•-)C2He
222
2.35
2.25
240
2.43
2.35
2.01
097
1.91
2.00
1.98
2.14
2.21
2.30
2.39
2.44
2.12
2.17
2.25
2.30
2.34
2.36
241
2.12
0.95
1.71
213
2.21
222
2.29
2.40
2.32
2.33
1.69
2.09
2.18
2.28
2.17
225
2.14
1.28
1.38
1.92
2.12
2.17
2.18
2.29
2.42
2.11
2.32
2.38
2.39
2.39
2.29
1.03
1.49
212
2.08
2.14
2.23
2.35
2.40
2.15
0.33
2.58
0.95
C2H4
0.73
0.43
0.57
0.51
0.51
0.53
3.69
1.46
0.35
0.4S
0.57
0.45
0.49
0.53
0.51
0.61
0.49
0.46
0.50
0.65
0.52
0.44
0.49
1.23
3.38
0.75
0.44
0.54
0.52
0.38
0.57
0.55
0.73
0.40
0.41
0.48
0.53
0.62
0.65
0.38
3.54
0.77
0.42
0.56
0.37
0.36
0.52
0.50
0.67
0.50
0.81
0.62
0.47
0.50
0.68
4.77
0.93
0.56
0.49
0.58
0.57
0.61
0.56
0.73
0.77
4.77
0.30
(«-)C2H4
0.66
086
0.69
089
0.91
093
0.69
0.72
0.67
0.64
0.66
0.66
0.67
0.66
0.89
0.90
0.86
0.88
0.90
0.90
0.91
0.93
092
0.83
0.54
0.92
085
0.87
0.88
0.89
086
0.90
0.92
075
0.74
0.74
0.74
0.75
0.74
0.74
0.37
0.76
0.67
0.83
0.83
0.88
0.90
0.90
0.89
0.91
092
0.94
0.94
0.94
0.92
0.32
1.07
0.86
0.87
0.88
0.69
0.91
0.93
0.85
0.11
1.07
0.32
=•*•=
H2CO
0.05
0.00
0.04
003
0.00
025
052
021
006
0.05
0.00
0.05
0.09
0.07
0.45
0.12
0.12
0.08
0.06
006
0.16
000
0.13
027
0.36
0.07
001
0.01
0.03
0.00
0.10
0.12
007
0.08
0.01
0.17
0.09
020
0.15
0.18
0.47
0.16
0.11
0.06
0.07
0.04
0.08
0.09
0.18
0.07
009
0.00
0.04
0.06
0.18
0.53
0.00
000
0.06
0.01
0.13
0.14
0.15
0.11
0.11
0.53
000
(»-|H2CC
0.20
0.2!
028
0.29
0.32
0.34
0.30
0.17
0.1!
0.17
oie
0.1S
0.22
0.24
0.23
0.21
0.11
0.22
027
0.3C
0.31
0.33
0.31
0.16
0.1C
0.16
0.18
021
027
0.28
0.30
0.34
0.14
0.14
0.16
0.20
0.22
0.24
0.25
0.21
0.18
0.19
0.18
0.19
0.23
0.25
0.30
0.17
0.19
0.24
0.29
0.29
032
0.32
0.20
0.17
017
0.17
0.17
020
0.20
0.29
0.23
0.06
0.34
0.14
«*=)—
ACTLI
0.62
0.45
047
0.96
I.Oi
1.17
1.01
0.75
0.75
1.21
0.95
0.65
0.9G
0.53
0.92
062
1.11
0.85
0.46
1.1G
1.3C
0.82
1.14
0.64
0.9C
083
0.69
0.31
0.99
087
1.19
192
1.62
1.46
2.10
1.08
1.40
1.87
1.73
1.64
1.21
0.86
1.37
1.05
0.36
0.16
047
1.03
1.32
0.74
1.03
1.21
099
1.30
1.71
1.60
0.94
0.91
1.09
065
1.50
1.13
1.43
1.04
0.40
2.10
0.16
«-)ACTLC
.02
.21
.4!
.53
.67
.76
-5(
0.90
0.96
0.90
0.94
0.98
1.18
1.25
1.19
1.45
0.93
1.15
1.42
1.57
1.6C
1.71
1.64
0.97
0.95
0.65
0.96
1.11
1.40
1.4S
1.5B
1.71
0.72
0.71
0.82
102
1.16
127
1.33
1.09
0.96
0.96
0.94
0.99
1.20
1.33
1.59
0.68
1.00
126
1.52
1.55
1.67
1.68
1.03
090
0.92
0.89
0.91
1.07
1.08
1.04
1.51
1.21
0.31
1.78
0.71
C4»
0.68
0.72
0.72
0.71
068
068
1.39
1.50
1.22
0.62
076
0.63
0.81
0.71
0.75
0.6!
06!
0.7;
0.7!
0.6!
071
072
06!
174
1.3!
0.7f
06!
065
0.7!
0.71
0.7:
082
1.0:
0.94
1.01
0.93
1.0C
1.03
0.95
1.59
1.67
1.1S
0.78
0.71
070
0.71
0.72
0.73
0.76
0.79
0.76
0.74
073
0.77
1.61
1.55
1.01
082
0.67
0.64
064
0.75
0.75
0.66
0.27
1.74
0.55
=^
(»->C4«
0.54
0.58
0.55
0.59
0.60
0.56
0.49
024
0.47
0.49
0.49
0.52
05.
05!
0.5!
0.6!
0.5:
0.55
0.5!
0.57
05!
0.59
052
0.23
0.4:
052
05<
0.51
O.Sf
0.5!
0.57
0.57
0.46
0.51
0.53
O.Sf
0.53
0.55
052
031
0.34
0.47
0.52
053
0.53
0.58
059
0.52
0.54
0.57
0.58
059
0.59
0.58
0.25
0.36
052
0.51
0.53
0.55
0.56
0.58
0.59
0.53
0.06
0.63
023
CH30H
1.90
1.66
1.90
2.08
2.1:
2.09
1.64
201
1.9!
1.&
1.97
2.0;
2.0!
2.1'
2.12
2.0"
1.90
1.9i
2.11
207
2.02
2.K
2.14
2.0!
1.47
232
1.9<
1.9C
1.6E
2.0!
222
23:
2.32
1.5C
1.45
1.47
1.55
1.61
1.57
1.77
0.75
1.83
1.44
1.87
1.91
1.93
204
2.04
202
2.08
2.24
2.21
223
2.11
212
0.74
2.80
1.87
1.93
2.03
204
2.11
2.10
229
1.95
0.30
2.80
0.74
=^=
+-)CH3OH
1.44
1.45
1.50
1.49
1.52
1.55
1.14
1.26
1.48
1.41
1.44
1.45
1.4!
1.41
1.4!
1.5!
1.44
1.4!
1.49
1.4!
1.53
1.5:
1.54
1.31
0.90
1.5*
1.42
1.45
1.47
1.4!
1.47
1.52
1.55
1.«
1.14
1.15
1.14
1.1E
1.17
I.It
O.SC
1.26
1.06
1.37
1.42
1.48
1.52
1.55
1.48
1.51
1.52
1.55
1.55
1.56
1.52
048
1.62
1.40
1.43
1.46
1.47
1.49
1.50
1.52
1.41
021
1.62
046
HCL
29.43
38.94
48.7
51.77
59.72
62.5!
57.11
28.11
2842
2554
26.0.
28.62
36.51
39 S-
37.57
50.01
222!
2645
35.83
47.51
52.51
55.21
5693
57.35
27.5;
26.7:
22.69
27.0*
34.61
46.51
51.42
55.21
62.4:
16.15
17.45
21.6:
30.7(
37.04
41.11
44.25
34.13
28.4i
28.33
26.7E
28.49
38.96
44.75
55.26
23.56
30.04
40.61
50.86
5372
57.00
5867
32.37
2562
2559
23.69
25.91
33.11
33.29
32.03
50.40
38.72
13.13
6253
16.79
^
(•-1HCL
026
0.33
0.40
041
0.45
0.48
0.43
0.24
0.26
024
025
026
032
034
0.32
0.39
022
0.25
0.31
038
042
043
046
0.44
026
0.26
0.23
026
0.30
0.38
0.40
0.43
0.4I
0.20
0.11
022
0.21
0.3-
0.34
03!
0.3!
0.2!
028
0.25
0.27
0.32
0.36
0.43
0.24
0.27
0.34
0.41
0.42
0.45
0.45
0.28
0.24
025
024
0.25
029
0.29
0.26
0.41
0.33
0.08
0.48
0.19
-------
APPENDIX D
FTIR FIELD DATA SHEETS
-------
Inlet HT
FTIR Temperature Readout Sheet
Outlet HT
Inlet Pump
Z77
-LI I
10
Outlet Pump
11
FTIR Pump
2ft
12
Pump Box
viv
7/
in
in.
13
Extra HT
14
FTIR Jumper
3Z7
15
Pump Jumper
•yjr
16
Hot Box
17
Hot Box
18
Extra HT
7/7?.
19
20
Electronics Box
•7
-------
Facility
Stack ID
Date
Run Number
\-hoi-M
FTIR Temperature Readout Sheet
-------
Facility
Stack ID
Date
Run Number
C&
//
C/-L5/9V
/-
FTIR Temperature Readout Sheet
Channel
Description
Inlet Stack
IIS
Outlet Stack
Inlet Probe
Outlet Probe
Inlet Filter
Outlet Filter
Inlet HT
Outlet HT
Inlet Pump
10
Outlet Pump
11
FTIR Pump
i£
12
Pump Box
13
Extra HT
14
FTIR Jumper
15
Pump Jumper
16
Hot Box
f?
17
Hot Box
18
Extra HT
19
20
Electronics Box
-------
APPENDIX E
PRE-TEST CALCULATIONS
-------
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 HC1 program from late 1997.
Appendix B
Potential Interferant Calculations:
These calculations determine potential spectral interferants for the analytes of interest (i.e., HC1).
The results for HC1 are given in the table below. The analysis region for HC1 is not given since it
is considered proprietary information.
TABLE 1
Interferant Calculations
: - Analyte
HC1 (target)
H,O (potential interferant)
CO2 (potential interferant)
H2CO (potential interferant)
CH4 (potential interferant)
"^'.jr^V^ ? «
Concentration I
0.1 ppmv
20%
20%
1 ppmv
20 ppmv
*\\iiBikK . m
Band area
0.0005436
0.2213
0.000002
0.0002100
0.0105
tt
IAFAAI ,
-
407
0.0036
0.386
19.3
AVT
:; ; Average^absorbance; i
0.00000322
0.00131
0.00006213
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: H2O and CH4.
Appendix C
Noise Level
This calculation determines instrumental noise level in the spectral analysis region for HC1. For
a 1 minute integration time, the RMS noise is found to be 0.00022 (absorbance units) in the HC1
spectral analysis region by the procedure given in Appendix G.
Appendix D
Estimatin Minimum Concentration Measurement Uncertainties CMAU)
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 (FRLO
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 (POLO
This section determines the fractional calibration uncertainties when analyzing each reference
spectrum. These results will be applied to the compounds analyzed in the HC1 analysis region.
The table below gives the results.
TABLE 2
FCU Determination
Analyte
H2O
HC1
CH,
ASC (ppm)
113000
253
491
ISC (H2O)
1 15000
-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.
Appendix H
Determining Sample Absorption Pathlength (Lsl and Fractional Analytical Uncertainty
Since the HC1 reference spectrum used in this program were measured at the same pathlength to
be used during testing, these calculations are not required.
-------
APPENDIX F
POST-TEST CALCULATIONS
-------
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 HC1 -Chemlime
Spectral File Name
RN020005.spa
RN020029.spa
Inlet/Outlet
Outlet
Inlet
Error (ppm)
0.23
0.23
Concentration (ppm)
22.6
22.7
•' FMU
0.010
0.010
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.
------- |