United States
 Environmental Protection
 Agency
Office of Air Quality
Planning and Standards
Research Triangle Park. NC 27711
EPA - 454/R-00-009
March 2000
  Air
&EPA
Final Report of Lime Manufacturing Industry
Fourier Transform Infrared Spectroscopy
National Lime and Stone Company
Carey, Ohio

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       Lime Kiln Source Characterization
I
o                        Final  Report
                         Contract No. 68-D7-0001
                         Work Assignment 2-03
                     National Lime and Stone Company
                              Carey, Ohio
                              Prepared for:

                             Michael L. Toney
                        Emission Measurement Center
                   Emission, Monitoring, and Analysis Division
                   Office of Air Quality Planning and Standards
                     U. S. Environmental Protection Agency
                   Research Triangle Park, North Carolina 27711
                              January 2000
                      U.S. Environmental Protection Agency
                      Jw 5. Library (PL-12J)
                      / •  A-t^t Ja^on Boulevard, 12th Floor
                      »-'"v.aeo. IL  60604-3590

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                                Table of Contents

                                                                              Page

1.0    INTRODUCTION	 1-1
      1.1     Objectives  	 1-1
      1.2     Brief Site Discussion 	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 	2-1
             2.2.1  Overview  	2-1
             2.2.2  FTIR Emission Results 	2-2

3.0    SAMPLING AND ANALYTICAL PROCEDURE  	3-1
      3.1     Determination of Gaseous Organic HAPs, HC1, and Criteria Pollutants by
             Fourier Transform Infrared Spectroscopy (FTER) 	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
                                         11

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                                  List of Figures

                                                                              Page

2-1    HC1 Inlet Run - Wet Scrubber	2-4
2-2    HC1 Outlet Run - Wet Scrubber	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
3-1.   Typical FTIR Operating Parameters 	3-6
3-2.   Compounds for Which Reference FTIR Spectra Are Available in the ERG Spectral
      Library 	3-10
4-1.   HC1 QA Spike Run 1 Results  	4-3
4-2.   HC1 QA Spike Run 2 Results  	4-4
4-3.   Gas Standard Analysis Results  	4-5
                                         in

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1.0    INTRODUCTION

       The purpose of this testing program is to: (1) quantify hydrogen chloride (HC1) emission
levels; and (2) gather screening data on other hazardous air pollutants (HAP) emissions from
lime production plants to support a national emission standard for hazardous air pollutants
(NESHAP).

       Three measurement methods were conducted at this facility:

             Fourier Transform Infrared Spectroscopy (FTIR) (EPA Draft Method 320);
             Gas Filter Correlation - Infrared (GFC-IR) (EPA Method 322); and
       •      Dioxm/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 HC1.

       The lime kiln facility and sampling locations tested in this program are detailed in the
report prepared  by PES.

1.1    Objectives

       The objective of the FTIR testing of the lime facility was to quantify HCl and perform
screening of other HAPs detectable by FTIR, using EPA Draft Method 320.


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1.2    Brief Site Discussion

       Testing was conducted at the National Line and Stone Company in Carey, Ohio. Testing
was performed on the inlet and outlet of a wet-scrubbing device on Kiln #1, a natural-gas fired
"doughnut" 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 National Line and Stone Company, located in Carey, 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

       The complete sampling and analytical matrix performed are presented in the report
prepared by PES. In this report, only FTIR-related test matrix will be provided.  FTER
spectroscopy was used, in accordance with EPA Draft Method 320, to quantify HCl and, in a
screening capacity,  to measure other HAPs that FTIR can detect.

       FTIR measurements were conducted in two sets:

       •      Unconditioned; and
       •      Conditioned.

       Unconditioned sampling was conducted for the duration 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 I-hour period to screen  for aromatic
species such as benzene, toluene, etc.
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       During each run (i.e., unconditioned or conditioned) the FTIR analysis time was divided
equally between inlet and outlet samples. Each location was monitored for no less than a total of
50 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 truly
representative of the location being tested in that set.


1.3,2  Test Schedule


       The test schedule for EPA Methods 23, 25A, and 322 measurements is given by the
report prepared by PES.  Section 2.1 gives the test log for the 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 for 35 minute intervals at the
             outlet and inlet, in order to synchronize with the GFC-IR measurements
             performed  by APCC.

             The EPA Work Assignment Manager authorized 1 hour total sample collection of
             the conditioned samples, Vi hour each on inlet and outlet.  If other HAPs were
             detected, then the run would extend to the full 2 hours, as originally planned. In
             this case, no additional HAPs  were detected in the conditioned samples.

             Some indicated sampling system temperatures were below the 350°F target that
             was stated  in the test plan. These temperatures are the highest attainable with
             these sampling system components.  It was determined after completion of the test
             program that the measured temperature of some of the sampling system
             components was a sensitive function of thermocouple location. When test
             thermocouples were inserted in the sample-wetted regions of the sampling system,
             they indicated temperatures above 350°F in all cases
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1.4    Test Report


       This final report, presenting all data collected and the results of the analyses, has been
prepared in four sections, and an appendix as described below:
              Section I provides an introduction to the testing effort and includes a brief
              description of the test site and an overview of the emissions measurement
              program;

              Section 2 gives a summary of the test results for the FTIR results for HCl and
              other detected species;

              Section 3 presents detailed descriptions of the sampling and analysis procedures;
              and;

              Section 4 provides details of the quality  assurance/quality control (QA/QC)
              procedures used on this program and the QC results.
A detailed description of the site, sampling locations, process and plant operation during the field

test is provided in the PES-prepared report. Copies of the 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
National Lime and Stone Company in Carey, Ohio on September 2, 1998. Results for the
extractive FTIR test conducted for HC1 and screening for selected HAPs are provided in this
section.  Other (non-HAP) species detected are also reported.  Testing was performed at the inlet
and outlet of the wet scrubber.

2.1   Emissions Test Log

      ERG performed extractive FTIR measurements for HCl and other HAPs.  Table 2-1
presents the emissions test log that shows the test date, location, run number, test type,  and run
times for each method.

                          Table 2-1.  Emissions Test Log
Date
9/02/98
9/02/98
9/02/98
Location
Wet Scrubber
(inlet/outlet)
Wet Scrubber
(inlet/outlet)
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)/
Sj/stem QC (outlet)
Run Time
08:06-09:21
12:50- 17:10
17:45- 18:45
17:06- 17:30
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
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.
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2-1

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       FTER data were collected by alternating sample analysis between inlet and outlet every
35 minutes.  Inlet and outlet samples were drawn on a continuous basis; only the FTIR sample
analysis was alternated between inlet and outlet.  The first 10 (or 25) data points from each
35 minute inlet (or outlet, respectively) measurement period were discarded to eliminate data for
samples containing both inlet and outlet sample gas. These data points correspond to the
apparent response time of the complete FTIR sampling and analysis system (details on
measurement of system response time are given below).  The measurement run contained a total
of 50 and 47 1-minute average data points for both inlet and outlet measurements, after
discarding the transient data points. A 1-minute average data point is generated by analysis of a
composite spectrum consisting of an average of 43 FTIR spectra collected over the  1 minute time
period.

       Section 2.1 gives the  schedule of the tests performed at the Redland Stone Products in
San Antonio, Texas.  Both unconditioned and conditioned samples were analyzed.  Conditioned
samples were generated by passing the raw  sample gas through a water vapor/carbon dioxide
scrubbing system (see Section 3.1.1 for details).  Conditioned samples extracted from the wet
scrubber were measured after unconditioned sample extraction for the next hour. One minute
average data points were generated by analysis of the composite spectrum consisting of an
average of 43 FTIR spectra collected over the 1 minute period.  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.

2.2.2  FTIR Emission Results

       This section contains the FTIR HC1 test results for the wet scrubber inlet and outlet.
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       2.2.2.1  FTIR HCI Test Results. The estimated FTIR HCl detection limit for this
study was between 0.11  and 0.18 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 each 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 92.1 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
Runl
9/02/98
12:50- 17:10
Inlet
56.19
7.13
65.54
45.43
50
Outlet
4.43
0.22
5.16
4.03
47
92.1
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 - National Lime and Stone Company - Wet Scrubber
    70.00
    60.00
    50.00
  5 40.00
  E

JO Q.
  c 30.00
  o
  O
    20.00
    10.00
     0.00
             -1	1	1—I	1	1-

                                                         Time

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     6.00
                   Figure 2-2. HCI Outlet Run - National Lime and Stone Company - Wet Scrubber
     5.00
     4.00
   0)
ro
     3.00
   o
   c
   o
  o
     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 and conditioned FTIR test runs. These species were measured concurrently with
HC1.  Results given below are organized by location.  No additional HAPs were detected in the
conditioned samples.


       Wet Scrubber Outlet/Inlet for Other Species Results—Tables 2-3 and 2-4 are a
summary of the FTIR results for other species detected.


          Table 2-3. Other Species Detected by FTIR - Wet Scrubber Inlet

                    (All values are ppmv, except CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
C02
u .
9.59
1.42
11.5
7.63
50
0060
CO
u
28.7
18.9
113
13.7
50
0.24
NO
U
37.9
7.22
48.9
27.9
50
6.9
H2CO
U
1.00
0.35
1.65
0.45
50
0.15
C +
*-4
U
2.50
0.81
3.55
1.61
50
0.14
CH4
U
5.66
1.29
12.1
365
50
22
H20
U
9.27
1.11
10.9
7.74
50
0.10
L'/C - Unconditioned (U) or Conditioned (C) Source Matrix
C4+ - Toial aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
NDP - Number of data points
EDL - Estimated detection limit for spectral region used for analysis
Note  Raw data reported in Appendix C.
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          Table 2-4. Other Species Detected by FTIR - Wet Scrubber Outlet

                    (All values are ppmv, except for CO2 and H2O in percent)
Parameter
U/C
Average
Std. Dev.
Max.
Min.
NDP
EDL
CH4
U
3.95
0.68
6.39
2.51
47
2 1
r +
*~4
u
0.85
0.08
1.02
0.73
47
0.14
CO2
u
9.28
0.175
9.62
8.96
47
0.061
CO
u
17.7
12.0
66.4
7.60
47
0.27
NO
U
38.4
2.62
44.3
33.6
47
6.6
H2O
U
13.1
0.115
13.3
12.8
47
0.11
 U/C - Unconditioned (U) or Conditioned (C) Source Matrix
 C4+ - Total aliphatic hydrocarbons larger than 3 carbons (ppmv hexane equivalent)
 NDP - Number of data points
,EDL - Estimated detection limit for spectra! region used for analysis
 Note Raw data reported 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
      FTIR

      The extractive FTER measurement method is based on continuous extraction of sample
gas from the stack, transporting the sample to the FTIR spectrometer and performing real-time
spectral measurement of the sample gas.  The sample gas spectra are analyzed in real time for
target analytes, archived and possibly re-analyzed at a later date for other target analytes.  This
section provides details on the FTIR sampling and measurement system.
3.1.1  FTIR Sampling Equipment

       The FTIR measurement system meets the sampling and analysis requirements set forth in
EPA Draft Method 320, "Measurement of Vapor Phase Organic and Inorganic Emissions By
Extractive Fourier Transform Infrared Spectroscopy." This system has been used with complete
success with many source categories, and can also be adapted to switch quickly between two
sources (i.e., inlet and outlet) with a single FTIR spectrometer.

       The sampling and measurement system consists of the following components:

       •      Heated probe;
       •      Heated filter;
       •      Heat-traced Teflon® sample line;
       •      Teflon® diaphragm, heated-head sample pump;

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       •      FTER 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
Sample
Gas In
                Spike or QA/QC C.as
                                                           Vaporization
                                                              block
              i
                              Syringe
                              Pump
                                                   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)
FTIR
Sample
Pump/
Flowmeter
                                                                 QA/QC Gas Standards
Sample Distribution Manifold
         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 matrix gas through a
PermaPure® dryer and a series of impingers filled with sodium (or lithium) hydroxide pellets.
The PermaPure® drier selectively removes water vapor and the sodium hydroxide pellets remove
CO; and other acid gases. The sample conditioning apparatus is switched into the FTIR sample
path by a valving system. Lower detection limits for some compounds can be achieved with a
conditioned sample.

3.1.2  Preparation for Sampling

       Before commencement of daily sampling operations, the following tasks were carried out:

       •      System leak check;
       •      Measurement of FTIR background spectrum;
       •      Instrumental QC; and
       •      Sampling and measurement system QC spike run.

Detailed descriptions of these tasks are described in the paragraphs below.

       The heated sampling lines,  probes, and a heated filter were positioned at the inlet and
outlet locations. All heated components were  brought to operating temperature, and a leak check
of both inlet and outlet sampling systems were performed. The leak check was performed by
plugging the end of the probe and watching the main sample rotameter to observe the reading.
Positive leak check was confirmed when the rotameter reading was zero.

       A background spectrum was measured using zero nitrogen through the cell.  Next the QC
gases were measured. They agreed to within ±6 percent (±10 percent for HC1) of target value.
The QC gases used for this program include:
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              Halocarbon 22 (H22), used to calibrate the pathlength. Halocarbon 22 is used for
              its highly linear response due to the lack of sharp spectral features, and is an
              extremely stable compound.

              Carbon monoxide (CO) used for 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. 1 .C of Draft Method 320 gives a description of the

dynamic spiking apparatus.


       The following FTER 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 A nalysis

       FTIR unconditioned sampling was performed simultaneously with the manual testing.
The stan 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. FTER  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. l-l ppm for typical FTIR analytes, while providing adequate dynamic range
(nominally  I-1.000 ppm).  Some of these parameters are sample matrix dependent.
                   Table 3-1. Typical FTIR Operating Parameters
Parameter
Spectral Range (cm"1)
Spectral Resolution (cm"1)
Optical Cell Pathlength (m)
Optical Cell Temperature (° C)
Sample Flow Rate (liters/minute)
Integration Time (minutes)
Value
400 - 4,000
0.5
3.4
185
9 (3.0 optical cell volumes/minute)
1 (Average of 43 spectra)
       Sample flow rate was determined by the data averaging interval and FTIR spectrometer
 sample cell volume. A minimum of three sample cell volumes of gas must flow through the
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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 cell pressure was monitored in real-time  in order to calculate analyte concentration
in parts-per-million. The cell was normally operated near atmospheric pressure with the cell
pressure continuously monitored.

       Sampling probe location was determined by the requirements set in EPA Method 1 in
terms of duct diameters upstream and downstream of disturbances.  Concurrent EPA Method 2
velocity measurements were not carried out at the same process stream location as the FTIR
sampling point to provide mass emission rate determination. The stack gas velocity and flow
rate were determined by the applicable manual test methods performed by PES. Velocity
information can be found in the report prepared by PES.

       Sampling and analysis procedures are straightforward for a single-source measurement.
Once QA/QC procedures were completed at the beginning of the test day, the sample was
allowed to flow continuously through the FTIR spectrometer cell  and the software was instructed
to start spectral data collection. The spectrometer collected one interferogram per second and
averaged a number of interferograms to form a time-integrated interferogram. The typical
averaging times range was approximately 1 minute. The interferogram was converted into a
spectrum and analyzed for the target analytes. After spectral analysis, the spectrum was stored
on the computer and later permanently archived. Spectral data collection was stopped after a

K \0091-02\002\003\NAT-LIME\NAT-L1ME.RPT            3-7

-------
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 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 FTER 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 30
minute sample collection
2 minute cell purge and 28
minute sample collection
Outlet
5 minute cell purge and 30
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 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
within ± 30 percent. The acceptable instrument diagnostic and system  response checked
 K \009I-02\002\003\NAT-LIME\NAT-LIME RPT
                                            3-8

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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  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 does 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 365° F(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 \0091 -O:\002\003\NAT-LIME\NAT-LIME.RPT            3-9

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   Table 3-2 .  Compounds for Which Reference FTIR Spectra Are Available
                          in the ERG Spectral Library3
1-butene
1,3-butadiene
2-methylpropane
2-propanol
2-methoxyethanol
2-methyI-2-propanol
2-methylbutane
4-vinylcyclohexane
acetaldehyde
acetic acid
acetone
acetylene
acrolein
ammonia
benzene
carbon monoxide
carbon dioxide
carbonyl sulfide
chlorobenzene
m-2-butene
cyclohexane
cyclopentane
cyclopropane
ethane
ethylbenzene
ethylene
formaldehyde
hydrogen fluoride
hydrogen chloride
isobutylene
w-xylene
m-cresol
methane
methanol
methyl ethyl ketone
methylene chloride
«-butanol
n-butane
n-pentane
nitric oxide
nitrogen dioxide
nitrous oxide
o-cresol
o-xylene
p-cresol
p-xylene
phenol
propane
propylene
styrene
sulfur dioxide
toluene
fn3/2s-2-butene
water vapor
 Spectra were collected at a cell temperature of 365° F (185° C).
KA0091 -02\002\003\N AT-L1MBN AT-L1ME.RPT
                                       3-10

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A.     Post-test Data Review procedure (on-site)

       1.      Examine the concentration vs. time series plot for each compound of interest, and
              identify regions with the following characteristics:

              •      sudden change in concentration;

              •      unrealistic concentration values;

              •      significant changes in 95 percent confidence intervals reported by
                     software; and

              •      sudden increase of noise in data.

       2.      Select representative spectra from the time periods indicated from Step 1.

       3.      Subtract from each representative spectrum chosen in  Step 2 a spectrum taken
              immediately prior in time  to the indicated time region.

       4.      Manually quantitate (including any 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).

       10.    Data found invalid are subject to re-measurement.
K \009I-02\002\003\NAT-LIME\NAT-LIME.RPT             3-1 1

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B.     Final Data Review (off-site)


       The procedures for final data review include those given above.  However, if a non-
recoverable error was found during this phase, the data are considered invalid. In addition, the
following procedures are carried out by the spectroscopist to perform a final data validation:
       1.      If any recoverable data errors are detected from the procedure, determine the
              cause and perform any necessary corrections.

       2.      For analytes that were not detected or detected at low levels:

              •       estimate detection limits from validated data;
              •       check for measurement bias.

       3.      Verify spreadsheet calculations by independent calculation (results in
              Appendix A).
3.1.5  FTIR QA/QC Procedures


       The FTIR QA/QC apparatus was 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 matrix gas to

provide information on system response, sample matrix effects, and potential sampling system

biases.  Spiking is accomplished by either:


       •      Direct introduction of a certified gas standard; or

       •      Volatilization of a spiking solution.
 K\009l-02\002\003\NAT-UME\NAT-UME.RPT            3-12

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       Certified gas standards are preferred due to simplicity of use, but many target analytes
cannot be obtained as certified gas standards, and must be spiked using standards generated by
volatilized solutions.

       Gaseous spiking is carried out by metering the spike gas into the sample stream at a
known rate. Spike levels are calculated from mass balance principles.  When certified gas
standards are used, a dilution  tracer, such as sulfur hexafluoride, is used to directly measure the
fraction of spike gas spiked into the sample.  This technique can be used instead of mass balance
calculations.

       FTIR method performance is gauged from the results of the QA/QC. Acceptable spiking
tests will meet Draft Method 320 criteria (i.e., accuracy of within ± 30 percent) or a statistical
equivalent when less than 12  spiked/unspiked pairs are collected. The EPA Draft Method 320
instructs the user to determine the percent spike recovery of 3 pairs of spiked/unspiked samples.
The Draft 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-\009I-02\002\003\NAT-LIME\NAT-LIME.RPT             3- 1 3

-------
4.0    QUALITY ASSURANCE/QUALITY CONTROL

       Specific QA/QC procedures were strictly followed during this test program to ensure the
production of useful and valid data throughout the project. A detailed presentation of QC
procedures for all sampling and analysis activities can be found in the Site Specific Test Plan and
Quality Assurance Project Plan for this project. This section reports all QC results so that the
data quality can be ascertained.

       In summary, a high degree of data quality was maintained throughout the project.  All
sampling system leak checks met the QC criteria as specified in Draft Method 320. Acceptable
spike recoveries and close agreement between duplicate analyses were shown for the  sample
analyses. The data completeness was 100 percent, based on changes authorized by the Work
Assignment Manager.

4.1    FTIR  Analytical Quality Control

       Dynamic analyte spiking was used for quality control/quality assurance of the complete
sampling and analysis system. Dynamic spiking is continuous spiking of the sample gas to
provide information on system response, sample matrix effects, and potential sampling system
biases. Spiking was accomplished by direct introduction of a certified gas standard.

       Gaseous spiking was carried out by metering the spike gas into the sample stream at a
known rate.  A sulfur hexafluoride dilution tracer was used to directly measure the fraction of
spike gas spiked into the sample. 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 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
K \009l-02\002\003\NAT-LIME\NAT-LlME.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 a CH4, NO:, and CO2 standard; and
       •       Pathlength calibration using H22.

Dynamic spiking runs were conducted twice daily: before and after testing. Six spiked/unspiked
data points were collected. Statistical calculations consistent with EPA Method 301 were
performed on the data.  Recovery of 70-130 percent was the acceptance criteria. Table 4-1
summarizes the dynamic spiking results.  On the inlet, 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, NO: and CO2 mixture
was conducted before and after daily testing activities. Acceptance  criteria are normally
±6 percent of target, using EPA protocol gases.  However, since the HC1 standard was obtained
at a ±5 percent analytical  tolerance, the acceptance criteria was set at ±10 percent. FTIR NOX is
measured as NO + NO,. Examination of Table 4-2 shows that all QC checks met the above
criteria.

K.\0091-02\002\003\NAT-LIME\NAT-LIME RPT            4-2

-------
   Table 4-1. HCI QA Spike Run 1 Results - National Lime and Stone Company
Outlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
71.55
6949
67.71
66.54
67.00
65.93
68.04
Spiked
(ppmv)
141.40
141.70
139.60
139.90
141.20
142.80
141.10
Corrected
Difference
(ppmv)
75.06
77.58
76.88
78.27
79.01
81.64
78.07
Spike
Level
(ppmv)
74.96
79.54
75.98
75.98
73.94
74.45
75.81
%
Recovery
imii





102.99
SF6
Cone.
(ppmv)
0.147
0.156
0.149
0.149
0.145
0.146
0.149
Dilution
Ratio
0.073
0.077
0.074
0.074
0.072
0.072
0.074
Inlet
Spike
Run
Number
I
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
8.61
8.18
7.75
7.52
7.26
7.32
7.77
Spiked
(ppmv)
22.97
22.18
21.51
21.13
21.35
20.93
21.68
Corrected
Difference
(ppmv)
14.86
14.49
14.22
14.06
14.55
14.05
14.37
Spike
Level
(ppmv)
15.21
15.60
15.47
15.60
16.51
15.60
15.67
%
Recovery
WMM&
wiMiifr,




91.75
SF6
Cone.
(ppmv)
0.117
0.120
0.119
0.120
0.127
0.120
0.121
Dilution
Ratio
0.059
0.060
0.060
0.060
0.064
0.060
0.060
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 recover)' is defined in Draft Method 320.

(Stock spike gas values for HCI and SF6 values are 253 ppmv and 5.08 ppmv. respectively).
                           Recovery =  100 x
   Corrected  Difference
       Spike level
                  Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
K \0091-02\002\003\NAT-UMBNAT-LIME.RPT
4-3

-------
   Table 4-2. HC1 QA Spike Run 2 Results - National Lime and Stone Company
Outlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
59.98
59.23
58.41
57.52
56.44
57.51
58.18
Spiked
(ppmv)
116.80
132.40
134.90
129.30
128.30
131.40
128.85
Corrected
Difference
(ppmv)
62.19
78.48
81.72
76.36
76.22
78.27
75.54
Spike
Level
(ppmv)
92.29
92.29
92.29
82.09
79.54
78.52
86.17
%
Recovery
y^M&,




WM^,
87.66
SF6
Cone.
(ppmv)
0.181
0.181
0.181
0.161
0.156
0 154
0.169
Dilution
Ratio
0.090
0.090
0.090
0.080
0.077
0.076
0.084
Inlet
Spike
Run
Number
1
2
3
4
5
6
Average
Lowest
Unspiked
Value (ppmv)
6.11
5.67
5.39
5.12
5.04
494
5.38
Spiked
(ppmv)
23.36
16.60
14.92
14.43
14.22
14.02
16.26
Corrected
Difference
(ppmv)
1772
11.17
9.77
9.53
9.41
9.30
11.15
Spike
Level
(ppmv)
20.15
11.05
11.44
11.18
11.70
11.44
12.83
%
Recovery
WMMb




•//////'<',////'///'
86.89
SF6
Cone.
(ppmv)
0.155
0.085
0.088
0.086
0.090
0.088
0.099
Dilution
Ratio
0.078
0.043
0.044
0.043
0.045
0.044
0.049
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 HC1 and SF6 values are 253 ppmv and 5.08 ppmv, respectively).
                        % Recovery =  100 x
Corrected Difference
     Spike level
                  Corrected Difference = Spiked - (1 - Dilution Ratio) X Unspiked
KA0091 -02\002\003\NAT-LIME\NAT-L1ME RPT
                                            4-4

-------
                     Table 4-3. Gas Standard Analysis Results

Date
8/31/98





9/01/98






Time
07:56 AM





02:02 AM






Compound
HC1
CO
CH4
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 N0; and CO, Gas Standard Accuracy; ±1%; 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.
K \0091-02\002\003\NAT-LIME\NAT-LIME RPT
                                          4-5

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                             APPENDIX A

                FTIR DATA SPREADSHEET CALCULATION
                            QA/QC SHEETS
KA0091 -02\002\003\N AT-LIME\NAT-LIME.RPT

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                                    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
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.
                                           V
                                            V
                                            V
1.  No mathematical errors
1.  No errors in the data macro

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                                   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:
 Source Location (INLET or OUTLE
 Run Description   /u\|J
                     x
             es;matcli references yal
             ingbycomparingme.p
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.
V
          at calculations are co
1. No mathematical errors
1.  No errors in the data macro


-------
                                  FTIR QA/QC REVIEW
                      Calculation and Methodology QA/QC Checklist
    For each facility tested, the reviewer will have:

               1.   Excel QA/QC workbook

               2.   Inlet and Outlet QA/QC information
 Facility Name:
                              (JO*
                                                                               DATE:
 Source Location (INLET or OUTLET)
                                                                               TIME:
 Run Description
 Reviewer:
                                                                               Date:
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)
                                            Z.
5.  Verify that the QA/QC value is zero. This
   indicated that both the original and the
   QA/QC values are identical.
     eckthatcalcalanoDsareco
1. No mathematical errors
1.  No errors in the data macro

-------
                                  FTIR QA/QC REVIEW
                      Calculation and Methodology QA/QC Checklist
    For each facility tested, the reviewer will have:

               1.  Excel QA/QC workbook

               2.  Inlet and Outlet QA/QC information
 Facility Name:
                                      n.u.,0
                                                                               DATE:
 Source Location (INLET or OUTLET)
                                                                               TIME:
 Run Description
 Reviewer:
                                                                               Date:
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)
                                        V
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
1.  No errors in the data macro

-------
                                  FTIR QA/QC REVIEW
                       Calculation and Methodology QA/QC Checklist
     For each facility tested,  the reviewer will have:

               1.  Excel QA/QC workbook

               2.  Inlet and Outlet QA/QC information
 Facility Name:
DATE:
 Source Location (INLET or OUTLET)
TIME:
  figb -??/<>
 Run Description
 Reviewer:
Date:
         entriesTraafclEEefereiicea
1.  Pollutants matches pollutants in both the
   original and QA/QC data
2.  Tunes 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
1.  No errors in the data macro

-------
                                  FTIR QA/QC REVIEW
                       Calculation and Methodology QA/QC Checklist
  •   For each facility tested, the reviewer will have:

               1.   Excel QA/QC workbook

               2.   Inlet and Outlet QA/QC information
  Facility Name:
  Source Location (INLET or OUTLET)
DATE:
TIME:
13SQ-/.It o
  Run Description   \KjJf\  <) \
                    OuO^T
                                                                               Date:
 1.  Pollutants matches pollutants in both the     .  S
    original and QA/QC data                 w
 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
 1.  No errors in the data macro
 2.

T

-------
                                 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:
                         .
                 Cftfel    LlP*  ILu.,0
                                      DATE:
Source Location (INLET or OUTLET)
                                      TIME:
Run Description
Reviewer:
                                      Date:
  Pollutants matches pollutants in both the
  original and QA/QC data	
  Times for Inlet/Outlet samples match.
  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.
V
  No errors in the data macro

-------
                                  FTIR QA/QC REVIEW
                       Calculation and Methodology QA/QC Checklist
  •  For each facility tested, the reviewer will have:

                1.   Excel QA/QC workbook

                2.   Inlet and Outlet QA/QC information
  Facility Name:
                           .
                   Cftfe/
                                                                              DATE:
  Source Location (INLET or OUTLET)
                                                                              TIME:
  Run Description

  Review:
                                                                              Date:
 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)
                                        V
 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
 1.  No errors in the data macro
 2.

T

-------
                              APPENDIX B




                 GAS CYLINDER CERTIFICATION SHEETS
K \0091 -02\002\003\NAT-LIME\NAT-LIME.RPT

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                                                                       REC'O AUG 141998
               SPECTRR GHSE5
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Eastern Research Group Inc.
900 Perimeter PanX
Morrisville, NC 27560
                                       CERTIFICATE
                                             OF
                                         ANALYSIS
 SGI ORDER #:         134942
 ITEM*:               1
 CERTIFICATION DATE:  8/10/98
 P.O.#:          "     9101008011-R132
 BLEND TYPE:         CERTIFIED
                                       CYUNDER # : 1689487Y
                                   CYLINDER PRES: 2000 psig
                                  CYLINDER VALVE: CGA 330
                                                 ANALYTICAL ACCURACY: + / - 5%
     COMPONENT
                  REQUESTED GAS
                      CONC
                                                                           ANALYSIS
Hydrogen Chloride
Sulfur Hexafluonde
                      50.0 ppm
                      2.00 ppm
54.3 ppm
2.01 ppm
Nitrogen
                      Balance
Balance
Sulfur Hexafluonde is +/- 2%
ANALYST:
A.
                 Ted Neeme
                                            DATE:
                                                                            8/10/98
                            USA • United Kingdom • Germany • Japan
                                       i IB o  saos

-------
              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
                                        CYLINDERS:    1852209Y
                                        CYLINDER PRES: 2000 PSIG
                                        P.O.*:          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:
-5).
               Ted Neeme
DATE:
8/29/97
                           USA • United Kingdom • Germany • Japan
                                     ISO  9 D O 2

-------
              SPECTRfl BUSES

              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  9 O 0 2

-------
              SPECTBfl GflSES
                                                             RECD M2Y 1 ^ 1998
        m^M 277 Coit Street • Irvington, NJ 07111 USA   Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-855'

SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
Eastern Research Group Inc.
900 Perimeter Park
Monrisville , 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.OJ:           9101008004-R986
                                       ANALYTICAL ACCURACY:
                                                /• 2%*
    COMPONENT
  Hydrogen Chloride
  Sulfur Hexafluoride

      Nitrogen
               REQUESTED GAS
                   CONC

                   250 ppm
                   5.00 ppm

                   Balance
                                                                     ANALYSIS
253 ppm
5.08 ppm

Balance
* Analytical Accuracy of Hydrogen Chloride is +/- 5%
ANALYST:
               Mikebeyle
                                         DATE:
 5/11/98
                           USA • United Kingdom • Germany • Japan
                                     iso  s a o ^

-------
  5b
SPECTRfl GRSES
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
Sutfur Hexafluonde
                          250 ppm
                          2.00 ppm
260 ppm
2.00 ppm
Nitrogen
                          Balance
Balance
Sulfur Hexafluonde is •*•/- 2%
ANALYST:
                Ted Neeme
                                              DATE:     8/10/98
                          USA • United Kingdom • Germany • Japan

-------
              SPECTBfl GflSES

              277 Coit Street • Irvington, NJ 07111 USA  Tel: (973) 372-2060 • (800) 929-2427 • Fax: (973) 372-855 <

SHIPPED FROM: 80 INDUSTRIAL DRIVE ALPHA, NJ. 08865 TEL: (908) 454-7455
SHIPPED TO:
        Eastern Research Group Inc.
        900 Perimeter Park
        Momsville , 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.OJ:          9101008004-R986
                                       ANALYTICAL ACCURACY:
    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     7
                ijseHDoy
                                                  DATE:     5/11/98
                           USA • United Kingdom • Germany • Japan
                                     ISO  3002

-------
  55
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*:              3
CERTIFICATION DATE:  8/10/98
P.O.#:               9101008011-R132
BLEND TYPE:         CERTIFIED
                                         CYLINDER*: 982153Y
                                      CYLINDER PRES: 2000 psig
                                     CYLINDER VALVE: CGA 330
    COMPONENT
                                              ANALYTICAL ACCURACY: + / - 5%
                      REQUESTED GAS
                          CONC
                                                                      ANALYSIS
Hydrogen Chloride
Sulfur Hexafluonde
                         1,000 ppm
                         2 00 ppm
1,030 ppm
2.02 ppm
Nitrogen
                          Balance
 Balance
Sulfur Hexafluoride is +/- 2%
ANALYST:
                Ted Neeme
                                                             DATE:
                                                         8/10/98
                          USA • United Kingdom • Germany • Japan
                                      r-i  o r-i

-------
r
                 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 J :
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

-------
              SPECTRR  GflSES
              277 Cort 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
                      CONC
                     40.0 ppm
                                                                       ANALYSIS
40.3 ppm
       Nitrogen
                      Balance
 Balance
ANALYST:
                Ted Neeme
                                         DATE:
10/16/97
                           USA • United Kingdom • Germany • Japan
                                      ISO  3 O O 3.

-------
           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
CYLINDER # :     CC79878
CYLINDER PRES: 2000 PSIG
CGA OUTLET:    660
CERTIFICATION DATE: 8/27/97
EXPIRATION DATE:   8/19/99

CERTIFICATION HISTORY
COMPONENT
Methane
Nitric Oxide
NOx
Carbon Dioxide

DATE OF
ASSAY
8/21/97
8/20/97
8/27/97
8/19/97

MEAN
CONCENTRATION
491 ppm
502.1 ppm
504.6 ppm
4.99 %

CERTIFIED
CONCENTRATION
491 ppm
503 ppm
503 ppm
4.99 %

ANALYTICAL
ACCURACY
+/- 1%
+/- 1%
Reference Value Only
+/- 1%

BALANCE
    Nitrogen
REFERENCE STANDARDS
COMPONENT
Methane
Nitric Oxide
Carbon Dioxide

SRM/NTRM*
SRM-2751
NTRM-81687
SRM-1674b

CYLINDER*
CAL013479
CC57165
CLM007273

CONCENTRATION
98.6 ppm
1009 ppm
6.98 %

INSTRUMENTATION
COMPONENT
Methane
Nitric Oxide
Carbon Dioxide

MAKE/MODEL
H. Packard-6890
Nicolet-760
Horiba-VIA-510

SERIAL #
US00001434
ADM9600121
571417045

DETECTOR
GC - FID
FTIR
NDIR

CALIBRATION
DATE(S)
8/21/97
8/27/97
7/25/97

THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
                                                         DATE:
               TED NEEME
                                                8/27/97

-------
                                 APPENDIX C




                                RAW FTIR DATA
K \0091 -02\002\003VNAT-LIME\NAT-LIME.RPT

-------
 > S S 8 5 S S S S S'S.R.S S S S g S £ Z S,S g 8 S|S SiS.B.SSSiSiSjS S,S SiSiS 3 S:S:S,S a,a:S!S:;,S:R:EiS Sl
:g,R S s'g'S S R E'X.R'S S S ! S S 5 S,S,?;:C:o;; s'glS-S R S SI8;S S H.SIS.S'X ? S.EIS'sigis S si;,S Eii|s S
 >?aiSSSK"S2 8't'S S S £ S ?'£,£ S.S £ Ell,SIC SISiRjS'R.S'SIK.RIgi"^
   SSSSSSSSBS R.S'S.S 8 SIR R S'S'SiS.JiRIS rs'S';|R:| S'S s SIS!S!B'S,3!S;8!«U:;,5!S»,S'5:»i8;S:R
   S S £ 5 1 g.S £ S S S S S S Z.S,B,S!S,S:;::S'X:S;8'R.S:Sii!S!! SlH.s 8:S;SlSig;g:=!8,s;S;S!B:8 S'S'^IS'S a
   ;: 2 = = - ~.= -'g - S.S S'S S SIS'S   SiS'S S:S:Si = es!=p,8'8:5 ^'S.SlS'S £.5:S|S!S;S,S,S;S'8 8.8 S.SiS'
   ; s a a ;'8 5 s.s a a s s s.e c c'e.a'C'S'S e;a a 8'8i8:8l8ig!8!s,8|8!8;8!8 S.SiS'S'SISigigigjSiS'g.giS1: 8
                                                                         ix.C'Sis1;, J'R;;;.R;S.!;S 2 s g s'c's'
 ;gggggggggg88 S g S g 888 g g'S g.g 8 g'g.g gjg'g g'g 8:8.8.8 8,8 S 81818 8 8 g g g g,8 8 8 S S
                    I'OIO O O O O O'O'O O'OIO'O O'O.OtO
                                                                                ».o o.o.o.o o o.o ooo
 :SSggS88888g 8 g'8 8'g 8888 g'818,8 gig,gig:
             SSRS S.R.S'SIRiR'R.R.R'R'SiRlSISIRIs's.SiSiRiRIRiSIRlRsiS SiS.S RiRiS;SiS]S!S:K!S:s,
 rj S S S S C X S a S 8 t H'S'ftiSiS'S'S.I S'S'S'RiS.S S'g'SISl.'S'SiS'SIS'RlS'SlSISiS'S.SISja^'S S:S!5iS's.S 5
'i S S E S'S £ 5 £ S S'S'S S S 5 S a.EJ£.8ISiC.5!g'«.SiSi8!9[8:gi«'>'g;Sl5;8lg.a!8i8i8b!8l8ig!S S'S'8'8.>- 8'$
                                                        s s.s S'SIK s;
                                                                                       is:s:s:a.s s,s x,x s s s
 is8S8gggggg88Sgggg8 8:8 8 g g g 8.8 888 g g '8.8 g.g 8 8 g g g 8 g g 8 ggggSSgggg
                        >000000000(
                                                    > o o.OiO:o o 0,0 oo o o 0:0.0 o 0,0 o o o o o o o o o o o
                lEE.SgZCS
                                            «i«)n — o>«og O'O N ^ cumin n to «.« « w g'O o.M,» M » vi Q »- 10 »-
 i8ggSgggS8gg8888gg88888g8g8gg:g88,S88S8S8S888S8g8Sg88S8g8
 5.OOOOOQOOOOOOOOOOOOOOOOOOOO1
                                                                  1OOOOOOOOOO O,O t
                                                                            SSRSS SIS RS'S 5838888*
 iSSSSgSSSSSSSS.SSSSSSSSSSSSSSSSSSSSSSSSSSSSS'gSSSSgSSSSSS
                                                                                sooooooooooooooo
 |88888gg88888888888888S888888!8 88888 8.8 888888888888888 8'8 8

                                                  "r»r>'n'°«TrtwpiSnnrinrN'n'^'
      8.B.S!
                       JNM O'JN r) •» -j.pj I-) (N J m jft IN m.r) ri.R R R R S S.S'
 oSSS
 lo'B,8R
              "- o f~- tfi •- a B p» o 2'5iT'v nia « »- *- 3>'^ oi«<5 A (N *• w o Jii^iiS11^ <
              n p  «itn w « irt e>« «>•» «<« IAIV «'tn o>i«iw>>» <* )P *'? o ^-t^!« ^) ^ '^'S «i« QUO (N in *r r«'a»i» •> ™ -|m •*m>n nins'a
                          i       il' S'E S £
                                                                                         IS'le I i
                                                                                        sisii'g g g
                                R'S S S'S S I Cf,^ 5 S S'SiSlS R S'S ^ S S $'£'5 S.S'E'^'ff'SiS
                                2 5 B 5 H 5 s'g 121 ? |,||| Iliilill S.B i - i i i i 11 § s
C   ^ » Ol V
I   ? S-S !
   SggSIEIggSSS t'
   8t«- «IP1 •-
. _ a ? S s
!! =
r»i
i!
  f S J 5 J   SJSSSKJSS s 'B.X.Bia'X.B i:S X SIS S X E S.S'K S S S S S S:S,S,S,S,X'K,S S S S S 5 S.E  !
 ^ s s R s   s; s ; ; s ? s ?,? s s s s j s;s'S.a;s:5 s ; *.f ,s i K,E s S'S.K s!s:g.5;S s ss s & s s 111
                                                                                                          1*
                                                                                                          K

-------
       	.-__»___._._*____....__	.. _          £   ~ S
       *tN(*tftuibRtMUiUt**4hA*«>**£**MWMMMMMWwwwwMMUWM(^MWt!*MWMU  ^ S £ « 3
JSf3SftfiiSSSS88KKSBSSSS38SKKBB23SS553SSB = S8838S28S28'afs|||
fflc8s3S33S3sss3saa2a2aaeaKsssssssss2sas2ssasssasssi!?sf|I|
iS=iisi|i55555555Si55555g535s35s2335555i5i33s5iKSss,'  ?i
SSS3SS2S3SSSSS5asS£ls = slsiS«;S3Sa85SJSSa:S2S3slsS|35Sf  i
ww^-JtJit" — *w«w>oioio — -'u»**.SSMtJa>w»i£3Stvw*5»Sw — w»-*oD'-«o*-'i>io*f3K)Sw!o
— S"* — »*5^jS£SDS53£o — Sii^S^SSSNJSSCS-uiSSSwSjSStrSSSSSSo^wIS  "  a


                                           	     15  I
ss = SBs
3§SSSS
gggggggggggggggggggggggggggggggggggggggggggggggggggS
 ggggggggggggggg



                                         — SoSS — So»S5oo^
       ggssssgi

                                                     5
o w -
ggSSggggggggggggggggggggggggggggggggggggggggggggggg^

                                                     2
g£ligggggggigggiiigiiigggg£ggggggg£gggiiligiigiglgg|
                                                     f

gggggliggggiggggiiiggggiillgggiggiigigililgilggiggi:

gggggggggggggggggggggggggggggggggggs

                                      °
                              — 88S8 —
                                        > — — ooooooooo

-------
                                APPENDIX D




                          FTIR FIELD DATA SHEETS
K \0091-02\002\003\NAT-LIME\NAT-LJME RPT

-------
                                                                                                                   "JO
  Facility
 Stack ID
   Date
Run Number
Recorded By

               tr
           KJc^r
  1
                                       FTIR Temperature  Readout Sheet
                                                       r
                                                                                                                  )MO
                                                                                                                  a MS-/




       'Time'*
                                   325
                                                 H 00
                                                       :'lt:Tlme
                                                        1MIT-
                                                              Time
                                                                     Time'

                                                                                              u.T f)
                                                                                                                        ^-\^o
           Inlet Stack
                            541
                                                                                     3^5
                                                                                                                571
          Outlet Stack
                                IOC,
                                                        tot.
           Inlet Probe
                         3MT-
                                                                                                          ^S3
          Outlet Probe
                  33S
                                                                                             555
                                                                                                        3m
                                                                                                                (0*1
                                                                                                                441
           Inlet Filter
                                                        vno
                                                                                   3US
                                                                                                                 "ins
          Outlet Filter
                  3zo
                                  33.2.
                                                  53 I
            Inlet HT
                                                 2-lo'Z-
                                                                                                          3U  ,-
                                                                      Z-11
                                                                                                              7.11
           Outlet HT
                    5Z-J-
                                                             32M
                                                                                                   32. t*
   10
   11
   12
 Inlet Pump^
                                   26?
                                                 ZMo
                                               uo
                                                                                     zss
                                                                                          Z.C.Z
Outlet Pump
 FTIR Pump
              Ztog,



              7-Uo
                                                                                     ill
                                                                                             3.15
                                                                                                        7.-70
Pump Box
                     \0l
                  I o
       \03
                                \02
                                       I 02.
                                                                                     10&
                                                                                                  (o1!
                                                                                                                         jo?
   13
   14
   15
   16
FTIR Jumper
3MM
                                                 5-4T-
                                              3SS
                                                                             3MS
Pump Jumper
                                          315
                                                               3i2
                                                                    3 18
           Hot Box
                                                                              36H
   17
           Hot Box
           3HO
                                          341
                                              3Mo
                                                  3 HO
                                                                                                 3.MO
                                                                                              3, MO
   18
   19
         Electronics Box
   20
                                                                                                   A.H<4 O.°fi.f

-------
Channel
      Description
                                          FTIR Temperature Readout Sheet
                              tfltft
                  w>
        Inlet Stack
                                  36,5
        Outlet Stack
               ill
        Inlet Probe
        Outlet Probe
         Inlet Filter
                            _M1
        Outlet Filter
         Inlet HT
                                    252
         Outlet HT
        Inlet Pump
                     nJL
  10
      Outlet Pump
  11
      FTIR Pump
ii
        Pump Box
  13
  14
      FTIR Jumper
                                    351
  15
      Pump Jumper
                 3tS
  16
         Hot Box
  17
         Hot Box
                                          •i
  18
19
20
       Electronics Box

-------
                               APPENDIX E




                        PRE-TEST CALCULATIONS
KA0091 -02\002\003\NAT-LIMDNAT-LIME RPT

-------
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
IAI/AAI
Average absorbance
        HCI (target)
   0.1 ppmv
0.0005436
               0.00000322
 H,Q (potential interferant)
     20%
  0.2213
  407
      0.00131
  CO: (potential interferant)
     20%
 0.000002
 0.0036
 H2CO (potential interferant)
    1 ppmv
0.0002100
  0.386
 CH4 (potential interferant)
   20 ppmv
  0.0105
  19.3
    0.00006213
                                                            AVT
                                              0.00137
Note: compounds in bold are known interferants. AVT is computed from target and known
interferants.
Known interferant criteria is IAI/AAI > 0.5

From the Table, two potential interferants are identified: 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(HC1)= 0.4 ppmv.
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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 (FRIT)

This calculation estimates the uncertainty in analysis, using band areas, of two sequentially
measured CTS spectra collected immediately before and after the HC1 reference spectrum. The
calculation is performed in the analysis region used for HC1. The result is:

FRU (HC1 region) = 0.093.

The corresponding value using CLS is somewhat lower.  For most analytes of interest, FRU
usually falls between 0.001 and 0.04 using CLS.

Appendix F

Determining Fractional Calibration Uncertainties (FCU)

This section determines the fractional calibration uncertainties when analyzing  each reference
spectrum. These results will be applied to the compounds analyzed in the HC1  analysis region.
The table below gives the results.
                          TABLE 2.  FCU DETERMINATION
Analyte
H,O
HC1
CFL
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.
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Appendix H

Determining Sample Absorption Pathlength CLs) and Fractional Analytical Uncertainty

Since the HCI reference spectrum used in this program were measured at the same pathlength to
be used during testing, these calculations are not required.
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                          APPENDIX F




                   POST-TEST CALCULATIONS
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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 - CAREY
Spectral File Name
RNOlOOll.spa
RN010046.spa
Inlet/Outlet
Outlet
Inlet
Error (ppm)
0.12
0.25
Concentration (ppm)
4.5
63.0
FMU
0.027
0.0039
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.
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                                     TECHNICAL REPORT DATA
                                (Please read Instructions on reverse before completing)
  1. REPORT NO.
    EPA- 454/R-00-009
                                                                    3. RECIPIENT'S ACCESSION NO.
  4. TITLE AND SUBTITLE
  Final Report of Lime Manufacturing Industry
  Fourier Transform Infrared Spectroscopy
  National Lime and Stone Company, Carey Ohio
5. REPORT DATE
  May 2000
                                                                    6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
   EMAD
                                                                     8. PERFORMING ORGANIZATION REPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS

   U.S. Environmental Protection Agency
   Office of Air Quality Planning and Standards
   Research Triangle Park, NC 27711
                                                                     10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D7-0001
  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.
1 7. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Hydrogen Chloride (HCL)
Hazardous Air Pollutants
18. DISTRIBUTION STATEMENT
Release Unlimited
_,_• m. T . 	
b. IDENTIFIERS/OPEN ENDED TERMS
Air Pollution control
Wet Scrubber
19. SECURITY CLASS (Report)
Unclassified
20. SECURITY CLASS (Page)
'Unclassified:
c. COSATI Field/Group

21. NO. OF PAGES
104
22. PRICE • . - -
EPA Form 2220-1 (Rev. 4-77)   PREVIOUS EDITION IS OBSOLETE

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