United States Environmental Protection Agency
Integrated Iron and Steel Industry Final Report Manual Testing
Volume 1 of 3
EPA - 454/R-99-042A
Air
EPA
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
LTV Steel Company Indiana Harbor Works East Chicago, Illinois
-------
Integrated Iron and Steel Industry
Final Report
Volume I of III
Contract No. 68-D7-0068
Work Assignment 2-13
LTV Steel Company
Indiana Harbor Works
East Chicago, Illinois
Prepared for:
Michael K. Ciolek
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
August 1999
fcERG
EASTERN
RESEARCH GROUP, INC
-------
TABLE OF CONTENTS
Page
1.0 INTRODUCTION 1-1
1.1 Objective 1-1
1.2 Brief Site Description 1-2
1.3 Emissions Measurements Program 1-2
1.3.1 Test Matrix 1-3
1.3.2 Test Schedule 1-3
1.3.3 Sampling Locations 1-3
1.3.4 Sampling and Analysis Methods 1-6
1.4 Quality Assurance/Quality Control (QA/QC) 1-6
1.5 Test Report 1-7
2.0 SUMMARY OF RESULTS 2-1
2.1 Emissions Test Log 2-1
2.2 D/F/PAH Results 2-1
2.2.1 Overview 2-1
2.2.2 D/F Emission Results 2-4
2.2.3 PAH Emission Results 2-7
2.3 Metals HAPs Results 2-11
2.3.1 Overview 2-11
2.3.2 Metal HAPs Emission Results 2-11
2.4 PM Results 2-16
2.4.1 PM Emissions Results 2-16
3.0 PROCESS DESCRIPTION AND PROCESS DATA (Prepared by RTI) 3-1
4.0 SAMPLING LOCATIONS 4-1
5.0 SAMPLING AND ANALYTICAL PROCEDURES BY ANALYTE 5-1
5.1 Particulate Matter and Metals Emissions Testing Using EPA Method 29 .... 5-1
5.1.1 Method 29 Sampling Equipment 5-1
5.1.2 Method 29 Sampling Equipment Preparation 5-3
5.1.2.1 Glassware Preparation 5-3
5.1.2.2 Reagent Preparation 5-4
5.1.2.3 Equipment Preparation 5-5
5.1.3 Method 29 Sampling Operations 5-7
5.1.3.1 Preliminary Measurements 5-7
5.1.3.2 Assembling the Train 5-7
5.1.3.3 Sampling Procedures 5-8
Cah/A:\TOC-CVR.WP6
iii
-------
TABLE OF CONTENTS (Continued)
Page
5.1.4 Method 29 Sample Recovery 5-12
5.1.5 Particulate Analysis 5-18
5.1.6 Metals Analytical Procedures 5-18
5.1.7 Quality Control for Metals Analytical Procedures 5-22
5.1.7.1 ICAP Standards and Quality Control Samples 5-23
5.1.7.2 Cold Vapor Atomic Absorption Standards and
Quality Control Samples 5-23
5.2 CDD/CDF and PAH Emissions Testing Using EPA Method 23 5-24
5.2.1 Method 23 Sampling Equipment 5-24
5.2.2 Method 23 Equipment Preparation 5-24
5.2.2.1 Glassware Preparation 5-26
5.2.2.2 XAD-2® Resin and Filters Preparation 5-26
5.2.2.3 Method 23 Sampling Train Preparation 5-28
5.2.3 Method 23 Sampling Operations 5-29
5.2.3.1 Preliminary Measurements 5-29
5.2.3.2 Assembling the Train 5-29
5.2.3.3 Sampling Procedures 5-30
5.2.4 CDD/CDF/PAH Sample Recovery 5-35
5.2.5 CDD/CDF/PAH Analytical Procedures 5-38
5.2.5.1 Preparation of Samples for Extraction 5-42
5.2.5.2 Calibration of GC/MS System 5-42
5.2.6 CDD/CDF Analytical Quality Control 5-42
5.2.6.1 CDD/CDF Quality Control Blanks 5-43
5.2.6.2 Quality Control Standards and Duplicates 5-44
5.2.7 Analytes and Detection Limits for Method 23 5-45
5.3 Analysis of Method 23 Samples for PAHs 5-47
5.4 EPA Methods 1-4 5-50
5.4.1 Traverse Point Location By EPA Method 1 5-50
5.4.2 Volumetric Flow Rate Determination by EPA Method 2 5-50
5.4.2.1 Sampling and Equipment Preparation 5-50
5.4.2.2 Sampling Operations 5-50
5.4.3 02 and C02 Concentrations by EPA Method 3 5-51
5.4.4 Average Moisture Determination by EPA Method 4 5-51
6.0 QUALITY ASSURANCE/QUALITY CONTROL 6-1
6.1 Sampling QC Results 6-1
6.1.1 D/F/PAH Sampling QC 6-1
6.1.2 Metals/PM Sampling QC 6-4
Cah/K:\7997\03\07-RPT\TOC-CVR.WP6 1V
-------
TABLE OF CONTENTS (Continued)
Page
6.2 Analytical QC Results 6-11
6.2.1 D/F/PAH Analytical Quality Control 6-11
6.2.2 Metals Analytical Quality Control 6-12
6.2.3 PM Analytical Quality Assurance 6-14
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
Reproduced trom
best available copy.
Cah/K:V799AQ3\07-RPTATOC-CVRWP6
V
-------
LIST OF TABLES
Page
1-1 Test Matrix, LTV Steel Plant, East Chicago, Illinois 1-4
2-1 Emissions Test Log, LTV Steel 2-2
2-2 Sample Volume Collected, dscm 2-3
2-3 Flue Gas Volumetric Flow Rates, dscmm 2-3
2-4 Dioxin/Furan Stack Gas Concentrations, Venturi Outlet 2-5
2-5 Dioxin/Furan Stack Emission Rate, Venturi Outlet 2-6
2-6 Dioxin/Furan 2,3,7,8-TCDD Toxicity Equivalent Stack Gas Concentrations,
Venturi Outlet 2-8
2-7 PAH Concentration, Venturi Outlet 2-9
2-8 PAH Stack Emission Rate, Venturi Outlet 2-10
2-9 Metals Results: Venturi Outlet, Run 1 (ng collected) 2-12
2-10 Metals Results: Venturi Outlet, Run 2 (jag collected) 2-12
2-11 Metals Results: Venturi Outlet, Run 3 (jig collected) 2-13
2-12 Metals Results: Venturi Inlet, Run 1 (p.g collected) 2-13
2-13 Metals Results: Venturi Inlet, Run 2 (p.g collected) 2-14
2-14 Metals Results: Venturi Inlet, Run 3 (jig collected) 2-14
2-15 Metals Stack Gas Concentration, Venturi Outlet 2-15
2-16 Metals Stack Gas Concentration, Venturi Inlet 2-15
2-17 Metals Stack Emission Rate, Venturi Outlet 2-17
2-18 Venturi Removal Efficiency for Metals 2-17
Cah/K:\7997V)3\07-RPT\TOC-CVR.WP6 V1
-------
LIST OF TABLES (Continued)
Page
2-19 Particulate Matter Concentration, Venturi Scurbber 2-18
2-20 Particulate Matter Emission Rate and Venturi Scrubber Removal Efficiency 2-18
5-1 Glassware Cleaning Procedure (Train Components) 5-4
5-2 Sampling Checklist 5-9
5-3 Analytical Detection Limits 5-17
5-4 Method 29 Detection Limits 5-19
5-5 Method 23 Glassware Cleaning Procedure (Train Components, Sample Containers
and Laboratory Glassware) 5-27
5-6 CDD/CDF Sampling Checklist 5-32
5-7 Method 23 Sample Fractions Shipped To Analytical Laboratory 5-38
5-8 CDD/CDF Congeners To Be Analyzed 5-39
5-9 PAH to be Analyzed 5-40
5-10 Method 23 Blanks Collected 5-43
5-11 Analytical Detection Limits For Dioxins/Furans 5-46
5-12 CDD/CDF Method Detection Limits 5-47
5-13 Analytical Detection Limits For PAHs 5-48
5-14 PAH Method Detection Limits 5-49
6-1 Summary of Leak Checks Performed, Per Port, Dioxin Testing, Outlet 6-2
6-2 Summary of Isokinetic Percentages 6-3
6-3 Dry Gas Meter Post Calibration Results 6-5
Cah/K:\7997\03\07-RPT\TOC-CVR.WP6
-------
LIST OF TABLES (Continued)
Page
6-4 Dioxin/Furan Field Blank Analysis Results 6-6
6-5 Summary of Leak Checks Performed, Per Port, Metals Testing, Outlet 6-7
6-6 Summary of Leak Checks Performed, Per Port, Metals Testing, Inlet 6-8
6-7 Metals QC Results: (ng detected) 6-10
Cah/K:\7997\03\07-RPT\TOC-CVR.WP6
viii
-------
LIST OF FIGURES
Page
1-1 Test Schedule 1-5
4-1 Venturi Inlet Sampling Location 4-2
4-2 Venturi Outlet Sampling Location 4-3
4-3 Outlet Traverse Point Layout 4-4
4-4 Inlet Traverse Point Layout 4-5
5-1 EPA Method 29 Sampling Train 5-2
5-2 Method 29 Sample Recovery Scheme 5-13
5-3 Method 29 Sample Preparation and Analysis Scheme 5-20
5-4 Method 23 Sampling Train Configuration 5-25
5-5 Method 23 Field Recovery Scheme 5-36
5-6 Extraction and Analysis Schematic for Method 23 Samples 5-41
Cah/K:\7997\03\07-RPT\TOC-CVR.WP6
IX
-------
-------
1.0 INTRODUCTION
Integrated iron and steel manufacturing is among the categories of major sources for
which national emission standards for hazardous air pollutants (NESHAPS) are to be issued by
November 2000 pursuant to Section 112 of the Clean Air Act. The integrated iron and steel
manufacturing category includes mills that produce steel from iron ore. Key processes and unit
operations include sinter production, iron production, steel making, continuous casting, and the
preparation of semi-finished and finished products.
Source tests are required to quantify and characterize the particulate matter (PM),
hazardous air pollutant (HAP) emissions, and the performance of a sintering plant equipped with
a venturi scrubber.
1.1 Objective
The objective of the testing at the LTV Steel plant in East Chicago, Illinois, was to
perform all activities necessary to characterize the venturi-scrubbed sintering plant windbox for
the following emission components:
• Particulate mass (PM) and metal HAPs using EPA Method 29; and
• Dioxins/furans (D/F) and polynuclear aromatic hydrocarbons (PAH) using EPA
Method 23.
In addition, the determination of total hydrocarbons using Method 25A and preliminary
screening for organic HAPs using a Fourier Transform Infrared (FTIR) monitoring instrument
were conducted by Midwest Research Institute (MRI) under a separate work assignment.
Testing by ERG and MRI occurred simultaneously. The FTIR element is not included within
this final report.
1-1
-------
Testing was performed at the inlet and outlet simultaneously. ERG coordinated all field
test activities with MRI personnel.
1.2 Brief Site Description
The sintering process is used to agglomerate fine raw materials into a product suitable for
charging into a blast furnace. Raw materials processed include ore, fines, limestone, coke, flue
dust, basic oxygen furnace (BOF) slag, pellet chips, filter cake and mill scale. The principal
emission point at a sinter plant is the exhaust from the sintering machine windbox. Emission
controls include baghouses and wet venturi scrubbers.
Major process units operated by LTV Steel at the East Chicago, Illinois, location include
one sintering machine, two blast furnaces, BOFs, a continuous caster, and several finishing mills.
The plant has a rated capacity of 5,280 tons per day (tpd) of sinter. The plant operates
24 hours per day, 310 days per year (shutdown every other Thursday). Feed materials for the
sinter plant are stored in ten storage bins. The feed to the sinter machine consists of slag, ore,
scale, lime, flue dust, coke breeze, filter cake, dolomite, slag metallic fines, Heckett fines, and
kish fines.
1.3 Emissions Measurements Program
This section provides an overview of the emissions measurements program conducted at
LTV Steel Company in East Chicago, Illinois. Included in the this section are summaries of the
test matrix, sampling locations, sampling methods, and laboratory analysis. Additional detail on
these topics is provided in the sections that follow.
1-2
-------
1.3.1 Test Matrix
The sampling and analytical matrix is presented in Table 1-1. Manual emissions tests
were employed; detailed descriptions of these sampling and analytical procedures are provided in
Section 5.0.
1.3.2 Test Schedule
The daily test schedule is presented in Figure 1-1. The test required two days of set-up,
three test days, and one tear-down day. Each test day was approximately 12 hours in length with
a typical working period being between 6:00 am and 8:00 pm.
The test schedule was based on the test duration assumed in Table 1-1. The only major
delay in the schedule occurred during set-up when the plant was shut down while the plant
maintenance crew removed the port caps at the inlet location.
1.3.3 Sampling Locations
The stack gas sampling was conducted at the inlet and outlet of the venturi scrubber. The
inlet location was a rectangular duct with four existing 4" ports positioned on the long vertical
side. A new 3" port was installed by the plant down stream of the existing ports to accommodate
the FTIR probe. Access to this location required the construction of a scaffolding platform
which was provided by the plant.
The outlet location was a circular stack with four 4" existing ports positioned 90 degrees
apart. The installation of an additional port for FTIR sampling was not possible. Therefore,
close coordination between ERG and MRI personnel was needed to accommodate the FTIR, as
well as the Method 23 and the Method 29 probes simultaneously in three of the four ports with
the necessary port changes during the manual methods testing.
1-3
-------
Table 1-1. Test Matrix, LTV Steel Plant, East Chicago, Illinois
Sample
Location
Number
Of Runs
Sample
Type
Reference
Method
Sample
Duration*
Analysis
Method
Laboratory
Venturi
Inlet
3
Gas Velocity/
Volume/Moisture
EPA Methods 1 -4
4 Hrs
Volumetric/Gravimetric
ERG
Venturi
Inlet
3
Total
Particulates/Metals (Pb,
Cr, Cd, Be, Ni, Co, As,
Sb, Mn, Se, Hg)
EPA Method 29
4 Hrs
Gravimetric/Atomic
Absorption/ICAP
ERG and
Triangle Labs
Venturi
Outlet
3
Gas Velocity/
Volume/Moisture
EPA Methods 1-4
4 Hrs
Volumetric/Gravimetric
ERG
Venturi
Outlet
3
Total Particulates/
Metals (Pb, Cr, Cd, Be,
Ni, As, Sb, Co, Mn, Se,
Hg)
EPA Method 29
4 Hrs
Gravimetric Atomic
Absorption/ICAP
ERG and
Triangle Labs
Venturi
Outlet
3
D/F/PAHs
EPA Method 23
4 Hrs
GC/HRMS, GC/MS
8290/8270
Triangle Labs
-------
1997
June
1997
Sunday
Monday
Tuesday
Wednesday
Thursday
Friday
Saturday
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Travel
23
Coordination
Meeting with
plant
personnel and
equipment
set-up
24
Set-up
25
Test Day #1
26
Test Day #2
27
Test Day #3
28
Travel
29
30
Figure 1-1. Test Schedule
1-5
-------
1.3.4 Sampling and Analysis Methods
Total particulate matter emissions along with 11 metal HAPs (Pb, Ni, Cr, Mn, Se, Be, Sb,
Co, Cd, As, and Hg) were determined using a single sampling train following the protocol
provided in EPA Method 29. Particulate loading on the filter and the front half rinse
(nozzle/probe, front half of the filter holder) was determined gravimetrically. Metals analyses
were then performed on the residue from this rinse, the filter and the back-half impinger catch
using inductively coupled argon plasma spectroscopy (ICAPS) for all metals except Hg. Cold
vapor atomic absorption (CVAA) was used for Hg. Flue gas samples for D/F and PAHs were
collected using EPA Method 23. Flue gas was extracted isokinetically and any D/F/PAH was
collected on the filter, the XAD-2® resin trap and in the impingers. The analysis was performed
using high resolution gas chromatography (HRGC) coupled with high resolution mass
spectrometry (HRMS) for D/F, and both GC/HRMS and GC/LRMS for the PAHs.
1.4 Quality Assurance/Quality Control (QA/QC)
All flue gas testing procedures followed comprehensive QA/QC procedures as outlined in
the Site Specific Test Plan (SSTP) and the Quality Assurance Project Plan (QAPP). A full
description of the resulting QA parameters is given in Section 6.
All post-test and port change leak checks met the criteria prescribed in the manual
methods procedure. The allowable isokinetic QC range of ±10% was met for all D/F/PAH and
metals/PM sampling runs. All post-test dry gas meter calibration checks were within 5% of the
full calibration factor. Field blanks (FB) for the D/F/PAH tests showed virtually no
contamination. However, the metals FB for the inlet and outlet locations did show some
contamination for Cr, Mn, Ni, Pb, Sb, and Se, due most likely to laboratory contamination. The
metals FB is discussed in detail in Sections 6.1.2 and 6.2.2.
1-6
-------
All analyses were completed under a strict QA/QC regimen. For the D/F/PAH results,
percent recoveries of all isotopically labeled compounds were within the lower and upper limits
of recovery as specified in the method. For the metals results, all matrix spike recoveries were
within the acceptable range.
The manual flue gas test data reflected vary little variation over the three runs. The
percent relative standard deviation (%RSD) for each of the D/F congeners ranged from 2.8 to 32.
The %RSD for the metals ranged from 2 to 25 and the gravimetric results ranged from 12 to 14.
These values indicate that the process was very stable during the test period.
1.5 Test Report
This final report, presenting all data collected and the results of the analyses, has been
prepared in six sections and two volumes as described below:
• Section 1 provides an introduction to the testing effort and includes a brief
description of the test site, an overview of the emissions measurements program
and a brief overview of the QC results;
• Section 2 gives a summary of the test results for the D/F/PAH, metals and PM
tests;
• Section 3 provides a description of the process and plant operation during the field
test. These data are to be supplied by EPA;
• Section 4 gives a discussion of the sampling locations;
• Section 5 presents detailed descriptions of the sampling and analysis procedures;
and
• Section 6 provides details of the quality assurance/quality control procedures used
on this program and the QC results.
The appendices containing copies of the actual field data sheets and the results of the
laboratory analyses are contained in a separate volume.
1-7
-------
-------
2.0 SUMMARY OF RESULTS
This section provides the results of the emissions test program conducted at the LTV
Steel Company sintering operation from June 23 to June 27, 1997. Included in this section are
results of manual tests conducted for D/F/PAH, metal HAPs and PM.
2.1 Emissions Test Log
Nine tests were conducted over a three day period (3 D/F/PAH and 6 Metals/PM).
Table 2-1 presents the emissions test log which shows the test date, location, run number, test
type, run times and port change times for each test method.
Table 2-2 shows the volume of stack gas sampled for each run in dry standard cubic
meters (dscm) and Table 2-3 shows the stack gas volumetric flow rate during each run in dry
standard cubic meters per minute (dscmm). The percent relative standard deviation (%RSD)
calculated for the three runs for each test method (shown in Table 2-3) was less than 3%,
indicating that the process flow was very constant over the three test days. All related field data
sheets are given in Appendix E.
2.2 D/F/PAH RESULTS
2.2.1 Overview
Three 4-hour D/F/PAH emission test runs were completed at LTV Steel during the week
of June 23, 1997. Three test runs were completed at the outlet of the venturi scrubber associated
with the sintering plant windbox. The sample collection protocol followed EPA Method 23
while the analysis protocol was modified to allow the analysis of the sample extract for PAHs.
2-1
-------
Table 2-1. Emissions Test Log, LTV Steel
Date
Location
Run Number
Test Type
Run Time
6/25/97
Outlet, Port C
1
D/F/PAH
0931-1031
Outlet, Port D
1
D/F/PAH
1211-1311
Outlet, Port A
1
D/F/PAH
1406-1506
Outlet, Port B
1
D/F/PAH
1601-1701
Outlet, Port D
1
Metals/PM
0930-1030
Outlet, Port A
1
Metals/PM
1210-1310
Outlet, Port B
1
Metals/PM
1405-1505
Outlet, Port C
1
Metals/PM
1600-1700
Inlet, Port A
1
Metals/PM
0931-1031
Inlet, Port B
1
Metals/PM
1210-1310
Inlet, Port C
1
Metals/PM
1405-1505
Inlet, Port D
1
Metals/PM
1600-1700
6/26/97
Outlet, Port B
2
D/F/PAH
0956-1056
Outlet, Port A
2
D/F/PAH
1126-1226
Outlet, Port D
2
D/F/PAH
1306-1406
Outlet, Port C
2
D/F/PAH
1436-1536
Outlet, Port C
2
Metals/PM
0955-1055
Outlet, Port B
2
Metals/PM
1125-1225
Outlet, Port A
2
Metals/PM
1305-1405
Outlet, Port D
2
Metals/PM
1435-1535
Inlet, Port A
2
Metals/PM
0955-1055
Inlet, Port B
2
Metals/PM
1125-1225
Inlet, Port C
2
Metals/PM
1305-1405
Inlet, Port D
2
Metals/PM
1435-1535
6/27/97
Outlet, Port C
3
D/F/PAH
0841-0941
Outlet, Port D
3
D/F/PAH
1001-1101
Outlet, Port A
3
D/F/PAH
1126-1226
Outlet, Port B
3
D/F/PAH
1246-1346
Outlet, Port D
3
Metals/PM
0840-0940
Outlet, Port A
3
Metals/PM
1000-1100
Outlet, Port B
3
Metals/PM
1125-1225
Outlet, Port C
3
Metals/PM
1245-1345
Inlet, Port A
3
Metals/PM
0835-0935
Inlet, Port B
3
Metals/PM
1000-1100
Inlet, Port C
3
Metals/PM
1121-1221
Inlet, Port D
3
Metals/PM
1242-1342
2-2
-------
Table 2-2. Sample Volume Collected, dscm*
Location
Parameter
Run 1
Run 2
Run 3
Average
%RSD
Outlet
D/F/PAH
4.22
4.24
4.29
4.25
0.85
Outlet
Metals/PM
4.35
4.14
4.16
4.22
2.75
Inlet
Metals/PM
1.76
1.81
1.76
1.78
1.54
*dscm, dry standard cubic meters. Standard conditions are defined as 1 atm and 68°F
Table 2-3. Flue Gas Volumetric Flow Rates, dscmm*
Location
Parameter
Run 1
Run 2
Run 3
Average
%RSD
Outlet
D/F/PAH
7432
7497
7689
7539
1.77
Outlet
Metals/PM
7691
7614
7388
7564
2.08
Inlet
Metals/PM
7026
6826
7238
7030
2.93
*dscmm, dry standard cubic meters per minute. Standard conditions are defined as 1 atm and 68 °F
2-3
-------
This modification to the sample preparation procedure and subsequent analysis is discussed in
Section 5 of this report.
2.2.2 D/F Emission Results
Table 2-4 presents the concentration, in nanograms per dry standard cubic meter
(ng/dscm), for the selected D/F congeners by run number, the average concentration over the
three runs and the %RSD. All results except for the 2,3,7,8-tetrachlorodibenzofuran
(2,3,7,8-TCDF) were determined by high resolution gas chromatography (HRGC)/high
resolution mass spectrometry (HRMS) using a DB-5 capillary gas chromatographic column. The
2,3,7,8-TCDF was determined by HRGC/HRMS using a DB-225 column which gives improved
chromatographic resolution for this compound over the DB-5 and thus a more accurate
quantitation.
As noted in Table 2-4, the reported concentration of several congeners may be over-
estimated due to the presence of an associated diphenyl ether (DPE) that coelutes with the peak
of interest. However, these values are at or very near the detection limit for that compound or
they are very consistent with the value(s) from the other test runs that do not have this DPE
interferent and should be considered as estimated maximum possible concentrations (EMPC).
These values are included in all calculations. Any compound that was not detected is reported as
a "less than value" with this value being the instrumental detection limit. A "less than" value
rather than a "0" is used in all appropriate calculations. The %RSDs reported in Table 2-4 for the
three runs by compound are generally less than 15% indicating excellent reproducibility. In a
few cases, the %RSDs are higher where the concentrations are near the detection limit or the
presence of a DPE is indicated. Increased variability would not be unusual in these cases.
Table 2-5 shows the D/F stack emission rates from the venturi outlet. These values were
calculated from the average concentrations from Table 2-4 and the average stack flow rate from
Table 2-3.
2-4
-------
Table 2-4. Dioxin/Furan Stack Gas Concentrations, Venturi Outlet
Congener
ng/dscm
Run 1
Run 2
Run 3
Average
%RSD
2,3,7,8 -TCDD
0.0193
0.0193
0.0143
0.0173
16.4
1,2,3,7,8-PeCDD
0.050
0.050
0.047
0.049
3.5
1,2,3,4,7,8-HxCDD
0.0093
0.014'3
0.0093
o
o
25.1
1,2,3,6,7,8-HxCDD
0.222
0.210
0.217
0.216
2.8
1,2,3,7,8,9-HxCDD
0.114
0.099
0.093
0.102
10.2
1,2,3,4,6,7,8—HpCDD
0.260
0.260
0.219
0.246
9.5
1,2,3,46,7,8,9-OCDD
0.196
0.168
0.163'
0.176
10.2
2,3,7,8-TCDF2
0.260
0.210
0.170
0.214
21.1
1,2,3,7,8-PeCDF
0.140
0.127
0.098
0.122
17.6
2,3,4,7,8-PeCDF
0.132
0.132
0.107
0.124
11.6
1,2,3,4,7,8-HxCDF
0.158
0.163
0.126
0.149
13.5
1,2,3,6,7,8-HxCDF
0.059
0.064
0.051
0.058
10.8
2,3,4,6,7,8-HxCDF
0.054
0.057
0.040
0.050
18.4
1,2,3,7,8,9-HxCDF
0.0051,3
0.0073
<0.007
0.0063
21.3
1,2,3,4,6,7,8-HpCDF
0.088
0.090
0.084
0.087
3.3
1,2,3,4,7,8,9-HpCDF
0.0123
0.0141,3
0.012'-3
0.0133
11.1
1,2,3,46,7,8,9-OCDF
0.0383
0.0241-3
0.0473
0.0363
32.3
1 Maximum value, may include interference from a diphenyl ether
2 Determined from DB-225 GC column
3 Amount detected is less than 5 times the detection limit and should be considered only an
estimate
2-5
-------
Table 2-5. Dioxin/Furan Stack Emission Rate, Venturi Outlet
Congener
Average Concentration
ng/dscm
Average Emission Rate
Hg/Hr
2,3,7,8 -TCDD
0.0173
7.693
1,2,3,7,8-PeCDD
0.049
22.2
1,2,3,4,7,8-HxCDD1
0.0113
4.983
1,2,3,6,7,8-HxCDD
0.216
97.7
1,2,3,7,8,9-HxCDD
0.102
46.1
1,2,3,4,6,7,8—HpCDD
0.246
111
1,2,3,46,7,8,9-OCDD1
0.176
79.6
2,3,7,8-TCDF2
0.214
96.8
1,2,3,7,8-PeCDF
0.122
55.2
2,3,4,7,8-PeCDF
0.124
56.1
1,2,3,4,7,8-HxCDF
0.149
67.4
1,2,3,6,7,8-HxCDF
0.058
26.2
2,3,4,6,7,8-HxCDF
0.050
22.6
1,2,3,7,8,9-HxCDF1
0.0063
2.713
1,2,3,4,6,7,8-HpCDF
0.087
39.4
1,2,3,4,7,8,9-HpCDF1
0.0133
5.883
1,2,3,46,7,8,9-OCDF1
0.0363
16.33
1 Maximum value, may include interference from a diphenyl ether
2 Determined from DB-225 GC column
3 Amount detected is less than 5 times the detection limit and should be considered only an
estimate
2-6
-------
Table 2-6 shows the congener concentrations in ng/dscm converted to 2,3,7,8-
tetrachlorodibenzo-p-dioxin toxicity equivalents as well as a summation of the values presented
as total chlorinated dioxins and total chlorinated fiirans. All D/F analytical raw data can be
found in Appendix A.
2.2.3 PAH Emission Results
Table 2-7 presents the concentration, in micrograms per dry standard cubic meter
(|ig/dscm), for the selected PAH compounds by run number, the average concentration over the
three runs and the %RSD. All sample extracts were initially analyzed by high resolution
chromatography (HRGC)/high resolution mass spectrometry (HRMS) using a DB-5 capillary gas
chromatographic column. However, the high levels of many of the PAHs saturated the HRMS
resulting, for the most part, in data that were mostly qualitative in nature. Therefore, the extracts
were reanalyzed on a low resolution mass spectrometer (LRMS) after dilution of the sample
extracts. The %RSDs reported in Table 2-7 for the three runs by compound are generally less
than 15% indicating excellent reproducibility. In a few cases, the %RSDs are higher where the
concentrations are near the detection limit. Increased variability would not be unusual in this
case.
Table 2-8 shows the PAH stack emission rates from the venturi outlet. These values were
calculated from the average concentrations from Table 2-7 and the average stack flow rate from
Table 2-3. All PAH analytical raw data can be found in Appendix B.
2-7
-------
Table 2-6. Dioxin/Furan 2,3,7,8-TCDD Toxicity Equivalent Stack Gas
Concentrations, Venturi Outlet
Congener
2,3,7,8-CDD
TEF4
ng/dscm
Run 1
Run 2
Run 3
Average
2,3,7,8 -TCDD
1.0
0.019
0.019
0.014
0.0173
1,2,3,7,8-PeCDD
0.5
0.025
0.025
0.024
0.025
1,2,3,4,7,8-HxCDD
0.1
0.0009
0.0014'
0.0009
0.00113
1,2,3,6,7,8-HxCDD
0.1
0.0222
0.0210
0.0217
0.0216
1,2,3,7,8,9-HxCDD
0.1
0.0114
0.0099
0.0093
0.0102
1,2,3,4,6,7,8—HpCDD
0.01
0.00260
0.00260
0.00219
0.00246
1,2,3,4,6,7,8,9-OCDD
0.001
0.000196
0.000168
0.000163'
0.000176
Total PCDD
0.0775
2,3,7,8-TCDF2
0.1
0.0260
0.0210
0.017
0.0213
1,2,3,7,8-PeCDF
0.05
0.007
0.0064
0.0049
0.0056
2,3,4,7,8-PeCDF
0.5
0.066
0.0066
0.054
0.062
1,2,3,4,7,8-HxCDF
0.1
0.0158
0.0163
0.0126
0.0149
1,2,3,6,7,8-HxCDF
0.1
0.0059
0.0064
0.0051
0.0058
2,3,4,6,7,8-HxCDF
0.1
0.0054
0.0057
0.0040
0.0050
1,2,3,7,8,9-HxCDF
0.1
0.0005'
0.0007
<0.0007
0.00063
1,2,3,4,6,7,8-HpCDF
0.01
0.00088
0.00090
0.00084
0.00087
1,2,3,4,7,8,9-HpCDF
0.01
0.00012
0.00014'
0.00012'
0.000133
1,2,3,4,6,7,8,9-OCDF
0.001
0.000038
0.000024'
0.000047
0.0000363
Total PCDF
0.1162
1 Maximum value, may include interference from a diphenyl ether
2 Determined from DB-225 GC column
3 The amount detected is less than 5 times the detection limit and should be considered only an
estimate
4 TEF, Toxicity Equivalent Factor
2-8
-------
Table 2-7. PAH Concentration, Venturi Outlet
PAHs
Concentration, |wg/dscm
Runs
Average
%RSD
1
2
3
Naphthalene*
76.5
90.0
68.5
78.3
13.9
2-Methylnaphthalene*
29.5
31.7
25.4
28.9
11.1
2-Chloronaphthalene
0.038
0.040
0.040
0.039
2.94
Acenaphthylene
8.35
8.62
5.86
7.61
20.0
Acenaphthene
3.24
3.98
3.23
3.48
12.3
Fluorene
5.31
6.18
4.72
5.40
13.6
Phenanthrene*
44.8
46.2
37.1
42.7
11.5
Anthracene
1.73
1.82
1.83
1.79
3.07
Fluoranthene
7.82
7.40
5.44
6.89
18.4
Pyrene
3.25
3.45
2.42
3.04
18.0
Benzo(a)anthracene
0.545
0.618
0.413
0.525
19.8
Chrysene
1.49
1.49
1.00
1.33
21.6
Benzo(b)fluoranthene
1.32
1.40
0.856
1.19
24.6
Benzo(k)fluoranthene
0.223
0.241
0.196
0.220
10.3
Benzo(e)pyrene
0.846
0.835
0.597
0.759
18.5
Benzo(a)pyrne
0.239
0.274
0.187
0.233
18.8
Perylene
0.043
0.071
0.061
0.058
24.3
Ideno(l,2,3-cd)pyrene
0.256
0.309
0.212
0.259
18.8
Dibenzo(a,h)anthracene
0.107
0.094
0.090
0.097
9.16
Benzo(g,h,i)perylene
0.360
0.413
0.296
0.356
16.4
* Concentrations taken from a sample dilution; should be considered estimated.
2-9
-------
Table 2-8. PAH Stack Emission Rate, Venturi Outlet
PAHs
Average Concentration
(fig/dscm)
Emission Rate
(g/hr)
Naphthalene*
78.3
35.4
2-Methylnaphthalene*
28.9
13.1
2-Chloronaphthalene
0.039
0.018
Acenaphthylene
7.61
3.44
Acenaphthene
3.48
1.58
Fluorene
5.40
2.44
Phenanthrene*
42.7
19.3
Anthracene
1.79
0.811
Fluoranthene
6.89
3.12
Pyrene
3.04
1.38
Benzo(a)anthracene
0.525
0.238
Chrysene
1.33
0.599
Benzo(b)fluoranthene
1.19
0.539
Benzo(k)fluoranthene
0.220
0.100
Benzo(e)pyrene
0.759
0.343
Benzo(a)pyrene
0.233
0.106
Perylene
0.058
0.026
Ideno( 1,2,3-cd)pyrene
0.259
0.117
Dibenzo(a,h)anthracene
0.097
0.044
Benzo(g,h,i)perylene
0.356
0.161
*Concentrations taken from a sample dilution; should be considered estimated.
2-10
-------
2.3 Metals HAPs Results
2.3.1 Overview
Six 4-hour metals emission test runs were completed at LTV Steel during the week of
June 23, 1997. Three test runs were completed at the inlet and three at the outlet of the venturi
scrubber associated with the sintering plant windbox. The sample collection protocol followed
EPA Method 29 using a single sampling train to determine emission rates of 11 metal HAPs. A
total of five (5) fractions for each test run were presented to the laboratory for analysis (see
Section 5 of this report for details).
2.3.2 Metal HAPs Emission Results
Tables 2-9 through 2-14 show the results of the analysis, by fraction, for each of the three
samples collected at the outlet and at the inlet along with a total amount detected. Any metal that
was not detected is reported as a "less than" value with this value being the instrument detection
limit. A "less than" value rather than a "0" is used in all appropriate calculations. Using the
results shown in Tables 2-9 through 2-14 and the sample volume collected in the corresponding
train given in Table 2-2, the concentration of each metal was calculated. The concentration
(Hg/dscm) of each metal by run number, the average concentration and %RSD for the outlet and
inlet are given in Tables 2-15 and 2-16, respectively. There is an apparent analysis problem
associated with manganese for Run 3 outlet (103 jag/dscm) and with cobalt for Run 1 inlet
(0.051 |ig/dscm). These two values are not consistent with their other two associated test run
results. Sample contamination from field activities can be ruled out due to the obvious
consistency between runs for each of the other metals. If these two values are removed from the
data set, the average concentration given in Table 2-15 for manganese would be 17.3 |ig/dscm
and the average concentration given in Table 2-16 for cobalt would be 0.422 (ig/dscm.
2-11
-------
Table 2-9. Metals Results: Venturi Outlet, Run 1 (|jg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
<0.400
<2.68
<0.100
1.37
<0.360
4.91
As
3.96
<0.588
4.55
Be
<0.100
<0.118
<0.218
Cd
76.6
0.658
77.3
Co
<0.100
<0.118
<0.218
Cr
24.5
3.27
27.8
Mn
54.2
11.7
65.9
Ni
86.3
4.61
90.9
Pb
15,900
10.9
15911
Sb
7.23
<0.470
7.70
Se
18.7
21.6
40.3
Table 2-10. Metals Results: Venturi Outlet, Run 2 (pg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
<0.400
<2.64
<0.240
1.81
<2.60
7.69
As
4.33
<0.589
4.92
Be
<0.100
<0.118
<0.218
Cd
67.5
<0.118
67.6
Co
<0.100
<0.118
<0.218
Cr
17.2
1.46
18.7
Mn
56.1
24.4
80.5
Ni
117
0.507
118
Pb
15,000
1.09
15,000
Sb
5.81
<0.471
6.28
Se
18.7
15.8
34.5
2-12
-------
Table 2-11. Metals Results: Venturi Outlet, Run 3 (pg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
<0.400
<2.76
<0.180
2.94
<0.360
6.64
As
3.90
<0.585
4.49
Be
<0.100
<0.117
<0.217
Cd
72.7
<0.117
72.8
Co
<0.100
<0.117
<0.217
Cr
17.4
1.99
19.4
Mn*
115
314
429
Ni
66.4
0.509
66.9
Pb
16,300
1.95
16,300
Sb
6.30
0.471
6.77
Se
16.8
18.9
35.7
*Questionable Data
Table 2-12. Metals Results: Venturi Inlet, Run 1 (pg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
<0.400
<2.44
0.551
<0.840
<0.280
4.51
As
14.2
<0.598
14.8
Be
<0.100
<0.120
<0.220
Cd
86.1
0.882
87.0
Co*
<0.100
<0.120
<0.220
Cr
84.2
7.04
91.2
Mn
1,330
52.3
1,382
Ni
119
4.79
124
Pb
19,300
96.7
19,400
Sb
12.5
<0.478
13.0
Se
34.7
15.1
49.8
*Questionable Data
2-13
-------
Table 2-13. Metals Results: Venturi Inlet, Run 2 (pg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
0.469
<1.76
<0.240
<1.02
<0.260
3.75
As
1-8.4
<0.647
19.0
Be
<0.100
<0.129
<0.229
Cd
80.8
<0.129
80.9
Co
1.38
<0.129
1.50
Cr
101
1.64
103
Mn
1,800
6.65
1,800
Ni
82.9
1.15
84.1
Pb
18,500
1.39
18,500
Sb
9.93
<0.518
10.4
Se
40.6
20.9
61.5
Table 2-14. Metals Results: Venturi Inlet, Run 3 (pg collected)
Metal
Fraction #
1
2
3
4
5
Total
Hg
0.547
<1.76
<0.200
<1.04
<0.380
3.93
As
20.1
<0.647
20.7
Be
<0.100
<0.129
<0.229
Cd
84.8
<0.129
84.9
Co
1.87
<0.129
2.0
Cr
99.8
1.99
102
Mn
1,900
12.6
1,910
Ni
87.0
0.475
87.5
Pb
19,100
1.34
19,100
Sb
9.06
<0.518
9.58
Se
32.2
20.5
52.7
2-14
-------
Table 2-15. Metals Stack Gas Concentration, Venturi Outlet
Metal
jig/dscm
Run 1
Run 2
Run 3
Average
%RSD
Hg
1.13
1.86
1.60
1.53
24.2
As
1.05
1.19
1.08
1.10
6.74
Be
0.050
0.053
0.052
0.052
2.61
Cd
17.8
16.3
17.5
17.2
4.46
Co
0.050
0.053
0.052
0.050
2.61
Cr
6.37
4.52
4.66
5.18
19.9
Mn
15.2
19.4
103*
45.9
108
Ni
20.9
28.5
16.1
21.8
28.7
Pb
3658
3623
3919
3733
4.33
Sb
1.77
1.52
1.63
1.64
7.75
Se
9.26
8.33
8.58
8.73
5.52
*Questionable Data
Table 2-16. Metals Stack Gas Concentration, Venturi Inlet
Metal
Hg/dscm
Run 1
Run 2
Run 3
Average
%RSD
Hg
1.04
0.91
0.94
0.96
7.0
As
3.40
4.59
4.98
4.32
19.0
Be
0.051
0.055
0.055
0.054
4.96
Cd
20.0
19.5
20.4
20.0
2.17
Co
0.051*
0.362
0.481
0.30
74.6
Cr
21.0
24.9
24.5
23.5
9.2
Mn
318
437
460
405
19.0
Ni
28.5
20.3
21.0
23.3
19.5
Pb
4459
4469
4592
4507
1.64
Sb
2.99
2.51
2.30
2.60
13.5
Se
11.5
14.9
12.7
13.0
13.3
*Questionable Data
2-15
-------
Using this corrected value for manganese and the other listed values from Table 2-15 and
the average stack flow rate from Table 2-3 , the average emission rate from the venturi outlet for
each metal can be calculated. These results, in grams per hour, are given in Table 2-17. Using
these values from Table 2-17 in conjunction with the equivalent values for the inlet (see
Table 2-18), a removal efficiency for the venturi scrubber was calculated for each metal. All
metal analytical raw data are given in Appendix C.
2.4 PM Results
2.4.1 PM Emissions Results
Particulate matter emissions were determined from the same sampling trains used for the
collection of metals at the inlet and outlet of the venturi scrubber. Before metals analysis, PM
collected on the filter and in the front half acetone rinse (nozzle, probe, front-half filter holder)
was analyzed gravimetrically. PM stack gas concentrations, in grams per dry standard cubic
meter (g/dscm), the average and %RSD for the three test runs at the inlet and outlet are presented
in Table 2-19. The %RSD for both the inlet and outlet were less than 15, showing excellent
reproducibility for the sampling and analysis method as well as constant process conditions over
the 3 day test period.
Table 2-20 shows the average PM emission rate to be 482 pounds per hour (lb/hr). This
value was calculated from the average outlet concentration from Table 2-19 and the average
stack flow rate from Table 2-3. Using this value in conjunction with the equivalent value for the
inlet (see Table 2-20), a PM removal efficiency for the venturi scrubber was calculated to be
92.1%. The PM analytical raw data are given in Appendix D.
2-16
-------
Table 2-17. Metals Stack Emission Rate, Venturi Outlet
Metal
Average Concentration
Hg/dscm
Average Emission Rate
g/hr
Hg
1.53
0.693
As
1.10
0.501
Be
0.052
0.023
Cd
17.2
7.81
Co
0.050
0.023
Cr
5.18
2.35
Mn*
17.3
7.85
Ni
21.8
9.91
Pb
3733
1,690
Sb
1.64
0.743
Se
8.73
3.96
*Average of two test runs.
Table 2-18. Venturi Removal Efficiency for Metals
Metal
Average Inlet Rate
g/hr
Average Outlet Rate
g/hr
Removal Efficiency
%
Hg
0.406
0.693
-70.8
As
1.82
0.501
72.5
Be
0.023
0.023
-3.6
Cd
8.43
7.81
7.4
Co
0.178*
0.023
87.1
Cr
9.89
2.35
76.2
Mn
171
7.85*
95.4
Ni
9.82
9.91
-0.90
Pb
1901
1694
10.9
Sb
1.10
0.743
32.2
Se
5.48
3.96
27.7
*Average using data from two test runs.
2-17
-------
Table 2-19. Particulate Matter Concentration, Venturi Scrubber
Location
Run 1
g/dscm
Run 2
g/dscm
Run 3
g/dscm
Average
g/dscm
%RSD
Outlet
0.033
0.038
0.044
0.038
14.5
Inlet
0.451
0.531
0.575
0.519
12.1
Table 2-20. Particulate Matter Emission Rate and Venturi Scrubber Removal
Efficiency
Parameter
Average Inlet Rate*
lb/hr
Average Outlet Rate*
Ib/hr
Removal Efficiency
%
PM
482
38.0
92.1
*Average of 3 test runs
2-18
-------
3.0
LTV Steel's Sinter Plant
3.1 Overview
The primary purpose of the sinter plant is to recover the iron value from waste
materials generated at iron and steel plants by converting the materials to a product
that can be used in the blast furnace (as burden material). Many of these wastes have
little or no value otherwise and would require disposal if they could not be recycled by
this process. A secondary purpose of the sinter plant is to incorporate blast furnace flux
into the sinter rather than charging it separately into the furnace. Limestone wastes are
converted to lime on the sinter grate, and the lime is used as a fluxing agent in the blast
furnace. The raw material feed (sinter mix) consists of iron ore fines, chips from iron
ore pellets, fine limestone, slag from the steelmaking furnace, scale from the steel
rolling mill, residue from air and water pollution control equipment (blast furnace flue
dust and filter cake), coke breeze (undersize coke that cannot be used in the blast
furnace), and steel reverts.
There are currently 9 sinter plants in operation in the U.S. A total of 5 of these
plants use scrubbers to control emissions from the sinter plant windbox, and 4 use a
baghouse. The sinter plant at LTV Steel in East Chicago, IN, was chosen for testing to
evaluate hazardous air pollutants and emission control performance associated with
sinter plants that use scrubbers.
3.2 Process Description
LTV Steel's sinter plant at their Indiana Harbor Works was constructed in 1959
and is a part of the integrated iron and steel plant that also includes blast furnaces,
basic oxygen furnaces (BOFs), ladle metallurgy, continuous casting, rolling mills, and
galvanizing lines. The sinter plant has a maximum rated capacity of 5,280 tons per day
(tpd) and operates 24 hours per day, 7 days a week. Typically, the plant produces
3,800 tpd and operates 24 hours per day for about 310 days per year. The sinter
-------
machine is 8 feet wide and 168 feet long. The major processing steps in the sinter
plant include preparation of the sinter mix (feed material), sintering, discharge end
operations (crushing and screening), and cooling of the sinter product. Figure 3-1 is a
simplified schematic of the sintering process.
The typical feed composition of the sinter mix during the emission tests is shown
in Table 3-1.
TABLE 3-1. SUMMARY OF SINTER MIX (FEED) COMPONENTS
Feed material
Percent of total for the day
Test 1 (6/25/97)
Test 2 (6/26/97)
Test 3 (6/27/97)
Pellet chips (ore)
41.1
40.9
41.3
Mill scale
13.2
14.3
14.4
Limestone
16.6
15.9
15.8
Flue dust
2.7
3.0
3.0
Coke breeze
0.8
0.8
0.9
BOF slag
9.1
9.1
8.9
Fines
7.4
8.2
7.6
NMT blend
3.8
3.2
4.2
Filter cake
5.3
4.6
3.9
The raw materials are fed from 10 storage bins by a table feeder onto a moving
belt. This raw feed is mixed in a pug mill, where water is added to create the desired
consistency in the mix. A "hearth layer" of material, which is undersize sinter material
that is recycled from the screening operation, is first deposited on the grate bars of the
sinter pallets, and then the feed mix is added to a depth of about 14 inches.
The sinter feed passes through an ignition furnace that is 12 feet long. The
furnace has 9 side burners fueled by natural gas that ignite the surface of the sinter
2
-------
feed. The sinter pallets move continually through the ignition furnace at about 90 to
100 inches per minute over 21 vacuum chambers called "windboxes." A vacuum is
3
-------
Stack Clean BF recycle water
Venturi
scrubber
Service water
Water
return
Blowdown
Clean BF
recycle
water
Water return
Stack
Dust
returns
Breaker end
Venturi
scrubber
Raw materials
(pellet chips, mill scale,
coke breeze, flue dust
BOF slag, filter cake, Water
limestone)
Sinter to blast
furnace or
storage
Water spray
Natural
gas
* Windbox
i exhaust
Air
Hearth layer returns
Cold fines return
Pug
Mill
Breaker
and
screen
Ten raw
material
bins
Sinter
product
screening
Dropout
boxes
Cyclone
dust
collectors
Sintering
machine
windboxes
Settling
chamber
Hearth
layer
Sinter
cooler
Blast furnace
water recycle
system
FIGURE 3-1. SCHEMATIC OF MATERIAL FLOW IN THE SINTER PLANT
4
-------
created in the windbox by a 3,000 horsepower fan that draws heat through the sinter
bed and creates the fused "sintered" product.
The red hot sinter from the furnace continues to be transported on the pallets to
the breaker, where it is crushed, screened, and discharged to a rotary cooler. Three
fans are used to create a forced draft to cool the hot sinter product. In addition, water
sprays are used to cool the sinter and to suppress surface dust. The sinter is removed
from the bottom of the cooler with a plow that deposits the cooled material onto a
conveyor belt. The sinter is then conveyed over a double-deck screen and
subsequently deposited into a storage bin. An ore car is used to transport the finished
product to the blast furnace. Sinter material that passes through the screens ("fines") is
returned to the sinter process for use as the hearth layer or for addition to the sinter
mix.
Several operating parameters are monitored and controlled to ensure proper
operation of the sinter machine. These parameters include the feed rate of each of the
ten feed bins, the sinter furnace temperature, the temperature profile through the
various windboxes, draft on the windboxes, speed of the grate, and percent water in the
feed. The oil in the sinter feed, which comes primarily from rolling mill scale, is limited
to 0.2 percent. During the testing, the coke feed rate appeared to be the parameter
that was most often adjusted in order to control temperatures. To maintain the proper
chemistry in the blast furnace, an important quality control parameter that is monitored
and graphed on a control chart is the percent excess base:
(%CaO+%MgO) - (%Si02 + %AI203).
The sinter composition for the 3 tests days is summarized in Table 3-2 and shows that
the percent excess base ranged from 13.6 to 13.7 compared to a target of 14.0.
5
-------
TABLE 3-2. SUMMARY OF SINTER COMPOSITION
Component
Percent of total
Test 1 (6/25/97)
Test 2 (6/26/97)
Test 3 (6/27/97)
Fe
52.8
52.7
52.9
Si02
4.5
4.6
4.4
ai2o3
0.59
0.65
0.66
CaO
16.7
16.8
16.6
MgO
2.0
2.1
2.1
Excess base
13.6
13.7
13.6
3.4 Emission Control Equipment
Emissions are generated in the process as sinter dust and combustion products
and are discharged through the grates and windboxes to a common collector main.
Coarse dust particles settle out of the air stream in the collector main and are
discharged through flapper valves to a conveyor belt. This conveyor also receives the
returns from a series of hoppers that collect any particles that fall under the sinter
machine. This material is returned by conveyor to the sinter mix feed for recycle to the
process. The exhaust then passes through a battery of cyclones and a series of
chambers (originally designed for an electrostatic precipitator that is no longer used).
The cyclones and chambers remove dust particles, which are also deposited onto a
conveyor (through air actuated valves) for recycle to the process. The exhaust is
moved by a 6,000 horsepower fan to the primary control device, which is a double-
throat Kinpactor scrubber designed by American Air Filter. The parameters associated
with the scrubber that are monitored include the pressure drop across the scrubber,
flow rate of water to the scrubber, exhaust fan draft and amperage, and the scrubber
water blowdown rate.
6
-------
Typical operating conditions associated with the scrubber are summarized in
Table 3-3.
TABLE 3-3. TYPICAL SCRUBBER PARAMETERS
Parameter
Typical value
Liquid/gas ratio
14 gal/1,000 acfm
Water flow rate
3,100 gal/min
Gas flow rate
265,000 scfm
Pressure drop
38 to 46 inches of
water
pH of scrubber water
8
Inlet temperature
235 to 270 °F
Outlet temperature
120°F
Blowdown rate
240 gal/min
A scrubber is also used to control emissions from the discharge end (i.e.,
breaker, screens). The discharge end scrubber was not evaluated as part of this test
program.
Current State regulations limit particulate matter to 0.02 gr/dscf and 20 percent
opacity (6-minute average) for both scrubbers. In addition, the windbox scrubber is
limited to a mass rate of 49.7 Ib/hr and the discharge end scrubber is limited to 18.05
Ib/hr.
3.5 Monitoring Results During the Tests
The operating parameters associated with the process and control device were
recorded at 15-minute intervals throughout each test day. The process parameters that
were monitored included the feed rate from each of the 10 bins that were used in the
7
-------
sinter mix, the temperatures and the fan draft for the windboxes, percent water in the
feed, sinter machine speed, and the sinter production rate. The emission control device
parameters that were monitored included the pressure drop across the scrubber, the
water flow rate, blowdown rate, fan draft, and fan amps. Tables 3-4 and 3-5 present a
summary of the range of values for these parameters for each test period.
The process and control device appeared to be stable throughout the three test
days; consequently, sampling was conducted under normal and representative
conditions. The feed rates of mill scale and other materials were typical of the historical
rates in recent years that had been reported by the plant. In addition, the oil content of
the mill scale was typical (target is 0.2 percent, maximum) with an average of 0.21
percent oil (a range of 0.17 to 0.24 percent) based on the analysis of 5 samples. An
examination of the monitoring data showed that the average pressure drop across the
scrubber was 43.1, 42.8, and 42.4 inches of water for the 3 test days. The coke rate
seemed to be the most variable parameter during the tests because adjustments were
made frequently to change the sintering temperature. The coke rate for the 3 tests
averaged 1.7,1.15, and 0.67 tph; consequently, the emission test results may provide
some insight into the effect of coke rate on emissions. The windbox temperatures also
varied somewhat during the tests. Using Windbox 20 as an example, the average
temperatures during the 3 tests were 538, 567, and 443°F.
3.6 Analysis of Monitoring and Test Results
Table 3-6 summarizes the emission results for each run along with selected
parameters that were monitored during the test. Only a few comparisons can be made
because the process operated stably and consistently during the 3 test runs. One
difference is that the coke (fuel) rate during Run 3 was only 39 percent of the rate
during Run 1 and only 58 percent of the rate during Run 2. The lower fuel rate during
Run 3 is reflected in the lower windbox temperature during Run 3, which was about
100°F lower than in the previous 2 runs. The pollutants most likely to be affected by
8
-------
the change in combustion conditions are dioxins, furans, and PAHs. During Run 3, the
emission rates for all of these compounds were lower than in the previous 2 runs.
The highest emissions of particulate matter and lead occurred during Run 3.
The cause is not conclusive, but some of the possible factors affecting this, perhaps in
combination, were that Run 3 had the highest sinter feed and production rate and the
lowest average pressure drop across the scrubber. In addition, Table 3-4 indicates that
Run 3 had a higher feed rate of fines (pellet fines and BOF slag fines) than that
recorded during the previous 2 runs. Service water was used in the scrubber during
Run 1 and recycled blast furnace water was used during Runs 2 and 3. There is no
obvious difference in emissions that can be clearly attributed to the type of scrubber
water.
The major metal HAP that was found was lead, which accounted for over 97
percent of the total metal HAP emissions. Discussions with the plant and examination
of data from the analysis of blast furnace fines and sludge indicated that a likely source
of the lead emissions was from this fine material recycled from the blast furnace. Data
in the literature showed that the lead content of blast furnace dust and sludge was
generally in the range of 0.01 to 0.1 percent. At a typical feed rate for the dust and
sludge of 28,000 Ib/hr (14 tph), these materials would introduce 2.8 to 28 Ib/hr of lead
into the process, which could easily account for the lead that was found entering the
scrubber (4.2 Ib/hr). In addition, the small particle size of these pollution control
residues from the blast furnace may increase the probability that they become airborne,
and the volatility of lead and some lead compounds from combustion processes may
tend to increase the concentration of lead in the windbox emissions.
Another interesting result is the very low emission rate of dioxins, relative to what
had been reported from testing at German sinter plants. For example, the German
study reported concentrations of 23 to 68 ng TEQ/m3 from their initial studies and a
range of 5 to 10 ng TEQ/m3 for plants that optimized and improved their operation. The
9
-------
results for this sinter plant was much lower with an average concentration of 0.19 ng
TEQ/m3. On the basis of sinter production, the Germans reported emission levels in
the range of 10 to 100 yug/Mg of sinter compared to a measured level of 0.6 /ug/Mg of
sinter for this plant. The LTV sinter plant had emissions of dioxins and furans that were
on the order of 10 to 100 times less than that reported for German sinter plants.
The dioxin results are not unexpected because there are basic differences
between the operation of LTV's sinter plant and the German plants. The German study
attributed the formation of dioxin to the presence of chlorinated organics, primarily in
cutting oils, that were in the waste materials fed to the sintering process. In addition,
they stated that the use of electrostatic precipitators contributed to recombination and
formation of dioxin. In contrast, the LTV plant has eliminated the purchase and use of
chlorinated organics in their facility as part of a voluntary program of pollution
prevention, and any new chemical purchases must be approved by the environmental
department. Their rolling mill oils (lubricants and hydraulic fluids) do not contain
chlorinated compounds. In addition, routine analysis of waste materials going to the
sinter plant have not detected chlorinated solvent. Finally, the LTV plant does not use
an electrostatic precipitator. Consequently, dioxin rates at LTV that are much lower
than those reported by German sinter plants appear to be reasonable and explainable.
Table 3-7 through 3-9 presents a summary of the annual emissions and the
emission factors derived from this test.
10
-------
TABLE 3-4. PROCESS PARAMETER VALUES DURING THE TESTS
Parameter
Test 1 (6/25/97)
Test 2 (6/26/97)
Test 3 (6/27/97)
Feed rate (tph):
Mill scale
25.2 (24.8 - 25.5)
25.2 (24.9 - 25.5)
25.2 (24.8 - 25.6)
BOF slag/filter cake
16.7(16.1 -17.9)
16.9 (15.9-18.2)
16.9(15.5-17.9)
Fines
16.7(16.1 -17.6)
16.4 (15.9-18.0)
16.7 (15.3-18.0)
Pellet chips
77.4 (75.9 - 78.8)
77.7 (76.2 - 79.0)
77.6 (76.5 - 79.5)
Pellet fines- blend
9.5 (8.5-10.2)
10.7(10.1 -11.4)
12.3(11.3-13.6)
Limestone
27.2 (26.9 - 27.7)
27.5 (26.8 - 27.8)
27.7 (27.4 - 28.8)
Cold fines
19.6 (17.6-21.4)
17.2(15.2-19.5)
17.8 (16.8-23.2)
Coke breeze
1.7(1.5-1.9)
1.2 (0.9-1.5)
0.7 (0.34-1.1)
Flue dust
5.9 (5.8 - 6.0)
5.9 (5.8 - 6.0)
5.9 (5.8-6.0)
BOF slag fines
7.9 (7.6-8.2)
9.3 (9.4-10.1)
10.0 (9.8-10.1)
Other parameters:
Percent water
6.7-7.5
6.5-7.4
7.2-8.2
Grate speed
70-76
70-76
70-82
Windbox 20 temperature
(°F)
453 - 656
474 - 659
334 - 571
Windbox draft (in. water)
13.6-17.4
13.3-18.2
14.2-18.2
Feed rate (tph)
205-210
201 -212
209-213
Sinter production (tph)
155-158
153-161
159-161
11
-------
TABLE 3-5. CONTROL DEVICE OPERATING PARAMETERS DURING THE TESTS
Parameter
Test 1 (6/25/97)
Test 2 (6/26/97)
Test 3 (6/27/97)
Pressure drop (in.
water)
38.4 - 46.6
39.4 - 46.3
39.8 - 47.0
Water flow (gal/min)
3,040 - 3,085
3,080-3,130
3,080-3,110
Blowdown (gal/min)
236 - 239
242 - 246
241 - 244
Fan amps
663 - 695
685 - 700
700 - 730
Fan draft (in. water)
3.1 -5.8
3.2 - 5.8
3.8-5.1
Type of water
service (lake)
recycled blast furnace
12
-------
TABLE 3-6. SUMMARY OF RESULTS FOR EACH TEST RUN
Parameter
Units
Run 1
Run 2
Run 3
Average
PMa - inlet
Ib/hr
419
479
550
483
PM - outlet
Ib/hr
34
38
43
38
PM efficiency
percent
92
92
92
92
Lead - inlet
Ib/hr
4.1
4.0
4.4
4.2
Lead - outlet
Ib/hr
3.7
3.6
3.8
3.7
Lead efficiency
percent
9.8
10
14
12
HAP metals - in
Ib/hr
4.5
4.5
4.9
4.6
HAP metals - out
Ib/hr
3.8
3.7
3.9
3.8
Metals efficiency
percent
16
18
20
17
D/F congeners6
MQ/hr
810
768
694
757
D/F TEQC
Atg/hr
93
91
79
88
Total D/Fd
Mg/hr
5,650
5,380
4,820
5,280
7 PAHse
g/hr
1.9
2.0
1.4
1.7
16 PAHs
g/hr
69
78
61
69
TOTAL PAHs
g/hr
83
92
73
83
Sinter feed
tons/hr
208
208
211
209
Sinter production
tons/hr
156
159
160
158
Scrubber A p
in. water
43.1
42.8
42.4
42.8
Windbox 20
temperature
°F
538
567
443
516
Coke feed
tons/hr
1.7
1.2
0.7
1.2
a PM = particulate matter
b D/F congeners are those dioxins and furans that have a toxicity equivalent factor
relative to 2,3,7,8-TCDD.
c D/F TEQ is the toxicity equivalent expressed relative to 2,3,7,8-TCDD.
d Total D/F are all dioxins and furans that were reported.
e PAH = polycyclic aromatic hydrocarbons.
13
-------
TABLE 3-7 SUMMARY OF RESULTS FOR PM AND HAP METALS
Pollutant
Concentration (gr/dscf)
Emission rate (Ib/hr)
Efficiency
(%)
Annual rate (tpy)a
Emission factor (Ib/t
sinter)
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Particulate
matter
0.23
0.017
483
38
92
1,800
142
3.1
0.24
Pollutant:
HAP
Concentration (^g/DSCM)
Emission rate (g/hr)
Efficiency
(%)
Annual rate (tpy)
Emission factor (Ib/t
sinter)
metals
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Mercury
0.96
1.5
0.41
0.69
0
3.3 x 10"3
5.7 x 10"3
5.7 x 10"6
9.7 x 106
Arsenic
4.3
1.1
1.8
0.50
73
1.5 x 10"2
4.1 x 10'3
2.5 x 10"5
7.0 x10 6
Beryllium
0.054
0.052
0.023
0.023
0
1.9 x 104
1.9 x 10"4
3.2 x 10"7
3.3 x 107
Cadmium
20
17
8.4
7.8
7.4
6.9 x 10"2
6.4 x 10"2
1.2 x 10"4
1.1 x 10"4
Cobalt
0.30
0.050
0.18
0.023
87
1.5 x 10'3
1.9 x 10"4
2.5 x 10"6
3.3x107
Chromium
24
5.2
9.9
2.4
76
8.1 x 10"2
1.9 x 10"2
1.4 x 10"4
3.3 x10 s
Manganese
400
17
171
7.9
95
1.4
6.4 x 10"2
2.4 x 10"3
1.1 X10"4
Nickel
23
22
9.8
9.9
0
8.0 x 10"2
8.1 x 10"2
1.4 x 10"4
1.4 X10"4
Lead
4,500
3,700
1,900
1,690
11
16
1.4 x 10t1
2.7 x10"2
2.4 x10 2
Antimony
2.6
1.6
1.1
0.75
32
9.0 x10"3
6.1 x10'3
1.5 x 10 s
1.0 x105
Selenium
13
8.7
5.5
4.0
28
4.5 x 10"2
3.2 x 10'2
7.7 x 10"5
5.5 x10 s
Total HAP
metals
5,000
3,800
2,100
1,700
18
17
1.4 x 10*1
2.9 x 10"2
2.4 x10 2
a Based on operation for 24 hours per day for 310 days per year.
14
-------
TABLE 3-8 SUMMARY OF RESULTS FOR PAHS
Pollutant: PAHsa
Concentration
Cug/DSCM)
Emission rate
(g/hr)
Annual emissions'3
tpy
lb/ton sinter
Benzo(a)anthracene
0.53
0.24
0.0019
3.3 x 10"6
Chrysene
1.3
0.60
0.0049
8.4 x 10"6
Benzo(b)fluoranthene
1.2
0.54
0.0044
7.5 X10"6
Benzo(k)fluoranthene
0.22
0.10
0.00082
1.4 x 10"6
Benzo(a)pyrene
0.23
0.11
0.00086
1.5 x 10"6
lndeno(1,2,3-cd)pyrene
0.26
0.12
0.00096
1.6 x 10"6
Dibenzo(a,h)anthracene
0.097
0.044
0.00036
6.1 x 10"7
Total 7 PAHs
3.9
1.7
0.014
2.4 x 10'5
Naphthalene
78
35
0.29
4.9 x 10"4
Acenaphthylene
7.6
3.4
0.028
4.8 x 10"5
Acenaphthene
3.5
1.6
0.013
2.2 x10"5
Fluorene
5.4
2.4
0.020
3.4 x 10"5
Phenanthrene
43
19
0.16
2.7 x 10"4
Anthracene
1.8
0.81
0.0067
1.1 x 10"5
Fluoranthene
6.9
3.1
0.026
4.3 x 10"5
Pyrene
3.0
1.4
0.011
1.9 x 10"5
Benzo(g.h,l)perylene
0.36
0.16
0.0013
2.2 x10"6
Total 16 PAHs
153
69
0.57
9.7 x 10^
2-Methylnaphthalene
29
13
0.11
1.8 x 10*4
2-Chloronaphthalene
0.039
0.018
0.00015
2.5 x 10"7
Benzo(e)pyrene
0.76
0.30
0.0028
4.8 x 10"6
Perylene
0.058
0.026
0.00022
3.7 x10"7
Total - all PAHs
183
83
0.68
1.2x103
a PAH = polycyclic aromatic hydrocarbons.
b Based on operation for 24 hours per day for 310 days per year.
15
-------
TABLE 3-9. SUMMARY OF RESULTS FOR DIOXINS AND FURANS
Pollutant
Concentration
(ng/DSCM)
Emission rate
(yug/hr)
Annual emissions3
g/yr
lb/ton sinter
D/F TEQb
0.19
88
0.66
1.2 x 10"9
D/F Congeners0
1.7
757
5.6
1.1 x 10"6
D/F Totald
11.7
5,280
39
7.4 x 10"8
a Based on operation for 24 hours per day for 310 days per year.
b D/F TEQ is the toxicity equivalent expressed relative to 2,3,7,8-TCDD.
c D/F congeners are those dioxins and furans that have a toxicity equivalent factor relative to 2,3,7,8-
TCDD.
d Total D/F are all dioxins and furans that were reported.
16
-------
4.0 SAMPLING LOCATIONS
The sampling locations used during the emission testing program at the LTV Steel, East
Chicago, Illinois, plant are described in this section. Flue gas samples were collected at the inlet
and outlet of the sintering plant wet venturi scrubber using four ports at each location. The
configurations of the sampling locations are shown in Figures 4-1 and 4-2.
The test ports and their locations met the requirements of EPA Method 1. The inlet
location is a rectangular duct with dimensions of 5' 3" by 10' 10" with four 4" ports installed on
the vertical 10' side. The outlet location is a circular stack with an inside diameter (I.D.) of 12
feet with four 4" ports positioned 90 degrees apart. The position and number of traverse points
for the outlet and inlet locations are shown in Figures 4-3 and 4-4, respectively. A new sampling
port for FTIR sampling was installed at the inlet. Due to the risk of damage to the refractory of
the outlet stack, the installation of a new port for the FTIR was not possible. Therefore, the FTIR
probe was positioned in one of the existing four ports at the start of a test run and was moved to
one of the ports not occupied by the manual methods probes during each port change.
4-1
-------
Inlet Port Location
K>
I.D. Fan
Figure 4-1. Venturi Inlet Sampling Location
10' 10'
30
o
ro
«~—»
CO
c
'03
t
-------
Manual SampJtftg Port
FTlR Port
FlOW
Figure 4-2. Venturi Outlet Sampling Location
4-3
-------
12'
10'
• •
Ladder
1 f
FTIR
Figure 4-3. Outlet Traverse Point Layout
-------
10.5"
10" 10" i
i
31.5"
52.5"
4^
• i • ¦
77 L
5' 3"
Figure 4-4. Inlet Traverse Point Layout
4-5
-------
-------
5.0 SAMPLING AND ANALYTICAL PROCEDURES BY ANALYTE
The sampling and analytical procedures used for the sintering plant test program are the
most recent revisions of the published EPA methods. In this section, descriptions of each
sampling and analytical method by analyte are provided.
5.1 Particulate Matter and Metals Emissions Testing Using EPA Method 29
Sampling for Particulate Matter (PM) and metals was performed according to the EPA
Method 29 protocol. This method is applicable to the determination of particulate mass and Pb,
Ni, Cr, Mn, Se, Be, Sb, Co, Cd, As, and Hg emissions from various types of process controls
and combustion sources. Analyses of the test samples were performed for the metals listed
employing inductively-coupled argon plasma spectroscopy (ICAPS) and cold vapor atomic
absorption (CVAA) for mercury instrumental measurements. Mercury was analyzed using EPA
Method 7470A.
PM emissions were also determined from this sampling train. Particulate
concentrations are based on the weight gain of the filter and the front half acetone rinses (probe,
nozzle, and filter holder). The procedures which were used to determine particulate
concentrations from the Method 29 samples may have resulted in some mercury losses due to
volatilization during sample workup for PM determination. After the gravimetric analyses were
completed, the sample fractions were then analyzed for the target metals as discussed in
Section 5.1.6.
5.1.1 Method 29 Sampling Equipment
The Method 29 methodology uses the sampling train shown in Figure 5-1. The
7-impinger train consists of a borosilicate glass nozzle/probe liner followed by a heated filter
5-1
-------
Thermometer
Glass Filter Holder
Thermometer
Glass Probe Liner
Glass Probe Tip
Heated
Area
c>
c
Empty (Optional)
Empty
Silica Gel
5% HNO3/10% H202
4% KMn04/10% H2S04
Pitot Manometer
Vacuum Gauge
Orifice
Air-tight
Dry Gas Pump
Meter
-------
assembly with a Teflon® filter support, a series of impingers and the usual EPA Method 5
meterbox and vacuum pump. The sample was not exposed to any metal surfaces in this train.
The contents of the sequential impingers were:
• An empty knockout impinger is the first impinger;
• Two impingers with a 5% nitric acid (HNO3)/10% hydrogen peroxide (H202)
solution;
• An empty knockout impinger;
• Two impingers with a 4% potassium permanganate (KMnO4)/10% sulfuric acid
(H2S04) solution; and
• An impinger containing indicating silica gel.
5.1.2 Method 29 Sampling Equipment Preparation
5.1.2.1 Glassware Preparation
Glassware was washed in soapy water, rinsed with hot tap water, soaked in 10% HN03
for 12 hours, rinsed with Type II water, and then rinsed with acetone. This procedure included
all the glass components of the sampling train including the glass nozzles plus any sample
bottles, erlenmeyer flasks, petri dishes, graduated cylinders or stirring rods that are used during
recovery. Non-glass components (such as the Teflon@-coated filter screens and seals, tweezers,
Teflon® squeeze bottles, Nylon® probe brushes and Nylon® nozzle brushes) were cleaned
following the same procedure. The specifics of the cleaning procedure are presented in
Table 5-1.
5-3
-------
Table 5-1. Glassware Cleaning Procedure (Train Components)
NOTE: USE DISPOSABLE GLOVES AND ADEQUATE VENTILATION
1.
Soak all glassware in hot soapy water (Alconox®).
2.
Tap water rinse to remove soap.
3.
Distilled/deionized H20 rinse (X3).a
4.
Soak in 10% HN03 solution for 12 hours.
5.
Distilled/Deionized H20 rinse (X3).
6.
Acetone (X3).
7.
Cap glassware with clean glass plugs or Parafilm®.
8.
Mark cleaned glassware with color-coded identification sticker.
a(X3) = Three Times.
5.1.2.2 Reagent Preparation
The sample train filters were Pallflex Tissuequartz 2500 QAS filters. The acids and
hydrogen peroxide were Baker "Instra-analyzed" grade or equivalent. The peroxide was
purchased specifically for this test site.
The reagent water was Baker "Analyzed" low metals grade or equivalent. The lot
number, manufacturer and grade of each reagent that is used is recorded in the laboratory
notebook.
The HN03/H202 and KMn04/H2S04 solutions were prepared daily immediately prior
to sampling according to Section 4.2.1 of the reference method. The analyst wears both safety
glasses and protective gloves when the reagents are mixed and handled. Each reagent has its
own designated transfer and dilution glassware. This glassware was marked for identification
with a felt tip glass marking pen and used only for the reagent for which it was designated.
5-4
-------
5.1.2.3 Equipment Preparation
The remaining preparation included calibration and leak checking of the all the train
equipment, including meterboxes, thermocouples, nozzles, pitot tubes, and umbilicals.
Referenced calibration procedures were followed when available, and the results properly
documented and retained. A discussion of the techniques used to calibrate this equipment is
presented below.
Tvpe-S Pitot Tube Calibration. The EPA has specified guidelines concerning the
construction and geometry of an acceptable Type-S pitot tube. If the specified design and
construction guidelines are met, a pitot tube coefficient of 0.84 is used. Information pertaining to
the design and construction of the Type-S pitot tube is presented in detail in Section 3.1.1 of EPA
Document 600/4-77-027b. Only Type-S pitot tubes meeting the required EPA specifications are
used. Pitot tubes are inspected and documented as meeting EPA specifications prior to field
sampling.
Sampling Nozzle Calibration. Glass nozzles were used for isokinetic sampling.
Calculation of the isokinetic sampling rate requires that the cross sectional area of the sampling
nozzle be accurately and precisely known. All nozzles were thoroughly cleaned, visually
inspected and calibrated according to the procedure outlined in Section 3.4.2 of EPA Document
600/4-77-027b.
Temperature Measuring Device Calibration. Accurate temperature measurements
are required during source sampling. Bimetallic stem thermometers and thermocouple
temperature sensors are calibrated using the procedure described in Section 3.4.2 of EPA
document 600/4-77-027b. Each temperature sensor was calibrated at a minimum of two points
over the anticipated range of use against a NBS-traceable mercury-in-glass thermometer. All
sensors were calibrated prior to field sampling.
5-5
-------
Dry Gas Meter Device Calibration. Dry gas meters (DGMs) are used in the
Method 29 sampling trains to monitor the sampling rate and to measure the sample volume. All
DGMs were calibrated to document the volume correction factor just prior to shipping of the
equipment to the field. Post-test calibration checks were performed as soon as possible after the
equipment was returned to the ERG Laboratory. Pre- and post-test calibrations should agree to
within 5%.
Prior to calibration, a positive pressure leak check of the system was performed using
the procedure outlined in Section 3.3.2 of EPA document 600/4-77-237b. The system was
placed under approximately 10 inches of water pressure and a gauge oil manometer is used to
determine if a pressure decrease could be detected over a one-minute period. If leaks were
detected, they were eliminated before actual calibrations were performed.
After the sampling console was assembled and leak checked, the pump was to run for
15 minutes, to allow the pump and DGM to warm up. The valve was then adjusted to obtain the
desired flow rate. For the pre-test calibrations, data were collected at orifice manometer settings
(AH) of 0.5, 1.0, 1.5, 2.0, 3.0 and 4.0 in H20. Gas volumes of 5 ft3 were used for the two lower
orifice settings, and volumes of 10 ft3 are used for the higher settings. The individual gas meter
correction factors (Yf) were calculated for each orifice setting and averaged. The method
requires that each of the individual correction factors fall within ±2% of the average correction
factor or the meter is cleaned, adjusted, and recalibrated. In addition, ERG requires that the
average correction factor be within 1.00 ±1%. For the post-test calibration, the meter was
calibrated three times at the average orifice setting and vacuum which were used during the
actual test.
5-6
-------
5.1.3 Method 29 Sampling Operations
5.1.3.1 Preliminary Measurements
Prior to sampling, preliminary measurements are required to ensure isokinetic
sampling. These preliminary measurements include determining the traverse point locations and
performing a preliminary velocity traverse and a cyclonic flow check. These measurements were
used to calculate a "K factor." The K factor was used to determine an isokinetic sampling rate
from stack gas flow readings taken during sampling.
Measurements were then made of the duct inside diameter, port nozzle length, and the
distances to the nearest upstream and downstream flow disturbances. These measurements were
then used to determine sampling point locations by following EPA Reference Method 1
guidelines. The distances were then marked on the sampling probe using an indelible marker.
5.1.3.2 Assembling the Train
The assembly of the Method 29 sampling train components was completed in the
recovery trailer and final train assembly was performed at the stack location. First, the empty,
clean impingers were assembled and laid out in the proper order in the recovery trailer. Each
ground glass joint was carefully inspected for hairline cracks. After the impingers were loaded,
each impinger was weighed, and the initial weight and contents of each impinger were recorded
on a recovery data sheet. The impingers were connected together using clean glass U-tube
connectors and arranged in the impinger bucket. The height of all the impingers was
approximately the same to obtain a leak free seal. The open ends of the train were sealed with
Parafilm® or clean ground glass caps.
The filter was loaded into the filter holder in the recovery trailer. The filter holder was
then capped off and placed in the impinger bucket. To avoid contamination of the sample,
5-7
-------
sealing greases were not used. The train components were transferred to the sampling location
and assembled as previously shown in Figure 5-1.
5.1.3.3 Sampling Procedures
After the train was assembled, the heaters for the probe liner and heated filter box were
turned on. When the system reaches the appropriate temperatures, the sampling train was ready
for pre-test leak checking. The filter temperature was maintained at 120 ±14°C (248 ±25 °F).
The probe temperature was maintained above 100°C (212°F).
The sampling trains were leak checked at the start and finish of sampling. (Method 5
protocol requires post-test leak checks and recommends pre-test leak checks.) ERG protocol also
incorporates leak checks before and after every port change. An acceptable pre-test leak rate is
less than 0.02 acftn (ft3/min) at approximately 15 inches of mercury (in. Hg). If during testing, a
piece of glassware needed to be emptied or replaced, a leak check was performed before the
glassware piece was removed, and after the train was re-assembled.
To leak check the assembled train, the nozzle end was capped off and a vacuum of
15 in. Hg was pulled in the system. When the system was evacuated, the volume of gas flowing
through the system was timed for 60 seconds. After the leak rate was determined, the cap was
slowly removed from the nozzle end until the vacuum droped off, and then the pump was turned
off. If the leak rate requirement was not met, the train was systematically checked by first
capping the train at the filter, at the first impinger, etc., until the leak was located and corrected.
After a successful pre-test leak check was conducted, all train components were at their
specified temperatures and initial data were recorded [dry gas meter (DGM) reading], the test
was initiated. Sampling train data were recorded periodically (specific interval to be determined)
on standard data forms. A checklist for sampling is included in Table 5-2.
5-8
-------
Table 5-2. Sampling Checklist
Before Test Starts:
1. Check impinger set (right order and number). Verify probe markings, and re-
mark if necessary.
2. Check that you have all the correct pieces of glassware.
3. Check for data sheets and barometric pressure.
4. Bag sampling equipment needs to be ready for Method 3 analysis.
5. Leak check pitot tubes.
6. Examine meter box - level it and confirm that the pump is operational.
7. Assemble train to the filter and leak check at 15 in. Hg. Attach probe to train and
do final leak check; record leak rate and pressure on sampling log.
8. Check out thermocouples - make sure they are reading correctly.
9. Turn on heaters and check to see that their temperatures are increasing.
10. Check that cooling water is on and flowing. Add ice to impinger buckets.
11. Check isokinetic K-factor - make sure it is correct. (Refer to previous results to
confirm assumptions. Two people should calculate the K-factor independently to
double check it).
12. Have a spare probe liner, probe sheath, meter box and filter ready to go at
location.
5-9
-------
Table 5-2. Continued
During Test:
1. Notify crew chief of any sampling problems ASAP. Train operator should fill in
sampling log.
2. Perform simultaneous/concurrent testing with other locations (if applicable).
Maintain filter temperature between 248 °F ±25 °F. Keep temperature as steady as
possible. Maintain impinger temperatures below 68 °F. Maintain probe
temperature above 212°F.
3. Leak check between ports and record on sampling log.
4. Record sampling rate times and location for the fixed gas (CO, C02, 02) sample
(if applicable).
5. Blow back pitot tubes at inlet location every 15 minutes.
6. Change filter if pressure drop exceeds 20 in. Hg.
7. Check permanganate impinger solutions every 1/2 hr for reagent depletion.
8. Check impinger silica gel every 1/2 hr; if indicator disappears request a pre-filled
impinger from van lab and replace.
9. Check manometer fluid levels and zero every hour.
After Test is Completed:
1 Record final meter reading.
2. Check completeness of data sheet.
3. Do final leak check of sampling train at maximum vacuum during test.
4. Leak check each leg of pitot tubes.
5-10
-------
Table 5-2. Continued
5. Disassemble train. Cap sections. Take sections to recovery trailer.
6. Probe/cyclone recovery (use 500 mL bottles)
a) For acetone rinses (all trains)
Attach flask to end of probe
Add 50 mL of acetone
Put a brush down probe, and brush back and forth
Rinse back and forth in probe
Empty out acetone in sample jar
Do this 3 times so that the final combined acetone rinse volume is
< 150 mL.
b) - Rinse nozzle and probe 3X with O.IN HN03
Collect approximately 100 mL of rinse into sampling jar.
7. Reattach nozzle and cap for next day, store in dry safe place.
8. Make sure data sheets are completely filled out and give to location leader.
The leak rates and sampling start and stop times were recorded on the sampling task
log. Also, any other events that occur during sampling were recorded on the task log, such as
pitot cleaning, thermocouple malfunctions, heater malfunctions, or any other unusual
occurrences.
At the conclusion of the test run, the sample pump (or flow) was turned off, the probe
was removed from the duct, a final DGM reading was taken, and a post-test leak check was
completed. The procedure was identical to the pre-test procedure; however, the vacuum should
be at least one inch Hg higher than the highest vacuum attained during sampling. An acceptable
leak rate is less than 4% of the average sample rate or 0.02 acfm (whichever is lower). If a final
leak rate on-site did not meet the acceptance criterion, the test run may still be accepted upon
5-11
-------
approval of the EPA test administrator. If so, the measured leak rate was reduced by subtracting
the allowable leak rate from it and then multiplied for the period of time in which the leak
occurred. This "leaked volume" is then subtracted from the measured gas volume in order to
determine the final gas sample volume.
5.1.4 Method 29 Sample Recovery
Recovery procedures begin as soon as the probe was removed from the stack and the
post-test leak check was completed.
To facilitate transfer from the sampling location to the recovery trailer, the sampling
train was disassembled into three sections: the nozzle/probe liner, filter holder and impingers in
their bucket. Each of these sections was capped with Teflon® tape or Parafilm® before removal
to the recovery trailer. All train components were rinsed and the samples collected in separate,
prelabeled, precleaned sample containers to avoid cross contamination of inlet and outlet
samples.
Once in the trailers, the sampling train was recovered as separate front and back half
fractions. A diagram illustrating front half and back half sample recovery procedures is shown in
Figure 5-2. No equipment with exposed metal surfaces was used in the sample recovery
procedures. The weight gain in each of the impingers was recorded to determine the moisture
content in the flue gas. Following weighing of the impingers, the front half of the train was
recovered, which included the filter and all sample-exposed surfaces forward of the filter. The
probe liner was rinsed with acetone by tilting and rotating the probe while squirting acetone into
its upper end so that all inside surfaces were wetted. The acetone was quantitatively collected
into the appropriate bottle. This rinse was followed by additional brush/rinse procedures using a
non-metallic brush; the probe was held in an inclined position and acetone was squirted into the
upper end as the brush was pushed through with a twisting action. All of the acetone and
particulate was caught in the sample container. This procedure was repeated until no visible
5-12
-------
AR
FH
BH
Seal petri
dish with
tape
Filter
Rinse three
times with
0.1N HN03
Measure
implnger
contents
Rinse with
Acetone
Brush loose
particulate
onto filter
2nd & 3rd
impingers
HN03/H202
Rinse three
times with
0.1 N HN03
Rinse three
times with
0.1N HN03
Probe Liner
and Nozzle
Front Half of
Filter
Housing
Measure
Impinger
contents
Empty the
contents into
container
Empty the
contents into
container
Rinse three
times with
0.1N HN03
Rinse three
times with
0.1N HN03
1st impinger
(empty at
beginning of
test)
Filter support &
back half of filter
housing
Brush with
nonmetailic
brush &
rinse with
acetone
Check liner
to see if
particulate
removed; if
not, repeat
step above
Brush liner
with
nonmetailic
brush &
rinse with
acetone
Carefully
remove filter
from support
with
reflon®-coated
tweezers &
place in petrl
dish
* Number in parentheses indicates container number
Figure 5-2. Method 29 Sample Recovery Scheme
5-13
-------
particulate remains and finished with a final acetone rinse of the probe and brush. The front half
of the filter was also rinsed with acetone until all visible particulate was removed. After all front
half acetone washes were collected, the cap was tightened, the liquid level marked and the bottle
weighed to determine the acetone rinse volume. The method specifies that a total of 100 mL of
acetone must be used for rinsing these components. For blank correction purposes, the exact
weight or volume of acetone used was measured. An acetone reagent blank of approximately the
same volume as the acetone rinses was analyzed with the samples.
The nozzle/probe liner and front half of the filter holder were rinsed three times with
0.1N HN03 and placed into a separate amber bottle. Cap tightly, record the weight of the
combined rinse and mark the liquid level. The filter was placed in a clean, well-marked glass
petri dish (Container 1) and sealed with Teflon® tape. Approximately 100 mL of this rinse was
required.
Prior to recovering the back half impingers, the contents were weighed for moisture
content determinations. Any unusual appearance of the filter or impinger contents was noted.
The contents in the knockout impinger (if used) were recovered into a pre-weighed, pre-
labeled bottle with the contents from the HN03/H202 impingers (Container 4). These impingers
and connecting glassware were rinsed thoroughly with 0.1N HN03, the rinse was captured in the
impinger contents bottle, and a final weight was taken. Again, the method specifies a total of
100 mL of 0.1N HNO3 be used to rinse these components. The weight of reagent used for
rinsing was determined by weighing the impinger contents bottle before and after rinsing the
glassware. A nitric acid reagent blank of approximately the same volume as the rinse volume
was analyzed with the samples. The acidified permanganate impinger solutions were combined
into a single sample container. Any residue from the impingers was recovered with 25 mL of 8N
HC1 solution and was collected in a separate container.
5-14
-------
After final weighing, the silica gel from the train was saved for regeneration. The
ground glass fittings on the silica gel impinger were wiped off after sample recovery to assure a
leak tight fit for the next test.
A reagent blank was recovered in the field for each of the following reagents;
• Acetone blank - 100 mL sample size;
• 0.1N nitric acid blank - 300 mL sample size;
• 5% nitric acid/10% hydrogen peroxide blank - 200 mL sample size;
• Acidified potassium permanganate blank - 200 mL sample size (this blank should
have a vented cap);
• 8N hydrochloric acid blank - 225 mL sample size (25 mL 8N HC1 plus 200 mL
water);
• Dilution water - 200 mL sample size; and
• Filter blank - one each.
Each reagent blank was of the same lot as was used during the sampling program. The
volumes collected were greater than required for sample preparation in order to provide sufficient
amounts in case of sample loss during preparation or to compensate for larger volumes of train
rinses. Each lot number and reagent grade were recorded on the field blank label. One field
blank was collected using an on-site sampling train. One glassware proof blank was collected for
each train prior to sampling.
The liquid level of each sample container was marked on the bottle in order to
determine if any sample loss occurred during shipment. If sample loss occurred, the sample may
be voided or a method may be used to incorporate a correction factor to scale the final results
depending on the volume of the loss.
5-15
-------
Cold Vapor Atomic Absorption Spectroscopy (CVAAS) was used to analyze for
mercury by EPA method 7470A. The detection limits of the individual metals are dependent on
the detection limit of the analytical method, the volume of the aqueous sample presented for
analysis and the total volume of gaseous sample collected in the sampling trains. Following the
protocol of Method 29, the fractions that were collected for analysis from each train were:
• Fraction 1—Filter;
• Fraction 2~Probe and filter front half acetone rinses;
• Fraction 3—Probe and filter front half acid rinse;
• Fraction 4—Impingers 1-3 contents and acid rinse of impingers and filter back
half;
• Fraction 5a—Impinger 4 contents and 100 mL 0. IN nitric acid rinse;
• Fraction 5b—Impinger 5-6 contents plus 100 mL permanganate and 100 mL water
rinses; and
• Fraction 5c—25 mL 8N HCI acid rinse and water rinses of impingers 5-6, place in
containers with 200 mL water.
After sample preparation, Fractions 1-3 were combined for analysis for all target
analytes (an aliquot is removed for Hg). Fractions 4, 5a, 5b and 5c were analyzed individually
after preparation. Fraction 4 was analyzed for all analytes (aliquot for Hg removed). Fractions
5a, 5b, and 5c were analyzed for Hg only. Since there were multiple fractions to be analyzed
(5 for Hg and 2 for other metals) the method detection limit (MDL) is the sum of the individual
detection limits for each fraction analyzed. For Hg this will increase the MDL over that seen for
Method 101a where the permanganate is the only collection medium. Using an instrumental
detection limit (IDL) for cold vapor atomic absorption (CVAA) and inductively coupled argon
plasma (ICAP), Table 5-3 gives the total detectable amounts that were possible.
The method detection limits for the various metals of interest are summarized in
Table 5-4. The sampling flow rate at the inlet and outlet locations were dictated by the flow rate
5-16
-------
Table 5-3. Analytical Detection Limits
Metal
IDL
/Ug/mL
Analysis Fraction
Total
Detectable
Amount
/"g
1,/^g
2, Mg
3? Mg
4, jug
5, yug
Hg
0.0002
0.4
0.6
0.2
0.6
1 Mg
2.8
As
0.005
1.0
1.13
NA
NA
NA
2.1
Be
0.001
0.2
0.23
NA
NA
NA
0.43
Cd
0.001
0.2
0.23
NA
NA
NA
0.43
Cr
0.002
0.4
0.45
NA
NA
NA
0.85
Pb
0.002
0.4
0.45
NA
NA
NA
0.85
Sb
0.004
0.8
0.9
NA
NA
NA
1.7
Co
0.001
0.2
0.225
NA
NA
NA
0.43
Mn
0.002
0.4
0.45
NA
NA
NA
0.85
Ni
0.003
0.6
0.68
NA
NA
NA
1.28
Se
0.003
0.6
0.68
NA
NA
NA
1.28
Note: Hg analysis by CVAA Method 7470A, all others by Method 6010A (ICAPS). CVAA
assumes an analysis volume of 10 mL. NA = Not applicable.
5-17
-------
of the stack gas since isokinetic sampling was performed at these locations. The nominal sample
time and flow rate selected by the EPA Work Assignment Manager are presented in Table 5-4
along with the associated method detection limits.
5.1.5 Particulate Analysis
The same general gravimetric procedure described in Method 5, Section 4.3, was
followed. Both filters and precleaned beakers were weighed to a constant weight before use in
the field. The same balance used for taring was used for weighing the samples.
The acetone rinses were evaporated to dryness under a clean hood at 20°C (68 °F) in a
tared beaker. The residue was desiccated for 24 hours in a desiccator containing fresh room
temperature silica gel. The filter was also desiccated under the same conditions to a constant
weight. Weight gain was reported to the nearest 0.1 mg. Each replicate weighing must agree to
within 0.5 mg or 1% of total weight less tare weight, whichever is greater, between two
consecutive weighings, and must be at least 6 hours apart. The balance room was temperature
and humidity controlled. The filter tare and final weights will be determined under the same
conditions.
5.1.6 Metals Analytical Procedures
A diagram illustrating the sample preparation and analytical procedures for the target
metals is shown in Figure 5-3.
The acetone probe rinse (container No. 2) was allowed to reduce to dryness in a tared
beaker and any residue was weighed to a constant weight. This residue was then solubilized with
concentrated nitric acid and this solution was added to the nitric acid rinse of the probe
(Container No. 3). This combined solution was then acidified to a pH of 2 with concentrated
5-18
-------
Table 5-4. Method 29 Detection Limits
Sampling Time, hours
4
Sampling Rate, cfm
0.75
Sampling Volume,
5.1
cubic meters
MDL, Aig/m3
Hg
0.55
As
0.41
Be
0.08
Cd
0.08
Cr
0.17
Pb
0.17
Sb
0.33
Co
0.08
Mn
0.17
Ni
0.25
Se
0.25
5-19
-------
Container 3
Acid Probe Rinse
(Labeled FH)
Container 2
Acetone Probe Rinse (Labeled
AR)
Container 1
Filter
(Labeled F)
K>
O
Determine residue weight in
beaker
Reduce to dryness in a tared
beaker
Solubilize residue with conc.
UNO,
Reduce volume to near dryness
and digest with HF & conc.
HNOj
Acidify to pH 2 with conc.
HNO,
Desiccate to constant weight
Determine filter particulate
weight
Divide into 0.5 g sections &
digest each section with conc.
HF& HNO,
Filter & dilute to known volume
Anal. Fraction 1
n
Remove 50 to 100 mL aliquot
for Hg analysis by CVAAS
Analytical Fraction IB
Digest with acid and
permanganate at 95°C in a
water bath for 2 h
Analyze by 1CAP for target
metals Anal. Fraction 1A
a.
Analyze for metals by GFAAS*
Anal. Fraction 1A
Analyze aliquot for Hg using
CVAAS
•Analyze
Figure
by AAS for metals found at less than 2 ng/mL in digestate solution, if desired. Or analyze for each metal by AAS, if desired.
5-3. Method 29 Sample Preparation and Analysis Scheme
-------
Container 4 (HN03/H202) Impingers
(Labeled BH) (inlcude condensate
impinger, if used) Containers 5A, 5B, & 5C
Analyze by GFAAS for
Metals*
Analyze by ICAP for 15
target metals
Aliquot taken for
CVAAS for Hg analysis
Anal. Fraction 2B
Acidify remaining sample
to pH 2 with conc. HN03
Anal. Fraction 2A
Reduce volume to near
dryness and digest with
HN03 & H202
Digest with acid and
permanganate at 95 °C for
2 h and analyze for Hg by
CVAAS
Individually, three
separate digestions and
analyses: digest with acid
and permanganate at
95 °C for 2 h and analyze
for Hg by CVAAS
Analytical Fractions 3A,
3B, & 3C
~Analysis by AAS for metals found at less than 2 ng/mL in digestate solution, if desired. Or analyzed for each
metal by AAS, if desired.
Figure 5-3. Continued
5-21
-------
nitric acid, the volume reduced to near dryness and digested with concentrated nitric and
hydrofluoric acids in a microwave pressure vessel.
The filter (Container No. 1) was weighed to a constant weight and then divided into
0.5 g sections and digested with concentrated nitric and hydrofluoric acids in a microwave
pressure vessel. The microwave digestion took place over a period of 10 to 15 minutes in
intervals of 1 to 2 minutes at 600 watts. Both the digested filter and the digested probe rinses
were combined, filtered and brought to a known volume (nominally 200 mL). This analysis
fraction wass then divided for analysis by CVAA for Hg (following additional digestion) and by
ICAP for the other target metals.
An aliquot from the contents of container No. 4 (nitric acid/peroxide impinger
absorbing solution) was removed and digested following the procedures given in Method 29 and
then analyzed for Hg by CVAA. The remaining volume was acidified to pH 2, the volume
reduced to near dryness and digested in a microwave as discussed above. After bringing the
digestate to a known volume, the solution was analyzed by ICAP for the remaining target metals.
The contents of containers 5A, 5B and 5C were digested separately by the procedures
given in Method 29 and then analyzed for Hg by CVAA.
A total of two (2) fractions were analyzed for all target metals except Hg by
Method 601 OA and a total of five (5) fractions were analyzed for Hg by Method 7470A.
5.1.7 Quality Control for Metals Analytical Procedures
All quality control procedures specified in the test method were followed. All field
reagent blanks were processed, digested and analyzed as specified in the test method. For
optimum sensitivity in measurements, the concentrations of target metals in the solutions should
be at least 10 times analytical detection limits.
5-22
-------
5.1.7.1 ICAP Standards and Quality Control Samples
The quality control procedures included running two standards for instrument checks
(or frequency of 10%), two calibration blank runs (or frequency of 10%), one interference check
sample at the beginning of the analysis (must be within 10% or analyze by standard addition),
one quality control sample to check the accuracy of the calibration standards (must be within
10% of calibration), one duplicate analysis and one standard addition for every 10 samples (must
be within 5% of average or repeat all analysis).
Standards less than 1 /zg/mL of a metal were prepared daily; those with concentrations
greater than this were made weekly or bi-monthly.
All samples were analyzed in duplicate. A matrix spike on one front half sample and
one back half for each 10 field samples was analyzed. If recoveries of less than 75% or greater
than 120% were obtained for the matrix spike, each sample was analyzed by the method of
additions. One quality control sample was analyzed to check the accuracy of the calibration
standards. The results must be within 10% or the calibration will be repeated.
5.1.7.2 Cold Vapor Atomic Absorption Standards and Quality Control Samples
A lO/^g/mL intermediate Hg standard was prepared fresh weekly. A fresh daily
200 Hg/mL Hg working standard was also prepared. At least five separate aliquots of the
working Hg standard solution and a blank were used to prepare the standard curve. Quality
control samples were prepared by making a separate 10^g/mL standard and diluting it until the
control sample is within the calibration range. These procedures assessed the quality control of
the analysis, but do not address the potential negative bias due to Hg losses from the filter due to
volatilization.
5-23
-------
5.2 CDD/CDF and PAH Emissions Testing Using EPA Method 23
The sampling and analytical method for determining flue gas emissions of
Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans (CDD/CDF) is EPA
Method 23. Samples collected with this method were also analyzed for Polycyclic Aromatic
Hydrocarbons (PAHs) emissions.
5.2.1 Method 23 Sampling Equipment
The method uses the sampling train shown in Figure 5-4. Basically, the sampling
system is similar to a Method 5 train with the following exceptions:
• All components (glass probe/nozzle liner, all other glassware, filters) are pre-
cleaned using solvent rinses and extraction techniques; and
• A condensing coil and XAD-2® resin absorption module are located between the
filter and impinger train.
All sampling equipment specifications are detailed in the reference method.
5.2.2 Method 23 Equipment Preparation
In addition to the standard EPA Method 5 requirements, Method 23 includes several
unique preparation steps which ensure that the sampling train components are not contaminated
with organics that may interfere with analysis. The glassware, glass fiber filters and absorbing
resin were cleaned and the filters and resin were checked for 42 residuals before they were
packed.
5-24
-------
temperature
sensor
T
heated glass liner
M
i
Gas Flow
*S* type
pilot
k
Zl'.i .
/ \
Ui
K>
Ui
recirculation
pump
calibrated
orifice
gas exit
~
Figure 5-4. Method 23 Sampling Train Configuration
temperature
~sensor
fe XAD-2 trap
U
temperature
sensor
-f—3- -f—1
on
tea
bath
empty
dry gas
meter
~ W
11
>
100 ml
HPLC Water
i -i ¦
empty silica
»0l
IX-I
facuum
gauge
coarse
¦ vacuum pump
-------
5.2.2.1 Glassware Preparation
Glassware was cleaned as shown in Table 5-5. Glassware was washed in soapy water,
rinsed with distilled water, baked and then rinsed with acetone followed by methylene chloride.
Clean glassware was allowed to dry under a hood loosely covered with foil to prevent laboratory
contamination. Once the glassware was dry, the air exposed ends were sealed with methylene
chloride rinsed aluminum foil. All the glass components of the sampling train including the
glass nozzles plus any flasks, petri dishes, graduated cylinders and pipets that are used during
sampling and recovery were cleaned according to this procedure. Non-glass components (such
as the Teflon®-coated filter screens and seals, tweezers, Teflon® squeeze bottles, Nylon® probe
brushes and Nylon® nozzle brushes) were cleaned following the same procedure except that no
baking was performed.
5.2.2.2 XAD-2® Resin and Filters Preparation
XAD-2® absorbing resin and glass fiber filters were pre-cleaned by separate procedures
according to the specified method. Only pesticide grade solvents and HPLC grade water were
used to prepare for organic sampling, and to recover these samples. The lot number,
manufacturer and grade of each reagent used were recorded in the laboratory notebook.
To prepare the filters, a batch of 50 was placed in a Soxhlet extractor pre-cleaned by
extraction with toluene. The Soxhlet was charged with fresh toluene and refluxed for 16 hours.
After the extraction, the toluene was analyzed as described in Sections 5.2 and 5.3 of the
reference method for the presence of tetrachlorodibenzo-p-dioxin (TCDD),
tetrachlorodibenzofurans (TCDF) or PAHs. If these analytes are found, the filters are re-
extracted until the analyte is not detected. The filters were then dried completely under a clean
nitrogen (N2) stream. Each filter was individually checked for holes, tears, creases or
discoloration, and if any were found, was discarded. Acceptable filters were stored in pre-
cleaned petri dish, labeled by date of analyses and sealed with Teflon® tape.
5-26
-------
Table 5-5. Method 23 Glassware Cleaning Procedure (Train Components,
Sample Containers and Laboratory Glassware)
NOTE: USE VITON® GLOVES AND ADEQUATE VENTILATION WHEN RINSING
WITH SOLVENTS
1. Soak all glassware in hot soapy water (Alconox®).
2. Tap water rinse to remove soap.
3. Distilled/deionized H20 rinse (X3).a
4. Bake at 450°F for 2 hours.b
5. Acetone rinse (pesticide grade) (X3).
6. Methylene chloride (pesticide grade) (X3).
7. Cap glassware with clean glass plugs or methylene chloride rinsed aluminum foil.
8. Mark cleaned glassware with color-coded identification sticker.
9. Glassware is rinsed immediately before using with acetone and methylene
chloride (laboratory proof).
a(X3) = three times.
b Step (4) has been added to the cleanup procedure to replace the dichromate soak specified in the
reference method. ERG has demonstrated in the past that it sufficiently removes organic
artifacts. Step 4 is not used for probe liners and non-glass components of the train that cannot
withstand 450°F (i.e., Teflon©-coated filter screen and seals, tweezers, Teflon® squeeze bottles,
nylon probe and nozzle brushes).
5-27
-------
To prepare the absorbing resin, the XAD-2® resin was cleaned in the following
sequential order:
• Rinse with HPLC grade water, discard water;
• Soak in HPLC grade water overnight, discard water;
• Extract in Soxhlet with HPLC grade water for 8 hours, discard water;
• Extract with methanol for 22 hours, discard solvent;
• Extract with methylene chloride for 22 hours, discard solvent;
• Extract with methylene chloride for 22 hours, retain an aliquot of solvent for
analysis of CDDs, CDFs and PAHs by GC/MS; and
• Dry resin under a clean N2 stream.
Once the resin was completely dry, it was checked for the presence of methylene
chloride, CDDs, CDFs and PAHs as described in Section 3.1.2.3.1 of the reference method. If
any analytes are found, the resin is re-extracted. If methylene chloride is found, the resin is dried
until the excess solvent is removed. The absorbent is to be used within four weeks of cleaning.
The cleaned XAD-2® resin was spiked before shipment to the field with five
CDD/CDF and one PAH internal standards. Due to the special handling considerations required
for the internal standards, the spiking was performed by Triangle Laboratories. For convenience
and to minimize contamination, Triangle Laboratories also performed the resin and filter cleanup
procedures and loaded the resin into the glass traps.
5.2.2.3 Method 23 Sampling Train Preparation
The remaining preparation included calibration and leak checking of all sampling train
equipment, including meterboxes, thermocouples, nozzles, pitot tubes, and umbilicals.
5-28
-------
Referenced calibration procedures were followed when available. The results were properly
documented in a laboratory notebook or project file and retained.
5.2.3 Method 23 Sampling Operations
5.2.3.1 Preliminary Measurements
Prior to sampling (data collected during presurvey), preliminary measurements were
required to ensure isokinetic sampling. These measurements included determining the traverse
point locations, performing a preliminary velocity traverse, cyclonic flow check and moisture
determination. These measurements were used to calculate a "K factor." The K factor was used
to determine an isokinetic sampling rate from stack gas flow readings taken during sampling.
Measurements were then made of the duct inside diameter, port nozzle length, and the
distances to the nearest upstream and downstream flow disturbances. These measurements were
then used to determine sampling point locations by following EPA Reference Method 1
guidelines. The distances were then marked on the sampling probe using an indelible marker.
5.2.3.2 Assembling the Train
The assembly of the Method 23 sampling train components was completed in the
recovery trailer and final train assembly was performed at the stack location. First, the empty,
clean impingers were assembled and laid out in the proper order in the recovery trailer. Each
ground glass joint wass carefully inspected for hairline cracks. The first impinger was a
knockout impinger which has a short tip. The purpose of this impinger was to collect condensate
which formed in the coil and XAD-2® resin trap. The next two impingers were modified tip
impingers which each contained 100 mL of HPLC grade water. The fourth impinger was empty,
and the fifth impinger contained 200 to 300 grams of blue indicating silica gel. After the
impingers were loaded each impinger was weighed, the initial weight and contents of each
5-29
-------
impinger were recorded on a recovery data sheet. The heights of all the impingers were
approximately the same to obtain a leak free seal. The open ends of the train were sealed with
methylene chloride-rinsed aluminum foil, or clean ground glass caps.
The filter was loaded into the filter holder in the recovery trailer. The filter holder was
then capped off and placed with the resin trap and condenser coil (capped) into the impinger
bucket. A supply of precleaned foil and socket joints was also placed in the bucket in a clean
plastic bag for the convenience of the samplers. Sealing greases were not used thus avoiding
contamination of the sample. The train components were transferred to the sampling location
and assembled as previously shown in Figure 5-4.
5.2.3.3 Sampling Procedures
After the train was assembled, the heaters were turned on for the probe liner and heated
filter box and the sorbent module/condensor coil recirculating pump wass turned on. When the
system reached the appropriate temperatures, the sampling train was ready for pre-test
leakchecking. The temperature of the sorbent module resin must not exceed 50°C (120°F) at
any time and during testing it must not exceed 20°C (68°F). The filter temperature was
maintained at 120 ±14°F (248 ±25°F). The probe temperature was maintained above 100°C
(212°F).
The sampling trains were leak checked at the start and finish of sampling.
(Method 5/23 protocol only requires post-test leakchecks and recommends pre-test leakchecks.)
ERG protocol also incorporates leak checks before and after every port change. An acceptable
pre-test leak rate is less than 0.02 acfm (ft3/min) at approximately 15 inches of Hg. If during
testing, a piece of glassware needed to be emptied or replaced, a leak check was performed
before the glassware piece was removed, and after the train was re-assembled.
5-30
-------
To leak check the assembled train, the nozzle end was capped off and a vacuum of
15 inches Hg was pulled in the system. When the system was evacuated, the volume of gas
flowing through the system was timed for 60 seconds. After the leak rate was determined, the
cap was slowly removed from the nozzle end until the vacuum dropped off, and then the pump
was turned off. If the leak rate requirement was not met, the train was systematically checked by
first capping the train at the filter, at the first impinger, etc., until the leak was located and
corrected.
After a successful pre-test leak check had been conducted, all train components were at
their specified temperatures and initial data were recorded (DGM reading), the test was initiated.
Sampling train data were recorded periodically on standard data forms. A checklist for
CDD/CDF sampling is included in Table 5-6. A sampling operation that is unique to CDD/CDF
sampling is that the gas temperature entering the resin trap must be below 20°C (68°F). The gas
was cooled by a water jacket condenser through which ice water was circulated.
The leak rates and sampling start and stop times were recorded on the sampling task
log. Also, any other events that occurred during sampling were recorded on the task log such as
sorbent module heat excursions, pitot cleaning, thermocouple malfunctions, heater malfunctions
or any other unusual occurrances.
At the conclusion of the test run, the sample pump (or flow) was turned off, the probe
was removed from the duct, a final DGM reading was taken, and a post-test leak check was
completed. The procedure is identical to the pre-test procedure. However, the vacuum should
be at least one inch Hg higher than the highest vacuum attained during sampling. An acceptable
leak rate is less than 4% of the average sample rate of 0.02 acfm (whichever is lower).
5-31
-------
Table 5-6. CDD/CDF Sampling Checklist
Before test starts:
1. Check impinger set to verify the correct order, orientation and number of impingers. Verify
probe markings, and remark if necessary.
2. Check that you have all the correct pieces of glassware. Have a spare probe liner, probe
sheath, meter box and filter ready to go at location.
3. Check for data sheets and barometric pressure.
4. Bag sampling equipment for C02/02 needs to be ready except when using CEMs for C02/02
determinations.
5. Examine meter box - level it, zero the manometers and confirm that the pump is operational.
6. Verify the filter is loaded correctly and as tightly as possible; place filter in line with the
train and leak check at 15 inches Hg.
7. Add probe to train.
8. Check thermocouples - make sure they are reading correctly.
9. Conduct pitot leak check, recheck manometer zero.
10. Do final leak check; record leak rate and vacuum on sampling log.
11. Turn on variacs and check to see that the heat is increasing.
12. Check that cooling water is on and flowing. Add ice to impinger buckets.
13. Check isokinetic K-factor - make sure it is correct. (Refer to previous results to confirm
assumptions. Two people should calculate this independently to double check it.)
5-32
-------
Table 5-6. Continued
During Test:
1. Notify crew chief of any sampling problems ASAP. Train operator should fill in sampling
log and document any abnormalities.
2. Perform simultaneous/concurrent testing with other locations (if applicable). Maintain filter
temperature between 248°F ±25 °F. Keep temperature as steady as possible. Maintain the
resin trap and impinger temperatures below 68 °F. Maintain probe temperature above
212°F.
3. Leak check between ports and record on data sheet. Leak check if the test is stopped to
change silica gel, to decant condensate, or to change filters.
4. Record sampling times, rate, and location for the fixed gas bag sampling (CO, C02, 02), if
applicable.
5. Blow back pitot tubes periodically if moisture entrapment is expected.
6. Change filter if vacuum suddenly increases or exceeds 15 inches Hg.
7. Check impinger solutions every 1/2 hour; if the knockout impinger is approaching full, stop
test and empty it into a pre-weighed bottle and replace it in the train.
8. Check impinger silica gel every 1/2 hour; if indicator color begins to fade, request a
prefilled, preweighed impinger from the recovery trailer.
9. Check the ice in the impinger bucket frequently. If the stack gas temperatures are high, the
ice will melt at the bottom rapidly. Maintain condenser coil and silica gel impinger gas
temperatures below 20°C (68°F).
After test is completed:
1. Record final meter reading.
2. Do final leak check of sampling train at maximum vacuum during test.
3. Do final pitot leak check.
5-33
-------
Table 5-6. Continued
4. Check completeness of data sheet. Verify the impinger bucket identification is recorded on
the data sheets. Note any abnormal conditions.
5. Leak check, check functions (level, zero, etc.) of pitot tubes and inspect for tip damage.
6. Disassemble train, cap sections, and take each section and all data sheets down to recovery
trailer.
7. Probe recovery (use 950 mL bottles)
a) Bring probes into recovery trailer (or other enclosed area).
b) Wipe the exterior of the probe to remove any loose material that could contaminate the
sample.
c) Carefully remove the nozzle/probe liner and cap it off with prerinsed aluminum foil.
d) For acetone rinses (all trains)
Attach precleaned cyclone flask to probe to catch rinses
Wet all sides of probe interior with acetone
While holding the probe in an inclined position, put precleaned probe brush down
into probe and brush it in and out
Rinse the brush, while in the probe, with acetone
Do this at least 3 times until all the particulate has been recovered.
Recover acetone into a preweighed, prelabeled sample container
e) Follow the procedure outlined in (d) using methylene chloride. Recover the solvent
into the same acetone recovery bottle.
f) Follow the procedure outlined in (d) using toluene. Recover this solvent into a separate
preweighed prelabeled sample container.
8. Cap both ends of nozzle/probe liner for the next day, and store in dry safe place.
9. Make sure data sheets are completely filled out, legible, and give them to the Crew Chief.
5-34
-------
5.2.4 CDD/CDF/PAH Sample Recovery
To facilitate transfer from the sampling location to the recovery trailer, the sampling
train was disassembled into the following sections: the probe liner, filter holder, filter to
condenser glassware, condenser sorbent module, and the impingers in their bucket. Each of these
sections was capped with methylene chloride rinsed aluminum foil or ground glass caps before
removal to the recovery trailer. Once in the trailer, field recovery followed the scheme in
Figure 5-5. The samples were recovered and stored in cleaned amber glass bottles to prevent
light degradation.
The probe and nozzle was first rinsed with approximately 100 mL of acetone and
brushed to remove any particulate. This first rinse was followed with a rinse of methylene
chloride. Both of these rinses were collected in the same bottle. The same two solvents were
used to rinse the cyclone, front/back half filter holder, filter support, connecting glassware and
condenser. These rinses were added to the probe rinse bottle. All of the components listed
above were again rinsed with toluene, but collected in a separate container.
The contents of impingers 1-4 (H20) were collected in a separate bottle along with their
methylene chloride rinses.
The solvents used for train recovery were all pesticide grade. The use of the highest
grade reagents for train recovery was essential to prevent the introduction of chemical impurities
which interfere with the quantitative analytical determinations.
The train components recovered in the field are listed in Table 5-7. The sorbent module
was stored in coolers on ice at all times. The samples were delivered to the analytical laboratory
upon return to ERG accompanied by written information designating target analyses.
5-35
-------
Probe
Nozzle
Probe
Liner
Cyclone
Rinse with Acetone
Until all Particulate
is Removed
1^1
i
CO
o\
Rinse with 3
Aliquots of
Methylene
Chloride
Attach
250 mL flask
to Ball Joint
Rinse with
Acetone
Empty Flask
into 950 mL
Bottle-
Brush Liner and Rinse
with 3 Aliquots of
Acetone
I
Check Liner to see if
Particulate is
removed; if not, repeat
Rinse with
3 Aliquots
of Methylene
Chloride
Brush and
rinse with
acetone (3x)
Rinse with
3 Aliquots
of Methylene
Chloride
Front Half of
Filter Housing
Brush and
rinse with
acetone (3x)
Rinse with
3 Aliquots
of Methylene
Chloride
Rinse with
Toluene (3x)*
Rinse with
Toluene (3x)
Rinse with
Toluene (3x)
Rinse with
Toluene (3x)
*This fraction should not be combined with the other toluene
fractions
Figure 5-5. Method 23 Field Recovery Scheme
Filter Back Half of Connecting Condenser
Support Filter Housing Line
Rinse with
acetone (3x)
Rinse with
acetone (3x)
Rinse with
acetone (3x)
Rinse with
acetone (3x)
Rinse with methylene
chloride (3x) (at least
once let the rinse stand
5 min in unit)
Rinse with
methylene
chloride
(3x)
Rinse with
methylene
chloride (3x)
(at least once let
the rinse stand
5 min in unit)
Recover into
preweighed
bottle
I
PR ]
Rinse with Toluene (3x)
(at least once let the
rinse stand 5 min in unit)
Rinse with
Toluene (3x)
Toluene (3x) (at
least once let the
rinse stand 5 min
in unit)
PBT/CRT
-------
Filter
Carefully
remove filter
from support
with tweezers
Brush loose
Particulate
onto filter
Resin Trap
Secure XAD
trap openings
with glass balls
and clamps
Place in cooler
for storage
1st Impinger
(knockout)
Weigh
Impinger
Record weight
and
calculate gain
OJ
Seal in
petri dish
SM
Figure 5-5. Continued
2nd Impinger
3rd Impinger
Weigh
Impinger
Weigh
Impinger
Record weight
and
calculate gain
Record weight
and
calculate gain
4th Impinger
Weigh
Impinger
5th Impinger
(silica gel)
Weigh
Impinger
Record weight
and
calculate gain
Record weight
and
calculate gain
Save for
regeneration
Discard
Note: See Table 5-5 for Sample Fractions
Identification
-------
Table 5-7. Method 23 Sample Fractions Shipped To Analytical Laboratory
Container/
Component
Code
Fraction
1
F
Filter(s)
2
Pr3
Acetone and methylene chloride rinses of
nozzle/probe, cyclone, front half/back
filter holder, filter support, connecting
glassware, condenser
3
PRT
CRT
Toluene rinse of nozzle/probe, cyclone,
front half/back half filter holder, filter
support, connecting line and condenser
4
SM
XAD-2® resin trap (sorbent module)
5
IC
Contents of Impingers 1-4 (H20) plus
methylene chloride rinses
a Rinses include acetone and methylene chloride recovered into the same sample bottle.
5.2.5 CDD/CDF/PAH Analytical Procedures
The analytical procedure used to obtain analyte concentrations from a single flue gas
sample is high resolution gas chromatography (HRGC) and high resolution mass spectrometry
(HRMS) (resolution from 8000-10000 m/z). The target CDD/CDF congeners are listed in
Table 5-8. The PAH analytes are listed in Table 5-9. The analyses were performed by Triangle
Laboratories, Inc., by Method 23/8290.
The Method 23 samples were prepared and analyzed according to the scheme in
Figure 5-6. The XAD-2® (along with the acetone/methylene chloride rinses) was extracted with
methylene chloride and this extract was added to the extract from the extraction of the impinger
water. This combined extract was split 1:1, with one half being added to the toluene rinses and
toluene extract of the XAD® for D/F analysis, and the remaining being used for PAH analysis.
For the D/F analysis, isotopically-labeled surrogate compounds and internal standards and
surrogates that were used are described in detail in EPA Method 23.
5-38
-------
Table 5-8. CDD/CDF Congeners To Be Analyzed
DIOXINS:
2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD)
Total tetrachlorinated dibenzo-/?-dioxins (TCDD)
1,2,3,7,8-pentachlorodibenzo-p-dioxin (1,2,3,7,8-PeCDD)
Total pentachlorinated dibenzo-/?-dioxins (PeCDD)
l,2,4,5,7,8-hexachlorodibenzo-/?-dioxin (1,2,3,4,7,8-HxCDD)
1.2.3.6.7.8-hexachlorodibenzo-/7-dioxin (1,2,4,5,7,8-HxCDD)
1.2.3.7.8.9-hexachlorodibenzo-/?-dioxin (1,2,3,7,8,9-HxCDD)
Total hexachlorinated dibenzo-p-dioxins (HxCDD)
l,2,3,4,6,7,8-heptachlorodibenzo-/?-dioxin (1,2,3,4,6,7,8-HpCDD)
Total heptachlorinated dibenzo-p-dioxins (HpCDD)
Total octachlorinated dibenzo-/?-dioxins (OCDD)
FURANS:
2,3,7,8-tetrachlorodibenzofurans (2,3,7,8-TCDF)
Total tetrachlorinated dibenzofurans (TCDF)
1,2,3,7,8-pentachlorodibenzofuran (1,2,3,7,8-PeCDF)
2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF)
Total pentachlorinated dibenzofurans (PeCDF)
1,2,3,4,7,8-hexachlorodibenzofuran (1,2,3,4,7,8-HxCDF)
1,2,3,6,7,8-hexachlorodibenzofuran (1,2,3,6,7,8-HxCDF)
2.3.4.6.7.8-hexachlorodibenzofuran (2,3,4,6,7,8-HxCDF)
1.2.3.7.8.9-hexachlorodibenzofurans (1,2,3,7,8,9-HxCDF)
Total hexachlorinated dibenzofurans (HxCDF)
1.2.3.4.6.7.8-heptachlorodibenzofuran (1,2,3,4,6,7,8-HpCDF)
1.2.3.4.7.8.9-heptachlorodibenzofiiran (1,2,3,4,7,8,9-HpCDF)
Total heptachlorinated dibenzofurans (HpCDF)
Total octachlorinated dibenzofurans (OCDF)
5-39
-------
Table 5-9. PAH to be Analyzed
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthrene
Benzo(k)fluoranthrene
Benzo(g,h,i)perylene
Benzo(e)pyrene
2-Chloronaphthalene
Chrysene
Dibenzo(a,b)anthracene
Fluorenthene
Fluorene
Indeno( 1,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Phenanthrene
Pyrene
5-40
-------
ORGANICS SS SPIKE-I
D5-PHENOL 100 ug
1 , 4-DIBR0M0BENZENE-D4 100 ug
ORGANICS SS SPIKE-II
05-NITROBENZENE 100 ug
2 - FLUOROBIPHENYL 100 ug
1 , 3,5-TRICHLORO-
BENZENE-D3 100 ug
ORGANICS SS SPIKE-III
2,4., 8-TRIBROMOPHENOL 100 ug
ORGANICS SS SPIKE-IV
ANTHRACENE-D10
100 ug
ORGANICS SS SPIKE-V
PYRENE-D10
100 ug
COMBINE
SPLIT 1:1
SPLIT 1:1
KD TO
TOLUENE
RINSES
ROTOVAP
SOXHLET IN
MeCL2-1st
SOXHLET IN
TOLUENE-2n<3
LIQ-LIQ
EXTRACT-MeCl2
00 PCOOs/Fs CLEANUP
CONDENSATE
IMPINGER
ADO TO SOX
FOR MeCl2
EXTRACTION
50* MeCL2
EXTRACT
TO DIOXINS
FILTER + XAO
ADD TO SOXHLET
ADO TO SOX
FOR TOLUENE
EXTRACTION
50% MeCL2
EXTRACT
TO ORGANICS
50* TOLUENE
EXTRACT
TO ARCHIVE
ANALYZE FOR
PAHs METHOD 8270
50% TOLUENE
EXTRACT
TO OIOXINS
ORGANICS SS
SPIKES-II & IV
SPIKE W/
ANALYZE FOR PCODs/Fs METHOO 8290X
XAO
PRESPIKED W/
4 ng D/F SS
100 ug
TERPHENYL-014
SPIKE W/
4 ng D/F IS
ORGANICS SS
SPIKES-I , III
Figure 5-6. Extraction and Analysis Schematic for Method 23 Samples
5-41
-------
Data from the mass spectrometer were recorded and stored on a computer file as well as
printed on paper. Results such as amount detected, detection limit, retention time, and internal
standard and surrogate standard recoveries were calculated by computer. The chromatograms
were retained by the analytical laboratory with copies included in the analytical report delivered
to ERG.
5.2.5.1 Preparation of Samples for Extraction
Upon receiving the sample shipment, the samples were checked against the Chain-of-
Custody forms and then assigned an analytical laboratory sample number. Each sample
component was reweighed to determine if leakage occurred during travel. Color, appearance,
and other particulars of the samples were noted. Samples were extracted within 21 days of
collection and processed through cleanup procedures before concentration and analysis.
5.2.5.2 Calibration of GC/MS System
A five-point calibration of the GC/MS system was performed to demonstrate
instrument linearity over the concentration range of interest. Relative response factors were
calculated for each congener or compound of interest. The response factors were verified on a
daily basis using a continuing calibration standard consisting of a mid-level isomer standard.
The instrument performance was acceptable only if the measured response factors for the labeled
and unlabeled compounds and the ion-abundance ratios were within the allowable limits
specified in the method.
5.2.6 CDD/CDF Analytical Quality Control
All quality control procedures specified in the test method were followed. Blanks were
used to determine analytical contamination, calibration standards were used for instrument
calibration and linearity checks, internal standards were used to determine isomer recoveries and
5-42
-------
adjust response factors for matrix effects, surrogate standards were used to measure the
collection efficiency of the sampling methodology and an alternate standard was used as a
column efficiency check.
5.2.6.1 CDD/CDF Quality Control Blanks
Four different types of sample blanks were collected for D/F analysis. The type of
blanks that are required are shown in Table 5-10.
Table 5-10. Method 23 Blanks Collected
Blank
Collection
Analysis
Field Blanks
One run collected and
analyzed
Analyze with flue gas
samples
Glassware Proof Blank
Each train to be used (2) will
be loaded and quantitatively
recovered prior to sampling
Archive for potential analysis
Method Blank
At least one for each
analytical batch
Analyze with each analytical
batch of flue gas samples
Reagent Blanks
One 1000 mL sample for
each reagent and lot
Archive for potential analysis
Reagent blanks of 1000 mL of each reagent used at the test site were saved for potential
analysis. Each reagent blank was of the same lot as was used during the sampling program.
Each lot number and reagent grade was recorded on the field blank label and in the laboratory
notebook (acetone, methylene chloride, toluene, HPLC water, filter, XAD-2®).
A glassware blank (proof blank) was recovered from each set of sample train glassware
that was used to collect the organic samples. The precleaned glassware, which consists of a
probe liner, filter holder, condensor coil, and impinger set, was loaded as if for sampling and then
quantitatively recovered exactly as the samples were. Analysis of the generated fractions were
5-43
-------
used to check the effectiveness of the glassware cleaning procedure only if sample analysis
indicates a potential contamination problem.
A field blank was collected from a set of D/F glassware that had been used to collect at
least one sample and had been recovered. The train was re-loaded, leak checked and left at a
sampling location during a test run. The train was then recovered. The purpose of the field
blank was to measure the level of contamination that occurs from handling, loading, recovering,
and transporting the sampling train. The field blanks were analyzed with the flue gas samples. If
they are unsatisfactory in terms of contamination, reagent blanks may be analyzed to determine
the specific source of contamination.
In addition to the three types of blanks that are required for the sampling program, the
analytical laboratory analyzed a method blank with each set of flue gas samples. This method
blank consisted of preparing and analyzing an aliquot of toluene by the exact procedure used for
the samples analysis. The purpose of this method blank was to verify that there was no
laboratory contamination of the field samples.
5.2.6.2 Quality Control Standards and Duplicates
Recoveries of the internal standards must be between 40 to 130% for the tetra-through
hexachlorinated compounds and in the range of 25 to 130% for the hepta-and octachlorinated
homologues. If these requirements are not met, the data will be acceptable if the signal to noise
ratio is greater than or equal to ten. If these requirements are met, the results for the native
(sampled) species are adjusted according to the internal standard recoveries.
Surrogate standard recoveries must be between 70 to 130%. If the recoveries of all
standards are less than 70%, the project director will be notified immediately to determine if the
surrogate results will be used to adjust the results of the native species.
5-44
-------
5.2.7 Analytes and Detection Limits for Method 23
The target analytes are the tetra- through octachlorinated dibenzodioxins and
chlorinated dibenzofiirans. The detection limit of the individual compounds is dependent on the
detection limit of the analytical method, the volume of the final extract and the total volume of
gaseous sample collected in the sampling trains. Following the protocol of Method 23, the
fractions to be collected for analysis from each train are:
• Fraction 1— Filter;
• Fraction 2—XAD-2® sorbent module;
• Fraction 3—Acetone and methylene chloride rinses of all train components prior to
sorbent module and;
• Fraction 4~Toluene rinses of all train components prior to the sorbent module.
• Fraction 5—Impinger contents 1-4 plus methylene chloride rinses
Following the sample preparation protocol outlined in Method 23, a single combined
sample was presented for analysis for D/F by high resolution gas chromatography/high
resolution mass spectrometry. (The individual samples were no longer available for analysis).
The final volume of this sample was 200 fxL of which a 2 /j.h aliquot was injected into the
instrument. Using an instrument detection limit of 50 pg for tetra-, 250 pg for penta- through
hepta-, and 500 pg for octa-, the total minimum detectable amounts were calculated and are given
in Table 5-11. Using a four hour sampling time as selected by the EPA Work Assignment
Manager at an assumed sampling rate of 0.75 cfm, the MDLs shown in Table 5-12 were
possible. The sampling flow rate at the outlet location was dictated by the flow rate of the stack
gas since isokinetic sampling was performed.
5-45
-------
Table 5-11. Analytical Detection Limits For Dioxins/Furans
Analyte
Total Detectable Amount, ng
Tetra CDDs
5
Penta CDDs
25
Hexa CDDs
25
Hepta CDDs
25
Octa CDDs
50
Tetra CDFs
5
Penta CDFs
25
Hexa CDFs
25
Hepta CDFs
25
Octa CDFs
50
NOTE: D/F analysis by High Resolution Mass Spectrometry assumes a 2 /uL injection of a
200 juL sample extract.
5-46
-------
Table 5-12. CDD/CDF Method Detection Limits
Sampling Time, Hours
4
Sampling Rate, cfm
0.75
Sample Volume, m3
5.1
MDL,ng/m3
Tetra CDDs
0.98
Penta CDDs
4.9
Hexa CDDs
4.9
Hepta CDDs
4.9
Octa CDDs
9.8
Tetra CDFs
0.98
Penta CDFs
4.9
Hexa CDFs
4.9
Hepta CDFs
4.9
Octa CDFs
9.8
5.3 Analysis of Method 23 Samples for PAHs
The Method 23 sample preparation scheme shown in Figure 5-6 includes the splitting
of prepared sample extracts for both CDD/CDF and PAH analyses. Split extracts were analyzed
for the PAH compounds shown in Table 5-9 using gas chromatography coupled with high
resolution mass spectrometry. However, due to high levels of some PAHs, the extracts were re-
analyzed using low resolution mass spectrometry. Table 5-13 lists the analytical detection limits
for each of the PAHs to be determined.
5-47
-------
Table 5-13. Analytical Detection Limits For PAHs
Analyte
Total Detectable Amount, /zg
Acenaphthene
20
Acenaphthylene
10
Anthracene
10
Benzo(a)anthraene
10
Benzo(b)fluoranthene
10
Benzo(k)fluorenthene
10
Benzo(g,h,i)perylene
10
Benzo(a)pyrene
10
Benzo(e)pyrene
10
2-Chloronaphthalene
10
Chrysene
10
Dibenzo(a,h)anthracene
10
Fluoranthene
20
Fluorene
35
Indeno(l,2,3-cd)pyrene
10
2-Methylnaphthalene
150
Naphthalene
900
Perylene
10
Phenanthrene
100
Pyrene
15
5-48
-------
Using a four hour sampling time as selected by the EPA Work Assignment Manager, at
an assumed sampling rate of 0.75 cfm, the method detection limits shown in Table 5-14 were
possible.
Table 5-14. PAH Method Detection Limits
Sampling Time, Hours
4
Sampling Rate, cfm
0.75
Sample Volume, m3
5.1
MDL,/ig/m3
Acenaphthene
8
Acenaphthylene
4
Anthracene
4
Benzo(a)anthracene
4
Benzo(b)fluoranthene
4
Benzo(k)fluoranthene
4
Benzo(g,h,i)perylene
4
Benzo(a)pyrene
4
Benzo(e)pyrene
4
2-Chloronaphthalene
4
Chrysene
4
Dibenzo(a,h)anthracene
4
Fluoranthene
8
Fluorene
14
Indeno( 1,2,3-cd)pyrene
4
2-Methy lnaphthal ene
59
Naphthalene
350
Perylene
4
Phenanthrene
40
Pyrene
6
5-49
-------
5.4
EPA Methods 1-4
5.4.1 Traverse Point Location By EPA Method 1
The number and location of sampling traverse points necessary for isokinetic and flow
sampling were dictated by EPA Method 1 protocol. These parameters were based upon how
much duct distance separates the sampling ports from the closest downstream and upstream flow
disturbances. The minimum number of traverse points for a circular duct with an I.D. of 12 feet
is 12.
5.4.2 Volumetric Flow Rate Determination by EPA Method 2
Volumetric flow rate was measured according to EPA Method 2. A type K
thermocouple and S-type pitot tube were used to measure flue gas temperature and velocity,
respectively.
5.4.2.1 Sampling and Equipment Preparation
For EPA Method 2, the pitot tubes were calibrated before use following the directions
in the method. Also, the pitots were leak checked before and after each run.
5.4.2.2 Sampling Operations
The parameters that were measured include the pressure drop across the pitots, stack
temperature, stack static and ambient pressure. These parameters were measured at each traverse
point, as applicable. A computer program was used to calculate the average velocity during the
sampling period.
5-50
-------
5.4.3 02 and C02 Concentrations by EPA Method 3
The 02 and C02 concentrations were determined by Fyrite following EPA Method 3.
Flue gas was extracted from the duct for analysis. The Method 3 analysis for 02 and C02 were
performed approximately every 30 minutes as a grab sample at the outlet and at the inlet.
5.4.4 Average Moisture Determination by EPA Method 4
The average flue gas moisture content was determined according to EPA Method 4.
Before sampling, the initial weight of the impingers was recorded. When sampling was
completed, the final weights of the impingers were recorded, and the weight gain was calculated.
The weight gain and the volume of gas sampled were used to calculate the average moisture
content (%) of the flue gas. The calculations were performed by computer. Method 4 was
incorporated in the technique used for the Method 29 manual sampling method that was used
during the test.
5-51
-------
-------
6.0 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 the results of all QC analyses so that the degree of data quality can be
ascertained.
In summary, a high degree of data quality was maintained throughout the project. All
sampling train leak checks met the QC criteria as specified in the methods. Isokinetic sampling
rates were kept within the 10% of 100% for all test runs. Good spike recoveries and close
agreement between duplicate analyses were shown for the sample analyses.
6.1 Sampling QC Results
The following sections discuss the QC results of the specific sampling methods
employed during this project.
6.1.1 D/F/PAH Sampling QC
Table 6-1 lists the pre- and post-test and port change leak check results. The acceptance
criteria are that all post-test leak checks must be less than 0.02 cfm or 4 percent of the average
sampling rate (whichever is less). All D/F/PAH leak checks met this criterion.
Table 6-2 presents the isokinetic sampling rates for the D/F/PAH sampling runs. The
acceptance criterion is that the average sampling rate must be within 10% of 100% isokinetic.
All sampling runs met this criterion.
6-1
-------
Table 6-1. Summary of Leak Checks Performed, Per Port, Dioxin Testing, Outlet
Date
Run #/Port
Initial leak
Check
Leak Check
Final Leak
Check
6/25/97
1/C
0.015 @ 17"
0.011 @ 10"
1/D
0.016 @ 12"
1/A
0.017 @ 10"
1/B
0.018 @ 15"
0.018 @ 15"
6/26/97
2/B
0.009 @ 17"
0.007 @ 10"
2/A
0.008 @ 7"
2/D
0.009 @ 9"
2/C
0.011 @9"
0.011 @9"
6/27/97
3/C
0.010 @ 10"
0.003 @ 12"
3/D
0.009 @ 12"
3/A
OK
3/B
0.011 @ 10"
0.011 @ 10"
6-2
-------
Table 6-2. Summary of Isokinetic Percentages
Date
Run#
Percent Isokinetic
Multi-Metals — Inlet
6/25/97
1
102.66
6/26/97
2
108.38
6/27/97
3
99.42
Multi-Metals — Outlet
6/25/97
1
103.74
6/26/97
2
99.66
6/27/97
3
103.25
Dioxin ~ Outlet
6/25/97
1
104.38
6/26/97
2
103.67
6/27/97
3
102.29
6-3
-------
All dry gas meters are fully calibrated every six months against an EPA approved
intermediate standard. The full calibration factor is used to correct the actual metered sample
volume to the true sample volume. To verify the full calibration, a post-test calibration is
performed. The full and post-test calibrations coefficients must be within 5% to meet ERG's
internal QA/QC acceptance criterion. As shown in Table 6-3, the meter box used for the
D/F/PAH testing met this criterion.
Field blanks are collected to verify the absence of any sample contamination. A
D/F/PAH train was assembled as if for sampling, leak checked at the sampling location, left at
the sampling location for the duration of a test run and then recovered. Table 6-4 presents the
analytical results for the field blank as well as the laboratory method blank. The only D/F
compounds detected in the field blank were 1,2,3,4,6,7,8,9-OCDD, 2,3,7,8-TCDF and
1,2,3,4,7,8-HxCDF, but at much lower amounts than in any of the test runs. Any PAHs detected
in the field blank were at levels less than 0.5% of any detected in the test runs. Because the
amount of contamination was so low, no blank corrections were made on the emissions results.
6.1.2 Metals/PM Sampling QC
Tables 6-5 and 6-6 list the pre- and post-test and port change leak check results for the
outlet and inlet sampling trains respectively. The acceptance criteria of less than 0.02 cfm or 4%
of the average sampling rate (whichever is less) were met by all sampling trains.
Table 6-2 presents the isokinetic sampling rates for the metals/PM sampling runs. The
sampling rate acceptance criterion of being within 10% of 100% isokinetic was met for all
sampling runs at both the inlet and outlet.
As shown in Table 6-3, the calibration coefficients of the meter boxes used for the
metals/PM testing were within 5% of their full calibration coefficient, thus meeting the
acceptance criterion.
6-4
-------
Table 6-3. Dry Gas Meter Post Calibration Results
Sampling Train
Meter Box
Number
Full
Calibration
Factor
Post-Test
Calibration
Factor
Post-Test*
Deviation %
D/F/PAH, Outlet
39
0.996
0.970
-2.61
Metals/PM, Outlet
38
0.984
0.971
-1.32
Metals/PM, Inlet
40
0.984
0.974
-1.02
Post-Test - Full
x 100
Full
-------
Table 6-4. Dioxin/Furan Field Blank Analysis Results
Congener
Field Blank
ng Detected
Lab Method Blank
ng detected
2,3,7,8 -TCDD
<0.03*
<0.01
1,2,3,7,8-PeCDD
<0.03
<0.02
1,2,3,4,7,8-HxCDD*
<0.02
<0.02
1,2,3,6,7,8-HxCDD
<0.02
<0.01
1,2,3,7,8,9-HxCDD
<0.04
<0.02
1,2,3,4,6,7,8—HpCDD
<0.04
0.02
1,2,3,46,7,8,9-OCDD*
0.10
<0.04*
2,3,7,8-TCDF**
0.02
<0.007
1,2,3,7,8-PeCDF
<0.02
<0.01
2,3,4,7,8-PeCDF
<0.02
<0.01
1,2,3,4,7,8-HxCDF
0.02
<0.02*
1,2,3,6,7,8-HxCDF
<0.01
<0.01
2,3,4,6,7,8-HxCDF
<0.02
<0.02
1,2,3,7,8,9-HxCDF
<0.02
<0.02
1,2,3,4,6,7,8-HpCDF
<0.03
<0.04*
1,2,3,4,7,8,9-HpCDF
<0.03*
<0.03
1,2,3,46,7,8,9-OCDF
<0.06*
0.08
* Maximum value, may include interference from a diphenyl ether
**Determined from DB-225 GC column
6-6
-------
Table 6-5. Summary of Leak Checks Performed, Per Port, Metals Testing, Outlet
Date
Run #/Port
Initial leak
Check
Leak Check
Final Leak
Check
6/25/97
1/D
0.015 @15"
*0.014 @ 10"
1/A
0.009 @ 10"
1/B
0.006 @ 8"
1/C
0.007 @ 10"
0.007 @ 10"
6/26/97
2/C
0.013 @ 12"
0.011 @9"
2/B
0.010 @7"
2/A
0.008 @ 7"
2/D
0.007 @ 7"
0.007 @ 7"
6/27/97
3/D
0.009 @ 10"
0.004 @ 7"
3/A
0.006 @ 9"
3/B
OK
3/C
0.004 @ 8"
0.004 @ 8"
*Volume Correction .04
6-7
-------
Table 6-6. Summary of Leak Checks Performed, Per Port, Metals Testing, Inlet
Date
Run #/Port
Initial leak
Check
Leak Check
Final Leak
Check
6/25/97
1/A
0.019 @ 15"
*0.03 @ 1"
1/B
OK
1/C
OK
1/D
0.001 @ 5"
0.001 @ 5"
6/26/97
2/A
0.01 @ 10"
0.01 @3"
2/B
0.01 @3"
2/C
0.01 @3"
2/D
0.01 @5"
0.01 @5"
6/27/97
3/A
0.001 @ 10"
0.01 @ 5"
3/B
0.001 @3"
3/C
0.001 @3"
3/D
0.001 @ 5"
0.001 @ 5"
*Volume Correction .03
6-8
-------
Table 6-7 presents the results from the two Method 29 (metals) field blanks, the reagent
blank and the average of three runs at both the outlet and inlet. Chromium, manganese, nickel,
lead, antimony and selenium were detected in both field blanks and in the reagent blank. The
amount of chromium detected in each of the three blanks was the same with the contribution
coming almost entirely from the filter. This value represents approximately 10% of that
observed in the inlet samples and approximately 50% of that observed in the outlet samples. The
amount of manganese detected varied in the three blanks and ranged between 7 |i.g in the reagent
blank to 129 ^ig in the inlet field blank, twice the amount detected in the outlet samples. These
levels could be due to field contamination, but because proportionately elevated levels for the
other metals were not detected in the blanks, and Run 3, Outlet had obvious laboratory
contamination (see Section 2.3.2), laboratory contamination is also suspected in this case. The
same scenario as discussed for manganese also applies to the lead results; however, any
contamination, either field or laboratory related, is insignificant (<0.2 %) when compared to the
amount detected in either the inlet or the outlet samples. The amount of nickel detected in the
reagent blank and the inlet field blank was the same (nominal 25 jig) while the outlet field blank
contained approximately 50 |ag. Again, the outlet field blank nickel result is probably due to
specific laboratory contamination as other metals do not reflect this amount as general field
contamination. Using the inlet field blank and reagent blank as being representative of
background levels of nickel, the blank contribution to the levels detected in the samples would be
approximately 25% of the total for both the inlet and outlet samples. Antimony was present in
all three blanks at approximately the same level in each. This amount is approximately the same
as that detected in the outlet samples and 50% of that detected in the inlet samples. The same is
true for the amount of selenium detected in the three blanks, but the value represents only 16% of
that detected in the outlet samples and 11% of that detected in the inlet samples. The analysis
results presented in Section 2.2 of this report have not been blank corrected.
6-9
-------
Table 6-7. Metals QC Results: (|jg detected)
Metal
Outlet
Field Blk
Inlet
Field Blk
Train
Reagent Blk
Average
Outlet Runs
Inlet Runs
Hg
<3.03
<3.26
<2.66
6.41
4.06
As
<1.08
<1.00
<1.00.
4.65
18.2
Be
<0.200
<0.200
<0.200
<0.218
<0.224
Cd
<0.200
<0.200
<0.200
72.6
84.3
Co
<0.200
<0.200
<0.200
<0.218
1.24
Cr
12.8
11.9
11.7
22.0
98.7
Mn
29.7
129
6.85
73.2*
1700
Ni
49.5
25.2
23.7
91.9
98.5
Pb
31.1
22.2
2.68
15700
19000
Sb
6.60
6.4
7.35
6.92
11.0
Se
7.10
6.20
6.35
36.8
54.7
* Average of two runs, apparent lab contamination in one test run
6-10
-------
6.2
Analytical QC Results
The following section reports QA parameters for the D/F/PAH and Metals/PM
analytical results.
6.2.1 D/F/PAH Analytical Quality Control
D/F—One sample was generated for D/F analysis for each stack gas sample collected
and was subjected to both a full screen and confirmation analysis. The full screen analyses were
conducted using a DB-5 GC column which allows the separation of each class of chlorinated
(i.e., tetra, penta, etc.) and fully resolves 2,3,7,8-TCDD from the other TCDD isomers. The
confirmation analysis, performed on a DB-225 GC column, is needed to fully resolve the
2,3,7,8-TCDF from the other TCDF isomers.
A component of the D/F QC program is adding isotopically labeled standards to each
sample during various stages of analysis to determine recovery efficiencies and to aid in the
quantitation of native D/F species. Four different types of standards are added:
• Surrogate standards are usually spiked on the XAD-2® absorbent prior to
sampling. Recovery of these compounds allows for the evaluation of overall
sample collection efficiency and analytical matrix effects.
• Internal standards are spiked after sampling but prior to extraction.
• Alternate standards are also spiked at this stage.
• Recovery percentages of internal standards are used in quantifying the D/F native
to the stack gas being sampled. Recovery of alternate standards for extraction/
fractionation efficiencies to be determined.
• Recovery standards are added after fractionation, just prior to analysis by
HRGC/HRMS.
6-11
-------
The recovery of each of the spiked isotopically labeled compounds was within the
acceptance criteria set forth in Method 23, except for the surrogate standard 13C12-1,2,3,4,7,8-
HxCDD in Run 1 and Run 2 at the venturi outlet. The percent recoveries were 69.3 and 68.8,
respectively, and were just outside of the lower limit of 70%. This low recovery will have no
effect on the reported results.
PAH—The sample extracts were originally analyzed by HRGC/HRMS, but due to the
high level of many of the PAHs found in the samples, the instrument detector became saturated,
resulting in data that were not reliable. Therefore, the sample extracts were reanalyzed on a low
resolution mass spectrometer (LRMS) following the protocol given in EPA Method 8270A.
Unfortunately, the isotopically labeled spiking compounds associated with the PAH analysis that
were originally spiked at a level commensurate with HRMS were below the detection limit of the
LRMS. It is assumed, however, that the acceptable extraction efficiencies demonstrated for the
D/F related spiking standards is indicative of similar acceptable extraction efficiencies for the
PAH target compounds. All internal standard areas were within Method 8270A quality control
criteria.
6.2.2 Metals Analytical Quality Control
ICAP Metals—The analytical methods used for the stack gas samples are discussed in
Section 5 of this report. The following paragraphs discuss the metals QC results.
Serial dilutions were performed on the Outlet Run 1 front half and back samples for the
ICAP metals. A serial dilution is performed to determine if there is any interference specific to
an analyte in the native sample matrix. The relative percent difference (RPD) between the
analysis of the undiluted and the serially diluted sample is determined. Only those analytes
with detectable amounts above 10 times the reportable detection limit (RDL) after dilution are
reported. Cadmium, manganese, nickel, lead and selenium in the front half sample were within
6-12
-------
the ±10% RPD criterion. Chromium had a RPD of 12.1% which does not indicate any
significant interferent. Selenium in the back half sample had an RPD of 8.70%.
Duplicate ICAP analysis was performed on Outlet Run 2 front half and back half
samples. Only those analytes with detectable amounts above 10 times the reportable detection
limit are reported. The RPD between the two analyses must be ±20% to be acceptable. All of
the metals detected above 10 times the RDL demonstrated RPDs less than 10%.
Post digestion matrix spikes were performed on the Outlet Run 1 front half and back
samples for the ICAP metals. Each of the target metals is spiked at a known level into an aliquot
of the sample. A percent recovery between 75 and 125 is acceptable and indicates the lack of
interference from the native sample matrix. The percent recovery for all the metals except
cadmium, manganese, nickel and lead in the front half sample were within 75-125% range. The
level of spike for these metals was insignificant compared to the native amount and could not be
quantitated. The % recovery for all of the metals in the back half sample were within the
acceptance criterion.
No ICAP metals were detected in the laboratory method blank above the instrument
detection limit and the recoveries of each of the metals in the laboratory control spike were
within the acceptance criterion of 80-120%.
CVAA—Every sample was analyzed in duplicate for the presence of mercury. All
duplicate analyses were within the acceptance criterion of ±20%. Matrix spikes and matrix spike
duplicates were performed on the back-half (nitric acid/peroxide) impinger contents of all test
runs, both inlet and outlet. Percent recoveries for all sample spikes were within the acceptance
criterion of 75-125. All laboratory control spikes and laboratory control spike duplicates were
also within this acceptance criterion.
6-13
-------
6.2.3 PM Analytical Quality Assurance
All filters and acetone probe rinse residues were weighed to a constant weight
following the procedures given in EPA Method 5. The acetone probe rinse residues were blank
corrected using a known volume of acetone reagent. The five place analytical balance calibration
was verified prior to use by weighing a series of Class S weights which covered the range of
weights encountered with the samples.
6-14
-------
r
TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing)
1. REPORT NO. Z
EPA- 454/R-99-042a
3. RECIPIENTS ACCESSION NO.
4. TITLE AND SUBTITLE
integrated boa atdStcd bdanryfimd Report Mznuil Testing
Volume I of m
LTV Steel Company foduni Habor Worin East Chicago, Dmaa
5. REPORT DATE
August 1999
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
EMAD
t. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMINO 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-D7-0068
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
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
i6. abstract Integrated iron and steel manufacturing is among the categories of major sources for
which national emission standards for hazardous air pollutants (NESHAPS) are to be issued by
November 2000 pursuant to Section 112 of the Clean Air Act. The integrated iron and steel
manufacturing category includes mills that produce steel from iron ore. Key processes and unit
operations include sinter production, iron production, steel making, continuous casting, and the
preparation of semi-finished and finished products. Source tests are required to quantify and
hazardous air pollutant (HAP) emissions, and the performance of a sintering plant equipped with
characterize the particulate matter (PM), a venturi scrubber.
17. KEY WORDS AND DOCUMENT ANALYSIS
jl DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Fidd'Group
Particulate Matter, Dioxin/Furan, PAH, Metals
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
------- |