United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA- 454/R-99-041a
August 1999
Air
&EPA
i
Integrated Iron and Steel Industry Final Report
Manual Testing
Volume I of
Youngstown Sinter Company
Youngstown, Ohio
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Integrated Iron and Steel Industry
Final Report
Volume I of III
Contract No. 68-D7-0068
Work Assignment 2-13
Youngstown Sinter Company
Youngstown, Ohio
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
EASTERN RESEARCH GROUP, INC
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Integrated Iron and Steel Industry
Final Report
Contract No. 68-D7-0068
Work Assignment 2-13
Youngstown Sinter Company
Youngstown, Ohio
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
-------
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 2-6
2.3 Metals HAPs Results 2-12
2.3.1 Overview 2-12
2.3.2 Metal HAPs Emission Results 2-12
2.4 PM Results 2-20
2.4.1 PM Emissions Results 2-20
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
111
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TABLE OF CONTENTS (Continued)
Page
5.1.4 Method 29 Sample Recovery 5-12
5.1.5 Particulate Analysis 5-19
5.1.6 Metals Analytical Procedures 5-20
5.1.7 Quality Control for Metals Analytical Procedures 5-23
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 5-24
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 5-26
5.2.2.1 Glassware Preparation 5-26
5.2.2.2 XAD-2® Resin and Filters Preparation 5-28
5.2.2.3 Method 23 Sampling Train Preparation 5-29
5.2.3 Method 23 Sampling Operations 5-29
5.2.3.1 Preliminary Measurements 5-29
5.2.3.2 Assembling the Train 5-30
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 5-43
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 5-49
5.4.1 Traverse Point Location By EPA Method 1 5-49
5.4.2 Volumetric Flow Rate Determination by EPA Method 2 5-49
5.4.2.1 Sampling and Equipment Preparation 5-49
5.4.2.2 Sampling Operations 5-49
5.4.3 O2 and CO2 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 6-5
IV
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TABLE OF CONTENTS (Continued)
Page
6.2 Analytical QC Results ' ,6-8
6.2.1 D/F/PAH Analytical Quality Control 6-8
6.2.2 Metals Analytical Quality Control 6-9
6.2.3 PM Analytical Quality Assurance 6-11
APPENDICES
A D/F Laboratory Analysis Data
B PAH Laboratory Analysis Data
C Metals Laboratory Analysis Data
D Particulate Matter Laboratory Analysis Data
E Field Data Sheets
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LIST OF TABLES
Page
1-1 Test Matrixj Youngstown Sinter Company, Youngstown, Ohio 1-4
2-1 Emissions Test Log, Youngstown Sinter Company 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, Strand Baghouse Outlet, Runs 3 through 5 . 2-5
2-5 Dioxin/Furan Stack Emission Rate, Strand Baghouse Outlet, Runs 1 thorugh 5 2-7
2-6 Dioxin/Furan Stack Emission Rate, Strand Baghouse Outlet 2-8
2-7 Dioxin/Furan 2,3,7,8-TCDD Toxicity Equivalent Stack Gas Concentrations,
Strand Baghouse Outlet 2-9
2-8 PAH Concentration, Strand Baghouse Outlet, Runs 3 through 5 2-10
2-9 PAH Concentration, Strand Baghouse Outlet, Runs 1 thorugh 5 2-11
2-10 PAH Stack Emission Rate, Venturi Outlet 2-13
2-11 Metals Results: Strand Baghouse Inlet, Run 1 (ug collected) 2-14
2-12 Metals Results: Strand Baghouse Inlet, Run 2 (ug collected) 2-14
2-13 Metals Results: Strand Baghouse Inlet, Run 3 (jag collected) 2-15
2-14 Metals Results: Strand Baghouse Outlet, Run 1 (ug collected) 2-15
2-15 Metals Results: Strand Baghouse Outlet, Run 2 (jug collected) 2-16
2-16 Metals Results: Strand Baghouse Outlet, Run 3 (ug collected) 2-16
2-17 Metals Results: Baghouse A Outlet, Run 1 (ug collected) 2-17
2-18 Metals Results: Baghouse A Outlet, Run 2 (ug collected) 2-17
2-19 Metals Results: Baghouse A Outlet, Run 3 (ug collected) 2-18
vi
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LIST OF TABLES (Continued)
Page
2-20 Metals Stack Gas Concentration: Strand Baghouse Inlet 2-18
2-21 Metals Stack Gas Concentration: Strand Baghouse Outlet 2-19
2-22 Metals Stack Emission Concentration: Baghouse A Outlet 2-19
2-23 Metals Stack Emission Rate, Strand Baghouse Outlet 2-21
2-24 Metals Stack Emission Rate, Baghouse A Outlet 2-21
2-25 Strand Baghouse Removal Efficiency for Metals 2-22
2-26 Paniculate Matter Concentration 2-22
2-27 Paniculate Matter Emission Rates and Removal Efficiency 2-23
5-1 Glassware Cleaning Procedure (Train Components) 5-4
5-2 Sampling Checklist 5-9
5-3 Analytical Detection Limits 5-18
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
vii
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LIST OF TABLES (Continued)
Page
5-13 Analytical Detection Limits For PAHs 5-48
5-14 PAH Method Detection Limits 5-50
6-1 Summary of D/F/PAH Leak Checks, Strand Baghouse Outlet 6-2
6-2 Summary of Isokinetic Percentages 6-3
6-3 Dry Gas Meter Post Calibration Results 6-4
6-4 Dioxin/Furan Field Blank Analysis Results 6-4
6-5 Summary of Metals Train Leak Checks, Strand Baghouse Outlet 6-6
6-6 Summary of Metals Train Leak Checks, Strand Baghouse Inlet '. 6-6
6-7 Summary of Metals Train Leak Checks, Baghouse A Outlet 6-7
6-8 Metals QC Results: (|jg detected) 6-7
vni
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LIST OF FIGURES
Page
1-1 Test Schedule 1-5
4-1 Strand Baghouse Inlet Sampling Location 4-2
4-2 Strand Baghouse Outlet Sampling Location 4-3
4-3 Baghouse A Outlet Sampling Location 4-4
4-4 Strand Baghouse Inlet Traverse Point Layout 4-5
4-5 Strand Baghouse Outlet Traverse Point Layout 4-6
4-6 Baghouse A Traverse Point Layout 4-7
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 5-21
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
IX
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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 paniculate matter (PM),
hazardous air pollutant (HAP) emissions, and the performance of a sintering plant equipped with
baghouse control devices.
1.1 Objective
The objective of the testing at the Youngstown Sinter Company (YSC) plant in
Youngstown, Ohio, was to perform all activities necessary to characterize the baghouse sintering
plant windbox (Strand Baghouse) for the following emission components:
• Paniculate mass (PM) and metal HAPs using EPA Method 29; and
• Dioxins/furans (D/F) and polynuclear aromatic hydrocarbons (PAH) using EPA
Method 23.
The discharge end baghouse (Baghouse A) was tested for the following emission
components:
Paniculate mass (PM) and metal HAPs using EPA Method 29.
In addition, the determination of total hydrocarbons using Method 25A and preliminary
screening for organic HAPs using a Fourier Transform Infrared (FTIR) monitoring instrument
1-1
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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.
Testing at the Strand Baghouse was performed at the inlet and outlet simultaneously.
Testing at Baghouse A was performed at the outlet only. 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. Emissions
were controlled by baghouses.
The plant has a rated capacity of 2,900 tons per day (tpd) of sinter. The plant operates
24 hours per day, 6 days per week, with 1 day scheduled for routine maintenance. In operation,
150-170 truckloads per day of raw materials are brought into the plant and 140-160 truckloads
per day of finished sinter are shipped from the plant. Raw materials are stored at the site. Two
feeder tables blend mill scale, BOF slag, and crushed ore pellets by volume and the mixture is
transferred by conveyor to the sinter plant. The mixture is referred to as pre-blend. YSC used
200,000 tons of their own material and 500,000 tons of material that are purchased from other
sources each year. Their specification on the oil content of the mill scale is a maximum of
0.2 percent.
1.3 Emissions Measurements Program
This section provides an overview of the emissions measurements program conducted at
Youngstown Sinter Company. Included in the this section are summaries of the test matrix,
1-2
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sampling locations, sampling methods, and laboratory analysis. Additional detail on these topics
is provided in the sections that follow.
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 one day of set-up and
five test days. 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.
1.3.3 Sampling Locations
The stack gas sampling was conducted at the inlet and outlet of the sintering plant Strand
Baghouse and Baghouse A outlet. The inlet location was a rectangular duct with four new 4"
ports (installed by the plant) positioned on the long vertical side. Access to this location required
the use of a man lift which was provided by the plant.
The test ports and their locations met the requirements of EPA Method 1. The Strand
baghouse inlet location was a rectangular duct with dimensions of 11' by 10' with four 4" ports
installed on the vertical 10' side. The Strand baghouse outlet location was a circular stack with
an inside diameter (I.D.) of 9 feet. The Baghouse A outlet was a circular stack with an ID. of 6'.
1-3
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Table 1-1. Test Matrix, Youngstown Sinter Company, Youngstown, Ohio
Sample
Location
Strand BH1
Inlet
Strand BH
Inlet
Strand BH &
Baghouse A
Outlet
Strand BH &
Baghouse A
Outlet
Strand BH
Outlet
Number
of Runs
3
3
3
3
5
Sample
Type
Gas Velocity/
Volume/Moisture
Total Particulates/Metals
(Pb, Cr, Cd, Be, Ni, Co,
As, Sb, Mn, Se, Hg)
Gas Velocity/
Volume/Moisture
Total Particulates/ Metals
(Pb, Cr, Cd, Be, Ni, As,
Sb, Co, Mn, Se, Hg)
D/F/PAHs
Reference
Method
EPA Methods 1-4
EPA Method 29
EPA Methods 1-4
EPA Method 29
EPA Method 23
Sample
Duration
4Hrs
4Hrs
4Hrs
(2 Hrs for
Baghouse A)
4 Hrs
(2 Hrs for
Baghouse A)
4 Hrs
Analysis
Method
Volumetric/Gravimetric
Gravimetric/Atomic
Absorption/ICAP
Volumetric/Gravimetric
Gravimetric/ Atomic
Absorption/ICAP
GC/HRMS2
8290/8270
Laboratory
ERG
ERG and
Triangle Labs
ERG
ERG and
Triangle Labs
Triangle Labs
'BH = Baghouse
2PAHs analyzed by low resolution mass spectrometry (LRMS)
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1997
August
1997
SUNDAY
3
10
Travel
17
Travel
24
31
MONDAY
4
11
Coordination
Meeting with
plant and
setup
18
25
TUESDAY
5
12
Test Day #1
19
26
WEDNESDAY
6
13
Test Day #2
20
27
THURSDAY
7
14
Test Day #3
21
28
FRIDAY
1
8
15
Set-up BHA
and Test
Day #4
22
29
SATURDAY
2
9
16
Test Day #5
and Tear
Down
23
30
Figure 1-1. Test Schedule
1-5
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The position and number of traverse points for each location are shown in Section 4 of this
report. A new sampling port for the FTIR sampling was installed at the outlet of the Strand
baghouse. Existing ports on top of the Strand baghouse inlet duct were used for FTIR sampling.
1.3.4 Sampling and Analysis Methods
Total paniculate 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 front half rinse, the filter and the contents of the
first two impinger catches using inductively coupled argon plasma spectroscopy (ICAPS) for all
metals except Hg. Cold vapor atomic absorption (CVAA) was used for the analysis of all
fractions 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
gas chromatography/low resolution mass spectrometry (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 Strand baghouse inlet location did indicate the
1-6
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possibility of some carry over for Mn and Pb, due most likely to high levels encountered during
sampling. The metals FB is discussed in detail in Sections 6.1.2 and 6.2.2.
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.
1.5 Test Report
This final report, presenting all data collected and the results of the analyses, has been
prepared in six sections and three 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 two separate volumes.
1-7
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2.0 SUMMARY OF RESULTS
This section provides the results of the emissions test program conducted at the
Youngstown Sinter Company operation from August 11 to August 16, 1997. Included in this
section are results of manual tests conducted for D/F/PAH, metal HAPs and PM.
2.1 Emissions Test Log
Fourteen tests were conducted over a five day period (5 D/F/PAH and 9 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 number of runs for each test method (shown in Table 2-3) was less than 6%,
indicating that the process flow was very constant over the five test days. All related field data
sheets are given in Appendix E.
2.2 D/F/PAH RESULTS
2.2.1 Overview
Five 4-hour D/F/PAH emission test runs were completed at the Youngstown Sinter
Company during the week of August 11, 1997. Five test runs were completed at the outlet of the
Strand baghouse associated with the sintering plant windbox. The sample collection protocol
followed EPA Method 23 while the analysis protocol was modified to also allow for the analysis
of the sample extracts for PAHs. This modification to the sample preparation procedure and
subsequent analysis is discussed in Section 5 of this report. A total of five D/F/PAH tests were
performed at the Strand baghouse outlet where only three were scheduled. For Run 1 and Run 2
2-1
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Table 2-1. Emissions Test Log, Youngstown Sinter Company
Date
8/12/97
8/13/97
8/14/97
8/15/97
8/16/97
Location1
SBH, Outlet, Port B
SBH, Outlet, Port A
SBH, Outlet, Port A
SBH, Outlet, Port B
SBH, Inlet, Port A
SBH, Inlet, Port B
SBH, Inlet, Port C
SBH, Inlet, Port D
SBH, Outlet, Port A
SBH, Outlet, Port B
SBH, Outlet, Port A
SBH, Outlet, Port B
SBH, Outlet, Port A
SBH, Inlet, Port A
SBH, Inlet, Port B
SBH, Inlet, Port C
SBH, Inlet, Port D
SBH, Outlet, Port B
SBH, Outlet, Port A
SBH, Outlet, Port A
SBH, Outlet, Port B
SBH, Inlet, Port A
SBH, Inlet, Port B
SBH, Inlet, Port C
SBH, Inlet, Port D
SBH, Outlet, Port A
SBH, Outlet, Port B
BHA, Outlet, Port A
BHA Outlet, Port B
BHA, Outlet, Port A
BHA, Outlet, Port B
BHA, Outlet, Port A
BHA, Outlet, Port B
Run Number
1
1
1
1
1
1
1
1
2
3
3
2
2
2
2
2
2
4
4
3
3
3
3
3
3
5
5
1
1
2
2
3
3
Test Type
D/F/PAH
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
D/F/PAH
D/F/PAH
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
D/F/PAH
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
D/F/PAH
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Metals/PM
Run Time
1355-16082
1800-2007
1355-16082
1800-2007
1335-1435
1445-16182
1754-1854
1906-2001
1055-1 2553
1530-18124
0800-1 OOO5
1055-1255
1530-18124
1103-1203
1210-1310
1530-17134
1 830-2035
1245-1445
1610-1810
1245-1445
1610-1810
1250-1350
1400-1500
1610-1710
1725-1850
0830-1030
1055-1255
1100-1200
1211-1311
1538-1638
1649-1749
0823-0923
0930-1030
'SBH = Strand baghouse; BHA = Baghouse A
2Plant down for approximately 33 minutes during this period.
3Run 2 terminated after first port due to bad leak check.
4Plant down for approximately 30 minutes during this period.
5Second port sampling continued on 8/14/97.
2-2
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Table 2-2. Sample Volume Collected, dscm1
Location2
SBH, Outlet
SBH, Outlet
SBH, Inlet
BHA, Outlet
Parameter
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Runl
5.97
5.85
2.82
2.33
Run 2
2.90
5.74
2.77
2.32
Run 3
6.02
5.54
2.92
2.13
Run 4
5.90
NA4
NA
NA
Run 5
5.91
NA
NA
NA
Average
Runs 1-5
5.34
NA
NA
NA
Average
Runs 1-33
5.94
5.71
2.84
2.26
Runs 1-3
%RSD3
1.12
2.75
2.69
4.98
to
'dscm, dry standard cubic meters. Standard conditions are defined as 1 atm and 68 °F.
2SBH = Strand baghouse, BHA = Baghouse A.
3Used Runs 3 through 5 for D/F/PAHs.
4NA = not applicable.
Table 2-3. Flue Gas Volumetric Flow Rates, dscmm1
Location2
SBH, Outlet
SBH, Outlet
SBH, Inlet
BHA, Outlet
Parameter
D/F/PAH
Metals/PM
Metals/PM
Metals/PM
Runl
7851
7858
9488
2312
Run 2
7585
7748
9021
2338
Run 3
7706
7797
9456
2098
Run 4
7754
NA4
NA
NA
RunS
7631
NA
NA
NA
Average
Runs 1-5
7705
NA
NA
NA
Average
Runs 1-33
7697
7801
9322
2249
Runs 1-3
%RSD3
0.81
0.71
2.80
5.84
'dscmm, dry standard cubic meters per minute. Standard conditions are defined as 1 atm and 68 °F.
2SBH = Strand baghouse, BHA = Baghouse A.
3Used Runs 3 through 5 for D/F/PAHs.
4NA = not applicable.
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unacceptable leak checks were observed after the completion of the first port traverse sampling.
The long (15') probe, coupled with stack vibrations caused the glass cyclone by-pass to crack,
thus creating a small leak. The cyclone by-pass was replaced and Run 1 was continued. At the
end of Run 1, a successful leak check was observed. The same problem occurred for Run 2.
However, Run 2 was aborted after the first port traverse sampling. The sampling equipment was
then modified to provide extra support for the probe. Runs 1 and 2 should be considered as
questionable.
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 (Runs 3, 4, and 5) and the %RSD. All results except for the 2,3,7,8-tetrachloro
dibenzofufan (2,3,7,8-TCDF) were determined by high resolution gas chromatography
(HRGC)Thigh 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 reported instrumental detection limit. A "less than"
value rather than a "0" is used in all appropriate calculations. These data have not been blank
corrected. The %RSDs reported in Table 2-4 for the three runs (Runs 3, 4, and 5) by compound
are generally less than 20% indicating excellent reproducibility. In a few cases, the %RSDs are
2-4
-------
Table 2-4. Dioxin/Furan Stack Gas Concentrations, Strand Baghouse Outlet,
Runs 3 through 5
Congener
2,3,7,8 -TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF2
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Run 3
0.0731
0.158
0.0316
0.266
0.118
0.141
0.0781
1.91
0.582
0.532
0.249
0.0881
0.0581
<0.0332
0.0631
<0.0665
<0.0997
Run 4
0.0915
0.187
0.0237
0.288
0.114
0.137
0.27 11
2.17
0.797
0.712
0.288
0.103
0.0542
0.00683
0.0644
<0.0339
0.0288
ng/dscm
Run 5
0.0728
0.203
0.0237'
0.305
0.124
0.130
0.0558
1.90
0.677
0.643
0.271
0.0982
0.0542
0.0 1023
0.0575
<0.0338
<0.0677
Average
0.079
0.182
0.0261
0.286
0.118
0.136
0.1351
1.99
0.685
0.629
0.269
0.097
0.056
0.0173
0.062
<0.045
<0.065
%RSD
13.6
12.5
17.2
6.8
4.2
4.1
87.7
7.7
15.7
14.5
7.2
8.1
4.1
86.1
5.9
42.0
54.3
' 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
-------
higher where the concentrations are near the detection limit or the presence of a DPE is indicated.
Increased variability is not unusual in these cases. The %RSDs reported in Table 2-5 for Runs 1-
5 are generally higher (mostly under 50%) for all compounds as compared to those in Table 2-4,
but include Runs 1 and 2 which resulted in questionable data.
Table 2-6 shows the D/F average stack emission rates from the Strand baghouse outlet
using Runs 3 through 5. This value was calculated from the average concentration from
Table 2-4 and the average stack flow rate from Table 2-3.
Table 2-7 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 furans. All D/F analytical raw data can be
found in Appendix A.
2.2.3 PAH Emission Results
Table 2-8 presents the concentration, in micrograms per dry standard cubic meter
(|jg/dscm), for the selected PAH compounds by run number, the average concentration over the
last three runs (Runs 3,4, and 5) and the %RSD. Due to the levels of PAHs encountered, the
extracts were analyzed on a low resolution mass spectrometer (LRMS) after dilution of the
sample extracts. The %RSDs reported in Table 2-8 for the three runs by compound are generally
less than 20% 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 2-9 presents the concentrations and %RSDs for Runs 1 through 5. For these five
runs, the compound %RSDs are generally less than 40%. This higher variability is most likely
due to the limited value of the data from Runs 1 and 2. Any compound that was not detected is
reported as a "less than" value with this value being the reported instrument detection limit. A
"less than" value rather than a "0" is used in all appropriate calculations. These data have not
been blank corrected.
2-6
-------
Table 2-5. Dioxin/Furan Stack Gas Concentrations, Strand Baghouse Outlet, Runs 1 through 5
Congener
2,3,7,8 -TCDD
1,2,3,7,8-PeCDD
1 ,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF2
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Runl
0.104
0.285
0.064
0.637
0.268
0.302
0.161
2.58
1.12
1.16
0.653
0.235
0.147
0.0173
0.147
<0.034
<0.067
Run 2
0.0827
0.214
0.0517
0.482
0.196
0.234
0.128
2.03
0.827
0.827
0.413
0.145
0.0861'
0.0103
0.103'
<0.069
<0.103
Run 3
0.0731
0.158
0.0316
0.266
0.118
0.141
0.0781
1.91
0.582
0.532
0.249
0.0881
0.0581
<0.0332
0.0631
<0.0665
<0.0997
ng/dscm
Run 4
0.0915
0.187
0.0237
0.288
0.114
0.137
0.271'
2.17
0.797
0.712
0.288
0.103
0.0542
0.00683
0.0644
<0.0339
0.02883
Run5
0.0728
0.203
0.0237'
0.305
0.1.24
0.130
0.0558
1.90
0.677
0.643
0.271
0.0982
0.0542
0.0 1023
0.0575
<0.0338
<0.0677
Average
0.085
0.209
0.039'
0.395
0.164
0.189
0.139'
2.12
0.801
0.774
0.375
0.134
0.080
<0.015
0.087
<0.047
<0.0732
%RSD
15.5
22.6
46.2
40.4
41.1
40.2
61.1
13.2
25.6
30.9
44.9
45.1
49.9
68.4
43.9
39.3
41.2
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.
-------
Table 2-6. Dioxin/Furan Stack Emission Rate, Strand Baghouse Outlet
Congener
2,3,7,8 -TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF2
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Average Concentration
Runs 3 - 5
ng/dscm
0.079
0.182
0.0261
0.286
0.118
0.136
0.1351
1.99
0.685
0.629
0.269
0.097
0.056
0.0173
0.062
<0.045
<0.065
Average Emission Rate
Mg/Hr
36.5
84.1
12.0'
132
54.7
62.9
62.4'
919
316
290
124
44.6
25.9
7.723
28.5
<20.7
<30.2
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.
2-8
-------
Table 2-7. Dioxin/Furan 2,3,7,8-TCDD Toxicity Equivalent Stack Gas
Concentrations, Strand Baghouse Outlet
Congener
2,3,7,8 -TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDD
TEF1
1
0.5
0.1
0.1
0.1
0.01
0.001
ng/dscm
Run 3
0.0731
0.0789
0.00316
0.0266
0.0118
0.00141
0.000078
Run 4
0.0915
0.093
0.00237
0.0288
0.0114
0.00137
0.00027 12
Run 5
0.0728
0.102
0.002372
0.0305
0.0124
0.00130
0.000056
Total PCDD
2,3,7,8-TCDF3
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.001
0.191
0.0291
0.266
0.0249
0.00880
0.00581
<0.00332
0.000631
<0.000664
<0.0000997
0.217
0.0398
0.356
0.0288
0.0103
0.00542
0.000684
0.000644
<0.000339
0.0000288
0.190
0.0338
0.321
0.0271
0.00981
0.00541
0.00 102"
0.000575
<0.000338
<0.000677
Total PCDF
Average
0.0791
0.0912
0.002632
0.0286
0.0118
0.00136
0.0001 352
0.215
0.199
0.0342
0.314
0.0269
0.0097
0.00555
0.001674
0.000617
<0.000447
<0.0000654
0.592
'TEF, Toxicity Equivalent Factor
2Maximum value, may include interference from a diphenyl ether
Determined from DB-225 GC column
4The amount detected is less than 5 times the detection limit and should be considered only an estimate.
2-9
-------
Table 2-8. PAH Concentration, Strand Baghouse Outlet, Runs 3 through 5
PAHs
Naphthalene
2-Methylnaphthalene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Ideno( 1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Concentration, pg/dscm
Runs
3
486
386
<0.920
31.4'
18.3'
36.9
245
42.7
128
52.5
19.81
29.4'
7.71'
3.17'
3.70'
1.48'
<0.488
<0.390
<0.538
0.286'
4
446
373
3.03'
31.8'
17.2'
35.0
205
31.5'
88.7
51.4
20.0'
38.8
9.05'
3.90'
4.90'
1.97'
• <0.539
<0.431
<0.595
<0.475
5
502
387
<1.27
40.4
21.61
49.1
299
58.5
150
60.3
23.7'
35.5
9.66'
1.31'
4.22'
2.76'
<0.645
<0.479
<0.638
<0.496
Average
478
382
1.74'
34.51
19.0'
40.3
250
44.2'
122
54.8
21.2'
34.6'
8.81'
2.79'
4.28'
2.07'
<0.557
<0.433
<0.590
<0.419
%RSD
6.0
2.0
64.9
14.8
11.9
18.9
18.8
30.7
25.5
8.9
10.5
13.8
11.3
47.7
14.1
31.2
14.3
10.2
8.5
27.6
'Amount detected is less than 5 times the detection limit and should be considered only an estimate.
2-10
-------
Table 2-9. PAH Concentration, Strand Baghouse Outlet, Runs 1 through 5
PAHs
Naphthalene
2-Methylnaphthalene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Ideno(l,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Concentration, ug/dscm
Runs
1
506
419
2.93'
35.9
21.6'
44.0
248
44.3
131
58.7
29.3'
47.4
15.4'
4.37'
7.27'
3.611
0.894'
<0.394
<0.544
0.575'
2
481
394
2.06'
31.21
17.3'
38.7'
234
39.4'
98.4
60.3'
23.6'
38.8'
12.0'
4.04'
5.58'
2.82'
<1.75
<1.40
<1.94
<1.55
3
486
386
<0.920
31.41
18.3'
36.9
245
42.7
128
52.5
19.8'
29.4'
7.71'
3.17'
3.70'
1.48'
<0.488
<0.390
<0.538
0.286'
4
446
373
3.03'
31.81
17.2'
35.0
205
31.5'
88.7
51.4
20.0'
38.8
9.05'
3.90'
4.90'
1.97'
<0.539
<0.431
<0.595
<0.475
5
502
387
<1.27
40.4
21.6'
49.1
299
58.5
150
60.3
23.7'
35.5
9.66'
1.31'
4.22'
2.76'
<0.645
<0.479
<0.638
<0.496
Average
484
392
2.04'
34. 11
19.2'
40.7'
246
43.3'
119
56.6'
23.3'
38.0'
10.8'
3.36'
5.14'
2.53'
<0.864
<0.618
<0.850
<0.675
%RSD
4.9
4.3
46.5
11.7
11.5
14.0
13.8
22.8
21.2
7.7
16.6
17.2
27.9
36.5
27.0
32.6
60.3
70.8
71.5
73.8
'Amount detected is less than 5 times the detection limit and should be considered only an estimate.
-------
Table 2-10 shows the average PAH stack emission rate from the Strand baghouse outlet
using data from Runs 3 through 5. These values were calculated from the average concentrations
from Table 2-8 and the average stack flow rate from Table 2-3. All PAH analytical raw data can
be found in Appendix B.
2.3 Metals HAPs Results
2.3.1 Overview
Nine metals emission test runs were completed at Youngstown Sinter Company during
the week of August 11, 1997. Three test runs were completed at the Strand baghouse inlet, three
at the Strand baghouse outlet, and three at the outlet of Baghouse A. 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 2-11 through 2-19 show the results of the analysis, by fraction by analyte, for each
of the three samples collected at the outlet and at the inlet of the Strand baghouse and the three
Baghouse A outlet samples 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. These data have not been
blank corrected (see Section 6 for further discussion). Using the results shown in Tables 2-11
through 2-19 and the sample volume collected in the corresponding train given in Table 2-2, the
concentration of each metal in the stack gas was calculated. The concentration (ug/dscm) of
each metal by run number, the average concentration and %RSD for the Strand baghouse inlet
and outlet tests are given in Tables 2-20 and 2-21, respectively, and given in Table 2-22 for the
Baghouse A outlet. The %RSDs reported in Table 2-20 by metal are generally less than 15%
indicating excellent reproducibility. Tables 2-21 and 2-22 present a higher overall
2-12
-------
Table 2-10. PAH Stack Emission Rate, Strand Baghouse Outlet
PAHs
Naphthalene
2-Methylnaphthalene
2-ChloronaphthaIene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
B enzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Ideno( 1 ,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Average Concentration
Runs 3-5
(ug/dscm)
478
382
1.74'
34.5'
19.0'
40.3
250
44.2'
122
54.8
21.2'
34.6'
8.81'
2.79'
4.28'
2.07'
<0.557
<0.433
<0.590
<0.419
Average Emission Rate
(g/hr)
221
176
0.804'
16.01.
8.80'
18.8
115
20.4'
56.3
25.3
9.79'
16.0'
4.07'
1.29'
1.98'
0.956'
<0.257
<0.200
<0.273
<0.194
'Amount detected is less than 5 times the detection limit and should be considered only an estimate.
2-13
-------
Table 2-11. Metals Results: Strand Baghouse Inlet, Run 1 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
I
1. 32
21.9
<0.100
74.5
29.7
242
6270
43.2
14800
5.2
31.2
2
3.25
4.13
<0.115
20.4
11.2
40.9
859
10.2
3830
<0.462
27.3
3
<0.280
4
10.4
5
<1.10
Total
<16.3
26.0
<0.215
94.9
40.9
283
7129
53.4
18630
5.66
58.5
Table 2-12. Metals Results: Strand Baghouse Inlet, Run 2 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
0.422
16.7
<0.100
66.5
16.5
203
4900
37.2
16700
7.79
18.3
2
4.03
5.48
<0.114
27.0
1.32
35.0
824
11.0
4700
<0.456
42.8
3
<0.392
4
10.6
5
<1.20
Total
<16.6
22.2
<0.214
93.5
17.8
238
5724
48.2
21400
8.25
61.1
2-14
-------
Table 2-13. Metals Results: Strand Baghouse Inlet, Run 3 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
16.7
<0.100
63.2
18.6
207
5240
41.2
16000
6.96
23.8
2
8.16
5.39
<0.113
21.9
2.18
39.3
877
13.2
4810
<0.450
53.4
3
<0.504
4
10.5
5
<0.600
Total
<20.2
22.1
<0.213
85.1
20.8
246
6117
54.4
20810
7.14
77.2
Table 2-14. Metals Results: Strand Baghouse Outlet, Run 1 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
1.51
<0.100
1.93
0.64
10.4
17.3
6.83
120
4.46
4.46
2
14.4
1.6
<0.116
<0.116
0.534
12.9
27.7
2.34
4.48
<0.465
110
3
<0.360
4
10.7
5
<1.18
Total
<27.04
3.11
<0.216
<2.046
1.174
23.3
45.0
9.17
124
<4.93
114
2-15
-------
Table 2-15. Metals Results: Strand Baghouse Outlet, Run 2 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
1.43
<0.100
0.209
. 0.48
15.8
18.1
11.5
110
8.56
8.02
2
15.0
1.44
<0.114
0.446
<0.156
14.2
352
3.31
6.77
<0.454
102
3
<0.304
4
13.5
5
<1.20
Total
<30.4
2.87
<0.214
0.655
<0.636
30.0
370
14.8
117
<9.01
110
Table 2-16. Metals Results: Strand Baghouse Outlet, Run 3 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
1.18
<0.100
0.116
0.41
12.8
18.6
8.51
116
6.37
6.36
2
16.4
0.615
<0.114
0.314
<0.114
10.4
66
3.01
7.47
<0.457
79
3
<0.200
4
10.7
5
<0.800
Total
<28.5
1.80
<0.214
0.430
<0.524
23.2
84.6
11.5
123
<6.83
85.4
2-16
-------
Table 2-17. Metals Results: Baghouse A Outlet, Run 1 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb '
Se
Fraction #
1
<0.400
1.16
<0.100
<0.100
1.13
13.8
12.1
10.4
6.62
8.2
7.36
2
<1.96
<0.628
<0.126
<0.126
<0.126
1.52
13.4
0.979
6.33
<0.503
<0.377
3
<0.200
4
<0.488
5
<0.408
Total
<3.46
<1.79
<0.226
<0.226
<1.26
15.3
25.5
11.4
13.0
8.70
7.74
Table 2-18. Metals Results: Baghouse A Outlet, Run 2 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
1.12
<0.100
<0.100
0.270
14.7
12.8
9.42
8.98
7.74
6.98
2
<2.72
<0.586
<0.117
0.210
<0.117
7.03
259
8.15
4.64
<0.469
<0.352
3
<0.320
4
<1.22
5
<1.04
Total
<5.70
<1.71
<0.217
0.310
<0.387
21.7
272
17.6
13.6
<8.21
<7.33
2-17
-------
Table 2-19. Metals Results: Baghouse A Outlet, Run 3 (ug collected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Fraction #
1
<0.400
1.03
<0.100
<0.100
0.24
12.9
10.6
8.49
21.2
6.82
6.32
2
<2.52
<0.594
<0.119
0.215
<0.119
10.2
114
12.6
4.76
<0.475
<0.357
3
<0.256
4
<1.22
5
<0.800
Total
<5.20
<1.62
<0.219
<0.315
<0.359
23.1
125
21.9
26.0
<7.30
<6.68
Table 2-20. Metals Stack Gas Concentration: Strand Baghouse Inlet
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
ug/dscm
Runl
5.78
9.22
0.076
33.7
14.5
100
2528
18.9
6606
2.01
20.7
Run 2
5.99
8.01
0.077
33.8
6.43
85.9
2066
17.4
7726
2.98
22.1
Run 3
6.92
7.57
0.073
29.1
7.12
84.2
2095
18.6
7127
2.45
26.4
Average
6.23
8.27
0.075
32.2
9.35
90.2
2230
18.3
7153
2.48
23.1
%RSD
9.71
10.3
2.99
8.18
47.9
9.82
11.6
4.44
7.83
19.6
12.9
2-18
-------
Table 2-21. Metals Stack Gas Concentration: Strand Baghouse Outlet
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
ug/dscm
Runl
4.62
0.532
0.037
0.350
0.201
3.98
7.69
1.57
21.2
0.842
19.5
Run 2
5.30
0.500
0.037
0.114
0.111
5.23
64.5
2.58
20.4
1.57
19.2
Run 3
5.14
0.325
0.039
0.078
0.095
4.19
15.3
2.08
22.2
1.23
15.4
Average
5.02
0.452
0.038
0.180
0.135
4.47
29.1
2.07
21.3
1.21
18.0
%RSD
7.08
24.6
2.39
81.8
42.2
14.9
106
24.4
4.29
30.1
12.6
Table 2-22. Metals Stack Gas Concentration: Baghouse A Outlet
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
ug/dscm
Runl
1.48
0.768
0.097
0.097
0.541
6.57
10.9
4.89
5.58
3.73
3.32
Run 2
2.46
0.737
0.094
0.134
0.167
9.35
117
7.59
5.86
3.54
3.16
Run 3
2.44
0.761
0.103
0.148
0.169
10.8
58.7
10.3
12.2
3.43
3.14
Average
2.13
0.755
0.098
0.126
0.292
8.92
62.3
7.59
7.88
3.57
3.21
%RSD
26.2
2.15
4.80
20.8
73.8
24.3
85.5
35.5
47.5
4.35
3.16
2-19
-------
reproducibility at less than 35%. In the case where a %RSD is higher, the concentrations
detected are near the detection limit. Increased variability is not unusual in this case. The value
of Mn in fraction 2 of the Strand baghouse Run 2 outlet (see Table 2-15) is high and not
consistent with the other two runs. The most likely cause is laboratory contamination as the
other metals results are consistent over the three test runs. The same situation was encountered
for Baghouse A outlet Run 2 (see Table 2-18).
Using the average concentration values listed in Tables 2-21 and 2-22 and the average
stack flow rate from Table 2-3 , the average emission rate from the Strand baghouse and
Baghouse A outlets for each metal can be calculated. These results, in grams per hour, are given
in Table 2-23 and 2-24, respectively. Using these values from Table 2-23 in conjunction with the
equivalent values for the inlet (see Table 2-25), a removal efficiency for the Strand baghouse
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 as used for
the collection of metals at the Strand baghouse inlet and outlet and Baghouse A outlet. 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 of three test runs and %RSD for the three test
runs at the inlet and outlet are presented in Table 2-26. The %RSD for the inlet of the Strand
baghouse was less than 26% indicating good reproducibility for the sampling and analysis
method. The %RSD for the outlet of the Strand baghouse was 56% and 38% for Baghouse A
outlet. This higher variability is most likely due to the gravimetric measurements made on very
low amounts of particulate matter collected.
2-20
-------
Table 2-23. Metals Stack Emission Rate, Strand Baghouse Outlet
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Average Concentration
pg/dscm
5.02
0.452
0.038
0.180
0.135
4.47
29.1
2.07
21.3
1.21
18.0
Average Emission Rate
g/Hr
2.35
0.212
0.018
0.084
0.063
2.09
13.6
0.969
9.97
0.566
8.43
Table 2-24. Metals Stack Emission Rate, Baghouse A Outlet
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Average Concentration
Hg/dscm
2.13
0.755
0.098
0.126
0.292
8.92
62.3
7.59
7.88
3.57
3.21
Average Emission Rate
g/Hr
0.287
0.102
0.013
0.017
0.039
1.20
8.41
1.02
1.06
0.482
0.433
2-21
-------
Table 2-25. Strand Baghouse Removal Efficiency for Metals
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Average Emission
Rate Inlet
g/Hr
3.48
4.63
0.042
18.0
5.23
50.5
1247
10.2
4001
1.39
12.9
Average Emission
Rate Outlet
g/Hr
2.35
0.212
0.018
0.084
0.063
2.09
13.6
0.969
9.97
0.566
8.43
Removal
Efficiency1
%
32.6
95.4
57.6
99.5
98.8
95.9
98.9
90.5
99.8
59.2
34.8
% Removal Efficiency =
Inlet Rate-Outlet Rate
Inlet Rate
x 100
Table 2-26. Participate Matter Concentration
Location
Strand Baghouse Inlet
Strand Baghouse Outlet
Baghouse A Outlet
g/dscm
Runl
1.56
0.00226
0.00172
Run 2
0.935
0.000697
0.00216
Run 3
1.19
0.00126
0.000939
Average
1.23
0.0014
0.0016
%RSD
25.7
56.2
38.4
2-22
-------
Table 2-27 shows the average PM emission rate from the Strand baghouse to be
1.44 pounds per hour (Ib/hr). This value was calculated from the average outlet concentration
from Table 2-26 and the average stack flow rate from Table 2-3. Using this value in conjunction
with the equivalent value for the inlet (see Table 2-27), a PM removal efficiency for the Strand
baghouse was calculated to be 99.9%. The emission rate of paniculate from Baghouse A is
0.48 Ib/hr. The PM analytical raw data are given in Appendix D.
Table 2-27. Particulate Matter Emission Rates and Removal Efficiency
Location
Strand Baghouse
Baghouse A
Average Inlet Rate
Ib/Hr
1515
NA
Average Outlet Rate
Ib/Hr
1.44
0.476
Removal
Efficiency1
%
99.9
NA
% Removal Efficiency =
Inlet Rate - Outlet Rate
Inlet Rate
x 100
2-23
-------
3.0 Youngstown Sinter Company's Sinter Plant (Prepared by RTI)
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 recover lime from wastes and to convert limestone to lime, which 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, blast furnace flue dust, coke breeze (undersize coke that cannot be used in the
blast furnace), and dolomite.
There are currently 10 sinter plants in operation in the U.S. A total of 6 of these plants
use scrubbers to control emissions from the sinter plant windbox, and 4 use a baghouse. The
sinter plant at Youngstown Sinter Plant, Youngstown, OH, a wholly owned subsidiary of WCI
Steel Company, was chosen for testing to evaluate hazardous air pollutants and emission control
performance associated with sinter plants that use baghouses.
3.2 Process Description
The Youngstown sinter plant is operated by Youngstown Sinter Company, a wholly
owned subsidiary of WCI Steel. The plant was purchased from LTV Steel Company and was
brought on line in June 1991. The sinter plant is located a few miles from the WCI Steel
integrated iron and steel plant in Warren, OH. The integrated plant includes one blast furnace, a
basic oxygen furnace (EOF) shop containing two EOF vessels, ladle metallurgy, continuous
casting, rolling mills, and galvanizing lines. The sinter plant has a capacity of 60,000 tons per
month (tpm) and operates 24 hours per day with 2 days scheduled downtime every seven days for
routine maintenance. 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 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
Ore fines
Mill scale
Limestone
Flue dust
Coke breeze
EOF slag
Pellet chips
Dolomite
Composition (% of feed)
27.70
12.79
12.15
9.07
0.63
16.51
19.73
1.42
Feed Rate (tons/day)
880
406
385
288
20
524
625
4.5
The raw materials are brought into the sinter plant by truck and are stored at the site.
Two feeder tables blend mill scale, EOF slag, and crushed ore pellets by volume, and the mixture
is transferred by conveyor to the sinter plant and fed into the sinter machine through a series of
bins. Limestone, dolomite, coke fines, and cold fines recycled from the sintering process are also
contained in bins and are blended into 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 so that the sinter mixture does not burn through to the grate, and then the feed
mix is added to a depth of about 17 inches. The plant has found that a deeper bed results in
fewer fines being generated.
The sinter feed passes through an ignition furnace, and the surface of the sinter feed is
ignited with natural gas. The sinter pallets move continually through the ignition furnace at
-------
law materials
preblend (consisting of mill
scale, BOF slag, and crushed
>re pellets); coke breeze;
imestone; dolomite; and
lue dust]
•«* Stack
r -c" i
Baghouse
;
Raw
material bins
Water
Pug ,
Sta
.
Dust
returns *
Natural
gas
r _ Hearth
""* mill ' layer *
Cold fines return
ck
^ ~\
Windbox
Baghouse _
2
"t"
Dropout ^
boxes
Windbox
exhaust
Sintering
machine* t
windboxes
T ' '
Fugitives from various
transfer points, conveyors, etc.
A.
tack
"N.
"A" \
Baghouse A
^
A •
^ Stack : f
! ir
Chemical dust
suppressant
1
Alternate
truck
loadout
A L
;
[Cooler II Truck
Baghouse II loadout 1
Water spray ^
«;_ Sintp
Air wnire
Breaker Sinter ^ S
and screen ^ cooler
I Hearth layer returns
r
>inter product
screening
FIGURE 1. SCHEMATIC OF MATERIAL FLOW IN SINTER PLANT
-------
about 6.3 to 7.0 feet per minute over 21 vacuum chambers called "windboxes." A vacuum is
created in the windbox by a 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 250-foot linear four-stack sinter
cooler. The sinter is removed from the cooler and transported by covered conveyor to the truck
loadout station. The sinter plant has two truck loadout stations, and all of the sinter is transported
to the blast furnace by truck. The larger station is evacuated to a hood which goes to the cooler
baghouse; the building is open but has a curtain over each end to contain emissions with an
opening for the trucks to enter and exit.
The smaller truck loadout station is used to provide more capacity and is normally used to
handle production from the midnight shift; the station utilizes chemical dust suppression. The
sinter is transferred by a covered conveyor from the sinter cooler to a storage building as needed,
and is then transferred by a covered conveyor to the truck loadout station. Emissions from the
sinter storage building are evacuated to the A baghouse. SoLong, manufactured by Midwest, is
used for dust suppression at the truck loadout station. The chemical acts as a polymer and binds
the dust to the sinter during truck loading; SoLong is applied to the sinter as the product exits the
covered conveyor and drops into the bed of each truck. Very little emissions from the loading
process were observed to escape capture at the larger truck loadout station. Some emissions
were observed from the unenclosed area at the top of the conveyor and from the truck as the
sinter was being loaded. Dust emissions were minimal but were noticeable depending on the
truck being loaded. 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 percentage of oil in each of the
feed materials is analyzed and the total amount of oil in the sinter feed is limited to less than 0.1
percent. To maintain the proper chemistry in the blast furnace, an important quality control
parameter that is monitored is the sinter basicity:
(CaCM-MgO)/(SiO2+Al2O3)
The sinter composition for the four tests days is summarized in Table 3-2 and shows that the
sinter basicity ranged from 2.72 to 2.92.
Table 3-2. Summary of Sinter Composition
Component
Fe
SiO2
A1A
CaO
MgO
Sinter basicity
Percent of total
Test 1
(08/12/97)
53.23
4.82
0.90
14.69
2.09
2.90
Test 2
(08/13/97)
52.23
5.47
0.98
15.30
2.16
2.72
Test 3
(08/14/97)
52.42
5.21
0.91
15.03
2.23
2.84
Test 4
(08/15/97)
52.20
5.17
0.89
15.40
2.28
2.92
3.4 Emission Control Equipment
Emissions are generated in the process as sinter dust and combustion products are
discharged through the grates and the 21 windboxes to a common collector main and are then
collected by the strand baghouse. The pulse jet baghouse is manufactured by Environmental
Elements and uses Nomex® bags that are coated with an acid-resistant finish. There are fourteen
modules, each containing 306 bags. The bags are 6 inches in diameter and 15 feet in length, and
-------
the total cloth area for each module is 7,215 square feet. The gross air-to-cloth ratio is 3.96
acfm/ft2 and the net air-to-cloth ratio, with one module off-line for cleaning is 4.26 acfm/ft2.
The flow to the baghouse is approximately 400,000 cubic feet per minute. A preheat
burner is used to minimize condensation and to bring the gas up to the desired inlet temperature.
The dust is removed from the baghouse by rotary screw to bins where it is stored on the ground
to gather moisture and is blended back into the sinter feed. The parameters associated with the
baghouse that are monitored include the pressure drop across the baghouse, inlet temperature,
stack temperature, damper percent, and fan amps.
Typical operating conditions associated with the baghouse are summarized in Table 3-3.
Current State regulations limit paniculate matter to 50 pounds per hour for the strand baghouse.
Table 3-3. Typical Baghouse Parameters
Parameter
Pressure drop
Gas flow rate
Inlet temperature
Outlet temperature
Damper Percent
Fan Amps
Typical value
10 to 13 inches of water
400,000 scfm
235 to 270 °F
120°F
90%
659-735
Three additional baghouses are used to control emissions from the sinter plant. The C
baghouse, a pulse jet baghouse utilizing polyester bags, is used to control emissions from the
material handling bins and the conveyors that transfer the sinter mix to the sinter machine. The
cooler baghouse controls emissions from the sinter cooler and from the main truck loadout
station. The baghouse is a shaker baghouse that utilizes Nomex® bags and contains nine
compartments. Eight of the compartments are used for the cooler and one compartment is used
-------
for the truck loadout station. There are four 200 horsepower fans on the sinter cooler. The first
fan is the dirtiest fan and is directed back to hoods on the sinter machine and sent back through
as preheat air. The other 3 fans are ducted to the baghouse. In addition, the truck loadout station
has a 70,000 cubic feet per minute fan. These baghouses were not evaluated as part of this test
program.
The A baghouse that serves the discharge end of the sinter plant was evaluated as part of
this test program. A schematic of A baghouse is shown in Figure 2. This baghouse controls
emissions from discharge end emission points, including the hood before the sinter machine; the
hood over sinter discharge; the sinter breaker and hot screen which is enclosed by a cloth curtain;
the tail end of the sinter cooler; emissions from each of the ten sinter feed bins; a variety of
transfer points for the transport of sinter, dust, and fines; and emissions from sinter bins located
in the sinter overflow storage area. At any point where there is hot sinter, emissions are first
ducted to a cyclone before going to the baghouse.
The plant sprays the roads twice per week to minimize dust emissions, except during the
winter months. All of the baghouses are monitored on a weekly basis by an outside contractor,
Fastway, Inc., to check the operation and for any visible opacity. A whole compartment is dye-
tested if there is more than 5 percent visible emissions observed, and the broken bags are then
replaced. Every other month, a complete compartment of either the strand or cooler baghouse is
replaced; each compartment is replaced approximately every 3 years.
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 temperatures and the fan draft for the windboxes, percent water in the feed, sinter
machine speed, and the temperature of each of the four cooling fans. In addition, the turn
supervisor's report provided additional information, including tons per hour of pre-blend, and
-------
Sinter storage bins
Yi
A Baghouse
Cooler tail
S = Sinter
D = Dust
B = Burden
Figure 2. Schematic of Pick-Up Points for A Baghouse.
-------
tons per 8-hour turn of limestone, dolomite, coke fines, and cold fines. The emission control
device parameters that were monitored included the pressure drop across the baghouse, damper
percent, inlet temperature, stack temperature, fan amps, and the pressure drop of each of the 14
compartments of the baghouse. Tables 3-4 and 3-5 present a summary of the range df values for
these parameters for each test period. Table 3-6 presents a summary of the pressure drops of
each compartment of the baghouse for the four days of testing.
The process and control device appeared to be stable throughout the four test days;
consequently, sampling was conducted under normal and representative conditions. An
examination of the monitoring data showed that the average pressure drop across the baghouse
was 10.8, 12.0, 12.9 and 13.5 inches of water for the 4 test days. The pressure drop across the
baghouse did increase slightly during each day of testing. On the third day, the compartments
were double cleaned to try to reduce the pressure drop. The temperatures and draft of the
windboxes varied somewhat during the tests; plant operators stated that the temperature of
windboxes 19 and 20, should generally be 475-500 °F to achieve proper burnthrough of the
sinter bed.
During each run of testing performed on A baghouse, the pressure drops of each
compartment and the pressure drop across the baghouse were monitored periodically, generally
every 20 to 30 minutes. The plant does not monitor any other parameters on A baghouse; since
the A baghouse is responsible for the capture and control of dust sources throughout the sintering
process, malfunctions are readily apparent. Table 3-7 presents a summary of the pressure drops
of each compartment and the pressure drop across the baghouse during each test period.
3.6 Analysis of Monitoring and Test Results
Table 3-8 summarizes the emission results for each run for key pollutants from the outlet
of the control device on the sinter strand, 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 pressure drop across the strand
baghouse increased over the four days of testing, from an average of 10.78 on the first day of
testing, to an average of 13.48 on the final day of testing. However, the results were fairly stable
and did not appear to be impacted by the increased pressure drop over the course of testing.
Table 3-9 presents emission results for each run for key pollutants from the A baghouse outlet.
Particulate matter and HAP metal emissions were fairly steady over three runs. One
interesting factor is that while paniculate matter emissions during Run 2 were three times lower
than during Run 1, and two times lower than during Run 3, HAP metal emissions were steady
over the course of the three runs. The major metal HAPs that were found were lead and
manganese; both were effectively captured and controlled by both the Strand baghouse and A
baghouse.
Another interesting result is the very low emission rate of dioxins, relative to what had
been reported from testing at German sinter plants. 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 results for this sinter plant was much lower, with
an average concentration of 0.807 ng TEQ/m3. On the basis of sinter production, the Germans
reported emission levels in the range of 10 to 100 ,ug/Mg of sinter compared to a measured level
of 0.6 /ug/Mg of sinter for this plant. The WCI 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 WCI'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
WCI plant, like most U.S. integrated plants, has eliminated the purchase and use of chlorinated
organics in their facility. Their rolling mill oils (lubricants and hydraulic fluids) do not contain
10
-------
chlorinated compounds. In addition, routine analysis of waste materials going to the sinter plant
have not detected chlorinated solvent. Finally, the WCI plant does not use an electrostatic
precipitator. Consequently, dioxin rates at WCI that are much lower than those reported by
German sinter plants appear to be reasonable and explainable.
A surprising result is the emission rate of polycyclic aromatic hydrocarbons (PAHs) that
was measured during the testing. Emissions for PAHs were slightly higher than paniculate
matter emissions from the outlet of the strand baghouse. These results were consistent over all
test runs; even though the first two test runs resulted in questionable data, the results still are
consistent with the remaining three test runs. It is not known if the higher emissions were
present in the inlet stream or if the baghouse performed poorly in the capture and control of
PAHs emissions, since inlet testing for PAHs was not performed. The major PAHs present in
the outlet stream were naphthalene and 2-methylnaphthalene, with 3,660 and 2,920 pounds per
year being emitted respectively.
Table 3-10 presents a summary of particulate matter and metal HAP results for the strand
baghouse, including concentrations, efficiencies, annual emission rates, and emissions factors for
each metal HAP. Table 3-11 presents similar results for polycyclic aromatic hydrocarbons and
dioxins and furans. Table 3-12 presents a summary of results for the A baghouse for particulate
matter and metal HAPs. The information contained in Tables 3-11 and 3-12 does not contain
efficiencies since inlet testing was not performed.
11
-------
Table 3-4. Process Parameter Ranges During The Tests
Parameter
Test 1
(8/12/97)
Test 2
(8/13/97)
Test 3
(8/14/97)
Test 4
(8/15/97)
Feed rate:
Pre-blend (ore) (tons/hour)
Limestone (tons/turn)
Dolomite (tons/turn)
Coke fines (tons/turn)
Cold fines (tons/turn)
120
144
43
19
1738
120
114
39
17
1545
120
167
43
18
1787
120
Other parameters:
Percent water
Grate speed (feet/min)
Windbox 1 temperature (°F)
Windbox 1 draft (in. H2O)
Windbox 3 temperature (°F)
Windbox 3 draft (in. H2O)
Windbox 13 temperature (°F)
Windbox 13 draft (in. H2O)
Windbox 18 temperature (°F)
Windbox 18 draft (in. H2O)
Windbox 19 temperature (°F)
Windbox 19 draft (in. H2O)
Windbox 20 temperature (°F)
Windbox 20 draft (in. H2O)
Windbox 21 temperature (°F)
Windbox 21 draft (in. H2O)
7.0 - 7.2
—
177-211
18.0-22.1
167-195
16.2-20.3
187-266
—
327-463
14.7-18.3
396-542
16.4-21.1
373-580
14.5-18.9
—
14.9-17.7
6.7 - 7.6
—
150-202
20.3-23.5
108-186
18.6-21.5
184-233
—
251-459
16.6-19.9
357-513
18.4-21.9
391-546
17.0-20.7
360-465
15.7-19.3
6.8-7.0
—
157-207
19.5-22.3
149-181
18.1-20.5
169-231
—
288-457
15.7-18.5
350-460
18.0-20.4
372-496
16.2-18.9
332-429
15.1-17.5
6.7 - 6.8
6.3 - 7.0
166-220
19.5-21.8
159-198
18.0-20.1
165-342
—
301-521
16.0-17.8
363-545
17.2-20.5
385-545
16.5-18.6
355-443
15.3-17.2
12
-------
Parameter
Test 1
(8/12/97)
Test 2
(8/13/97)
Test 3
(8/14/97)
Test 4
(8/15/97)
Cooling Fan Temperatures (°F)
A
B
C
D
420-463
505-546
430-460
185-243
411-460
405-544
205-458
116-237
395-415
456-530
372-440
157-200
376-413
456-507
385-435
172-192
Table 3-5. Control Device Operating Parameters — Windbox Baghouse
Parameter
Pressure drop (in. H2O)
Inlet Temp. (°F)
Stack Temp. (°F)
Fan amps
Damper (%)
Test 1
(08/12/97)
9.30-11.87
242 - 265
243 - 248
684 - 735
88.9-90.1
Test 2
(08/13/97)
10.60-12.59
217-253
231-248
667-690
89.5-91.2
Test 3
(08/14/97)
11.61-13.57
211-245
216-243
667-694
88.8-90.9
Test 4
(08/15/97)
12.09-14.12
217-236
227-248
659-690
89.0-90.8
13
-------
Table 3-6. Pressure Drop Across Each Compartment of The Windbox Baghouse
Compartment
Pressure Drop
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Total
Test 1
(08/12/97)
7.0-8.6
8.2-9.2
7.1-8.6
5.6-8.0
7.1-8.5
6.6-7.9
6.4-8.0
6.7-8.4
7.6-9.4
7.1-9.0
6.8-8.9
7.6-9.4
6.4-9.0
6.4-9.2
9.9-11.5
Test 2
(08/13/97)
6.8-9.3
6.7-9.6
8.6-9.8
6.8-8.8
8.0-9.8
7.8-9.3
7.1-9.4
6.0-8.8
8.6-9.9
7.8-9.7
7.3-9.4
8.8-10+
7.6-10+
7.6-10+
10.0-11.5
Test3
(08/14/97)
7.0-9.6
6.9-9.8 .
9.4-10+
7.4-9.8
9.1-10+
8.3-9.9
8.9-10.0
7.7-9.7
9.4-10+
9.3-10+
8.5-10+
9.6-10+
9.8-10+
9.4-10+
11.4-12.3
Test 4
(08/15/97)
8.6-9.9
8.0-10.0
9.9-10+
7.9-10+
10.0-10+
8.9-10+
9.7-10+
7.2-10+
9.5-10+
9.9-10+
8.2-10+
10+
10.0-10+
8.5-10+
12.0-13.0
Table 3-7. Pressure Drop Across Each Compartment of "A" Baghouse
Compartment
1
2
3
4
Total
Test 1 (08/15/97)
2.6-3.8
2.8-3.7
4.7-5.5
4.4-6.0
7.7-8.1
Test2&3 (08/1 6/97)
3.0-4.7
3.7-5.5
1.5-2.0
5.5-7.4
7.9-10.9
14
-------
TABLE 3-8. Strand Baghouse Summary of Results for Each Test Run
Test Day
Sinter production
Baghouse AP
Windbox 20 Temp.
Baghouse Inlet Temp.
Baghouse Outlet Temp.
Parameter
PM" — outlet
Pb — outlet
Mn — outlet
HAP metals — outlet
Units
tons/hour
in. H:O
OF
op
oF
Units
Ib/hr
Ib/hr
Ib/hr
Ib/hr
Dioxin/furan congeners'1
Dioxin/furan TEQC
7 PAHsu
16PAHs
Total PAHs
//g/hr
/ug/hr
g/hr
g/hr
g/hr
Dayl
110
10.78
474
252
246
Runl
2.35
0.0220
0.0080
0.0628
Runs 1 & 2
Questionable
data;
unacceptable
leak checks
Day 2
110
12.00
467
240
240
Run 2
0.71
0.0209
0.0661
0.1224
Run 3
2,142
342
28.90
510
691
Day 3
110
12.88
446
230
230
Run 3
1.30
0.0229
0.0158
0.0681
Run 4
2,444
404
34.75
457
634
Day 4
110
13.48
457
231
238
Runs4&5
Not
necessary to
do more
than 3 runs
Run 5
2,186
375
33.88
575
755
Average
110
12.28
461
238
238
Average
1.45
0.0219
0.0300
0.0845
Average
2,257
374
32.51
514
693
° PM = paniculate matter
h 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
u PAH = polycyclic aromatic hydrocarbons
Table 3-9. A Baghouse Summary of Results for Each Test Run
Parameter
PM" — outlet
Mn — outlet
HAP metals — outlet
Units
Ib/hour
Ib/hour
Ib/hour
Runl
0.53
0.0033
0.012
Run 2
0.67
0.036
0.046
Run 3
0.26
0.016
0.028
Average
0.48
0.019
0.029
' PM = paniculate matter
15
-------
Table 3-10. Strand Baghouse Summary of Results for Particulate Matter and Metal HAPs
Pollutant —
Particulate Matter
Pollutant — HAP
Metals
Mercury
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Manganese
Nickel
Lead
Antimony
Selenium
HAP metals
Inlet
Ib/hr
1,520
g/dscm
1.23
Concentration
(/^ g/dscm)
Inlet
6.23
8.27
0.075
32.2
9.35
90.2
2230
18.3
7153
2.48
23.1
9,573
Outlet
5.02
0.452
0.038
0.180
0.135
4.47
29.1
2.07
21.3
1.21
18.0
82
Outlet
Ib/hr
1.45
g/dscm
0.0014
Emission rate
(g/hr)
Inlet
3.5
4.6
0.04
18.0
5.2
50.5
1,247
10.2
4,001
1.4
12.9
5,354
Outlet
2.35
0.21
0.02
0.08
0.06
2.09
13.62
0.97
9.97
0.57
8.42
38
Efficiency
%
99.9
Efficiency
(%)
32.5
95.4
57.7
99.5
98.8
95.9
98.9
90.5
99.8
59.3
34.7
99.3
Annual Rate,b tpy
Inlet
5,700
Outlet
5.36
Annual rate (tpy)
Inlet
0.03
0.04
0.00
0.15
0.04
0.41
10.16
0.08
32.61
0.01
0.11
44
Outlet
0.02
0.00
0.00
0.00
0.00
0.02
0.11
0.01
0.08
0.00
0.07
0.31
Emission Factor (Ib/ton of sinter)
Inlet
13.8
Outlet
0.013
Emission factor (Ib/t sinter)
Inlet
7.0 x 10'5
9.3 x ID'5
8.4 x 10'7
3.6 x 10-4
1.0 xlO'4
l.OxlO'3
2.5 x 10'2
2.0 x 10-4
8.0 x 10'2
2.8 x 10'5
2.6 x 10^
1.1 x 10"'
Outlet
4.7 x 10 5
4.2 x 106
3.6 x 10'7
1.7x lO'6
1.3x 10'6
4.2 x 10'5
2.7 x 10'4
1.9xlO'5
2.0 x 10-4
1.1 x lO'5
1.7x10-"
7.7 x 10"4
a PM = particulate matter
b Based on operation for 24 hours per day, 6 days per week, 52 weeks per year (7400 hours/year).
16
-------
Table 3-11. Strand Baghouse Summary of Results for PAHs and Dioxin/Furans
Pollutant — Polycyclic Aromatic
Hydrocarbons (PAHs)
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
B enzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Ideno( 1 ,2,3-cd)pyrene
7 PAHs (Total)
Acenaphthene
Acenaphthylene
Anthracene
Benzo(g,h,i)perylene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Outlet
g/hr
9.79
0.956
4.07
1.29
16.0
<0.273
<0.200
32.6
8.80
16.0
20.4
<0.194
56.3
18.8
221
115
25.3
/wg/dscm
21.2
2.07
8.81
2.79
34.6
0.590
0.433
70.7
19.0
34.5
44.2
0.419
122
40.3
478
250
54.8
Annual Emissions, Outlet of
Control Device3
tpy
0.0799
0.0078
0.0332
0.0105
0.1305
0.0022
0.0016
0.266
0.072
0.1305
0.1664
0.0016
0.459
0.1534
1.80
0.938
0.206
Emission Factor,
Sinter Basis
Outlet of Control
Device
Ib/ton
1.96xl04
1.92x10-'
8.16x10-'
2.58x10''
3.21X10"4
5.47xlO'6
4.01xlO'6
6.53x10-"
1.76X10"1
3.21X10'4
4.09X1Q-4
3.89x1 0'6
1.13xlO'3
3.77x10^
4.43xlO'3
2.30x10-'
5.07X10"4
17
-------
Pollutant — Polycyclic Aromatic
Hydrocarbons (PAHs)
16 PAHs (Total)
2-methylnaphthalene
2-chloronaphthalene
Benzo(e)pyrene
Perylene
Total PAHs
Pollutant — Dioxin/Furans
D/F congenersb
D/F TEQC
Outlet
g/hr
514
176
0.804
1.98
<0.257
693
/ug/dscm
1114
382
1.74
4.27
0.557
1503
Outlet
Mg/hr
2,257
374
ng/dscm
4.877
0.807
Annual Emissions, Outlet of
Control Device"
tpy
4.19
1.44
0.0066
0.0162
0.0021
5.65
Annual Emissions, Outlet of
Control Devicd"
grams/year
16.70
2.77
Emission Factor,
Sinter Basis
Outlet of Control
Device
Ib/ton
1.03X10'2
3.53x10-'
1.61X10'5
3.97x1 Q-5
5.15xlO'6
1.39xlO'2
Emission Factor,
Sinter Basis
Outlet of Control
Device
Ib/ton
5.11xlO-8
8.48xlO'9
a Based on operation for 24 hours per day, 6 days per week, 52 weeks per year (7400 hours/year).
h 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.
18
-------
Table 3-12. Discharge End Baghouse ("A") - Results for Particulate Matter and Metal
Haps
Pollutant — Particulate
Matter
PMa
Pollutant — Metal
HAPs
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Mercury
Manganese
Nickel
Lead
Antimony
Selenium
HAP metals
Outlet
Ib/hr
0.48
gr/dscf
0.0007
Outlet
g/hr
0.10
0.013
0.017
0.039
1.2
0.29
8.4
1.0
1.1
0.48
0.43
13.1
/ug/dscm
0.755
0.098
0.126
0.292
8.92
2.13
62.3
7.59
7.88
3.57
3.21
96.9
Emissions'1
tpy
1.8
Emissions'1
tpy
0.0008
0.0001
0.0001
0.0003
0.0099
0.0024
0.070
0.0084
0.0086
0.0040
0.0036
0.11
Emission Factor
Ib/ton sinter
0.0044
Emission Factor
Ib/ton sinter
2.4 x 10'6
2.6 x 10'7
3.4 x 10'7
7.8 x 10'7
2.4 x 10'5
5.8 x 10'6
1.7 x 10"4
2.0 x 10's
2.2 x 10'5
9.6 x 10'6
8.6 x 10'6
2.6 x 10"4
a PM = particulate matter
b Based on operation for 24 hours per day, 6 days per week,
52 weeks per year (7400 hours/year)
19
-------
4.0 SAMPLING LOCATIONS
The sampling locations used during the emission testing program at the Youngstown
Sinter Company are described in this section. Flue gas samples were collected at the inlet and
outlet of the sintering plant Strand baghouse and Baghouse A outlet using four ports for the inlet
and two ports for the outlets. The configurations of the sampling locations are shown in
Figures 4-1,4-2, and 4-3.
The test ports and their locations met the requirements of EPA Method 1. The Strand
baghouse inlet location was a rectangular duct with dimensions of 11' by 10' with four 4" ports
installed on the vertical 10' side. The Strand baghouse outlet location was a circular stack with
an inside diameter (ID.) of 9 feet. The Baghouse A outlet was a circular stack with an I.D. of 6'.
The position and number of traverse points for each location are shown in Figures 4-4, 4-5, and
4-6, respectively.
4-1
-------
0
U)
D
O
D)
CO
c
CO
FTIR Port
Flow
Manual Test Ports
26'
_OB
0.
O)
c
0
CO
1
Figure 4-1. Strand Baghouse Inlet Sampling Location
-------
91 I.D.
64'9" 60'
II
I
Figure 4-2. Strand Baghouse Outlet Sampling Location
-------
1
75' 70'
1 1
6' I.D.
Figure 4-3. Baghouse A Outlet Sampling Location
-------
17"
8'4"
11'
«
112"
82"
52"
22"
10'
i-ii
Figure 4-4. Strand Baghouse Inlet Traverse Point Layout
-------
O\
FTIR
Figure 4-5. Strand Baghouse Outlet Traverse Point Layout
-------
Figure 4-6. Baghouse A Traverse Point Layout
-------
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 paniculate 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 front half of the 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
-------
Ul
K>
(Q
(D
cn
2
IV)
CD
Q>
i!
3
Glass Probe Liner
Glass Probe Tip
Thermometer
5.
Glass Filter Holder
Silica Gel
D»tM *
Pilot Manometer
5% HNO3/10%H2O2
4% KMnO4/10% H2SO4
Orifice
Dry Gas
Meter
Vacuum Gauge
Air-tight
Pump
-------
assembly with a Teflon® filter support, a series of impingers and a standard 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 (H2O2)
solution;
• An empty knockout impinger;
• Two impingers with a 4% potassium permanganate (KMnO4)/10% sulfuric acid
(H2SO4) 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% HNO-,
for 12 hours, rinsed with Type n water, and then rinsed with acetone. This procedure included
all the glass components of the sampling train including the glass nozzles plus any 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 and 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 H2O rinse (X3).a
4. Soak in 10% HNO3 solution for 12 hours.
5. Distilled/Deionized H2O 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 was used was recorded.
The HNO3/H,O2 and KMnO4/H2SO4 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
were used. Pitot tubes were 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 were 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
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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 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 H2O. 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 (Yj) 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
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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 nipple 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 using clean glass U-tube connectors and
arranged in the impinger bucket. The height of all the impingers was approximately the same to
aid in obtaining a leak free seal. The open ends of the train were sealed with Parafilm®.
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,
sealing greases were not used. The train components were transferred to the sampling location
and assembled as previously shown in Figure 5-1.
5-7
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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 reached 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 acfm (ftVmin) 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 every five minutes on standard data forms. A
checklist for sampling is included as Table 5-2.
5-8
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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, and in correct order.
3. Check for data sheets and barometric pressure.
4. Sampling equipment needs to be ready for Method 3 analysis.
5. Leak check pi tot 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. 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
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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, CO2, O2) sample
(if applicable).
5. Blow back pitot tubes 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-
weighed impinger from the 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
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Table 5-2. Continued
5. Disassemble train. Cap sections. Take sections to recovery trailer.
6. Nozzle 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
<150mL.
b) - Rinse nozzle and probe 3X with O.IN HNO3
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
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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 began 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 before removal to the
recovery trailer. All train components were rinsed and the samples collected in separate,
prelabeled, precleaned sample containers.
Once in the trailer, 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 of the flue gas. Following the 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
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Probe Liner
and Nozzle
Front Half of
Filter
Housing
Rinse with
Acetone
Brush liner
with
nonmetallic
brush &
rinse with
acetone
Check liner
to see if
paniculate
removed; if
not, repeat
step above
Brush with
nonmetallic
brush &
rinse with
acetone
Rinse three
times with
0.1NHNO3
Rinse three
times with
0.1NHN03
FH AR
(3)' (2)
Filter support &
back half of filter
housing
• Number in parentheses indicates container number
Figure 5-2. Method 29 Sample Recovery Scheme
5-13
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I
Empty the
ImpingcrNu. 4
contents into
container
Rinse with
100 mL
0. IN HMO,
(UN HMO,
(SA)
4ih Impinger
(Empty) and 5th
;md 6th impingcrs
(Acidified KMnO4)
Measure
impingcr
contents
KMnO4
(SB)
I
Empty the
inpingcrs
Nas. 5 & 6
contents into
ituincr
Rinse three times
with permanganate
reagent, then with water
Remove any
residue with
25mL8N
HC1 solution
Last Impingcr
Weigh tor
moisture
Discard
KNHC1
(SC)
Method 29 Sample Recovery Scheme, Continued
Figure 5-2. Continued
5-14
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particulate remains and finished with a final acetone rinse of the probe and brush. The front half
of the filter holder 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 HNO3 and placed into a separate amber bottle. The bottle was capped tightly, weighed and
the liquid level marked. Approximately 100 mL of this rinse was required. The filter was placed
in a clean, well-marked glass petri dish (Container 1) and sealed with Teflon® tape.
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 content of the knockout impinger was recovered into a pre-weighed, pre-labeled
bottle with the contents from the HNO3/H2O2 impingers (Container 4). These impingers and
connecting glassware were rinsed thoroughly with 0. IN HNO3, the rinse captured in the impinger
contents bottle, and a final weight taken. Again, the method specifies a total of 100 mL of 0. IN
HNO3 be used to rinse these components. A nitric acid reagent blank of approximately the same
volume as the rinse volume was collected 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 collected in a separate container.
After final weighing, the silica gel from the train was saved for regeneration. The
ground glass fittings on the silica gel impinger were wiped clean after sample recovery to assure
a leak tight fit for the next test.
5-15
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A reagent blank was recovered in the field for each of the following reagents;
• Acetone blank - 100 mL sample size;
• 0. IN 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);
• Deionized water - 200 mL sample size; and
• Filter blank - one each.
Each reagent blank was of the same lot as 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 at each location 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 correction factor may be used to scale the final results depending on the volume of
the loss.
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:
5-16
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• 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 0.1N nitric acid rinse;
• Fraction 5b—Impinger 5-6 contents plus 100 mL permanganate and 100 mL water
rinses; and
• Fraction 5c~25 mL 8N HC1 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 10la where the permanganate is the only collection medium. Using an instrumental
detection limit (DDL) 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
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.
5-17
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Table 5-3. Analytical Detection Limits
Metal
Hg
As
Be
Cd
Cr
Pb
Sb
Co
Mn
Ni
Se
IDL
Hg/mL
0.0002
0.005
0.001
0.001
0.002
0.002
0.004
0.001
0.002
0.003
0.003
Analysis Fraction
1, "g
0.4
1.0
0.2
0.2
0.4
0.4
0.8
0.2
0.4
0.6
0.6
2,ug
0.6
1.13
0.23
0.23
0.45
0.45
0.9
0.225
0.45
0.68
0.68
3, ug
0.2
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
4, ug
0.6
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
5,ug
i M§
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Total
Detectable
Amount
ug
2.8
2.1
0.43
0.43
0.85
0.85
1.7
0.43
0.85
1.28
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.
5-18
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Table 5-4. Method 29 Detection Limits
Sampling Time, Hours
Sampling Rate, cfm
Sampling Volume, m3
Hg
As
Be
Cd
Cr
Pb
Sb
Co
Mn
Ni
Se
4
0.75
5.1
MDL, jig/m3
0.55
0.41
0.08
0.08
0.17
0.17
0.33
0.08
0.17
0.25
0.25
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 room temperature
in a tared beaker. The residue was desiccated for 24 hours in a desiccator containing activated
silica gel. The filter was also desiccated under the same conditions. Each was then weighed to a
constant weight, reporting the weight gain to the nearest 0.1 mg. Replicate weighings were
performed until two consecutive weighing agreed to within 0.5 mg or 1% of total weight less tare
5-19
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weight, whichever was greater, between two consecutive weighings, at least 6 hours apart. The
balance room was temperature and humidity controlled. The filter tare and final weights were
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 taken 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/nozzle
(Container No. 3). This combined solution was then acidified to a pH of 2 with concentrated
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 was then divided for analysis by CVAA for Hg (following additional digestion) and by
ICAPS for the other target metals.
5-20
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Container 3
Acid Probe Rinse
(Labeled FH)
Reduce volume to near dryness
and digest with HF & cone.
HNO3
Container 2
Acetone Probe Rinse (Labeled
AR)
Acidify to pH 2 with cone.
HNOj
Reduce to dryness in a tared
beaker
Determine residue weight in
beaker
Solubilize residue with cone.
HNO,
Container 1
Filter
(Labeled F)
Desiccate to constant weight
Determine filter paniculate
weight
Divide into 0.5 g sections &
digest each section with cone.
HF & HMO,
to
Filter & dilute to known volume
Anal. Fraction 1
r
Analyze by ICAP for target
metals Anal. Fraction 1A
Analyze for metals by GFAAS*
Anal. Fraction 1A
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 aliquot for Hg using
CVAAS
'Analyze by AAS for metals found at less than 2 ug/mL in digestate solution, if desired. Or analyze for each metal by AAS, if desired.
Figure 5-3. Method 29 Sample Preparation and Analysis Scheme
-------
Container 4 (HNO,/H2O2) Impingers
(Labeled BH) (inlcude condensate
impinger, if used)
Aliquot taken for CVAAS
for Hg analysis Anal.
Fraction 2B
Digest with acid and
permanganate at 95 °C for
2 h and analyze for Hg by
CVAAS
Acidify remaining sample
to pH 2 with cone. HNO,
Anal. Fraction 2A
Reduce volume to near
dryness and digest with
HNO, & H,02
Analyze by ICAP for 15
target metals
Analyze by GFAAS for
Metals*
Containers 5A, 5B, & 5C
Individually, three
separate digestions and
analyses: digest with acid
and permanganate at
95 °C for 2 hand analyze
for Hg by CVAAS
Analytical Fractions 3A,
3B, & 3C
*Analysis by AAS for metals found at less than 2 ug/mL in digestate solution, if desired. Or analyzed for each metal
by AAS, if desired.
Figure 5-3. Continued
5-22
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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 ICAPS 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 6010A 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.
5.1.7.1 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).
5-23
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Standards less than 1 //g/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. One quality control sample was analyzed
to check the accuracy of the calibration standards. If the results were not within 10% the
calibration was repeated.
5.1.7.2 Cold Vapor Atomic Absorption Standards and Quality Control Samples
A lOyUg/mL intermediate Hg standard was prepared fresh weekly. A daily 200 mg/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 lO^g/mL standard and diluting it until the control sample
was within the calibration range. These procedures assessed the quality control of the analysis,
but did not address the potential negative bias due to Hg losses from the filter due to
volatilization during gravimetric analysis.
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-/?-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:
5-24
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to
heated glass liner
temperature
W sensor
^>»
Gas Flow
•S'type
pilot
manometer
XAO-2 nap
temperature
• sensor
circulation
pump
calibrated
orifice
manometer
i-l •' N
ice
bath
empty
-*--*-
diygas
meter
it
-x-
x coarse
I -^ri- vacuum pump
'acuum
gauge
Figure 5-4. Method 23 Sampling Train Configuration
-------
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.
5.2.2.1 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/nozzle
brushes) were cleaned following the same procedure except that no baking was performed.
5-26
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Table 5-5. Method 23 Glassware Cleaning Procedure (Train Components,
Sample Containers and Laboratory Glassware)
NOTE: USE VFTON® 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 H2O rinse (X3).a
4. Bake at 450°F for 2 hours.6
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).
!1(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
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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.
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-/?-dioxin (TCDD),
tetrachlorodibenzofurans (TCDF) or PAHs. If these analytes are found, the filters are re-
extracted until the analyte was 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, were discarded. Acceptable filters were stored in a
pre-cleaned petri dish, labeled by date of analyses and sealed with Teflon® tape.
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.
5-28
-------
.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 were found, the resin was re-extracted. If methylene chloride was found, the resin
was dried until the excess solvent was removed. The absorbent was 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.
Referenced calibration procedures were followed when available. The results were documented.
5.2.3 Method 23 Sampling Operations
5.2.3.1 Preliminary Measurements
Prior to sampling, 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 nipple length, and the
distances to the nearest upstream and downstream flow disturbances. These measurements were
5-29
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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 was carefully inspected for hairline cracks. The first impinger was a knockout
impinger which had 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,
each containing 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 impinger were
recorded on a recovery data sheet. The heights of all the impingers were approximately the same
to aid in obtaining a leak free seal. The open ends of the train were sealed with methylene
chloride-rinsed aluminum foil.
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 was turned on. When the
system reached the appropriate temperatures, the sampling train was ready for pre-test leak
5-30
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checking. 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 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 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.
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 every five minutes on standard data forms. A checklist for
CDD/CDF sampling is included as 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, pilot cleaning, thermocouple malfunctions, heater malfunctions
or any other unusual occurrances.
5-31
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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 CO2/O2 needs to be ready except when using CEMs for CO2/O2
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
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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, CO2, O2), 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
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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
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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 was at
least one inch Hg higher than the highest vacuum attained during sampling. An acceptable leak
rate was less than 4% of the average sample rate or 0.02 acfm (whichever is lower).
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 minimize
sample degradation by exposure to light.
The probe and nozzle was first rinsed with approximately 100 mL of acetone and
brushed to remove any paniculate. 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 (H2O) were discarded.
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 could interfere with the quantitative analytical determinations.
5-35
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Ui
I
u>
p
N
robe P
ozzle L
robe Cy
iner
clone Front
Filler
Half of Filter Back h
lousing Support Filter H
(alfof Conn
ousing Li
ecting Conde
ne
nser
1
Rinse with Acetone Attach
Until all Participate 250 mL flask Brush and Brush and
is Removed to Ball Joint rinse with rinse with Rinse with Rinse with Rinse with Rinse with
acetone (3x) acetone (3x) acetone (3x) acetone (3x) acetone (3x) acetone (3x)
Rinse wi
ofM
0
Rinse
Toluene
*This
Rinse with
Acetone
Empty Flask
into 950 m L
Bottle
Brush Liner and Rinse
with 3 Aliquots of
Acetone
Check Liner to see if
Paniculate is
removed; if not, repeat
h 3 Aliquots Rinse with Rinse with Rinse with
ethylene 3 Aliquots 3 Aliquots 3 Aliquots
loride ofMelhylene ofMethylene ofMethylene
Chloride Chloride Chloride
with Rin
(3x)* Tolu
se with Rins
sne (3x) Tolue
e with Rins
,ne (3x) Tolue
fraction should not be combined with the other toluene
fractions
Rinse with methylene Rinse with Rinse with
chloride (3x) (at least methylene methylene
once let the rinse stand chloride chloride (3x)
5 min in unit) (3x) (at least once let
the rinse stand
5 min in unit)
Recover into
pre weighed
bottle
PR ;:/.••
e with Rinse with "
ne (3x) (at least on«
stand 5 m
PRT/CRT
"oluene (3x) Rinss
, let the rinse Toluet
n in unit)
: with Toluene (3
le (3x) least once 1
rinse stand
in unit
x)(at
etthe
5 min
)
Figure 5-5. Method 23 Field Recovery Scheme
-------
Filter
Carefully
remove filler
from support
with tweezers
Resin Trap
Secure XAD
trap openings
with glass balls
and clamps
1st Impinger
(knockout)
Weigh
Impinger
2nd Impinger
Weigh
Impinger
3rd Impinger
Weigh
Impinger
4th Impinger
Weigh
Impinger
5th Impinger
(silica gel)
Weigh
Impinger
Ui
OJ
Brush loose
Paniculate
onto Tiller
Seal in
petri dish
Place in cooler
for storage
,. I F.-
Record weight
and
calcula
te gain
Record weight
and
calcula
te gain
Record weight
and
calcula
te gain
. Record weight
and
calcula
te gain
Record weight
and
calculate gain
Save for
regeneration
Discard
Note: See Table 5-5 for Sample Fractions Identification
'••. .:-:.SM •:,-.:;
Figure 5-5. Continued
-------
The train components recovered in the field are listed in Table 5-7. The sorbent
modules were 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.
Table 5-7. Method 23 Sample Fractions Shipped To Analytical Laboratory
Container/
Component
1
2
3
4
5
Code
F
Pi*
PRT
CRT
SM
1C
Fraction
Filter(s)
Acetone and methylene chloride rinses of
nozzle/probe, cyclone, front half/back filter
holder, filter support, connecting
glassware, condenser
Toluene rinse of nozzle/probe, cyclone,
front half/back half filter holder, filter
support, connecting line and condenser
XAD-2® resin trap (sorbent module)
Contents of Impingers 1-4 (H,O) plus
methylene chloride rinses
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
5-38
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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-p-dioxins (TCDD)
1,2,3,7,8-pentachlorodibenzo-p-dioxin (1 ,2,3,7,8-PeCDD)
Total pentachlorinated dibenzo-p-dioxins (PeCDD)
l,2,4,5,7,8-hexachlorodibenzo-p-dioxin(l,2,3,4,7,8-HxCDD)
1 ,2,3,6,7,8-hexachlorodibenzo-p-dioxin ( 1 ,2,4,5,7,8-HxCDD)
Total hexachlorinated dibenzo-p-dioxins (HxCDD)
l,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin(l,2,3,4,6,7,8-HpCDD)
Total heptachlorinated dibenzo-p-dioxins (HpCDD)
Total octachlorinated dibenzo-p-dioxins (OCDD)
FURANS:
2,3,7,8-tetrachlorodibenzofurans(2,3,7,8-TCDF)
Total tetrachlorinated dibenzofurans (TCDF)
l,2,3,7,8-pentachlorodibenzofuran(l,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-heptachlorodibenzofuran (1 ,2,3,4,7,8,9-HpCDF)
Total heptachlorinated dibenzofurans (HpCDF)
Total octachlorinated dibenzofurans (OCDF)
5-39
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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
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Spikewith4ngD/FIS
Organics SS
Spikes-I. Ill, &V
Organics SS Soike-l
d,-Phenol lOOug
1,4-Dibromobenzene-d4 100 ug
Organics SS Spike-11
d,-Nitrobenzene lOOug
2-FIuorobiphenyl lOOug
1,3,5-Trichlorobenzene-d, 100 ug
Qrganics SS Spike-lV
2,4,6-Tribromophenol 100 ug
Organics SS Spike-lV
Anthracene-d,,, lOOug
Organics SS Spike-lV
Pyrene-d,,, 100 ug
Impinger
+
Condensate
Spike with D/F AS
4 ng Organics SS
Spikes-11 & IV
Analyze for PCDDs/Fs Method 8290X
Extraction and Analysis Schematic for Method 23 Samples
Figure 5-6. Extraction and Analysis Schematic for Method 23 Samples
5-41
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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.
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.
5-42
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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
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
Field Blanks
Glassware Proof Blank
Method Blank
Reagent Blanks
Collection
One run collected and
analyzed
Each train to be used (2) will
be loaded and quantitatively
recovered prior to sampling
At least one for each
analytical batch
One 1000 mL sample for
each reagent and lot
Analysis
Analyze with flue gas
samples
Archive for potential analysis
Analyze with each analytical
batch of flue gas samples
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®).
5-43
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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, condenser 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
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. The train was prepared as if for sampling, 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 help
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.
5-44
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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.
5.2.7 Analytes and Detection Limits for Method 23
The target analytes are the tetra- through octachlorinated dibenzodioxins and
chlorinated dibenzofurans. 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 fjL of which a 2 ,uL 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
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Table 5-11. Analytical Detection Limits For Dioxins/Furans
Analyte
Tetra CDDs
Penta CDDs
Hexa CDDs
Hepta CDDs
Octa CDDs
Tetra CDFs
Penta CDFs
Hexa CDFs
Hepta CDFs
Octa CDFs
Total Detectable Amount, ng
5
25
25
25
50
5
25
25
25
50
NOTE: D/F analysis by High Resolution Mass Spectrometry assumes a 2 /uL injection of a
200 yL sample extract.
5-46
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Table 5-12. CDD/CDF Method Detection Limits
Sampling Time, Hours
Sampling Rate, cfm
Sample Volume, m3
Tetra CDDs
Penta CDDs
Hexa CDDs
Hepta CDDs
Octa CDDs
Tetra CDFs
Penta CDFs
Hexa CDFs
Hepta CDFs
Octa CDFs
4
0.75
5.1
MDL, ng/m3
0.98
4.9
4.9
4.9
9.8
0.98
4.9
4.9
4.9
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. Due to the high levels of some PAHs, the extracts
were analyzed using low resolution mass spectrometry. Table 5-13 lists the analytical detection
limits for each of the PAHs to be determined.
5-47
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Table 5-13. Analytical Detection Limits For PAHs
Analyte
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthraene
Benzo(b)fluoranthene
Benzo(k)fluorenthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
2-Chloronaphthalene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno( 1 ,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Phenanthrene
Pyrene
Total Detectable Amount, //g
20
10
10
10
10
10
10
10
10
10
10
10
20
35
10
150
900
10
100
15
5-48
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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.
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 sampling
were dictated by EPA Method I 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 ID. 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 pilots 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
5-49
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Table 5-14. PAH Method Detection Limits
Sampling Time, Hours
Sampling Rate, cfm
Sample Volume, m3
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
2-Chloronaphthalene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l ,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Phenanthrene
Pyrene
4
0.75
5.1
MDL, jig/m3
8
4
4
4
4
4
4
4
4
4
4
4
8
14
4
59
350
4
40
6
5-50
-------
point, as applicable. A computer program was used to calculate the average velocity during the
sampling period.
5.4.3 O2 and CO2 Concentrations by EPA Method 3
The O2 and CO, concentrations were determined by using a Fyrite analyzer following
EPA Method 3. Flue gas was extracted from the duct for analysis. The Method 3 analysis for O2
and CO2 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
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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, except for the first
and second D/F/PAH sampling runs. Five total D/F/PAH runs were performed in order to obtain
sufficient data of good quality. Isokinetic sampling rates were kept within the 10% of 100% for
all test runs. Acceptable 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, except as
discussed for Runs 1 and 2.
6-1
-------
Table 6-1. Summary of D/F/PAH Leak Checks, Strand Baghouse Outlet
Date
8/12/97
8/13/97
8/14/97
8/15/97
Run #/Port
1/B
I/A
2/B
2/A
3/B
3/A
4/B
4/A
5/A
5/B
Initial leak
Check
0.010 @ 10"
0.010® 16"
0.009 @ 10"
0.014® 15"
0.004 @ 19"
Port Change
Leak Check
Broken by-pass
Broken by-pass
0.010 @ 10"
0.014 @ 12"
0.006 @ 17"
Final Leak Check
Not Taken
Stopped sampling @ 1 Hour
0.009 @ 12"
0.020 @ 17"
0.004 @ 19"
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.
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
6-2
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Table 6-2. Summary of Isokinetic Percentages
Date
Run#
Percent Isokinetic
Multi-Metals — Strand Baghouse Inlet
8/12/97
8/13/97
8/14/97
1
2
3
101
104
105
Multi-Metals — Strand Baghouse Outlet
8/12/97
8/13/97
8/14/97
1
2
3
97.1
96.7
92.7
Multi-Metals — Baghouse A Outlet
8/15/97
8/15/97
8/16/97
1
2
3
94.3
92.8
94.9
Dioxin/PAHs — Strand Baghouse Outlet
8/12/97
8/13/97
8/1 3 and 8/1 4/97
8/14/97
8/15/97
1
2
3
4
5
99.2
99.9
102
99.3
101
6-3
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Table 6-3. Dry Gas Meter Post Calibration Results
Sampling Train
D/F/PAH, Strand Baghouse Outlet
Metals/PM, Strand Baghouse Outlet
Metals/PM, Strand Baghouse Inlet
and Baghouse A Outlet
Meter Box
Number
39
36
38
Full
Calibration
Factor
0.996
0.997
0.984
Post-Test
Calibration
Factor
1.001
0.990
0.978
Post-Test*
Deviation %
0.5
-0.7
-0.6
Post - Full
Full
x 100
Table 6-4. Dioxin/Furan Field Blank Analysis Results
Congener
2,3,7,8 -TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Field Blank
ng Detected
<0.01
<0.02
<0.02
<0.01
<0.01
<0.02
0.07
0.05
<0.01
<0.01
<0.01
<0.007
<0.01
<0.01
<0.01
<0.02
<0.03
Lab Method Blank
ng Detected
<0.01
<0.03
<0.03
<0.02
<0.02
<0.03
<0.07
<0.01
<0.02
<0.02
<0.02
<0.01
<0.01
<0.02
<0.02
<0.03
<0.05
6-4
-------
1,2,3,4,7,8-HxCDF, but at levels at the detection limit and much lower 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.
6.7.2 Metals/PM Sampling QC
Tables 6-5 and 6-6 list the pre- and post-test and port change leak check results for the
Strand baghouse outlet and inlet sampling trains respectively. Table 6-7 lists the leak check
results for the Baghouse A outlet. 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.
Table 6-8 presents the analytical results for the three Method 29 field blanks, a reagent
blank train (which was prepared from components consisting of an unused filter, and aliquots of
nitric acid, deionized water and hydrogen peroxide reagents) and the average of the three
sampling runs performed at each of three locations (Strand baghouse inlet and outlet and
Baghouse A outlet). Of the target metals found in the reagent blank train more than 90% of the
amount detected can be attributed to the filter The amounts of Hg, As, Be, Cd, Co, Cr, Ni, Sb,
and Se detected in the three field blanks are equivalent to that detected in the reagent field blank
and again coming from contributions from the filter. The consistency between these data for
these metals indicate that good sample recovery was achieved and that no residual sample was
6-5
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Table 6-5. Summary of Metals Train Leak Checks, Strand Baghouse Outlet
Date
8/12/97
8/13/97
8/14/97
Run #/Port
I/A
1/B
2/B
2/A
3/A
3/B
Initial leak
Check
0.011 @ 15"
0.009 @ 12"
0.012 @ 15"
Leak Check
0.009 @ 10"
0.002 @ 18"
0.011 @ 18"
Final Leak
Check
0.006 @ 16"
0.011 @ 19"
0.008 @ 19"
Table 6-6. Summary of Metals Train Leak Checks, Strand Baghouse Inlet
Date
8/12/97
8/13/97
8/14/97
Run #/Port
I/A
1/B
1/C
1/D
2/A
2/B
2/C
2/D
3/A
3/B
3/C
3/D
Initial leak
Check
0.008 @ 10"
0.015 @ 15"
0.00 @ 10"
Leak Check
0.0088 @ 14"
0.025 @ 14"
0.00 @ 14"
0.00 @ 15"
0.00 @ 15"
0.00 @ 10"
0.002® 11"
0.016 @ 13"
0.016 @ 22"
Final Leak
Check
0.009 @ 10"
0.018 @ 15"
0.012 @ 23"
6-6
-------
Table 6-7. Summary of Metals Train Leak Checks, Baghouse A Outlet
Date
8/15/97
8/15/97
8/16/97
Run #/Port
I/A
1/B
2/B
2/A
3/A
3/B
Initial leak
Check
0.016 @ 10"
0.020 @ 10"
0.020 @ 10"
Leak Check
0.016 @ 13"
0.020 @ 15"
0.016 @ 10"
Final Leak
Check
0.016 @ 13.5"
0.20 @ 14"
0.012 @ 15"
Table 6-8. Metals QC Results: (ug detected)
Metal
Hg
As
Be
Cd
Co
Cr
Mn
Ni
Pb
Sb
Se
Strand
Baghouse
Outlet
Field Blk
<4.008
1.56
<0.200
0.219
0.310
13.7
95.6
9.36
26.0
7.43
6.67
Strand
Baghouse
Inlet
Field Blk
<4.21
1.497
<0.200
0.432
0.390
10.6
304
7.71
156
4.90
4.56
Baghouse
A Outlet
Field Blk
<2.82
1.53
<0.200
<0.200
0.320
14.8
4.92
10.2
1.40
8.94
8.01
Train
Reagent
Blk
<4.67
1.45
<0.200
<0.200
0.430
14.5
8.33
8.79
1.21
8.03
7.06
Average Run Values
Strand
Outlet
28.6
2.59
<0.215
1.04
0.778
25.5
167
11.8
122
6.92
103
Strand
Inlet
17.3
27.2
0.314
91.8
26.6
111
6460
56.1
20304
7.51
75.0
Baghouse
A Outlet
<4.79
1.71
<0.221
<0.284
0.667
20.1
141
16.7
17.5
8.07
7.25
6-7
-------
carried over to the next train being prepared. However, carry over to the next train being
prepared most likely occurred for Mn and Pb as indicated by the high levels detected in the Stand
Baghouse inlet and outlet field blanks compared to the reagent field blank and the Baghouse A
field blank. This carry over is probably due to the significantly higher levels of these two metals
collected in the trains during the three sampling runs and not laboratory contamination or field
contamination. This carry over may have biased high the results for these two metals in the
Strand Baghouse data. The Baghouse A results do not appear to be affected by any analyte carry
over. The results presented in this report have not been blank corrected.
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.
6-8
-------
• 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.
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 13C12-1,2,3,4,7,8,9-
HpCDF in Run 3 at the Strand baghouse outlet. The percent recovery was 68.8%, which was just
outside of the lower limit of 70%. This low recovery will have no effect on the reported results.
PAH—The sample extracts were analyzed after sample dilution by HRGC/LRMS, due
to the high level of many of the PAHs found in the samples. The sample extracts were analyzed
following the protocol given in EPA Method 8270A. The internal standard areas for Runs 1 and
3 were high for chrysene-d,2 and perylene-d,2 specificed in Method 8270A quality control
criteria. The perylene-d,2 internal standard was high for Runs 4 and 5 only. This high value was
observed each time after multiple analysis indicating the likely presence of a matrix effect. The
analytes quantified against the internal standards should be considered as estimates (see
Appendix B for raw data).
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
6-9
-------
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, and lead in the front half sample were within the ±10% RPD
criterion. Chromium had a RPD of 24.5% which does not indicate any significant interferent.
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 lead
in the front half sample were within 75-125% range. The level of spike for this metal was
insignificant compared to the native amount and could not be quantitated. The percent recovery
for all of the metals except selenium in the back half sample were within the acceptance criterion.
Again, the level of spike for selenium was insignificant compared to the native amount and could
not be quantitated.
No ICAP metals except nickel were detected in the laboratory method blank above the
instrument detection limit. Nickel was detected at 6.55 ug/L which is not considered significant
based on the detection limit (less than 3 times the DL). 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 front-half (filler and probe rinses) and back-half (nitric
acid/peroxide) impinger contents, as well as KMNO4, nitric, and hydrochloric acid rinses.
Percent recoveries for all sample spikes were within the acceptance criterion of 75-125. All
6-10
-------
laboratory control spikes and laboratory control spike duplicates were also within this acceptance
criterion. .
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.
6-11
-------
TECHNICAL REPORT DATA
(Pleat ftttd Insouciant on the smrar teforv comflletutgt
REPORT NO.
EPA-454/R-99-C41 a
2.
3. RECIPIENT'S ACCESSION NO..
TITLE AND SUBTITLE
Integrated Iron and Steel Industry Final Report Manual Testing
Volume I of m - Youngstown Sinter Company Youngstown, Ohio
9. REPORT DATE .-»::i ,.,
Ssptenter 1999 . •"
, «***-
ft, PERFORMING ORGANIZATfOttCODI
AUTHORISI
ft, PERFORMING ORGANIZATION MWQirr NO.
EMAD
INQ OHOANIZATION NAME AND ADDRESS
1O. PROGRAM ELEMENT NO..
Eastern- flesearth
EF?A- Cbntv
2. SPONSORING AGENCY NAME AND ADDRESS
'U.S..Bpyironmental.Protection Agency
Research Triangle Park, N-.C. 27711
IX TYPE OP REPORT AND PUKOO COVERED
14. SPONSORING AGENCY COD!
EPA/2GO/C4
9. SUPPLEMENTARY NOTES
••i ~. -V4 i*'."
6. ABSTRACT
The purpose of the testing at the Youngstown Sinter Company (YSC) plant in Yciurig^tcwn-;:.unijo was to perform
all activities necessary to characterize the baghouse sintering plant windbox (Strand :Bagfiouse)' for the
following emission ccmponents: 1) Particulate matter and metal HAPs using EPA' Method, 29;. and:2) .Dioxins/
furans (D/F) and polynuclear aromatic hydrocarbons (PAH) using EPA Method 23 in supportr of "a national
emission standard for hazardous air pollutants (NESHAP) for the Integrated Iron and Steels Manufacturing
category. . : . ..- ..-. . -;.»••-,• . ......
Sampling was also performed on the discharge end baghouse (Baghouse A) for PM and'
7. MACT Rule Support
KEY WORDS AND DOCUMENT ANALYSIS.
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Fiekl/Gioup
MACT Support for,the •
Integrated Iron and Steel
Industry (Sintering)
18. DISTRIBUTION STATEMENT
RELEASE UNLMTTH)
19. SECURITY CLASS i Tlia Keponi
21. NO. OF PAGES
135
20. SECURITY CLASS iT'itis page.
22. PRICE
EPA Fetm 2220-1 (R«». 4—77) PREVIOUS EDITION is OBSOUETE
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