United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 2771 1
EPA-600/2-79-190
September 1979
Research and Development
&EPA
Level 1 Assessment
of Uncontrolled Q-BOP
Emissions
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-190
September 1979
Level 1 Assessment of Uncontrolled
Q-BOP Emissions
by
C. W. Westbrook
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, N.C. 27709
Contract No. 68-02-2630
Task No.3
Program Element Nos. 1AB604C and 1BB610C
EPA Project Officer: Robert V. Hendriks
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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CONTENTS
Page
ABSTRACT 1i i
FIGURES v
TABLES vi
ACKNOWLEDGEMENT viii
1.0 INTRODUCTION 1
2.0 CONCLUSIONS 2
3.0 TEST DESCRIPTION 5
3.1 Q-BOP Facility, Republic Steel, Chicago, Illinois 5
3.2 Sampling Equipment Preparation and Sample Recovery 10
4.0 TEST RESULTS 19
4.1 On-Site Results 19
4.2 Analysis of SASS Samples 20
4.2.1 Total Particulate Loading 20
4.2.2 Level I Organic Analysis 20
4.2.3 GC-MS Analysis 23
4.2.4 Inorganic Analysis 24
APPENDICES
A. LEVEL I ORGANIC ANALYSIS OF SAMPLE 1C1F, IX, AND INORGANIC
ANALYSIS DATA 53
B. OBSERVATIONS OF ACUREX AND RTI PERSONNEL 73
IV
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FIGURES
Fjgure
1 Schematic of Q-BOP vessel 6
2 Q-BOP emission control system 7
3 Sampling Site on Secondary Gas Cleaning System 14
4 SASS field data 15
5 Analytical procedures 21
A-l GC-MS Total Ion Plot for Sample IX, LC2 and 3 66
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TABLES
Table Page
1 Summary of Particulate Data—Uncontrolled Emissions 2
2 Summary of Organic Data—Uncontrolled Emissions 3
3 Distribution of Inorganics Exceeding MATE Values 4
4 SASS Train Cleaning Procedures 11
5 SASS Train Sampling Procedures 13
6 SASS Train Sample Recovery Procedure's 16
7 SASS Train Sample Recovery Procedures . 17
8 Scrap and Hot Metal Addition 18
9 Summary of Sampling Data for Q-BOP Shop Republic Steel,
Chicago, Illinois 19
10 Sample Code 20
11 Total Mass of Emitted Particles 22
12 Total Organics Emitted 22
13 Organic Extract Summary, Sample 1C1F 25
14 Organic Extract Summary, IX - XAD-2 Sample and Module Rinse 27
15 Arsenic, Mercury, and Antimony by Atomic Absorption
Spectroscopy 29
16 Total Inorganics by Spark Source Mass Spectrometry 30
17 SSMS Analysis Sheet, Sample 1 PW 33
18 SSMS Analysis Sheet, Sample 1C310 37
19 SSMS Analysis Sheet,'Sample 1C! 41
20 SSMS Analysis Sheet, Sample 1 X and Blank 45
21 SSMS Analysis Sheet, Sample 2553-1-0 49
A-l LC Analysis Report, Sample 1C1F 54
A-2 IR Report—Sample No. 1C1F, Cut LC-1 55
A-3 IR Report—Sample No. 1C1F, Cut LC-2 55.
A-4 IR Report—Sample No. 1C1F, Cut LC-3 56
A-5 IR Report—Sample No. 1C1F, Cut LC-4 56
A-6 IR Report—Sample No. 1C1F, Cut LC-5 57
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TABLES (cont'd)
Tables Page
A-7 IR Report—Sample No. 1C1F, Cut LC-6 57
A-8 IR Report—Sample No. 1C1F, Cut LC-7 57
A-9 LR Mass Spectroscopy Report--Sample 1C1F, Cut LC-1 58
A-10 LR Mass Spectroscopy Report—Sample 1C1F, Cut LC-2 58
A-ll LR Mass Spectroscopy Report--Sample 1C1F, Cut LC-3 58
A-12 LR Mass Spectroscopy Report—Sample 1C1F, Cuts LC-4-7 59
A-13 LC Analysis Report, Sample IX + Module Rinse 60
A-14 IR Report—Sample No. IX, Cut LC-1 61
A-15 IR Report—Sample No. IX, Cut LC-2' 61
A-16 IR Report—Sample No. IX, Cut LC-3 62
A-17 IR Report—Sample No. IX, Cut LC-4 62
A-18 IR Report—Sample No. IX, Cut LC-5 63
A-19 IR Report—Sample No. IX, Cut LC-6 63
A-20 LR Mass Spectroscopy Report—Sample IX, Cut LC-1 64
A-21 LR Mass Spectroscopy Report—Sample IX, Cut LC-2 64
A-22 LR Mass Spectroscopy Report—Sample IX, Cut LC-3 65
Ar-23 LR Mass Spectroscopy Report—Sample IX, Cut LC-4-7 65
A-24 SSMS Analysis of Sample No. 1 PW 67
A-25 SSMS Analysis of Sample No. 1C310 68
A-26 SSMS Analysis of Sample No. 1C1F 69
A-27 SSMS Analysis of Sample No. IX 70
A-28 SSMS Analysis of Sample No. IX-Blank 70
A-29 SSMS Analysis of Sample No. 1IMP1 71
A-30 SSMS Analysis of Sample No. 1MP1-Blank 71
A-31 SSMS Average Detection Limits 72
VTI
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ACKNOWLEDGEMENT
This report has been submitted by Research Triangle Institute in partial
fulfillment of the requirements of EPA Contract No. 68-02-2630. The author is
grateful to Mr. Robert V. Hendriks, Project Officer, for his advice and
technical direction.
RTI also wishes to acknowledge the significant contributions made by
personnel of Acurex Corporation who designed and carried out the sampling
program under EPA Contract 68-01-4142, Task ,12. Special thanks are extended
to Mr. James Steiner who prepared the Acurex sampling report.
The efforts of Dr. Robert Handy of RTI, who directed the organic work and
interpreted the IR and LRMS spectra are also appreciated. Appreciation is
also expressed to Republic Steel Corporation for their cooperation and
assistance with this project.
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1.0 INTRODUCTION
Q-BOPs, bottom blown Basic Oxygen Process for steelmaking, are of
interest to the Environmental Protection Agency (EPA) because of their potential
for high particulate and organic compound emissions. Of particular interest
are emissions generated during the hot metal addition to precharged scrap
metal. Information was needed to characterize the emission of inorganic and
organic components during this phase of the Q-BOP steelmaking process. To
supply this data, Acurex Corporation was assigned by EPA the task of sampling
the emissions from the charging operation (before entering the air pollution
control equipment) at Republic Steel Corporation's, Chicago, Illinois plant.
The Research Triangle Institute (RTI) was responsible for the analysis of the
collected samples.
This report, prepared by Research Triangle Institute, integrates the
process description, details of the sampling program and data obtained during
sampling—all of which are provided by Acurex Corporation in final report
form, observations and data collected by RTI personnel, and results of RTI's
chemical analyses.
Section 2 presents conclusions made by RTI based on the test data.
Section 3 presents a description of the test, including the facility, process,
and sampling protocol used and Section 4 gives details of the test results.
The Appendices contain details of the analytical results and observations made
during the test.
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2.0 CONCLUSIONS
This test at a Q-BOP was conducted to determine if potentially hazardous
materials are produced during the hot metal addition cycle of the process.
Tests were conducted by IERL-RTP Level 1 procedures in the secondary emission
collection system during eight hot metal additions (four process cycles).
The partgculate emissions are given in Table 1. During the brief period
of actual hot metal addition, particulates are emitted at a fairly high rate
O
(1300 mg/m ). Emissions are not excessive, however, when calculated on a
t
Kg/ton of charge or Kg/cycle basis. Data in Table 11, Section 4 show that
about 69 percent of the particulate is greater than 10 microns and 14 percent
falls in the 1-3 u size. It is important to realize that testing occurred
only during actual hot metal addition. Thus these results do not reflect
emissions which occur during the 0« blow cycle or during other periods when
the vessel is turned down (i.e., scrap charge, metal sampling, etc.) or the
brief period between hot metal addition from the two ladles.
TABLE 1. SUMMARY OF PARTICULATE DATA—UNCONTROLLED EMISSIONS
Stack Gas Volumetric Flowrate, m /min 11,495*
3
Particulate Concentration, mg/m 1,300
Particulate Generated, Kg/min 14.9
Kg/average cycle (257 tons charged) 32.9
Kg/ton hot metal added (average) 0.16
Kg/ton steel scrap (average) 0.64
Kg/ton of total charge 0.13
*Average flowrate during preliminary tests was 9,372 m /min which is consistent
with system design value.
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Total organic content of the uncontrolled emissions is given in Table 2.
About 50 percent of the 64.1 mg/m total organics was associated with the
<3 vi dusts. The XAD-2 resin captured about 30 percent of the total with the
balance in the probe and cyclone rinses. High'boiling point (GRAV) material
accounted for about 75 percent of the organic material. Aliphatic hydrocarbons
were the predominate species emitted. Fused aromatics over 216 mw were also
emitted at high levels (~5 mg/m ). The emissions also contain alcohols,
amines, amides, esters, and carboxylic acids. The Low Resolution Mass Spectro-
graph (LRMS) analysis (Appendix A) contain several molecular weights that
could be associated with carcinogenic material however, GC-MS analysis indicates
these components are fragments of high molecular weight organics and not known
carcinogens. Comparison of the organic category concentrations with Air-
Health MATE values indicates that control is needed for fused aromatics (96
percent), amines (~50 percent), and carboxylic acids ("50 percent).
= TABLE 2. SUMMARY OF ORGANIC DATA—UNCONTROLLED EMISSIONS
Stack Gas Volumetric Flowrate, m /min 11,495*
Total Organic Concentration, mg/m 64.1
Organic Generated, Kg/min Q.74
Kg/average cycle (257 tons charged) 1.6
Kg/ton hot metal added (average) 0.0079
Kg/ton steel scrap (average) 0.031
Kg/ton of total charge 0.0063
o
*Average flowrate during preliminary tests was 9,372 m /min which is consistent
with system design value.
A summary of inorganic emissions is given in Table 16, Section 4. These
data indicate that the uncontrolled discharge of emissions generated during hot
metal addition would exceed Air-Health MATE values for nickel, iron, chromium,
calcium, arsenic, lead, and possibly sulfur and phosphorus. To meet these
criteria, a control efficiency of, respectively, 92, 89-99, 99.6,75, 90, 63, 0-
87, and 0-81 percent might be required.
Table 3 gives the distribution of these elements in the different SASS
train samples. Only sulfur and phosphorous would not be substantially removed
by collection of the particulate matter.
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TABLE 3. DISTRIBUTION OF INORGANICS EXCEEDING MATE VALUES
1PW
1C310
1C!
IX
1 IMP 1
Ni Fe
53 14
7 85
7
—
34
Cr
65
28
3
—
5
Ca
5
41
54
—
—
As
30
46
18
5
—
Pb
13
13
59
15
—
S
4
5
15
72
4
P
5
26
2
66
--
As percent of total emitted.
The data obtained in this test supports, the conclusions that:
1. Particulates are produced in high concentration during hot
metal addition.
2. Organics are emitted in surprisingly high concentrations.
3. About 50 percent of the organic matter is associated with
the <3 y particulates.
4. Fused aromatics, amines, carboxylic acids, and several inorganic
elements are generated at sufficiently high levels that some
degree of control may be needed.
5. Fused aromatics are predominately >216 mw but appear to contain no
carcinogenic material.
4
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3.0 TEST DESCRIPTION
Contained in this Section is a description of the Q-BOP facility tested,
process and operating data, the sampling data obtained, and sampling protocol
used.
3'.1 Q-BOP FACILITY, REPUBLIC STEEL, CHICAGO, ILLINOIS
The Q-BOP shop at Republic Steel, Chicago contains two vessels each rated
at 225 tons/heat. Six to eight heats can normally be completed in an eight
/
hour shift. Figure 1 is a schematic of the Q-BOP vessel and ancilliary
equipment. A schematic of the emissions control system is in Figure 2.
The Q-BOP vessel differs from the conventional BOF by introducing oxygen
through tuyeres in the bottom of the vessel rather than through a lance above
the charged material. Introducing oxygen in this way may result in better
control of the steelmaking process.
As illustrated in the Figures, each vessel is in a separate enclosure
(referred to as a "doghouse") and is connected to separate gas collecting and
cleaning systems. Each gas collecting system consists of two separate systems—
a primary system to collect the emissions during oxygen blow and a secondary
system to collect emissions during the addition of scrap and hot metal, tapping,
slagging, and when the vessel is idle. The emissions collected by the primary
and secondary systems enter a common (for each vessel) gas cleaning system
(wet scrubber).
At the start of a heat,' the vessel is tilted, the enclosure doors opened,
and a charge of scrap metal added. While the vessel is being charged, nitrogen
(or a natural gas/air mixture) is blown through the tuyeres in the vessel
bottom to prevent plugging. As soon as the vessel is tilted more than 20°, the
secondary hood collection system is automatically actuated while the primary
system is decreased to about 10 to 20 percent of full capacity by adjusting
dampers in the respective ductworks. In addition, the damper isolating both
secondary collection systems is opened which allows both ID fans to exhaust
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Bumper
Secondary hood
Hot metal charging ladle
Furnace charging doors
(retractable)
Slag pot
Water cooled hood
Hood transfer car
Adjustable skirt
Tapping emissions duct
Seal ring
Furnace enclosure
Operating
floor
Teemi ng
ladle
Shop air in draft
during slagging &
tapping
Figure 1. Schematic of Q-BOP vessel.
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Isolation
damper
open
Q-BOP No.,1 Furnace Enclosure
Secondary hood No. 1
Shut off No. 1
open
Quencher No. 1
80% open
Quencher No. 2
20% open
•Bell valve No. 2
Shut off No. 2
closed
Secondary hood No. 2
Q-BOP No. 2
Furnace enclosure
Fan No. 1
Stack No. 1
tack No. 2
Fan No. 2
Scrubber No. 2
Figure 2. Q-BOP emission control system.
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gas from the secondary hood and vessel enclosure. The design operating point
for a fan for the secondary collection system is 272,000 acfm at 120°F and -86
in. water (7704 acmm at 49°C and 160 mm of Hg, fan inlet conditions). Acurex's
conversion of this flowrate to conditions anticipated in the secondary hood
yielded a value of 209,000 acfm (5,920 acmm) or 418,000 acfm (11,840 acmm) for
two fans. PECOR (system designer) estimated leakage through the primary hood
system and quench at 44,000 acfm (1,246 acmm) leaving 374,000 acfm (10,594
acmm) to actually collect fume during charging and tapping (referred to as
high fixed flowrate).
Scrap preheating is not employed although the capability has been built
into the system. Occasionally, scrap with a high moisture content may be
dried with a purge before hot metal is added to the vessel.
Most of the scrap used is revert or mill scrap (e.g., rejected ingots,
crop ends from blooms and billets, blast furnace molds, etc.) which is of
known chemical composition. Number one scrap is purchased from outside suppliers
and typically consists of material from steel consuming industries (e.g.,
appliances, steel furniture, beams, angles, channels, etc.). Pit scrap (spillage,
skulls, etc.) may also be used.
After scrap addition, hot metal from the blast furnace, if available, can
be added to the vessel. If hot metal is not available, the doors to the en-
closure are closed and the flowrate through the secondary collection system is
reduced to "low fixed flow" (occurs whenever vessel is idling). Generally
speaking, hot metal is usually available and is added to the vessel using
ladles and an overhead crane. The rate at which N2 (only N2) is blown into
the tuyeres is increased during hot metal addition to prevent plugging. Two
ladles are required to charge a vessel with enough hot metal for a heat. The
fumes generated during hot metal addition are captured by the secondary hood
(high fixed flowrate) and are sent to both gas cleaning systems for removal.
The doors to the enclosure are closed as the hot metal ladle is withdrawn.
The vessel is now charged and turned to the vertical position for 02 b]ow.
Since the secondary collection system is activated by vessel position, it is
automatically shut off when the vessel is less than 20° from vertical. The
isolation damper is closed and the valve in the primary collection is opened.
8
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As soon as the vessel, reaches the vertical position, the moveable hood is
lowered to the mouth of the vessel, the N2 purge is shut off and CL is blown
through the tuyeres. The 02 blow rate is constant and does not vary during a
heat. The length of the Op blow varies from approximately 12 to 15 minutes
depending on the grade of steel being made. Once the 02 blow flowrate has been
established, fluxes are blown into the vessel through the tuyeres. Rough
estimates of fluxes added are: burnt lime 30,000 to 35,000 Ibs., dolomitic
lime 6,000 to 7,000 Ibs., and fluorspar 2,000 to 3,000 Ibs. The amount of
additions vary but are known and recorded in the pulpit. This suppressed
combustion process produces a CO-rich gas and hence 02 infiltration into the
system is dangerous (explosion could result). Sensors located downstream of
the ID fan measure the amount of CO and 02 in the system. Should 02 enter the
system upstream of the ID fan, 02 blow is terminated and N2 is blown through
the tuyeres. Also, an Ng purge of the ductwork is activated until a safe
operating condition is reached.
After completing the 02 blow, the vessel is turned down for temperature.
The secondary collection system is activated and the doors of the enclosure are
opened just enough for an operator to insert the thermocouple into the vessel.
If the metal temperature is too low, an 02 reblow may be necessary. If the
metal temperature is too hot, N2 and/or dolomitic lime can be blown into the
system to produce the desired cooling effect. If the metal temperature is
right, an operator takes a sample of the metal for chemical analysis. The time
consumed during this turndown is approximately 5 minutes and the secondary
collection system is in operation.
The vessel is now ready to be tapped. Tapping time varies with the size
of the tap hole but is normally 5 minutes. The vessel is tapped into a ladle
and additional agents are added directly to the ladle to produce the desired
chemical composition. The temperature of the molten steel is also measured and
recorded. Again, the secondary collection system was actuated as soon as the
vessel was turned down to the tap position (doors on "doghouse" closed).
Occasionally, (one heat in six) the vessel is "shot" by the operator.
This process involves the introduction of N2 and dolomitic lime into the
tuyeres to splatter the slag remaining in the vessel onto its walls to coat
the lining. After this operation has been completed, the vessel is rotated
-------
through the vertical position and down to the slag position ("doghouse" doors
closed). The slag in the vessel is poured into a ladle under the operating
floor and the vessel is now ready for another heat:
Collected emissions are quenched by water sprays and cleansed in a water
scrubber. Pressure drop across the scrubber is about 75 in. of water (140 mm
Hg). Water recirculation rate is about 2500 gpm. Scrubber effluent water,
about 250 gpm, is treated with flocculants and clarified prior to recycle. The
solids removed are presently stored on plant property. Attempts to recycle
these solids by briquetting have not been very successful.
3.2 SAMPLING EQUIPMENT PREPARATION AND SAMPLE RECOVERY
The test equipment used was the Source Assessment Sampling System (SASS).
Table 4 details the procedures used to clean the system prior to the test run.
All solvents used were Mallinckrodt Nanograde reagent except the methylene
chloride (0. T. Baker Instra Analyzed). The 30 percent peroxide (H202),
ammonium persulfate, and silver nitrate were Mallinckrodt Analytical Grade
reagents. Deionized water was from Hinckley and Schmitt.
The partially assembled system was sealed with aluminum foil and trans-
ported to the test site. The complete system was then assembled, leak checked,
and impinger solutions added. All system components had been calibrated prior
to the testing.
Prior to the SASS test, Acurex conducted a 24 point velocity and tempera-
ture traverse across the secondary emission collection duct during simulated
hot metal addition conditions. The observed gas flowrate was 330,887 dscfm
(9,372 dscmm) or 368,038 acfm (10,424 acmm) which compares well with the design
value of 374,000 acfm (10,593 acmm). A nozzle size of 0.3750 in. (0.95 cm)
was selected for the SASS test.
The SASS test was conducted at a single point (mid-point) in the secondary
hood duct only 1/2 of a stack diameter upstream of the downcomer to the twin
venturi quencher and 1.5 diameters downstream of a bend in the duct. Flowrate
through the SASS train was about 4 scfm (0.11 scmm) to insure proper separation
of particulates in the cyclones. The probe and oven were maintained at 204°C
10
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TABLE 4. SASS TRAIN CLEANING PROCEDURES
SASS Train
Component
Sampling nozzle
5- ft glass- lined
probe
|10u cyclone and cup
Connector tube
|3u cyclone and cup
Connector tube
\lu cyclone and cup
Connector tube
142 urn filter
holder
s
Teflon- lined hose
Organic module and
condensate jar
Teflon-lined hose
Impingers, con-
nectors, and stems
Cleaning Procedures
Tap
Wash, Brush Water
Soap, Water Rinse
X X-
X X
X X
X X
X X
X X
X X
X X
X X
X X
Xf X
X X
\
X X
.s
15* HN03
Acid Soak
X
X
X
X
X
X
X
X
X
. X
X
X
X
DI
Water Methanol
Rinse Rinse
X X
X X
X X
X X
X X
X X
X X
X X
X X
X '.X
X X
X
X
Hethylene
Chloride Isopropanol
Rinse Rinse
X
X
X
X
X
X
X
X
X
X
X
X
X
n
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(400°F), considerably above the stack gas temperatdre of about 65°C (150°F).
The XAD-2 cartridge and impinger train were maintained, respectively, at 15°C
(60°F) and 21-27°C (70-80°F). The SASS sampling procedures are outlined in
Table 5.
The sample point location is shown in Figure 3. Data acquired during the
test are shown in Figure 4. Level 1 sampling procedures normally require the
o o
collection of 30 m (1000 ft ) of gas; however, this volume of gas was not
collected since the hot metal addition portion of the Q-BOP cycle is only 1 to
2 minutes in length. A total of eight separate hot metal additions to the Q-
BOP vessel were sampled during the test.
Tables 6 and 7 indicate the sample recovery procedures used by Acurex.
Table 8 gives the details of the scrap and hot metal addition rates.
12
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> ATTACH NOZZLE TO PROBE
> ATTACH PROBE TO OVEN
• ATTACH CYCLONES AND FILTER HOLDER
• ATTACH TEFLON HOSE TO FILTER HOLDER
ASSEMBLE SASS TRAIN COMPONENTS
AT SAMPLING SITE
LEVEL AND ZERO MAGNEHEUC
GAUGES IN CONTROL MODULE
I
• CONNECT TEFLON HOSE TO ORGANIC MODULE
• CONNECT ORGANIC MODULE TO IMPINGERS
• CONNECT IMPtNGERS
• CONNECT IMPINGER TRAIN TO PUMPS
• CONNECT PUMPS TO CONTROL MODULE
LEAK CHECK FROM FRONT ON
10:, CYCLONE AT 20" H
TAKE BLANKS
RECORD LEAD RATE AND FILTER
NUMBER ON FIELD DATA SHEET
PREPARE OXIDIZING IMPINGEH
SOLUTIONS IN OFFICE
• IMPINGER «1 75O ml. 30% H,0,
• IMPINGER *2. *2 750 ml 0 2M
INH4l2S2Og and 0 02M 4gNO3
• IMPINGER »4 750 gm SILICA GEL
CHARGE IMPINGER TRAIN AT
SAMPLING SITE AND HEAT
UP TRAIN TO 400° F
ADO ICE TO IMPINGER
TRAIN AS NEEDED
TEAM LEADER CHECK WITH
PROCESS OPERATOR
INSURE PROCESS
OPERATING PROPERLY
POSITION PROBE AT SINGLE
SAMPLING POINT IN OUCT
• RECORD CLOCK TIME
• RECORD DRY GAS METER READING
• RECORD .IP. T^. T,
• SET AH C 2.00 1 - 4 ictml
• READ REMAINING GAUGES
T
START SASS TEST
GATHER PROCESS DATA
1
SAMPLE AT 4 jclm DURING
HOT METAL ADDITION
RECORD STOP TIME AND OTHER DATA
RECORD DATA ON FIELD
DATA SHEET
STOP SAMPLING. REMOVE
PR08E FROM OUCT WAIT
FOR NEXT ADDITION
INSERT PROBE IN OUCT
AND CONTINUE SAMPLING
REPEAT UNTIL TEST IS COMPLETE
RECORD FINAL READINGS
DISASSEMBLE SASS TRAIN.
SEAL COMPONENTS IN FOIL
AND TRANSPORT TO OFFICE
TABLE 5. SASS TRAIN SAMPLING PROCEDURES
13
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Isolation
Sampling
Platform
Downcomer to twin venturi quencher
Single Horizontal Sampling Port
1
Figure 3. Sampling site on secondary gas cleaning system.
14
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PLANT Republic Steel Corp. Chicago BATE J/1*/78 ^^SocccnJ^MN ur 1 * *
inrATinu Unccol 9 flnMnt TIME 11:00 a.m. STATIC PRESSURE (1N.HU.J -6.0
«A?I2lAWIER IN) 20 RU» SASS AMBIENT PRESSURE (IN.HG.) 29.53
STACK DIAMETER (IN.) 120 «u« TYPE S PITOT COEFFICIENT 0.778
FILTER NUMBER 178-71
LEAK RATE 0.025 6 20"
STACK PRESSURE (IN.HG.) 29.05
MOLECULAR HEIGHT (LB/LB-HOLE)
METER BOX NUMBER 0038
ORIFICE METER COEFFICIENT 3.789
PROBE LENGTH (FT.) 5' glass
NOZZLE DIAMETER (IN.) 0.275
PARTICULAR SAMPLING DATA
Heat Sampling *%»»
' T'*ie Number
4'6"
1.2
20764
0.7
2.1
20765
0.8
1.2
20766
0.65
4'6"
1.3S
20777
O.B
Stack Gas Probe
Temp Temp
m (°FI
128 400
147
129 400
149 402
156
161
157
_
140 399
162
144 398
157
167
148 399
157
144 406
154
161
162
114 408
1GO
149
Average
151.7
Oven- Dry Gas Meter Temp
Temp Inlet
<°Fll (°F)
400 56
54
54
400 54
54
54
54
398 54
54
401 53
S3
63
394 S3
53
396 53
53
53
396 S3
53
S3
Average
63.53
Average
Outlet
56
54
54
53
53
S3
S3
54
54
53
S3
S3
S3
S3
53
S3
S3
53
53
51
Average
53.35
53.45"
Veloci ty
Head
(in. ws.)
3.3
3.5
3.3
3.3
3.4
3.2
3.3
3.2
J.4
3.7
3.4
3.6
3.5
3.4
3.5
3.4
3.4
3.4
3.3
3.3
3.4
Orifice
Meter
(in. wg.)
2.2
2.4
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
Average
2.22
Gas Meter Organic
Volume Module
(ft.3) Temp.
0 46
6.187
6.187 41
8.826
8.828 40
17.233
17.233 41
20.836
20.836 44
26.672
25.672 42
27.973
27.973 46
33.592
33.592 44
36.401
Total
36.462
W
1.817
1.871
1.817
1.817
1.817
1.844
1.789
1.817
1.789
t 844
1.817
1.844
1.897
1.871
1.844
1.871
1.844
1.844
1.844
1.817
1.B17
1 .844
1.836
"EOF
*aP during idle 0.65" wg
T during Idle I30-I50°f
In between ladles aP 2.6
T 100
&P during scrap 3"
Ts 114
In between tables 2.6
110
FIGURE 4. SASS Field Data
-------
SAMPLING NDZILE. ,
PflOOE 10,. CYCLONE
RINSE AND BHUSH WITH 1:1
UETHANOUMETHVIENE
CHLORIDE
TRANSFER WASHWGS to
LABELED AMUR
OLASS BOTTLE
CONNECTOR TUB*
AND 3f CVCIONE
If CVCLONE OUST
RINSE AND SHUSH WITH
1:1 METHANOUMETIIttEME
CHLORIDE
CONNECTOR TUBE
AND 1)1 CYCLONE
TRANSFER OUST TO LABELED
POLYETHYLENE JAR
p CVCIONE DUST
HINSE AND MUSH WITH
1.1 MEIHANOUMEIIIVLENE
CHLORIDE
CONNECTOR TOM
AND HI IER HOLDER
TRANSFER OUST TO LABELED
POLYETHYLENE JAR
TRANSFER WASHINGS TO
LABELED AMBER
GLASS BOTTLE
SEAL FOR SHIPMENT TO
RESEARCH TRIANGLE
INSTITUTE
OiASS FiaER FILTERS
HINSE AMD BRUSH WITH 1.1
MtTHANOLIMEIIIirUKE
CHLORIDE
SEAL FOB SHl>MENI TO
RESEADCH IRIANOLE
INSTITUTE
TRANSFER FILTER TO
SEPARATE LABELED
HTRI DISH
TRANSFER WASHINGS TO
LABELED AMBER
GLASS BOTTLE
SEAL FOR SHIPMENT TO
RESEARCH TRIANGLE
INSTITUTE
TABLE 6. SASS TRAIN SAMPLE RECOVERY PROCEDURES
-------
TEFLON HOSE AND INTERNAL
SURFACES OF ORGANIC
MODULE
XAO 2 CARTRIDGE
RINSE AND BRUSH WITH
METHYLENE CHLORIDE
TRANSFER XAO 1 TO
AMBER GLASS JAB
TRANSFER WASHINGS
TO LABELED AMBER
GLASS BOTTLE
RINSE WITH I t
IPA/OI WATER
RINSE CARTOIDGE WITH
METHYLENE CHLORIDE
SEAL FOR SHIPMENT TO
RESEARCH TRIANGLE INSTITUTE
TRANSFER WASIUNGS
TO LABELED AMBER
GLASS BOTTLE
TRANSFER WASHINGS TO
LABELED AMBER GLASS JAR
CONTAINING XAD 2
SEAL FOR SHIPMENT 10
RESEARCH TRIANGLE INSTITUTE
MEASURE VOLUME
AND RECORD
RINSE CONNECTOR.
SIEM BOTIIE WITH
I I IPA/EO WATER
TRANSf EH IMPINGER
CONTENTS IO LABELED
POLYETHYLENE UOTI1E
SEAL fOH SHIPMENT TO
RESEARCH TRIANGLE INSTITUTE
SEAL FOR SHIPMENT TO
RESEARCH TRIANGLE INSTITUTE
IMPINGED! 2 13
MEASURE VOLUME
AND RECORD
WEIGH SILICA GEL
AND DISCARD
RINSE CONNECTOR.
STEM. BOTTLE WIIH
I I IPAIID WATER
TRANSFER IMPINGEH
CONTENTS TO LABELED
POLYETHYLENE BOTTLE
SEAL FOR SHIPMENT TO
DESEADCH TRIANGLE INSTITUTE
•NO CONDENSAIE COLLECTED IN GLASS CONOENSAIE JAR
TABLE 7. SASS TRAIN SAMPLE RECOVERY PROCEDURES
-------
. TABLE 8. SCRAP AND HOT METAL ADDITION
Date
3/15/78
Heat
No.
20764
20765
20766
20767
Scrap Addition3
Pit Scrap
20,000
20,000
20,000
20,000
Ingot
Butts
~
—
10,000
10,000
Butts
83,000
84,000
72,000
74,000
Hot Metal Addition*
Ladle 1 Ladle 2
201,000 212,000
200,000 211,400
201,000 211,000
209,000 200,000
Sampling Time
3:44:05 pm - 3:45:25 pm
3:48 pm - 3:48:40 pm
4:33:50 pm - 4:35:50 pm
4:40:10 pm - 4:41 pm
5:39:20 pm - 5:40:25 pm
5:43:50 pm - 5:44:30 pm
6:38:50 pm - 6:40:05 pm
6:43:43 pm 6:44:30 pm
aAll values in Ibs.
18
-------
4.0 TEST RESULTS
4.1 ON-SITE RESULTS
The Acurex Corporation acquired the data at the sampling site (Table 9).
The overall sampling rate was near isokinetic (104 percent). Eight separate
periods of hot metal addition to scrap were sampled over a period of three
hours for a total sampling time of 8.8 minutes. Gas volume collected was
1.027 m3 well below the 30 m3 (1,000 ft3) recommended by Level 1 protocol
because of the shortness (about 1 minute) of the hot metal addition periods.
No on-site gas analyses for low molecular weight organics or inorganic
species were made.
TABLE 9. SUMMARY OF SAMPLING DATA FOR Q-BOP SHOP REPUBLIC STEEL,
CHICAGO. ILLINOIS
Date of Test:
Volume of Gas Sampled:
Stack Gas Temperature:
Stack Gas Pressure:
Stack Gas Dry Molecular Weight:
Stack Gas Wet Molecular Weight:
Stack Gas Moisture:
Stack Gas Velocity:
Stack Gas Volumetric Flowrate:
Total Sampling Time:
SASS Train Flowrate:
% Isokinetic:
3/15/78
36.2578 dscf
151.7°F
29.05 inches Hg
28.96 Ib/lb-mole
28.73 Ib/lb-mole
2.07%
104.5 ft/sec (single point)
405,812 dscfm3
8.8 minutes
4.12 dscfm
104.0
^Average flowrate measured during preliminary tests was 330,887 dscfm,
which is consistent with design value for system.
19
-------
4.2 ANALYSIS OF SASS SAMPLES
Data presented in this Section are results of analyses performed by
Research Triangle Institute. Table 10 shows the sample code used. Figure 6
shows the analysis procedure used for each sample.
TABLE 10. SAMPLE CODE
1C10 >10 micron cyclone dust
1C3 3-10 micron cyclone dust
1C310 Combined 1C10 and 1C3
1C! 1-3 micron cyclone dust
IF <1 y filter
1C1F Combined 1C! and IF
1PW Probe and cyclone rinses
IX XAD-2 resin and organic module
rinse '
1IMP1 1st impinger
1IMP23 Combined 2nd and 3rd impinger
4.2.1 Total Particulate Loading
The total mass of particulates in the Q-BOP secondary emission control
system (before any air pollution control equipment) and the concentration are
3
given in Table 11. Of the 1300 mg/m total particulates, 68.7 percent is
greater than 10 v in size, and 14 percent was captured by the 1 y cyclone.
Only two percent was captured by the filter (<1 y size).
4.2.2 Level I Organic Analysis
Total organic material extracted from the various SASS train components
is summarized in Table 12. About half of the total organic captured ,is
associated with the less than 3 y dust (1 y cyclone and filter). Thus the
average composition of these dusts is about 15.7 percent organic material.
This is particularly interesting since no organic material was found in the
>3 y particles. The organic material on the dusts is about 58 percent GRAV
20
-------
I §
1C 10
1C 3
IC1
IF
IPW
IX
ISC
I imp 1
I imp 23
• Dry Weight
•^
1 —
\ Combining
> SSMS
^Tcsio
• m
> As/Hg/Sb
V
A
*>>
^
\ Soxhiet Extractior
> TCO
> GRAV
^^ 1C1F
o
1
u.
o
O
£ a g
ts
R3
£
O
>
CC
a
c o
o ^
tj "•
2 o
LL -J
0 CO "
~ s s
Q. EC 0
- -j a
Figure 5. Analytical Procedures.
21
-------
(high boiling point) material. (It is also somewhat surprising that any TCO
(low boiling point) material was found on the dusts since the cyclones were
operated at 204°C (400°F).
TABLE 11. TOTAL MASS OF EMITTED PARTICLES
Process:
Sampling Point:
Q-BOP, Republic Steel, Chicago, IL
Secondary Emission Control Duct During
Hot Metal Addition
Volume of Gas Sampled:
Total Parti culates
10 y cyclone
3 y cyclone
1 y cyclone
Filter
Probe and Cyclone
Rinses
Total
1 .027 dscm
Grams Captured
0.9163
0.0713
0.1874
0.0264
0.1320
1.3334
Concentration mg/m
892
69
182
26
129
1298
TABLE 12. TOTAL ORGANICS EMITTED
Process:
Sampling Point:
Q-BOP, Republic Steel, Chicago, IL
Secondary Emission Control Duct During
Hot Metal Addition
Volume of Gas Sampled: 1.027 dscm
Total Organics
1C310
1C1F
IX
Probe and Cyclone Rinses
Total
22
-------
'About 32 percent of the organic material was captured by the XAD-2 resin.
About 96 percent of the material was GRAV (high boiling point).
The organic extract from 1C1F (1 y cyclone and <1 y filter) were fractioned
by liquid chromatography into seven fractions. Each fraction was analyzed for
TCO (total chromatographical organics) and GRAV as well as by IR and LRMS.
The LC, IR, and LRMS data are given in The Appendixes. From these data the
organic species in each extract were classified into compound categories and
the concentration of each category estimated. Concentration estimates are
based on GRAV material only since Level 1 procedures remove TCO before IR or
LRMS spectra are obtained. Strong peaks in the IR and LRMS were assigned
intensity factors of 100; weak peaks were assigned intensities of 10. The
GRAV concentration in mg/m -was then apportioned to each compound category
according to its intensity factor so that the sum for all categories in a
specific LC fraction equalled the GRAV concentration for that fraction.
Tables 13 and 14 present these results.
Interesting aspects of the data are:
1. Aliphatic hydrocarbons are the predominate category in both
samples.
2. Fused aromatics (MW >216) are the second major category for the
<3 y dusts.
3. The emissions contain a wide variety of compounds including
carboxylic acids, esters, amides, and alcohols.
4. The LRMS data (Appendix A) contains several molecular weight
identifications characteristic of known carcinogens however,
GC-MS shows that these are due to fragments of high molecular
weight aliphatics.
4.2.3 GC-MS Analysis
Although 1C1F (2y cyclone and filter) contains an appreciable quantity
of fused aromatic material, the M/&+ LRMS analysis indicates that none of the
material corresponds to known carcinogens. Sample Ix (the x AD-Z resin extract),
although containing appreciably less fused aromatic than 1C1F, does have several
LRMS M/£+'s that correspond to known carcinogens and these components are
found in LC fractions 2 and 3.
23
-------
These LC fractions were combined and a single GC-MS run made. A 1.5 M
column packed with 1 percent Dexel 300 was used in the GC. Single ion plots
were obtained for M/& 's of 178, 202, 252, 278, and 300. Retention times in
the GC and the MS spectra obtained strongly indicate that the sample contained
primarily aliphatic hydrocarbons. No carcinogenic compounds were identified.
The components actually eluted were not identified. The total ion plat is in
the Appendix.
4.2.4 Inorganic Analysis
Atomic absorption analysis of the samples are presented in Table 15,
arsenic, mercury, and antimony were near or below detection limits for all
samples.
The Spark Source Mass Spectrographic (SSMS) analyses of the same samples,
however, show a much higher emission level of arsenic and antimony. A summary
of the SSMS data is given in Table 16. Tables 17 through 21 give the SSMS
data for each sample. The original data for the samples are given in Appendix A.
24
-------
TABLE 13. ORGANIC EXTRACT SUMMARY
Sample
1C1F
o
Total Organic*, mg/m0
TCO, mo
GRAV, mo
LC1'
8.2
2.1
6.3
LC2
10.8
9.0
2.1
LC3
4.2
0.0
4.3
LC4
• i.o
0.0
1.0
LC5
0.0
0.0
0.0
LCG
5.9
0.0
6.1
LC7
0.0
-0.0
0.0'
2
30.1
11.1
18.8
Category
Based on GRAV weight only
Aliphatics
Haloaliphalics
Substituted Benzenes
Halobenzenes
Fused Aromatics
Hetero N Compounds
Hetero 0 Compounds
Hetero S Compounds
Alkyl S Coumpounds
Nitriles
Aldehydes, Ketones
Nitro Aromatics
Ethers, Epoxides
Alcohols
Phenols
Amines
100/5.5
10/0.6
-.
S
10/0.09
100/0.9
10/0.09
100/0.9
. „ - •
10/0.2
10/0.2
100/3.8
•
i
100/0.2
100/0.2
100/0.2
10/0.02
100/0.2
10/0.02
100/0.2
'
10/0.1
10/0.1
100/1.1
lo/o.-i.
100/1.1
5.5
0.69
1.1
0.29
•4.7
0.3
0.2
0.2
0.1
n.n?
0.2
0.02
0.2
1.1
0.1
1.1
NS
-------
TABLE 13. (cont'd)
ORGANIC EXTRACT SUMMARY
IClf
o
Total Organic*, mg/m°
TCO, mg
GRAV, mg
LCT
LC2
LC3
LC4
•
LC5
LCG
LC7
-.
•
2
Category Int/mg/m
Ami des
Esters
Carboxylic Acids
Sulfonic Acids and Sulf oxides
•
•
•
t
«t
•
. .• •
<
100/1.1
100/1.1
100/1.1
10/0.1
* *
1.1
1.1
1.1
0.1
•
ro
-------
TABLE 14. ORGANIC EXTRACT SUMMARY
Sample IX - XAD-2 Sample and Module Rinse
n
TotalOrganics, mg/m
TCO. mg
GRAV. mg
LC1 '
2.8
0.0
2.9
LC2
1.3
0.0
1.3
LC3
1.3
0.7
0.6
LC4
' 0.6
0.0
0.6
LC5
0.2
0.0
0.2
LCG
5.0
0.0
5.1
LC7
1-3.
:.0.0
1.3-
2
12. .5
0.7
'12.0
Category Int/mg/m
Aliphatics
Haloaliphatics
Substituted Benzenes
Halobenzenes
Fused Aromatics
Hetero N Compounds
• * ...I
Hetero 0 Compounds
Hetero S Compounds
Alkyl S Compounds
Ni trilps
. Aldehydes, Ketones
Nitro Aromatics
Ethers, Epoxides
Alcohols
Phenols
Amines
100/2.5
10/0.3
%
100/0.3
100/0.3
10/0.3
100/0.3
. _ . •
100/0.3
100/0.15
100/0.15
•
*
100/0.15
100/0.15
10/0.02
10/0.02
100/0.2
inn/n ?
100/0.2
10/0.02
12/0.02
10/0.005
10/0.005
100/0. OE
10/0. OOE
in/n.nnF
100/0. OE
10/0. OOE
10/0. OOE
10/0. OOE
'10/0. OOE
10/0. OOE
10/0. 14
100/1.4
10/0.14,
10/0.05
100/0.5
10/0.14! 10/0.05
2.5
0.6
0.3
0.18
0.18
0.16
0.025
0.205
0.005
n.-?ns
0.4
0.025
0.48
1.5
0,64
0.20
ro
-------
TABLE 14. (cont'd)
ORGANIC EXTRACT SUMMARY
Sample IX - XAD-2 Sample and Module Rinse
-. ~x
q
Total Organics, mg/m
TCO, mg
GRAV.mg
LCI '
LC2
LC3
*
LC4
•
LC5
LC6
LC7
•• •'. .•''
• . -i .' v '
2
fl • .
\
Category
Int/mg/m3
Affrides
Esters
Carboxylic Acids
Sulfonic acids and Sulf oxides
'•
.'
- '
' . .
• -
'..
«
i
•
«
10/0.02
-
10/0.005
100/0.05
10/0.14
100/1.4
100/1.4
10/0.14
* >
10/0.05
10/0.05
100/0.5
10/0.05
0.20
1.50
1.9
0.19
•
ro
oo
-------
TABLE 15. ARSENIC, MERCURY AND ANTIMONY BY ATOMIC ABSORPTION
SPECTROSCQPY
Sample
As
mg/m
Sb
Probe and Cyclone
Rinses
1C310
1-3 y cyclone
IX
1IMP1
1IMP23
Total
<0.00064
<0.0000064
<0.000019
<0. 00009
<0. 00009
0
0
0
<0. 00063
<0.0031
<0. 000009
0
0
0'
<0.0031
<0.00014
<0. 000027
0
0
0
<0.0019
29
-------
TABLE 16. TOTAL INORGANICS BY SPARK SOURCE MASS
SPECTROMETRY
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carb'on
Boron
Beryllium
Lithium
llydroycn
Air Health
MATE Values
or Range,
mg/rci:
0-.2
0;015
0.05
0.7-9.0
5.0
0.001
0.5
6.0
16
2
1-440
0.1-1.0
10
5.2-10
. 6-10
2-53
3-10
0.002
0.022
At Sou res
Mass/Voluma
mj/ro3 or
W/L
0.10
0.18
<0.0043
85.3
3.8
0.26
<0.042
0.13
64.
0.92
7.9
0.53
4.2
0.43
2.3
0.056
0.013
0.000064
0.00073
Percent
Control
Needed
0
92
0
99-89
0
99.6
0
n
75
0
0-87
0-81
0
0
0
0
0
0
0
3Q
-------
-TABLE 16. (cont'd)
Element
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
.Zirconium
Yltrium
Strontium
Rubidium
Bromine
•Selenium
Arsenic
Germanium
Gallium
Zinc
Air Health
Mate Values
or Range,
mg/m^
37
110
0.5
82
0.5
10
U.UI
•
5.0
22
5.0
1.0
3,1
120
10
0.2
0.002
0.56
1 0.50
4.0
At Source
MjjsA'olume
m£/nr or
W/L
<0. 00081
<0.0012
0.020
<0. 00008
<0. 00059
-------
TABLE 16. (cont'd)
[Element
'Uranium
Thorium
Bismuth
lead
Thallium
Mercury
Gold
Platinum
IriJium
Osmium
nhcnium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Eibium
Holmiurn
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Air Health
MATE Values
or Range,
mg/nr
0.15
9.3
51
AtSourct
Maw/Volums
ms/rtr or
W/L
<0.0007
0.41
o.nrm
<0. 000032
<0.0002
' <0. 000021
<0. 000037
<0. 000009
<0. 00039
- <0. 00061
O.0001 .
Percent
Control
Needed
63
0
0
32
-------
TABLE 17. SSMS ANALYSIS SHEET
Contractor
Research Triangle.Institute
Republic Steel, Chicago, IL Marrh iQ?a
SamplaSite Sample Acquisition Data "al u" l:7/0
Type of soures Q-BOP Secondary Emission dust during hot metal addition
Te« Number - . - Sample ID Number
Sample Description Participate from nozzle and probe wash
GCA
Responsible Analyst Date Analyzed
Calculations and Report Reviewed By .. __, — Report Data
Instrument ; Resolution
Internal Standard (s) -
original Sample voiumeor Man 0.054 g tested (0.132 gms at source)
Dilution Factor •—
Brief Description of Electrode Preparation .
33
-------
TftplF 17, front '(H
Element
Copper
Jickcl
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Line Used
lor
Estimate
Uncorrected
Sample
Value
Blank
Vtlui
Corrected
Sample
Value
•
Sensitivity
High/Low
Cilibritioa
Standards or
Concentritlon
Added
Assigned
Concentration*
62.0
750.0
12,0
9.4 .(%)_
0.23 (%)
0.13 (%)
21.0
12.0
2.6 (%)
150.0
0.27 (%)
200.0
0.64 (%)
0.11 (%)
1.3 (%)
220.0
29.0
0.086
0.086
At Sourct
Mass/Volume
mg/m3 or
W/L
0.008
0.096
0.0015
12.1
0.30
0.17
0.0027
0.0015
3.34
0.019
0.35
0.026
0.92
0.14
1.67
0.028
0.0037
0.00001
0.00001
co
•Results: PPM value (in original sample) or I • interference; NC • not tomputod; NC • sample value below blank; ND • not detectable «2o Llenk).
-------
co
en
TARIF17. (cont'd) _
ilement
Cerium
Lanthanum
Baiium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
lihodium
flutlicnium
Molybdenum
Niobium
Zirconium
Yltriiini
Strontium
Rubidium
Oromine
Solenium
Arsenic
Germanium
Gallium
Line Used
(or
Enimatt
Uncarrected
Simple
Value
Blank
Valuo
Conocted
Sample
Value
Sensitivity
Hi(j!i/Low
Cilibrition
Standards or
Concintrition
Added
••
s
Assigned
Concentretlon*
1.3
0.68
80.0
<0.052
3.6
1.5
12.0
IS
7.2
0.73
O.47
150.0
0.90-
3.4
0.70
52.0
1.2
5.0
27(5
49.0
4. 1
.0
290.0
At Sourct
Mats/Volume
mj/m3 or
PO/L
0.00017
0.000057
0.010
<0. 0000067
0.00046
0.00019
0.0015
0.00093
0.000094
<0. 00006
0.0193
0.00012
0.00044
0.00009
0.0067
0.00015
.0019
<0.0015
0.0063
0.00053
0.00064
.037
•neiulti: PPM value (in oriuini.1 sample) or 1 • interference; NC • not computed; HG • sample valuo below blank; WD • not detectable «2o blank).
-------
TABLE 17. (cont'
-------
Contractor
TABLE 18. SSMS ANALYSIS SHEET
Research Triangle Institute
Republic Steel, Chicago, IL s.^,. Aa,uiihioil D,t. March 1978
Typeofsourca Q"BQP Secondary Emission Dust During Hot Metal Addition
Test Number Sample ID Number 1C31Q
Description 3-10 v and <10 y Cyclone Catches
Responsible Analyst "CA , , Oats Analyzed
Calculations and Report Reviewed By ' Report Data
Instrument - •. _. Resolution
Internal Standard (s) ; ,
Original Sampl. Volume or Mass 0.0730g (0.9876 at SOUrce)
Dilution Factor : ,
Brief Description of Electrode Preparation
37.,-
-------
TABLE 18. (cont'd)
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vonodium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Baron
Beryllium
Lithium
Hydrogen
Line Used
lor
Estimate
-
Uneorrected
Sample
Value
Blank
Value
Corrected
Sample
Value
Sensitivity
(
High/Low
Calibration
Standards or
Conceiitrtllon
Added
Assigned
Concentration*
15.
14.
1.7
7.6 (%)
0.35 (%)
76.
39.
120.
2.7 (%]
45.
390.
150.
0.32 (%)
230.
670.
8.3
6.5
0.026
0.12
At Sourct
Mass/Volume
mg/m' or
W/L
0.014
0.013
0.0016
73
3.4
0.073
0.038
0.115
26.0
0.043
0.38
0. 14
3.1
0.22
0.64
0.008
0.0063
0.000025
0.00012
LO
00
'Results: PPM value (in original sample) or I • interference; NC • not computed; NG • simple value below blanV; ND • not detectable «2o blank).
-------
oo
!£>
TABLE 1
IfAUUU
Element
Cerium
Lanthanum
larium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Pollodium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yiifiuin
Slfoniiiiin
Rubidium
Bromine
Solenium
Arsenic
Germanium
Gallium
g (rnnt.'d)
Line U«d
lor
Enimiie
Unconrected
Simple
Valua
Blank
Value
Corrected
Sumplt
. Value
Santitivity
High/Low
Cilibritioii
Sundardi or
Concentration
Added
H
Anignid
Concantrititm*
0.46
0.94
7.5
0.028
0.071
< 0.68
0.55
1.3
IS
0.12
< 0.25
< 0.066
< 0.41
2.1
4.5
3.9
1.1
28.
0.56
26.
<14.
10.
< 0.50
1.3
12.
At Source
Mm/Volume
mg/m3 or
Wl/L
0.00044
0.00090
0.0072
0.000027
0.000068
<0. 00065
0.00053
0.0013
IS
0.00012
<0. 00024
<0. 000063
<0. 00039
0.0020
0.0043
0.0038
0.0011
0.027
0.00054
0.025
<0.013
0.0096
^.00048
0.0013
0.012
"Roiults: PPM value (in original sample) or 1 - intcrferoiico; NC • not computed; NO • wmplo valno below blunk; NO • not detcctnlile «2o blond).
-------
TARIF Ifl. (cont'cO
Element
Uranium
Thorium
Bismuth
.cod
Thallium
Mercury
Cold
Platinum
Iridium
Osmium
Rhenium
Titnflslon
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
lloliniurn
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Line Used
(or
Estimate
*£
Uncorrected
Simple
Vilui
Blink
Value
Corrected
Sample
Value
Sensitivity
High/Low
Calibration
SUndards or
Concentration
Added
Assigned
Coneentrition*
56.
0.73
<0.17
<0.27
<0.35
<0.083
At Source
MiH/VoIume
mj/rn^ or
W/L
0.054
0.00070
<0.00016
<0. 00026
<0. 00024
0.000080
•Rciulu: PPM value (in original ample) or 1 • intcrfertnce; NC • not computed; KG - sample value below blank; NO - noi 4iucuUi « 2o Wank)
-------
TABLE 19. SSMS ANALYSIS SHEET
contractor Research Triangle Institute
Republic Steel, Chicago, IL March 1978
Sample Sita • Sample Acquisition Data
Typsofsourw Q-BOP Secondary Emission Dust During Hot Metal Addition
Test Number . . Sample ID Number
Sample Description T-3 nCydone Catch
GCA
Responsible Analyst - Date Analyzed
Calculations and Report Reviavsed By f Report Date
Instrument '. • Resolution
Internal Standard(s) -- .
Original Sample Volume or Mass ' JL
Dilution Factor
Brief Description of Electrode Preparation .
41
-------
r\>
TABLE 19. (cont'd)
Element
tapper
Nickul
Cobalt
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Clilorine
Sulphur
Phosplioruj
Silicon
Aluminum
Magnosium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
llydroycn
Line Used
for
Estimate
-
-
Uncorrected
Sample
Value
Blank
Value
Corrected
Sample
Value
•
Sensitivity
High/Low
Cilibmion
Stindirdi or
Concentritlon
Added
Anlgned
Concentration*
26.
65.
2.2
4.0
580.
44.
4.8
80.
19. (%)
190.
0.65 (7°)
62.
0.14 (%
390.
0.94
110.
14.
~\o
3.3
At Source
Mass/Volume
mg/m3 or
W/L
0.0047
0.012
0.00040
0.00073
0.106
0.0080
0.00088
0.015
34.7
0.035
1.2
0.011
0.26
0.071
0.00017
0.020
.OO^b
0.000029
0.00060
PPM value (in original simple) or I • interference; NC • not computed; NO • sample value below blank; NO • not detectable «2o blink).
-------
TABLE 1-9. (cont'd)
Element
jQfium
Lanthanum
tarium
tasium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Stronlium
Rubidium
Bromino
Selenium
Arsenic
Germanium
Gallium
Zinc
Lint Used
(or
Estimate
.
Uncorreettd
Samplt
Value
Blank
Value
Corrected
Sample
. Valua
Saniitivity
High/Low
Calibration
Standards or
Concintration
Added
*i
Assigned
Concentration*
<1.1
-------
TABLE 19. (cont'd)
Element
Uranium
Thorium
Uismuih
Lead
Thallium
Mercury
Gold
Platinum
Indium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
llolmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Line Uwrf
tor
Estimate
. v.
'-
Uneorrccted
Simple
Vilue
Blink
Value
Corrected
Simple
Vulue
>
Sensitivity
High/Low
Cilibntion
Standtids or
ConctnUition
Added
Assigned
Concentrition*
<3.0
0.13 (%]
< 1.1
AtSourci
Mist/Volume
mjArr or
W/L
<0. 00055
0.24
^.0002
•Results: PPM value (In original sample) or I • interference; NC • not computed; NG • sample value bctow blank; NO • not detectable «2o blink)
-------
Contractor
-TABLE 20. SSMS ANALYSIS SHEET
Research Triangle Institute
Republic Steel, Chicago, IL c , , . n March 1978
Sample Site • Sample Acquisition Data
Q"BOP Secondary Emission Dust During Hot Metal Addition
Test Number _ , _ , _ s.mp,.,n "* X 5nd B1a"k
Sam?!. Description Parr bombed XAD-2 Resin and Blank
Rasponsibla Analyst u - , __ Oata Analyzed
Calculations and Report Reviewed By - Report Date
Instrument - Resolution
Internal Standard(s) - -
5.0 ml 130 grams at source
9K
Dilution Factor
Original Sample Volume or Mass
25
Brief Description of Electrode Preparation
1.0 grams resin Parr bombed and taken up in 25 ml of solution. 5.0 ml of
solution used in test. Same procedure for sample and blank.
45
-------
TABLE 20. (cont'd)
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanaijium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
lithium
Hydrogen
Lino Used
for
Estimate
Uncorrected
Sample
Valui
0.29
0.039
0.0007
0.31
0.020
0.015
0.0010
0.012
0.63
0.49
8.2
0.11
0.17
0.27
0.053
0.18
0.0013
0.0013
Blank
Value
0.27
0.096
0.002C
0.28
0.036
0.026
0.0018
0.016
0.71
0.23
6.4
0.31
1.1
0.10
0.23
0.0034
0.0017
Corrected
Sample
Vnlua
0.02
NG
NG
0.03
. NG
NG
NG
NG
NG
0.26
1.8
0.11
. NG
NG
NG
NG
NG
NG
Sensitivity
Hioh/Low
Calibration
Standards or
Concentration
Added
Assigned
Concentration*
0.5
NG
NG
0.75
NG
NG
NG
NG
NG
6.5
45
2.8
NG
NG
NG
NG
NG
NG
AtSouret
Miss/Volum*
mj/m' or
W/L
0.06
0.095
0.82
5.7
0.35
en
•Results: PPM vsliio (in original sainpla) or I • intcrfervnce; NC • not computed; NG • sample value Iclow blank; ND -not detectable «2oLlank).
-------
TABLE 20. (cant'd}
ilement
!erium
Lanthanum
larium
Cesium
odine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yltrlum
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc '
Lini Used
lor
Estimate
Unconected
Simple
Value
0.010
- -
IS
<0.0006
<0.0016
0.019
0.0017
0.010
<0.0054
0.0043
< 0.0008
0.70
Blank
Value
0.0030
o.oiy
IS
0.0059
0.024
0.0031
0.0087
0.0040
0.0010
0.91
Corrected
Sampl*
. Value
NG
NG
TS
NG
<0.0006
<0.0016
NG
NG
0.001
<0.0054
0.0003
NG
NG
Sensitivity
Hinh/Low
Cilibntion
Sunderds or
Concentration
Added
H
Anljned
Concentiation*
NG
NG
I*
NR
<0.015
<0.04
NG
f\|G
n.n?R
0.135
0.0075
NG
NG
At Source
Miss/Volume
ma/in' or
«/L
-------
TABLE 20. (cont'd)
ilement
Jranium
Thorium
Jismuth
.cad
Thallium
vlcrcury
Gold
'lalinum
Iriilium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Eibium
llolinium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Lint Uwd
(or
Estlmati
—
Uncorrected
Simple
Vilui
0,043
..
Blink
Value
0.024
Corrected
Simple
Value
0.019
Sensitivity
,
High/Low
Cilibntion
Sundirdi or
Conctntrition
Added
Auipnid
Concentritlon*
0.48
At Source
Mist/Volume
mj/m^ or
W/L
0.061
'
00
•nesulls: PPM value (in original sample) or I •interference; NC-not computed; NG • sample value below blank; NO-not detectable (<2o blank)
-------
Contractor
Sample Site
TABLE 21. SSMS ANALYSIS SHEET
Research Triangle Institute
Republic Steel, Chicago, IL
Sample Acquisition Date
March 1978
Type of Sourca
Test Number
Sample Description First Impinqer Solution
Sample ID Number
2553-1-0
Responsible Analyst
Calculations and Report Reviewed By
Date Analyzed
Report Data
Instrument
Internal Standard(s)
Original Sample Volume or Mass
Dilution Factor
20.0 ml
Brief Description of Electrode Preparation
Resolution
870 ml at source
49
-------
TABLE 21. (cont'd)
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Line Used
(or
Estimate
"• ^
"
Uncorrected
Sample
Value
0.021
0.074
0.0009
0.11
0.014
0.017
0.0001
0.0003
0.022
0.011
0.38
0.0020
0.12
0.0094
0.0046
0.16
0.0015
<0.0001
Blank
Value
0.0036
0.0023
0.0001
0.027
0.0013
0.0010
<0.0001
0.0011
0.18
0.015
0.044
0.0034
0.16
0.0059
0.0051
0.45
0.0026
3 or
W/L
0.014
0.061
<0.0008
0.07
0.011
0.014
<0.0001
0.29
0.0030
-tn
O
• Results: PPM value (in original Mtnplo) or I • interference; NC - not computed; NG • sample value below blank; N D • not detectable « 20 blink).
-------
TABLE ;21; (eont'd)-
Element
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ru(henium
Molybdenum
Niobium
Zirconium
Ylifium
Strontium
Rubidium
Oromino
Solonluni
Artenic
Germanium
Gallium .
Zinc
Lint Used
for
Estimate
.
,-
*
Unconicted
Simple
Value
0.0007
__
< 0.0005
IS
0.0038
< 0.0003
< 0.0001.
< 0.0005
< 0.0001
0.0001
0.0067
Blink
Vilua
0.0018
< 0.0019
IS
0.0017
0.0043
Corrected
Sample
. Value
NG
NG
IS
0.0038
< 0.0003
< 0.0001
NG
< 0.0001
0.0001
0.0024
Sensitivity
High/Low
Calibration
Standards or
Concentration
Addnd
'
Assigned
Concentration*
NG
NG
IS
0.0038
< 0.0003
< 0.0001
NG
< 0.0001
0.0001
0.0024
At Source
Mill/Volume
mg/nr or
jVL
0.0032
< 0.0003
< 0.0001
NG
< 0.0001
0.0001
0.0020
•Results: PPM vilue (in original temple} or I - Interference; NC • not computed; NG • umplo value below blank; ND • not delectable «2o blank).
-------
TABLE 21. (cont'd)
Element
Jranium
Thorium
Jismuih
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Y tier hium
Thulium
Erbium
Holinium
Oyjprusium
Terbium
Gadolinium
Europium
Samarium -
Neodymium
Praseodymium
Line Utod
(or
Estimate
~ —
— -
Uncorrecled
Simpla
Vilui
0.0014
x
..
0.0062
Blank
Valui
0.0090
0.16
\
Corrected
Simple
Value
NG
NG
Sensitivity
IliQh/Low
Cilibntion
Standards or
Concentration
Added
Assigned
Concentration*
N|ft
NG
At Source
Mitt/Volume
mj/m3 or
W/L
•Results: PPM value (In original sample) or 1 • iiitcrfomice; NC • nut computed; NO • sample value below blank; HO • not delectable «2o blank)
en
ro
-------
APPENDIX A
LEVEL I ORGANIC ANALYSES OF SAMPLE 1C1F, IX, AND INORGANIC ANALYSIS DATA
53
-------
Contractor
TABLE A-l. LC ANALYSIS REPORT
Research Triangle Institute
Type of Sourca
Test Number
site Republic Steel, Chicago, IL &„,„,. AGquisitioIJ Oa« March 15, 1978
Q-BOP, Secondary Emission Dust
1
Sampl* ID Number
1C1F
Sample Dajcription.
Uncontrolled Emissions During Hot Metal Addition
0.2138 gms (0.0982 gm extracted - 45.9% each catch)
Original Sampl* Volume or Mas .
J. Cortese
Responsible Analyst
Date Analyzed
Calculations and Report Reviewed By
Handy, Westbrook
Report Data.
Column Row Rats
Observations
Column Temperature
Total Sampls
Taken for LC2
Recovered
TCO
mg
13.9
5.4
4.3
GRAV
mg
19.6
7.7
7.8
Total
mg
33.5
13.1
12.1
Concentration
mg/M3
32.6
12.8
11.8
Fraction
1
2
3
4
5
6
7
Sum
TCO4 in mg
Total
2.1
9.0
0.0
0.0
0.0
0.0
0.0
11.1
Blank
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Cor-
rected
2.1
9.0
.0.0
0.0
0.0
0.0
0.0
11.1
GRAV4inmg
Total
7.1
4.6
4.3
2.0
0.0
6.1
1.5
25.6
Blank
0.8
2.5
0.0
1.0
0.0
0.0
2.5
6.8
Cor-
rected
6.3
2.1
4.3
1.0
0.0
6.1
0.0
18.8
Total*
mg
8.4
n.i
4.3
1.0
0.0
6.1
0.0
30.9
Concentration^
tng/M3
8.2
10.8
4.2
1.0
0.0
5.9
0.0
30.1 '' '
1. Quantity in entire sample, determined before LC
2. Portion of whole sample used for LC, actual mg
3. Quantity recovered from LC column, actual mg
4. Total mg computed back to total sample
5. Total mg divided by total volume
54
-------
TABLE A-2. IR REPORT—SAMPLE NO. 1C1F. CUT LC-1
v, cm
-1
1 y particulate and < 1 u filter
Total Sample SRAV = 6.3 mg
I Assignment Possible Categories
2852-2954
1463
1376
810
v, cm
3035
2872-2958
1602
1456
1377
748-976
S
M
M
W
TABLE
I
M
S
W
S
S
M
CH, aliphatic
CH, aliphatic
CH, aliphatic
CH, substituted
A-3. IR REPORT— SAMPLE NO.
1 u parti culate and < 1 u
Total Sample SRAV =• 2.
Assignment
CH, aromatic/
olefinic
CH, aliphatic
C=C, aromatic
CH, aliphatic
CH, aliphatic
CH, multiplet
Aliphatics
Hal oalipha tics
1C1F. CUT LC-2
filter
1 mg
Possible Categories
Haloaliphatics
Substituted benzenes
Halobenzenes
Fused aromatics
100
10
I
10
100
10
100
55
-------
v, cm
3405
3054
2860-2960
1721
1602, 1577
1502
1452
1402
1308
694-795
Contamination
v, cm
3375-3400
3048
2854-2955
1733
1583, 1495
1458, 1382
1301
1157
694, 756
I
M
M
S
M
S
S
M
S
S
S
TABLE
I
W
W
S
M
S
S
S
M
S
=^==
1 y parti oil ate and <
Total Sample GRAV =
Assignment
NH or OH*
CH, aromatic
CH, aliphatic
CO, ketone/ester*
OC, aromatic
OC, aromatic
CH, aliphatic
Alcohol /phenol*
Aromatic amine*
CH, multiplet
A-5. IR REPORT—SAMPLE
1 u parti cul ate and <
Total Sample GRAV =
Assignment
NH or OH*
CH, aromatic
CH, aliphatic
C0=0, ketone
CH, aromatic
CH, aliphatic
Aromatic amine*
COC, ether
CH, substitute
1 y filter
4.3 mg
Possible Categories
Substitute Benzenes
Halobenzenes
Fused aromatics
NO. 1C1F, CUT LC-4
1 y filter
1.0 mg
Possible Categories
Hetero N Compounds
Hetero 0 Compounds
Hetero S Compounds
Nitriles
Ethers, Epoxides
Aldehydes, Ketones
Nitroaromatics
I
100
10
100
I
100
100
100
10
100
100
10
Contamination
56
-------
TABLE A-6. IR REPORT—SAMPLE NO. 1C1F. CUT LC-5
1 y particulate and < 1 p filter
Quantity Not Sufficient
v, cm
3300-3400
2859-2955
1719, 1701
1570, 1600
1385, 1457
1248-1272
752
TABLE
I
w
s
s
w
M
M
W
TABLE
A-7. IR REPORT— SAMPLE NO.
1 y parti cul ate and < 1 u
Total Sample GRAV =6.1
Assignment
NH or OH (broad)
CH, aliphatic
Carboxylic acid/
ester
Amide, Amine
CH, aliphatic
COC, ester
CH, substitute
A-8. IR REPORT— SAMPLE NO.
1C1F. CUT LC-6
filter
mg
Possible Categories
Phenols
Esters
Hetero N Compounds
Alkyl S Compounds
Sulfonic Acids,
Sulf oxides
Carboxylic Acids
Alcohols
Amides
1C1F. CUT LC-7
I
10
100
100
10
10
10
100
100
100
u particulate and < 1 u filter
Quantity Not Sufficient
57
-------
TABLE A-9. LR MASS SPECTROSCDPY REPORT—SAMPLE 1C1F, CUT LC-1
1 y particulate and < 1 y filter
Categories Relative Intensity
Aliphatics 100
Haloaliphatics 1
TABLE A-10. LR MASS SPECTROSCQPY REPORT—SAMPLE 1C1F. CUT LC-2
1 y particulate and < 1 p filter
Sample Weight Quantity Not Suitable For Analysis
TABLE A-ll. LR MASS SPECTRQSCOPY REPORT—SAMPLE 1C1F. CUT LC-3
1 y particulate and < 1 y filter
Categories Relative Intensity
Substitute Benzenes 1
Halobenzenes 1
Fused Aromatics (MW < 216) 1
Fused Aromatics (MW > 216) 100
Possible Identifications Mol. Wt. Relative Intensity
Indenopyrene, Benzoperylene 276 10
Strong hydrocarbon peaks observed between m/e + 300 and 486.
58
-------
TABLE A-12. LR MASS SPECTROSCOPY REPORT—SAMPLE 1C1F, CUTS LC-4-7
1 u particulate and < 1 y filter
Sample weights of LC 4, 5 and 7 were Quantity Not Suitable For analysis.
Mass spectra of LC fraction 6 was too complex for unequivocal category
identification.
59
-------
Contractor
Sample Site
TABLE A-13. LC ANALYSIS REPORT
Research Triangle Institute
Republic Steel, Chicago, IL
Sample Acquisition Date
March 1978
Type of source Q-BOP. Secondary Emission Dust
1
Test Number
Sample ID Number
IX + Module Rinse
sample
win™ Uncontrolled Emissions During Hot Metal Addition
130 gms.
Original Sampfe Volume or Mass
Responsible Analyst
J. Cortese
Date Analyzed
Calculations and Report Reviewed 8y Handy, WeStbrOOk
Report Oat*.
Column Flow Rata .
Qbsarvattons
Column Temperature
Total Sample
Taken for LC2
Recovered
TCO
mg
0.8
0.7
0.6
GRAV
mg
20.3
17.0
10.1
Total
mg
21.1
17.7
10.7
Concentration
mg/M
20.5.
17.2
10.4
Fraction
1
2
3
4
5
6
7
Sum
TCO4 in mg
Total
0.0
0.0
0.7
0.0
0.0
0.0
0.0
0.7
Blank
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Cor-
rected
0.0
0.0
0.7
0.0
•o.o
0.0
0.0
0.7
GRAV* in mg
Total
3.1
1.3
0.6
0.6
0.2
5.1
1.3
12.2
Blank
0.2
0.0
0.0
0.0
0.0
0.0
0.0
0.2
Cor-
rected
2.9
1.3
0.6
0.6
0.2
5.1
1.3
12.0
Total4
mg
2.9
1.3
1.3
0.6
0.2
5.1
1.3
12.7
Concentration^
mg/M3
2.8
1.3
1.3
0.6
0.2
5.0 ,
1.3/ /
12.5 /
1. Quantity in entire sample, determined before LC
2. Portion of whole sample used for LC, actual mg
3. Quantity recovered from LC column, actual mg
4. Total tng computed back to total sample
5. Total mg divided by total volume
"60
-------
v, cm
2854-2955
1456
1376
v, cm
2861-2955
1739
1263
1033, 1094
1456
1376
806
700
I
S
' M
M
TABLE
I
S
S
S
S
S
M
XAD-2 Resin
Total Sample GRAV =2.9
Assignment
CH, aliphatic
CH, aliphatic
CH, aliphatics
A-15. IR REPORT— SAMPLE NO.
XAD-2 Resin
Total Sample GRAV =1.3
Assignment
CH, alipatic
C=0, ester
or ketone
COC or CX,
aliphatic
(X=Halogen)
COC
CH, aliphatic
CH, aliphatic
Aliphatic
Aliphatic
mg
Possible Categories
Aliphatics
Haloaliphatics
. IX, CUT LC-2
mg
Possible Categories
Fused Aromatics
Ester or Ketone
Haloaromatic
Ether
Substituted
Benzenes
I
100
10
I
100
100
10
100
100
61
-------
TABLE A-16. IR REPORT—SAMPLE NO. TX. 'CUT LC-3
XAD-2 Resin
Total Sample GRAV » 0.6 mg
v, cm
2861-2955
1739
1263
1033, 1094
1456
1376
806
700
v, cm"
2857-2962
1735
1461
1274
1116
1379
702, 667
I
S
s
S
s
s
M
S
S
TABLE
I
S
S
S
M
W
•
Assignment
CH, aliphatic
00
COC or CX
aliphatic
(X-Halogen)
COC
CH, aliphatic
CH, aliphatic
Aliphatic
Aliphatic
A-17. IR REPORT— SAMPLE NO
XAD-2 Resin
Total Sample GRAV =0.6
Assignment
CH, aliphatic
C=0
CH, aliphatic
Ester or CX
(X=Halogen)
COC ether
CH, aliphatic
Aliphatic
Possible Categories
Fused Aromatics
Ester, Ketone
Haloaromatics
Ether
. TX, CUT LC-4
mg
Possible Categories
Hetero S Compounds
Nitrile
Aldehyde, Ketone
Ester
Ether
I
100
100
100
100
I
100
100
100
10
10
62
-------
TABLE A-18. IR REPORT—SAMPLE NO. T.X, CUT LC-5
v, cm
2861-2961
1739
1456, 1376
1263
1025, 1075,
700-806
v, cm
2500-3400
3300-3400
1700, 1725
1556
1275
1124
1456, 1381
711
I
S
S
M
S
1119 M
M
TABLE
I
M
M
S
M
S
S
S
S
XAD-2 Resin
Total Sample GRAV =0.2
Assignment
CH, aliphatic
OO, ester or
ketone
CH, aliphatic
COC or C-Halogen
COC
Aliphatic
A-19. IR REPORT— SAMPLE NO
XAD-2 Resin
Total Sample GRAV =5.1
Assignment
Carboxylate OH
bonded
NH or OH (broad)
Carboxylic acid,
ester, CO ketone
Carboxylate ion
Carboxylic acid,
ester or alkyl-
halide
COC, ether or COH,
alcohol
CH, aliphatic
Aliphatic
mg
Possible Categories
Hetero S Compounds
Ketone
Aldehyde, Ketone
Ester
Ether
. IX. CUT LC-6
mg
Possible Categories
Carboxylic Acid
Carboxylic Acid
Carboxylic Acid
Ester
Alcohol
I
100
100
100
100
10
I
100
100
100
63
-------
TABLE A-20. LR MASS SPECTRQSCOPY REPORT—SAMPLE IX. CUT LC-1
XAD-2 Sample and Module Rinse
Categories
Relative Intensity
Aliphatics
Haloaliphatics
100
1
TABLE A-21. LR MASS SPECTROSCOPY REPORT—SAMPLE TX. CUT LC-2
Categories
XAD-2 Sample and Module Rinse
Relative Intensity
Haloaliphatics
Substitute Benzenes
Halobenzenes
Fused Aromatics (MM < 216)
Fused Aromatics (MW > 216)
Possible Identifications
Mol. Wt.
Naphthalene
Phenanthrarene, anthracene
Fluoranthene, pyrene
Benzof!ouranthene,
benzopyrene
Intense hydrocarbon peaks observed between m/e + 358 and 666.
128
178
202
252
1
100
1
100
10
Relative Intensity
10
100
100
10
64
-------
TABLE A-22. LR MASS SPECTROSCOPY REPORT—SAMPLE IX, CUT LC-3
XAD-2 Sample and Module"Rinse
Categories Relative Intensity
Substitute Benzenes 10
Halobenzenes 1
Fused Aromatics (MW < 216) 1
Fused Aromatics (MW > 216) 10
Possible Identifications Mol. Wt. Relative Intensity
Dibenzanthracene 278 ' 10
Strong hydrocarbon peaks observed between m/e + 358 and 600.
TABLE A-23. LR MASS SPECTRQSCQPY REPQRT--SAMPLE IX. CUT LC-4-7
XAD-2 Sample and Module Rinse
Sample weights of LC 4 and 5 were Quantity Not Suitable for analysis.
Mass spectra of LC fractions 6 and 7 were too complex for unequivocal
category identification.
65
-------
FILE NAME 0003(4
SPECTRR 1 TO
TOTAL ION
11 Id
RELATIVE INTENSITY
40 60
66
-------
Element
TABLE A-24. SSMS ANALYSIS OF SAMPLE NO. 1 PW
(0.054 6) Particulate From Nozzle and Probe Wash
Value (ppm) Element Value (ppm)
BI
PB
W
ER
DY
TB
GD
EU
SM
ND
PR
CE
LA
BA
CS
I
SB
SN
IN
CD
PD
RU
MO
NB
ZR
Y
SR
1.2
410
2.8
< 0.25
< 0.33
< 0.16
< 0.29
< 0.071
< 1.0
1.3
< 0.16
1.3
0.68
80
< 0.052
3.6
1.5
12
IS*
7.2
0.73
< 0.47
150
0.90
3.4
0.70
52
RB
BR
SE
AS
CE
6A
ZN
CU
NI
. CO
FE
MN
CR
V
TI
CA
K
S
P
SI
AL
MG
NA
B
BE
LI
1.2
15
< 12
49
4.1
5
290
62
750
12
9.4 (%)
0.23(%)
0.13(%)
21
12
2.6 (%)
150
0.27(%)
200
0.64(%)
0.11(%)
1.3 (%)
220
29
0.086
0.086
*IS - indicates the element is an internal standard
67,
-------
TABLE A-25. SSMS ANALYSIS OF SAMPLE NO. 1C31Q
(0.0730 G) 3-10 y and > 10 y Cyclone Catches
Element Value (ppm) Element Value (ppm)
PB
W
DY
SM
ND
PR
CE
LA
BA
CS
I
TE
SB
SN
IN
CD
PD
RH
RU
MO
NB
ZR
Y
SR
RB
56
0.73
< 0.17
< 0.27
< 0.35
< 0.083
0.46
0.94
7.5
0.028
0.071
< 0.68
0.55
1.3
IS*
0.12
< 0.25
< 0.066
< 0.41
2.1
4.5
3.9
1.1
28
0.56
BR
SE
AS
GE
GA
ZN
CU
NI
CO
FE
MN
CR
V
TI
CA
K
S
P
SI
AL
MG
NA
B
BE
LI
26
< 14
10
< 0.50
1.3
12
15
14
1.7
7.6 (56)
0.35(56)
76
39
120
2.7 (56)
45
390
150
0.32(56)
230
670
8.3
6.5
0.026
0.12
*IS - indicates the element is an internal standard
-------
TABLE A-26. SSMS ANALYSIS OF SAMPLE NO. 1C1F
(0.0165 G) 1-3 p Cyclone Catch
Element Value (ppm) Element Value (ppm)
BI
PB
ND
CE
LA
BA
CS
I
TE
SB
SN
IN
CD
PD
MO
NB
ZR
Y
SR
RB
BR
SE
AS
< 3.0
0.13(%)
< 1.1
< 1.1
< 1.3
14
< 0.25
< 0.31
< 2.5
< 1.7
5.7
IS*
6.7
< 1.1
5.9
< 0.85
9.2
1.8
120
2.4
< 9.5
< 7.9
21
GE
GA
ZN
CU
NI
CO
FE
MN
CR
V
TI
CA
K
S
P
SI
AL
MG
NA
B
BE
LI
2.5
4.5
500
26
65
2.2
4.0
580
44
4.8
80
19 (%)
190
0.65(%)
62
0.14(%)
390
0.94
110
14
0.16
3.3
*IS - indicates the element is an internal standard
69-
-------
TABLE A-27. SSMS ANALYSIS OF SAMPLE NO. IX
(5.0 ml) Parr Bombed XAD-2 Resin
Element Value (ppm) Element Value (ppm)
PB
BA
IN
NB
ZR
SR
RB
SE
AS
GA
ZN
CU
NI
CO
0.043
0.010
IS*
< 0.0006
< 0.0016
0.019
0.0017
< 0.0054
0.0043
< 0.0008
0.70
0.29
0.039
0.0007
FE
MN
CR
V
TI
CA
K
S
SI
AL
MG
NA
B
LI
0.31
0.020
0.015
0.0010
0.012
0.63
0.49
8.2
0.17
0.27
0.053
0.18
0.0013
0.0013
*IS - indicates the element is an internal standard
TABLE A-28. SSMS ANALYSIS OF SAMPLE NO. 1X-BLANK
(5.0 ml) Parr Bombed XAD-2 Blank
Element Value (ppm) Element Value (ppm)
PB
CE
BA
IN
MO
SR
RB
BR
AS
GA
ZN
CU
NI
CO
FE
0.024
0.0030
0.019
IS*
0'.0059
0.024
0.0031
0.0087
0.0040
0.0010
0.91
0.27
0.096
0.0020
0.28
MN
CR
V
TI
CA
K
S
P
SI
AL
MG
NA
B
LI
0.036
0.026
0.0018
0.016
0.71
0.23
6.4
0.14
0.31
1.1
1.1
0.23
0.0034
0.0017
/
*IS- indicates the element is an internal standard
70
-------
TABLE A-29. SSMS ANALYSIS OF SAMPLE NO. 1IMP1
(20.0 ml) First Impinger Solution
Element Value (ppm) Element Value (ppm)
PB
W
BA
SN
IN
MO
SR
RB
BR
SE
AS
GA
ZN
CU
Ml
CO
0.0014
0.0062
0.0007
< 0.0005
IS*
0.0038
< 0.0003
< 0.0001
< 0.0005
< 0.0005
0.0001
< 0.0001
0.0067
0.021
0.074
0.0009
FE
MN
CR
V
TI
CA
K
S
P
- SI
AL
MG
NA
B
LI
0.11
0.014
0.017
0.0001
0.0003
0.022
0.011
0.38
0.0020
0.12
0.0094
0.0046
0.16
0.0015
0.0001
*IS - indicates the element is an internal standard
TABLE A-30. SSMS ANALYSIS OF SAMPLE NO. 1MP1-BLANK
(20.0 ml) First Impinger Blank (30% Peroxide Blank)
Element Value (ppm) Element Value (ppm)
PB
W
BA
SN
IN
BR
ZN
CU
NI
CO
FE
MN
CR
0.0090
0.16
0.0018
< 0.0019
IS*
0.0017
0.0043
0.0036
0.0023
< 0.0001
0.027
0.0013
0.0010
V
TI
CA
K
S
P
SI
AL
MG
NA
B
LI •
< 0.0001
0.0011
0.18
0.015
0.044
0.0034
0.16
0.0059
0.0051
0.45
0.0026
< 0.0001
*IS - indicates the element is an internal standard
71
-------
TABLE A-31. SSMS AVERAGE DETECTION LIMITS
Element
U
TH
BI
PB
TL
AU
IR
OS
RE
W
HF
LU
YB
TM
ER
HO
DY
TB
GD
EU
SM
ND
PR
CE
LA
BA
CS
I
TE
SB
SN
IN
CD
PD
Value (wG)
0.040
0.058
0.018
0.037
0.022
0.030
0.046
0.050
0.032
0.04-3
0.053
0.012
0.018
0.011
0.032
0.011
0.019
0.005
0.018
0.008
0.032
0.040
0.007
0.010
0.010
0.014
0.002
0.028
0.023
0.016
0.023
IS*
0.029
0.023
Element
RH
RU
MO
NB
ZR
Y
SR
RB
BR
SE
AS
GE
GA
ZN
CU
NI
CO
FE
MN
CR
V
TI
CA
K
S
P
SI
AL
MG
NA
B
BE
LI
Value (yG)
0.008
0.030
0.028
0.003
0.013
0.005
0.007
0.002
0.040
0.016
0.006
0.011
0.004
0.006
0.005
0.004
0.002
0.002
0.002
0.002
0.002
0.002
0.001
0.001
0.006
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
*IS - indicates the element is an internal standard
72
-------
APPENDIX B
OBSERVATIONS OF ACUREX AND RTI PERSONNEL
73
-------
Acurex personnel (Steiner) and RTI personnel (Coy) reviewed the
process data collection techniques during the first heat of the day
( 1:00 pm). RTI was also instructed in the use of the radio to alert Acurex,
the sampling crew and the EPA Region V opacity observer when to start the
actual test.
Operating problems with the bell valve in the quencher hindered
Republic Steel personnel and delayed the heats. Finally, the problems were
resolved and testing commenced at 3:30 pm. Dave Coy logged the following
process data during heat 20764:
(1)
(2)
Scrap Addition - 103,000 Ibs.
Hot Metal Addition - Ladle 1
pit scrap
butts
20,000 Ib.
83,000 Ib.
201,000 Ibs.
Start 3:44:05 pm end 3:45:25 pm
good fume control; puff 10 to 15 seconds
at end.
Ladle 2
212,000 Ibs.
(3)
blow -
start
end
Start 3:48 pm end 3:48:40 pm
poorer fume control; 70 to 80 percent
capture; fume exiting under ladle
3:49:25
4:04:21
(4)
(5)
(6)
(7)
clock blow time 14 min. 56 sec.
02 - 335,600 ft3
Hot Metal Transfer - Ladle 1 3:53 pm
Ladle 2 4:10 pm
Turndown (for temp and sample) - 4:04:21 pm
Rotate to Tap - start
end
tap emissions evident
4:19:30 pm
4:27:15 pm
Slag - 4:30
During HMA - Collection System No. 2
Hood Pressure: -04" H20
Quench Water: 2700 gpm
Stack Flow: 230,000 acfm
Scrubber Water: 2500 gpm
Pressure Drop: 75" H20
Collection System No. 1
200,000 acfm
Sampling was conducted during hot metal addition only (both ladles)
at the midpoint of the duct (5 feet from wall). The probe was removed
from the duct after HMA and was sealed until the next heat.
74
-------
Coy logged the following process data for heat 20765:
(1) Scrap Addition - 104,000 Ibs 20,000 Ib. pit scrap
84,000 Ib. butts
- start 4:31:30 pm end 4:31:55 pm
(2) Hot Metal Addition - Ladle 1 200,000 Ib
Start 4:33:50 pm end 4:35:50 pm
capture not good after 45 sec; fume escapes
under ladle <90 percent capture; large red
puff at end >50 percent capture
- Ladle 2 211,400 Ib.
Start 4:40:10 pm end 4:41:00 pm
fume escapes under ladle; not bad until after
30 seconds.
(3) 02 Blow - start 4:41:35 pm end 4:56:25 pm
clock blow time - 14 min. 43 sec.
02 - 331,900 ft3
(4) Turndown (for temp and sample) - 4:56:30 pm
(5) Rotate to Tap - start 5:10:30 pm end 5:18:20 pm
(6) Hot Metal Transfer - Ladle 1 5:17 pm
Ladle 2 5:25:25 pm
During HMA - Collection System No. 2 Collection System No. 1
Quench Water: 2700 gpm
Stack Flow: 230,000 acfm 200,000 acfm
Scrubber Water: 2500 gpm
Pressure Drop: 75" H20
Coy logged the following process data for heat 20766:
1) Scrap Addition - 102,000 Ib 10,000 Ib ingot butt
20,000 Ib pit scrap
72,000 Ib butts
- start 5:33:20 pm end 5:33:40 pm
(2) Hot Metal Addition - Ladle 1 201,000 Ib
start 5:39:20 pm end 5:40:25 pm
good fume control except 5 to 10 sec. with
minor fume under ladle
- Ladle 2 211,000 Ib
start 5:43:50 pm end 5:44:30 pm
(3) 02 Blow - start 5:45:05 end 6:00:01 pm
clock blow time 14 min. 56 sec.
02 - 335,700 ft3
(4) Turndown (for temp, and sample) - 6:00:15 pm
(5) Rotate to Tap - start 6:13:00 pm end 6:21:00 pm
75
-------
Coy recorded the following process data during heat 20767:
(1) Scrap Addition - 104,000 Ib 10,000 Ib ingot butt
20,000 Ib pit scrap
74,000 Ib butts
- start 6:24:25 pm end 6:24:57 pm
(2) Hot Metal Addition - Ladle 1 209,000 Ibs
start 6:38:50 pm end 6:40:05 pm
fume control poor throughout pour; puff of
red fume at end 50 to 75 percent capture
- Ladle 2 200,000 Ibs
start 6:43:43 pm end 6:44:30 pm
fume control good for 15 sec. then poor
until end -50 to 70 percent capture
(3) 02 Blow - start 6:45:10 pm end 7:00:00 pm
clock blow time 14 min. 40 sec.
02 - 331,800 ft3
Acurex and RTI consulted with the Q-BOP operator at this point in time and
learned there would be no more heats on this shift. The next shift came
on at 11:00 pm. Furthermore, Republic Steel was planning to switch over
from vessel No. 2 to vessel No. 1 the next morning which could take the
entire day. A decision was made to recover the SASS sample that day
rather than leave the sample sit in the sampling train overnight (and
perhaps another day if vessel changeover was not successful).
Acurex took the SASS train to the sample recovery area and
proceeded to recover the samples.
76
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO. ,
EPA-600/2-79-190
2.
. RECIPIENT'S ACCESSION NO.
TITLE AND SUBTITLE
Level 1 Assessment of Uncontrolled Q-BOP Emissions
5. REPORT DATE
September 1979
PERFORMING ORGANIZATION CODE
. AUTHOR(S)
C.W. Westbrook
I. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND AOORESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
1AB604C and 1BB610C
11. CONTRACT/GRANT NO.
68-02-2630, Task 3
2. SPONSORING AGENCY NAME ANO AOORESS
EPA, Office of Research and Development „
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT ANO PERIOD COVERED
Final: 3/78 fo
14. SPONSORING AGENCY CODE
EPA/600/13
5.SUPPLEMENTARY NOTES IERL-RTP project officer is Robert V. Hendriks, Mail Drop 62,
919/541-2733.
6. ABSTRACT
The report gives results of sampling and analysis of uncontrolled emissions
from a Q-BOP, a bottom-blown Basic Oxygen Process for steelmaking, undertaken to
characterize and quantify the particulate, organic, and inorganic species emitted
during hot metal addition to precharged scrap metal. Sampling was in the secondary
emission collection system before the emission control equipment and was conducted
using EPA Level 1 Environmental Assessment Methodology. Particulate concentration
was 1298 mg/cu m and total organic emissions were 64.1 mg/cu m. About 75% of this
material was high molecular weight organics. The less than 3 micrometer solids contaii
over half of all the organics emitted. Although the presence of several carcinogenic
polycyclic organic compounds was suggested by the LRMS analysis, GC-MS analysis
showed that no known carcinogenic compounds were in the emissions. SSMS analysis
indicated that eight elements might exceed Air-Health MATE values if emitted uncon-
trolled. Calculated control levels needed range from 63 to 99.6%.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.lDBNTIFISRS/OPEN ENDED TERMS
c. COSAT1 Field/Group
Pollution
Iron and Steel Industry
Steel Making
Sampling
Analyzing
Basic Converters
Oxygen Blown Converters
Dust
Organic
Pollution Control
Sources
Q-BOP Process
Particulate
Compound 3Stationary
13B 11G
11F 07C
13H
14B
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS f J
Unclassified
20. SECURITY CLASS (This page)
Unclassified
8S-
22. PRICE
SPA Form 2220*1 (9-73)
77
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