United States EPA-600/2-81-038
Environmental Protection
Agency March 1981
v°/EPA Research and
Development
LEVEL 1 ENVIRONMENTAL ASSESSMENT
OF ELECTRIC SUBMERGED-ARC
FURNACES PRODUCING FERROALLOYS
Prepared for
Effluent Guidelines Division
Office of Air Quality Planning and Standards
Office of Solid Waste
EPA Regional Offices 1 - 10
Prepared by
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
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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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ABSTRACT
An EPA-IERL/RTP Level 1 multimedia environmental assessment of the
ferroalloy industry was conducted. The report contains general industry
statistics and the results of sampling and analysis at three plants (six
furnaces total).
The industry is facing severe pressure from imported products and its
continued viability is uncertain. In addition, this report indicates that
the potential for serious environmental problems exists within some seg-
ments of the industry but does not prove that the pollution problems are
occurring. Specifically, the pollution potential of covered (mix-sealed
and sealed) furnaces is substantially higher than for open type furnaces,
primarily due to the high concentration of organics in gases generated by
covered furnaces. The covered furnaces are estimated to generate poly-
cyclic organic material (POM) at the rate of about 1,230 to 11,080 kg/yr
(2,710 to 24,430 Ib/yr) per megawatt of furnace capacity or 208,800 to
1,878,800 kg/yr (460,300 to 4,120,000 Ib/yr) for all U.S. furnaces of this
type. Open furnace POM generation rate is estimated to be 100 to 900 kg/yr
(220 to 1,980 Ib/yr) per megawatt of furnace capacity or 134,500 to
1,210,500 kg/yr (296,500 to 2,668,700 Ib/yr) for all U.S. furnaces of this
type. Covered furnaces comprise only 14 percent of the industry's pro-
duction capacity and no growth in their use is expected. These estimated
nationwide POM generation rates (estimated rates before the emission
control devices) are in the same order of magnitude as estimated POM
generation rates (before control devices) of slot type coke ovens, which
EPA considers to be a major emitter. However, the control devices, which
are in use on all U.S. ferroalloy furnaces, remove most of this material
from the gas stream. Samples from one mix-sealed furnace were analyzed by
GC/MS which gave positive identification of known organic carcinogens in
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both the clean gas discharged by the scrubber (but before passing through
the flare which 1s expected to destroy some organics) and in the water
discharged by the scrubber (which is treated before discharge from the
plant). Low resolution mass spectrographic (LRMS) analysis indicates the
presence of carcinogens in the cleaned scrubber discharged gas (before
flaring) of four of the five scrubber equipped furnaces tested, and the
water discharged from all scrubbers tested (before wastewater treatment),
and in the gases generated by one open furnace served by a baghouse (emis-
sions from the baghouse were not determined). LRMS indicated the presence
of carcinogens in the wastewater discharged by only one (no longer opera-
ting) of the three plants tested.
The report indicates areas in which further study and/or emissions
quantification is needed.
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TABLE OF CONTENTS
Abstract ii
List of Figures vii
List of Tables viii
Acknowledgments ... x
1.0 INTRODUCTION 1
2.0 SUMMARY OF STUDY 3
2.1 FERROALLOY PRODUCTION 3
2.2 MANUFACTURING METHODS 3
2.3 SUBMERGED ARC FURNACES 4
2.4 GENERAL POLLUTION POTENTIAL FROM SUBMERGED ARC FURNACES . . 5
2.5 SOLID WASTE DISPOSAL 6
2.6 FORMATION AND DEGRADATION OF POLYCYCLIC ORGANIC MATTER . . 6
2.7 ENERGY REQUIREMENTS 7
2.8 SAMPLING TEST RESULTS 7
3.0 CONCLUSIONS 19
4.0 RECOMMENDATIONS FOR FUTURE WORK 23
5.0 INDUSTRY BACKGROUND 27
5.1 INDUSTRY STATISTICS 28
5.2 FERROALLOY PLANTS IN THE UNITED STATES 33
6.0 FERROALLOY MANUFACTURE 37
6.1 SUBMERGED ARC FURNACE 37
6.2 VACUUM AND INDUCTION FURNACES 39
6.3 ELECTROLYTIC PROCESS 39
6.4 EXOTHERMIC PROCESSES 39
6.5 PHYSICAL CHEMISTRY OF THE SUBMERGED ARC PROCESS 40
7.0 SUBMERGED ARC FURNACES 41
7.1 FURNACE TYPES—ADVANTAGES AND DISADVANTAGES 41
7.1.1 Totally Open Furnaces 41
7.1.2 Close-Hooded Furnaces 42
7.1.3 Mix-Sealed Furnaces 43
7.1.4 Sealed Furnaces 44
7.2 ANCILLARY EQUIPMENT 44
iv
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TABLE OF CONTENTS (Continued)
7.3 POLLUTION POTENTIAL ...... . 45
7.3.1 Open Furnaces 45
7.3.2 Covered Furnaces ............. 48
7.3.3 Ancillary Equipment .......... 50
8.0 SOLID WASTE DISPOSAL ............... 51
9.0 POM DEGRADATION .... ............... 59
9.1 RATE OF POM FORMATION BY FERROALLOY FURNACES ....... 59
9.2 POM BEHAVIOR IN AQUEOUS SYSTEMS 63
9.3 POM BEHAVIOR IN AIR EMISSIONS 68
9.4 POM DESTRUCTION 69
10.0 POLLUTION CONTROL ENERGY REQUIREMENTS ............. 73
11.0 SCREENING SAMPLES ..... .......... 75
12.0 PLANT DESCRIPTIONS AND TEST RESULTS ....... . . 81
12.1 PLANT A TESTS 81
12.1.1 Plant A General Description 82
12.1.2 Furnace A-l Description ....... 85
12.1.3 Test Description, Furnace A-l 85
12.1.4 Test Results, Furnace A-l 90
12.1.5 Furnace A-2 Description .... 95
12.1.6 Test Description, Furnace A-2 100
12.1.7 Test Results, Furnace A-2 103
12.1.8 Plant A Final Wastewater Discharge 112
12.1.9 Plant A Summary ....... 112
12.2 PLANT B TESTS 117
12.2.1 Plant B General Description 117
12.2.2 Furnace B-l Description 120
12.2.3 Test Description, Furnace B-l 122
12.2.4 Test Results, Furnace B-l 123
12.2.5 Furnace B-2 Description 136
12.2.6 Test Description, Furnace B-2 142
12.2.7 Test Results, Furnace B-2 ............. 143
12.2.8 Plant B Final Wastewater Discharge 158
12.2.9 Plant B Summary 158
12.3 PLANT C TESTS 163
12.3.1 Plant C General Description ]63
12.3.2 Furnace C-l Description ]j>5
12.3.3 Test Description, Furnace C-l '67
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TABLE OF CONTENTS (Continued)
12.3.4 Test Results, Furnace C-l 168
12.3.5 Furnace C-2 Description 182
12.3.6 Test Description, Furnace C-2 183
12.3.7 Test Results, Furnace C-2 183
12.3.8 Plant C Final Wastewater Discharge 209
12.3.9 Plant C Summary 210
REFERENCES 217
APPENDIX A - INFRARED ANALYSIS REPORTS A-l
APPENDIX B - LOW RESOLUTION MASS SPECTROGRAPH RESULTS B-l
APPENDIX C - LC ANALYSIS REPORTS C-l
APPENDIX D - SPARK SOURCE MASS SPECTROGRAPH ORIGINAL DATA D-l
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LIST OF FIGURES
Number Page
1 Location of Submerged Arc Furnaces in the U.S 36
2 Submerged Arc Furnace for Ferroalloy Production 38
3 Emission Control System on Furnace A-l . . . 86
4 Furnace A-2 Emission Control System . .... 101
5 Emission Control System Furnace B-l ...... 121
6 Emission Control System Furnace B-2 . . ...... 141
7 Emission Control System, Furnaces C-l and C-2 ......... 166
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LIST OF TABLES
Number Page
1 Ferroalloy Furnaces Tested 8
2 Summary of Furnace Particulate Generation Data 9
3 Summary of Furnace Organic Generation Data 11
4 Summary of Particulate Air Emission Data 13
5 Summary of Data for Organics and Scrubber Discharge Gas .... 14
6 Scrubber Efficiencies, Percent 15
7 Plant Wastewater Discharge 15
8 General Statistics on Ferroalloys 29
9 Steel and Foundry Production 30
10 Ferroalloy Consumption 30
11 Power Consumption 31
12 Environmental Control Costs and Investment 32
13 Pollution Control Costs 32
14 Submerged Arc Furnaces in the U.S 34
15 Potential Particulate Emissions (1971) 46
16 The Ferroalloy Association Environmental Committee Solid Waste
Task Force Leachate Testing Results 53
17 Data From a Ferroalloy Company's Monitoring Wells at a Typical
Landfill 55
18 Data From a Ferroalloy Company's Monitoring Wells Surrounding
An Unlined Disposal Lagoon 56
19 Energy Requirements for Pollution Control In Ferroalloy Manu-
facture 74
20 Screening Samples 76
21 Submerged Arc Furnaces at Plant A 82
22 Furnace A-l Alloy Analysis 87
23 Raw Feed for Furnace A-l as Given by the Plant 88
24 Manganese Ore Analysis, Furnaces A-l and A-2 89
25 ORSAT Analysis, Furnace A-l 91
26 SASS Test Data, Furnace A-l 91
27 Particulates, Furnace A-l 92
28 Organics, Furnace A-l 94
29 Organic Extract Summary Table, Sample Al-X 96
30 Organic Extract Summary Table, Sample Al-SWD 98
31 Raw Feed for Furnace A-2 as Given by the Company 102
32 SASS Test Data, Furnace A-2 103
33 Particulates, Furnace A-2 105
34 Organics, Furnace A-2 106
35 Organic Extract Summary Table, Sample No. A2-X 108
36 Organic Extract Summary Table, Sample No. A2-SWD 110
37 Plant A Final Effluent 113
38 Organic Extract Summary Table, Sample No. A-PE 114
39 Emission Comparison, Furnaces A-l and A-2 116
40 Submerged Arc Furnaces 118
41 ORSAT Analysis, Furnace B-l 122
42 SASS Test Data, Furnace B-l 123
43 Raw Material Feed for Furnace B-l 124
44 Average Product Analysis, Furnace B-l 125
45 Particulate Levels Before Control Equipment, Furnace B-l .... 126
viii
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LIST OF TABLES (Continued)
Number
46 Furnace B-l, Hg, As, Sb Analysis by AAS
47 Furnace B-l, SSMS Analysis Summary ]2!f
48 SSMS Analysis Furnace B-l, Probe Solids 131
49 SSMS Analysis Furnace B-l, > 3u Solids 132
50 SSMS Analysis Furnace B-l,< 3y Solids 133
51 SSMS Analysis Furnace B-l, Impinger 1 Liquid • • ° 134
52 SSMS Analysis Furnace B-l, Impinger 1 Solids 135
53 Organic Extract Summary Table, Sample No. Bl-PW . . 137
54 Organic Extract Summary Table, Sample No. Bl-X 139
55 Raw Material Feed for Furnace B-2 144
56 Average Product Analysis, Furnace B-2 • 145
57 SASS Test Data, Furnace B-2 145
58 Particulates, Furnace B-2 146
59 Organics, Furnace B-2 148
60 Organic Extract Summary Table, Sample No. B2-PART 150
61 Organic Extract Summary Table, Sample No. B2-X . 152
62 Organic Extract Summary Table, Sample No. B2-K ......... 154
63 Organic Extract Summary Table, Sample No. B2-SWD 156
64 Plant Final Effluent 159
65 Organic Extract Summary Table, Sample No. B-PE ... 160
66 Data Comparison, Furnaces B-l and B-2 ........ 162
67 Raw Materials Feed for Furnace C-l ...... .... 169
68 Velocity Traverse, Furnace C-l Stack ... 170
69 ORSAT Analysis, Furnace C-l ........ 170
70 SASS Test Data, Furnace C-l 171
71 Particulates, Furnace C-l 172
72 Organics, Furnace C-l 174
73 Organic Extract Summary Table, Sample No. Cl-PART 176
74 Organic Extract Summary Table, Sample No. Cl-X 178
75 Organic Extract Summary Table, Sample No. Cl-SWD 180
76 Raw Material Consumption for Furnace C-2 184
77 Velocity Traverse, Furnace C-2 Stack 185
78 ORSAT Analysis, Furnace C-2 185
79 SASS Test Data, Furnace C-2 186
80 Particulates, Furnace C-2 187
81 Organics, Furnace C-2 189
82 Organic Extract Summary Table, Sample No. C2-PART ....... 191
83 Organic Extract Summary Table, Sample No. C2-X 193
84 Organic Extract Summary Table, Sample No. C2-SWD 195
85 DIP-MS Analysis of Furnace C-2 Scrubber Water 198
86 High Resolution Mass Spectrographic Analysis of Furnace C-2
Scrubber Discharge Water Extract 201
87 Results from 1% Dexsil 300 Column, Sample C2-X ......... 203
88 Results from 1.5% SP301 Liquid Crystal Column, Sample C2-X ... 205
89 Estimated Concentrations of Identified PAHs 207
90 Plant C Effluents 209
91 Organic Extract Summary Table, Sample No. C-P50 211
92 Organic Extract Summary Table, Sample No. C-TPD 213
93 Emission Comparison, Furnaces C-l and C-2 215
IX
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ACKNOWLEDGMENT
This report has been submitted by Research Triangle Institute in partial
fulfillment of the requirements of EPA Contract No. 68-02-2630. The authors
are grateful to Dr. Larry G. Twidwell,* who served as EPA Project Officer
throughout most of this study, and to Mr. Robert V. Hendriks for their advice
and technical direction.
RTI also wishes to acknowledge the contributions made by personnel of
Entropy Environmentalists, Inc. who carried out the sampling program and fre-
quently worked under adverse conditions. The authors also wish to express
appreciation to Dr. Robert Handy of RTI under whose direction most of the ana-
lytical work was done.
RTI wishes to extend special appreciation to the ferroalloy industry for
their cooperation with this study. Special thanks are extended to Mr. George
Watson, President of the Ferroalloy Association, and to the management and
personnel of Airco Alloys (U.S. plants owned by Airco Alloys were sold to SKW
Alloys, Inc., MacAlloy, Inc., and Autlan), Chromium Mining and Smelting
Corporation, Foote Mineral Company, Interlake, Inc., and Union Carbide Cor-
poration.
*Now at Montana College of Mineral Science and Technology.
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1.0 INTRODUCTION
In May 1974, EPA published the results of a study of the ferroalloy
industry which would serve as a useful background to this report. The study
discusses production methods, atmospheric emissions, pollution control equip-
ment, and the cost of air pollution control. In October of 1974, EPA pub-
2
lished two volumes containing background information for standards of
performance which gave justification for guidelines on particulate emissions.
Background information documents have also been published for water pollution
3 4
from submerged arc furnaces, from electrolytic ferroalloys, and for calcium
carbide manufacture. All of these sources provide information useful to the
reader.
While developing the guidelines for particulate emissions, EPA gave
serious consideration to standards that would require the use of sealed type
ferroalloy furnaces. The test data showed, among other advantages, that
particulate emissions from sealed furnaces were significantly lower than from
open type ferroalloy furnaces. Industry objected to adoption of this alter-
native on the grounds that sealed furnaces seriously restricted their ability
to manufacture different families of ferroalloy products in the same furnace
and could reduce their ability to respond to rapidly changing market demands.
EPA agreed with this objection and based the standards on best available
control technology for open type furnaces.
EPA did, however, decide to further investigate the subject of product
flexibility recognizing that solution of this problem could ultimately lead
to standards of performance based on sealed furnace technology. This task
was assigned to EPA's Industrial Environmental Research Laboratory (IERL) in
Research Triangle Park, N. C. As a first step, IERL analyzed some of the
samples previously obtained and found indications that sealed furnaces
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generated substantially more organics, including polynuclear aromatics
(PNA)S than did open furnaces, however, open furnaces also generated
significant quantities of these materials. To verify this finding, gases
generated by one sealed furnace, which was alternatively producing silico-
manganese and ferromanganese, were sampled and analyzed. That study,
which experienced some sampling difficulties, did indicate that a signif-
icant concentration of PNAs exist in the gases generated by the furnace and
that high energy venturi scrubbers might be effective in their capture.
Since there are closed, mix-sealed, and open furnaces in this country
prudence dictated that pollutants generated by and discharged from ferro-
alloys furnaces be more fully characterized. The present study is the
first phase of this effort. A complete multimedia environmental assessment
of the industry was desired, however, funding limitations prevented such a
comprehensive study. The study design which resulted from consideration of
funding limitations, and the need to explore the pollutant generation
potential of several ferroalloy furnaces, particularly the mix-sealed type,
does not include furnace types and mode of pollution control O-e., bag-
house or scrubber) in the same proportions as they exist in the industry.
The design is believed, however, to accomplish the next logical step in the
assessment and to represent the best approach for the available funds.
The primary objective of this study is to determine if there is a
significant difference in the types and amounts of organic pollutants
generated by open and mix-sealed furnaces. To accomplish this objective,
detailed testing, by EPA-IERL/RTP Level 1 procedures, was done at three
plants, two furnaces at each plant. Both open and mix-sealed furnaces were
tested and products included ferromanganese, 50 percent ferrosilicon, and
75 percent ferrosilicon. The study design does not allow a complete eluci-
dation of the separate effects of furnace type and product manufactured.
Also, since the gas from mix-sealed furnaces is flared, the actual organic
emission to the atmosphere generally cannot be determined.
This report is intended for use by EPA and industry in assessing the
pollution potential of submerged arc furnace production of ferroalloys and
as a guide in prioritizing their future expenditures of research funds and
efforts.
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2.0 SUMMARY OF STUDY
2.1 FERROALLOY PRODUCTION
The United States is one of the world's largest producers and consumers of
ferroalloys. Annual ferroalloy production in the U.S. is about 1.45 million
tonnes (1.6 million tons). Consumption of ferroalloys by the U.S. is about
2.1 million tonnes (2.3 million tons) annually. Domestic production has
decreased steadily since 1972 and is now at about 1945 levels. Imports have
risen from 2.4 percent of domestic consumption in 1945 to over 45 percent in
the years since 1975. This situation has arisen, not because of a reluctance
to produce by the domestic industry, but because imported materials are cheaper.
The availability of imports at lower prices is due to many factors including
lack of environmental restrictions, cheap energy, and, the industry claims,
dumping of ferroalloys on the U.S. market at unfair prices. The industry has
repeatedly said that unless the U.S. government takes positive action to limit
the influx of imports, possibly through quotas and high tariffs, the American
ferroalloy industry will not survive.
2.2 MANUFACTURING METHODS
Ferroalloys are manufactured primarily in submerged arc electric furnaces.
Other production and refining methods are vacuum and induction furnaces, exo-
thermic (alumino-silico-thermic) processes and electrolytic manufacture of
high purity metals.
The submerged arc furnace consists of a refractory lined crucible with a
tap hole near the hearth level to withdraw the molten product. Power is
supplied to the furnace through carbon electrodes which extend downward through
the charge material to a point slightly above the hearth. Charge materials,
which include ores, scrap iron, gravel, coal, coke, and sometimes woodchips,
are fed to the furnace as required to keep the crucible filled. The electric
current passing into the furnace raises the temperature of the charge into the
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range that the reduction reactions (basically removal of oxygen from the
metals) can occur. Large volumes of carbon monoxide gas are produced in
the reduction reactions. Furnace power consumption rates ranges from
about 7 megawatts to over 50 megawatts depending on furnace size and
product being made.
2.3 SUBMERGED ARC FURNACES
Furnaces are categorized by the type of furnace top cover used.
There are two basic categories (open and covered) and two subtypes for
each basic category. The open category is considered herein to be com-
posed of totally open furnaces in which there is an open gap of one meter
or more between the crucible top and the fume collecting hoods and close
hooded in which this gap is significantly reduced by movable doors or
panels that reduce the amount of air drawn into the hood system. The
covered category includes the mix-sealed furnaces in which a tight-fitting
cover is installed on the crucible and is partially sealed by raw materials
mounded over the openings in the cover through which the electrodes pass,
and sealed furnaces which are similar to the mix-sealed furnace except
mechanical seals are used around the electrodes. Two emission control
systems are used with covered furnaces, one system to withdraw gases from
beneath the cover (primary control system) and a hood system above the
cover to collect fumes escaping the cover (secondary control system).
There are advantages and disadvantages for each type of furnace. The
covered furnaces are advantageous because the gas volumes requiring collec-
tion and treatment are considerably less (sometimes by as much as a factor
of 50) than for open furnaces. The disadvantages are that a scrubber must
be used in the primary emission control system of the furnace because the
gas contains high concentrations (20-90 percent) of combustible gases
(explosion hazard) and organic tar (the cleaned gases are either flared or
used for fuel value) and that only certain types of products can be manu-
factured. Stoking the furnace charge is not possible with the covered
furnaces, and some products tend to form bridges in the furnace which can
lead to violent ejection of gas, charge material, and occasionally molten
metal, when the bridge collapses.
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Open furnaces have the advantages that stoking is possible; thus,
almost any product can be manufactured, with appropriate modifications to
electrode spacing, and that only one system is required for collection of
gases generated by the furnace Cdoes not include tapping controls, etc.).
Another advantage is that the gas burns as it leaves the surface of the
charge material in the furnace, destroying the carbon monoxide and most
organics. The major disadvantage is that large volumes of gas must be
handled by the collection and capture system.
2.4 GENERAL POLLUTION POTENTIAL FROM SUBMERGED ARC FURNACES
The pollution potential of covered furnaces is primarily due to high
concentrations of organics in the gases generated by the furnaces. Data
presented later show that the capture efficiency of scrubbers is greater
for particulate matter than for organics. The particulate escaping the
scrubbers contains 1-4 percent organic matter, generally high molecular
weight compounds, and includes polycyclic organics and known carcinogens.
Flares are used to burn the gases exiting the scrubbers. They are normally
(but not always) operating. The effectiveness with which the flares destroy
the organic material has not been determined. Scrubber discharge waters
also contain the organics and may present problems with solid waste disposal
and discharged water. Fumes going to the secondary and tapping emission
system may also contain organics.
Baghouses, which are generally recognized to be effective in removal
of particulate from gas streams, are used on most open furnaces. Signif-
icant amounts of dust were observed around some baghouses which indicate a
transfer problem [scattering of the dust by winds is possible) at some
plants. Calculations presented later indicate that baghouses have a low
potential for capturing organics, including fused aromatics and possibly
carcinogens, generated by the open furnaces. Scrubbers are used on some
open furnaces, and although generally effective for particulate control,
are less effective for organic capture. The use of scrubbers introduces
the possibility of metals and organics in plant discharge water and leach-
ing or percolation of these components from the wastewater ponds. Energy
usage by scrubbers is higher than for baghouses.
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Fumes are generated during tapping and are difficult to capture.
These fumes may contain organics which probably come from material used to
plug the tap hole and line the tap lip.
2.5 SOLID WASTE DISPOSAL
About 363,000 tonnes (400,000 tons) of solid waste are generated
annually by the ferroalloy industry or about 9,100 tonnes (10,000 tons),
on the average, for each plant. About 30 percent of this material may
contain wastes specifically listed as hazardous by proposed section 3001
of the Resources Conservation and Recovery Act (RCRA). About 85 percent
of the waste is disposed of in landfills or lagoons which are unlined.
The dusts and sludges may contain about 0.1 or 8 percent organic matter
for open and covered furnace production, respectively. Sludges, from
covered furnaces in particular, may contain high concentrations of poly-
nuclear aromatic hydrocarbons including known carcinogens. Industry tests
indicate that the dusts form a hard, fairly impermeable mass (permeability
K values of 10 to 10 cm/sec) when wetted and allowed to dry. Industry
data from monitor wells show virtually no contamination of groundwater
based on analysis for five metals (Ba, Cd, Cr, Pb, and Hg). No data are
available on organic leaching from these sludges. To the best of our
knowledge, there is no evidence available to prove or disprove that seal-
ing occurs.
2.6 FORMATION AND DEGRADATION OF POLYCYCLIC ORGANIC MATTER
Extrapolations of the data indicate that polycyclic organic matter
(POM) are generated by covered furnaces at the rate of about 1,230 to
11,080 kg/yr (2,710 to 24,430 Ib/yr) per megawatt of furnace capacity or
208,800 to 1,878,800 kg/yr (460,300 to 4,120,000 Ib/yr) for all U.S.
furnaces of this type. POM generation by open furnaces is estimated to be
about 100 to 900 kg/yr (220 to 1,980 Ib/yr) per megawatt of furnace capa-
city or 134,500 to 1,210,500 kg/yr (296,500 to 2,068,700 Ib/yr) for all
U.S. furnaces of this type. Calculations for both furnace types are based
on generation rates and are before collection and treatment by emission
control equipment. Thus, estimated nationwide POM generation rates by
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ferroalloy furnaces are in the same order of magnitude as the POM genera-
tion rate of slot type coke ovens, a major POM emitter, which are estimated
to be 317,000 to 3,200,000 kg/yr (7,000 to 7,000,000 Ib/yr) for all U.S.
coke ovens.
Some of this POM is captured by baghouses, some is destroyed by
flares, some escapes to the atmosphere and some, probably most, is col-
lected in scrubber waters. Information is presented which indicates that
the POM concentration in the clarified scrubber water should be less than
its solubility in pure water (POM materials are preferentially absorbed on
suspended solids). Since suspended solids are generally removed from the
scrubber water before chemical wastewater treatment and since previous
research has shown that POMs degrade at a slow rate, it is likely that
most POMs collected by the scrubber accumulate in solid waste disposal
sites and disposal lagoons.
Research work on the fate of polynuclear aromatic hydrocarbons (PNA),
a subcategory of POM, in the atmosphere has shown that nonmutagenic PNA
can be converted to active mutagens in air containing as little as 1 ppm
(volume) of N02, a typical urban pollutant.
2.7 ENERGY REQUIREMENTS
The industry consumes about 8,900,000 megawatt hours of electricity
annually. Pollution control devices account for about 6 percent of this
total. About 2 percent of the power used in operating sealed furnaces is
for pollution control and up to 11 percent of the power used in operating
open furnaces is for pollution control. Surprisingly, pollution control
energy requirements for mix-sealed furnaces with both primary and secondary
emission control system are almost the same as for open furnaces.
2.8 SAMPLING TEST RESULTS
Two furnaces at each of three plants were tested. Scrubbers were
used on five of the furnaces and samples were taken of scrubber waters and
of the scrubbed gas before it was flared. The one furnace tested which
was served by a baghouse was sampled before the pollution control devices.
Samples were also taken of the plant discharge wastewaters. All sampling
was done by IERL/RTP Level 1 procedures which should yield results accurate
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to within at least a factor of three of the actual concentration in the
stream sampled. Analysis of the samples concentrated on the organic
material and only limited testing was done for inorganic components.
The furnaces tested, products being manufactured, operating power
level, and type of pollution control equipment are presented in Table 1.
TABLE
FERROALLOY FURNACES TESTED
Furnace
Type
Product
Power Primary Emission**
MW Control System
A-l Mix-sealed* FeMn
A-2 Open FeMn
B-l Open 50% FeSi
B-2 Mix-sealed 50% FeSi
C-l Mix-sealed 75% FeSi
C-2 Mix-sealed 50% FeSi
11.4 Scrubber -
High Energy
15.8 Scrubber - ***
Medium Energy
48.4 Baghouses
48.0 Scrubber -
High Energy
15.5 Scrubber -
Low Energy -
Disintegrator type
16.8 Scrubber -
Low Energy -
Disintegrator type
*Mix-sealed furnaces vary in the degree of undercover combustion. Essenti-
ally complete combustion was occurring in furnace A-l during tests. Sub-
stantially less combustion was occurring in the other mix-sealed furnaces
tested.
**Flares are used to burn the scrubbed gas on all mix-sealed furnaces.
***Designed for high energy but operating at medium energy during test.
Summarized in Table 2 are the particulate generation rates by the
furnaces (before emission control). The data are only for particulate
going to the primary emission control systems. Thus, tapping and product
handling are not included. Also not included in the data are particulates
going to the secondary emission control systems of mix-sealed furnaces.
This should be considered when comparing data for open and mix-sealed
-------
TABLE 2. SUMMARY OF FURNACE PARTICULATE GENERATION DATA
Furnace
A-l
A-2
B-l
B-2
C-l
C-2
Type
Mix-sealed
Open
Open
Mix-sealed
Mix-sealed
Mix-sealed
Product
FeMn
FeMn
50% FeSi
50% FeS1
75% FeSi
50% FeSi
Operating
Power, MW
11.4
15.8
48.4
48.0
15.5
16.8
kg/hr
47.3
174.9
470.6
447.7
196.7
187.9
kg/MW-hr
4.1
11.1
9.7
9.3
12.7
11.2
kg/Mg alloy
10.1
26.0
49.2
46.0
103.0
68.9
-------
furnaces. For covered furnaces the data are the sum of the particulates
captured by and escaping the scrubber. For furnace B-l the data are for
particulates in the gas going to the baghouse.
With the exception of furnace A-l, there does not seem to be a signif-
icant difference in particulate generation rates from variations in product
type or type of furnace used when compared on a kg/MW-hr basis. Furnace A-l
seemed to be generating more secondary fume (based on visual estimates) than
typical mix-sealed furnaces which may account for the low value obtained.
When compared on a kg/Mg of alloy produced basis, it appears that partic-
ulate generation rates increase in the order of FeMn, 50 percent FeSi, and
75 percent FeSi. The data are not conclusive for different types of fur-
naces since particulate generation rates of furnaces B-l and B-2 are compar-
able but less than for furnace C-2, all 50 percent FeSi product. The
difference may be due to lower efficiency (kw-hr/kg product) in furnace C-2.
Summarized in Table 3 are the organic generation rate data (equivalent
to Table 2 for particulates). In this case, significant differences are
noted when the generation rates are compared on either a kg/MW-hr and kg/Mg
basis. The open furnaces obviously have lower overall organic generation
rates than the mix-sealed furnaces in which limited combustion was occurring.
It is interesting to note the variation in organic generation rates by the
different mix-sealed furnaces. Although the same product was being made in
furnaces B-2 and C-2, the organic generation rates differ by almost a
factor of 3. (A wider variation than expected for determination of total
organics by Level 1 procedures.) This is probably due to more combustion
under the cover of furnace C-2 (reflected in the Orsat analysis in Section
12). This would lead one to believe that the organics generated in furnace
C-l could be substantially higher if less undercover combustion was occurring.
Most interesting are the results for furnace A-l which had almost complete
undercover combustion. The trend observed for the mix-sealed and open
furnaces strongly indicates that more complete destruction of organics
would occur in sealed or mix-sealed furnaces in which complete undercover
combustion was occurring.
10
-------
TABLE 3. SUMMARY OF FURNACE ORGANIC GENERATION DATA
Furnace
A-l
A-2
B-l
B-2
C-l
C-2
Type
Mix-sealed
Open
Open
Mix-sealed
Mix-sealed
Mix-sealed
Product
FeMn
FeMn
50% FeSi
50% FeSi
75% FeSi
50% FeSi
Operating
Power, MW
11.4
15.8
48.4
48.0
15.5
16.8
kg/hr
0.72
5.5
12.0
76.7
19.6
9.9
kg/MW-hr
0.06
0.35
0.25
1.60
1.27
0.59
kg/Mg alloy
0.15
0.82
1.25
7.89
10.27
3.65
-------
Given in Tables 4 and 5 are, respectively, the data for particulate
and organic in the cleaned gas discharged from the scrubbers but before
passing through the flares, if used. Thus, particularly for organics, the
value may be higher than actually emitted to the atmosphere since some
destruction of organics by the flare is expected. With the exception of
furnaces B-l (which was sampled before emission control equipment), A-l
and B-2S particulate emission levels are near or exceed the New Source
Performance Standards [NSPS). (DO not apply to these furnaces). Inclu-
sion of secondary and tapping fumes could have resulted in most furnaces
exceeding NSPS requirements.
The efficiencies of the scrubbers for removal of particulate and
organic matter from the gases generated by the furnaces are given in Table
6. Although all scrubbers have particulate capture efficiencies of over
90 percent, a significant difference in capture efficiency for organics is
observed. As espected, the capture efficiency increased with an increase
in either pollutant inlet concentration or scrubber pressure drop.
The concentrations of particulate and organic in the plant discharge
wastewaters is given in Table 7. These effluents do not contain cooling
or sanitary water.
All samples collected during the test were extracted with methylene
chloride and analyzed by infrared (IR) and low resolution mass spectro-
graph (LRMS). The analyses are not adequate for individual compound
identification but do indicate compound categories and potential compounds
present. Both the cleaned gas and the water discharged by the scrubber
used for control of fumes generated by furnace C-2 were analyzed by gas
chromatograph-mass spectrograph [GC-MS) for exact compound identification.
The IR and LRMS analysis of furnaces A-l, A-2, and B-l, all of which
were achieving nearly complete combustion of the furnace gas, indicate a
low concentration of most organic categories. Potentially low concentra-
tions of the carcinogens, indeno(l,2,3-cd)pyrene and dibenzochrysene
isomer, in emissions to the air from furnace A-2 are indicated by LRMS
responses at masses 276 and 302, respectively. Similarly, low concen-
trations of the carcinogens, benzanthraeene and benzo(a)pyrene, in gases
12
-------
TABLE 4. SUMMARY OF PARTICIPATE AIR EMISSION DATA*
Furnace
A-l
A-2
B-2**
C-l
C-2
Type
Mix-sealed
Open
Mix- sea led
Mix-sealed
Mix-sealed
Product
FeMn
FeMn
50% FeSi
75% FeSi
50% FeSi
Operating
Power, MW
11.4
15.8
48.0
15.5
16.8
Concentration
mg/nm^
49.9
27.7
248.8
825.1
1242
kg emitted
per hour
0.76
5.32
2.24
7.75
12.96
kg emitted
per MW-hour
0.07
0.34
0.05
0.50
0.77
kg emitted
per Mg alloy
0.16
0.79
0.23
4.06
4.75
Calculated assuming the flares on furnaces B-2, C-l, and C-2 do not affect particulate emission rates. Test
data indicate that up to 4 percent of the particulate from mix-sealed furnaces may be organic matter that
may be destroyed by the flare.,
**0niy 1/4 of stated value actually goes to the flare and discharge to the air; 3/4 of the gas goes to the
lime kiln.
-------
TABLE 5. SUMMARY OF DATA FOR OR6ANICS IN SCRUBBER DISCHARGE GAS*
Furnace
A-l
A-2
B-2
C-l
C-2
Type
Mix-sealed
Open
Mix-sealed
Mix-sealed
Mix-sealed
Product
FeMn
FeMn
50% FeSi
75% FeSi
50% FeSi
Operating
Power, MW
11.4
15.8
48.0
15.5
16.8
Concentration
mg/nm3
20.03
23.98
283.72
487.43
195.6
kg emitted**
per hour
0.31
5.6
2.55
4.58
2.04
kg emitted**
per MW-hour
0.027
0.29
0.05
0.30
0.12
kg emitted**
per Mg alloy
0.07
0.68
0.26
2.40
0.75
*
This table summarizes the organic data obtained by sampling in the duct immediately after the scrubber and
before the flare, if used. It is expected that the flare will destroy a substantial fraction of the organics,
but adequate test methods do not yet exist to prove this. For furnace B-2, 3/4 of the gas is burned in
a lime kiln with only 1/4 of the stated value going to the flare. For furnaces A-l and A-2 the data are
for emissions to the atmosphere since the flare of furnace A-l could not operate (the gas burned under
the furnace cover) and a flare is not used on furnace A-2. The flares on furnaces C-l and C-2 were
operating about 75 percent of the time during the test.
**As used here, the term "emitted1 means material in the cleaned gas leaving the scrubber. Refer to the
note above.
-------
TABLE 6. SCRUBBER EFFICIENCIES, PERCENT
Furnace
A-l
A-2
B-2
C-l
C-2
Efficiency for
parti culates
98.4
97.0
99.5
96.1
93.1
Efficiency for
organics
57.2
16.2
96.7
76.7
79.5
TABLE 7. PLANT WASTEWATER DISCHARGE
Plant
A
B
C
Suspended Solids
mg/1 kg/day
9.4 230
2.3 25
17.8 145
mg/1
6.7
12.0
8.0
Organics
kg/ day
163
131
65
15
-------
generated by furnace B-l [before emission control equipment! are indicated
by LRMS responses at masses 228 and 252, respectively. No evidence of
potential carcinogens was found in emissions to the air [primary emission
control system) from furnace A-l. The scrubber discharge water from
furnace A-l contained organic compounds with masses Q.RMS analysis) of 228,
252, 256, and 302 which could be the carcinogens, benzanthracene, benzo(a)-
pyrene, dimethylbenzoanthracene, and dibenzochrysene isomer, respectively.
The scrubber discharge water from furnace A-2 contained, in addition to the
cited organic for furnace A-l, masses at 266 and 276 (dibenzofluorene and
indenoO ,2,3-cd)pyrene, respectively).
The scrubbed gases from the covered furnaces B-2, C-l, and C-2 (meas-
ured before the flares) all contain similar types of organic compounds
although the concentration from the B-2 furnace is lower than from the other
two, presumably due to the higher scrubber efficiency for furnace B-2. For
these furnaces, the LRMS analysis indicates significant concentrations of
fused aromatic organics at masses 252, 266, 276, and 302 which could be the
carcinogens, benzo(a)pyrene, dibenzofluorene, indenoQ,2,3-cd)pyrene, and
dibenzochrysene isomer, respectively. All scrubber discharge waters from
these furnaces contain relatively high concentrations of organics with
masses 228, 252, 256, 266, 276, and 302 which could be the carcinogens
cited previously. Evidence for potential carcinogens (at masses 228 and
252) was found only in the treated process discharge water from plants C.
No evidence of organic carcinogens was found for the treated water dis-
charged from plants A and B.
The GC-MS analysis of the scrubbed gases from furnace C-2 (before
flaring which should destroy some organics) gave positive identification of
13 polycyclic aromatic hydrocarbons [PAH) including the known carcinogens,
benz(a)anthracene, chrysene, benzo(a)pyrene, and indenoO,2,3-cd)pyrene.
Another 10 PAHs were tentatively identified and include the known carcinogen,
benz(j)fluoranthene. Comparison of these data and the Level 1 organic data
with DMEGs data indicate that benzo(a)pyrene in the scrubbed but not flared
gases from furnace C-2 exceed the DMEG value by up to a factor of 80,000.
Likewise, benzo(a)anthracene could exceed the DMEG value by a factor of up
to 230.
16
-------
To summarize these data, it seems clear that all ferroalloy furnaces
produce compounds that could be carcinogenic and that open types (where the
furnace gas is burned before reaching the emission control equipment)
produce substantially less than the covered (mix-sealed type) furnaces in
which little or no combustion occurs. Scrubbers used on the mix-sealed
furnaces capture a large fraction of the organic matter generated.
17
-------
18
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3.0 CONCLUSIONS
The conclusions of this report are based, in part, on sampling and
analysis data obtained using EPA-IERL/RTP Level 1 assessment procedures
which yield final results accurate to within at least 1/3 to 3 times the
actual value of the stream sampled. This approach is used to identify
potential environmental problems and is not in itself sufficient proof that
a problem exists. Appropriately, therefore, the data are interpreted using
the worst case approximation unless data exist to prove this approximation
invalid. Readers should be particularly cognizant of this when reviewing
LRMS and organic compound interpretations. While to some, the conclusions
may seem to be more positive than permissible considering the accuracy of
the data, they are consistent with the Level 1 philosophy briefly outlined
above.
1. U.S. production of ferroalloys has declined during the last decade to
about 1945 levels. Imports have risen from about 2.4 percent of
domestic consumption in 1945 to over 40 percent in the years since
1975.
2. Unless action is taken soon to stem the tide of imports, the continued
viability of the U.S. industry is questionable.
3. There are no plans to expand U.S. production capacity. Rather, some
furnaces are idle, some plants are being closed, and some older fur-
naces are being replaced by larger, more efficient furnaces.
4. There are basically two types of furnaces; open, 86 percent of in-
stalled capacity, in which combustion of the furnace gas occurs before
the emission control equipment, and covered, 14 percent of installed
capacity, in which the gas is combusted after passing through the
emission control system.
5. The pollution potential of covered (mix-sealed) furnaces is substan-
tially higher than for open furnaces, primarily due to much higher
organic generation rates by the covered furnaces. However, mix-
sealed furnaces appear to vary in the rate of organic production
(kg/MW-hr basis) probably due to varying rates of combustion under
the furnace cover. Open furnaces are estimated to generate POM at
the rate of about 100 to 9QO kg/yr (220 to 1,980 Ib/yr) per megawatt
of furnace capacity or 134,500 to 1,210,500 kg/yr (296,500 to
2,668,700 Ib/yr) for all U.S. furnaces of this type. The covered
19
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furnaces are estimated to generate POM at the rate of about 1,230 to
11,080 kg/yr (2,710 to 24,430 Ib/yr) per megawatt of furnace capacity
or 208,800 to 1,878,800 kg/yr (460,300 to 4,120,000 Ib/yr) for all
U.S. furnaces of this type. Control devices, which are in use on all
U.S. furnaces, remove most of this material from the furnace gas.
Thus, the estimated nationwide POM generation rates (estimated rates
before the emission control devices) are in the same order of magnitude
as POM generation rates [before control devices) of slot type coke
ovens, a major POM emitter, which are estimated to be 317,000 to
3,200,000 kg/yr (700,000 to 7,000,000 Ib/yr) for all U.S. coke ovens.
6. The industry generates about 363,000 tonnes (400,000 tons) of solid
waste annually. About 85 percent of which is disposed of in unlined
lagoons and landfills. Although the wastes contain known and/or
suspected hazardous inorganic and organic materials, there is some
evidence that the wastes are self-sealing and that heavy metals do
not leach into the groundwater.
7. The industry consumes about 9 million megawatt hours of electricity
annually, 6 percent of which is used for pollution control. Open and
mix-sealed furnaces use up to 5 times as much energy for pollution
control as does a typical totally sealed furnace.
8. For the six furnaces tested, there appears to be no significant
difference in the kg of particulate generated/megawatt hour of fur-
nace power (before emission control) as a function of furnace size,
type, or product being manufactured. There does appear to be a
difference in the kg of particulate (per megawatt hour of furnace
power) in the gas discharged from the scrubber, which appears to be
related to scrubber design and pressure drop, but may also be a
function of furnace type and/or product being manufactured.
9. Scrubbers appear to be less efficient for capturing organics than for
particulate capture.
10. Low resolution mass spectrographic analysis indicates the potential
presence of carcinogens in the cleaned gas from the scrubbers, before
it was flared, from four of five furnaces tested (the exception being
.one mix-sealed furnace in which complete undercover combustion was
apparently occurring), and in the gas from one open furnace which was
tested before emission control.
11. Low resolution mass spectrographic analysis indicates the presence of
potential carcinogens in all scrubber discharge waters and in the
plant discharge water from only one plant (no longer operating) of
the three tested.
12. Analysis of samples of one mix-sealed furnace by GC-MS techniques
gave positive identification of known carcinogens in the cleaned gas
discharged by the scrubber (but before passing through the flare which
may destroy some of the organics) and in the scrubber discharge water
(before wastewater treatment!"!two of these carcinogens could exceed
20
-------
DMEG values by factors of up to 200 and 80,000, respectively, if
significant destruction does not occur in the flare. These data
provide strong evidence that the preliminary identifications listed
above in 10 and 11 are probably correct.
13. Based on information obtained in these tests, we must conclude that
a potential for a significant multimedia environmental problem
exists with ferroalloy manufacture and that this potential is
significantly greater for plants using mix-sealed and sealed fur-
naces than for those using open furnaces. It has not been estab-
lished that a real environmental problem exists in any of the three
media--air, water, or solid waste.
21
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22
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4.0 RECOMMENDATIONS FOR FUTURE WORK
Identified in this report are several areas where the IERL/RTP Level
1 approach indicates that a potential exists for significant environmental
problems. This section indicates the areas in which the Level 2 and Level
3 work should proceed in order to provide a complete and accurate environ-
mental assessment.
The Level 1 data indicate significant amounts of organics, including
some known carcinogens, are produced by most furnaces, with the largest
amount (on a kg/megawatt hour of furnace power basis) being produced by the
covered (mix-sealed and sealed) types. Although the covered furnaces make
up only 14 percent of the industry (on a power consumption basis), the data
indicate they produce as much, if not more, POM than does the 86 percent of
the industry using open furnaces. Although the present trend is to retire
older covered furnaces, and the industry speculates that any future con-
struction would include only open type furnaces, some covered furnaces will
remain in operation and future construction of covered furnaces cannot be
ruled out completely. Therefore, it is necessary that any future work
consider both types of furnaces.
Any future work should proceed in a straightforward and logical
manner. That is, as a first step, more accurate testing should be done to
quantify the pollutants produced by the furnaces and determine how much is
ultimately discharged to the environment through any and all three media.
If these tests should prove that unacceptable amounts of pollutants are
emitted, or are disposed in an environmentally unsound manner, work should
be initiated to determine if the public is being, or is likely to be,
endangered. If these studies indicate public endangerment, studies should
be undertaken to reduce pollutant releases from the industry.
Specifically, the following additional work is recommended. More
accurate sampling (i.e., isokinetic, duct traverse, integrated composite
23
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water sampling) and analysis (GC-MS, for example) need to be used to
quantify discharges from the plants to all media. For plants using only
open furnaces and capturing and disposing of only dry dust (baghouse
control system), sampling will be required for emissions from the baghouse
and for surface water runoff and groundwater intrusions from the dust
disposal site. A few locations control emissions from open furnaces with
scrubbers or slurry the dust captured by the baghouse. The number and
size of these facilities are probably not large enough to warrant detailed
testing. Sampling in the gas stream before the control device (baghouse)
and of the collected baghouse dust is also recommended since these tests
will allow a measure of control efficiency for the contaminants, a measure
of contaminants entering the disposal sites, and an indication of possible
emissions in the event of control device failure (bag rupture, etc.).
Quantifying emissions to the air from covered (mix-sealed and sealed)
furnaces is extremely difficult since the gas is flared on discharge to
the atmosphere. At present, there are'no established techniques for
measuring emission rates from flares. It is recommended, therefore, that
the gas be sampled in the duct after the scrubber and before the flare.
This should provide a reasonable estimate of particulate emissions, although
some change in mass is to be expected since flaring may change the form of
some of the particulate components and is expected to burn-off some of the
organics on the particulate matter. Determining the actual organic emission
rate is complicated by the fact that the flare will destroy some of the
organic matter and the percentage destruction (for total organics or for
individual compounds) cannot be accurately measured. As a first approxi-
mation, it can be assumed that the flare is 100 percent effective and the
emission rate calculated based on the percent of time that the flares are
not operating. (Determination of the average percent of time that flares
do not operate may require a brief industry survey.) Other assumptions
about flare efficiency could be made. If adequate methods are developed,
and actual assessment of flare effectiveness should be made.
24
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The wastewater discharged by the plant should be analyzed for priority
pollutants including polynuclear aromatics. The possibility of leaching
inorganics and organics into the groundwater at disposal sites and lagoons
should be examined. This can be done by analyzing leachate from sludge
taken from a selected site and by taking samples from monitor wells at the
site. In conjunction with this work, studies should be made of the sludges
and dust to determine if they act as sealants for the disposal site.
It is recommended that in conjunction with the above tests, the water
discharged by the scrubbers on the furnace be tested since this provides
information as to the control efficiency of both the scrubber and the
wastewater treatment system.
If the above test should prove that unacceptable amounts of pollutants
are emitted or are disposed of in an environmentally unsound manner, work
should be initiated to determine if the public is, or is likely to be,
endangered. To accomplish this, modeling studies for the pollutants of
concern should be done to determine the potential impact on the population
surrounding a plant. An assessment of the health records of workers,
former employees, and, possibly the nearby population may be useful in
connection with this study.
If the weight of evidence gathered indicates public endangerment, work
should be initiated to reduce pollutants emitted by the industry. While we
cannot predict with certainty which pollutants would be involved or which
media would have the most impact, we can suggest some areas in which addi-
tional work might be fruitful. Included in these suggested efforts below
are some already being instituted by the industry.
1. Improved flare design and operability.
2. Improved scrubber efficiency, particularly for organics.
3. Reduced gas volume from open furnaces, possibly by the use of
close hooding.
4. Investigate the possibility of controlled undercover combustion
in mix-sealed and sealed type furnaces for organic matter destruc-
tion. (This would be a radical departure from conventional opera-
tion and would require extensive effort).
25
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5. Investigate improved water treatment methods, including clarifi-
cation and filtration for improved suspended solid removal and an
investigation of the applicability of reuse and/or recycle of
wastewater since this has the potential for significantly reducing
mass emissions of suspended solids (on which polycyclic aromatic
hydrocarbons can be absorbed) and dissolved materials.
60 Investigate alternate methods for treatment or disposal of solid
wastes generation.
26
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5.0 INDUSTRY BACKGROUND
Ferroalloy production is a small, but vital part of the iron and steel
industry. Ferroalloys are mixtures of iron and alloying elements which when
added to molten steel give it the unique character and properties needed
for different applications. About 18.1 kg C40 Ibs) of the alloy are used
in the production of 907 kg (one ton) of steel. This 2 percent addition is
a major factor in making the difference between the steel used in a paper
clip and that used in the girders for a bridge.
There are hundreds of various compositions and grades of ferroalloys,
but they can be grouped into three major categories: Manganese and manga-
nese alloys, silicon and silicon alloys, and chromium and chromium alloys.
Small amounts of other ferroalloys are produced which contain alloying
metals such as vanadium, columbium, molybdenum, and nickel. Although the
iron and steel industry is the largest consumer of 'ferroalloys, other
industries use some of the products. For example, silicon metal is used in
the aluminum industry as an alloying agent and in the chemical industry for
producing silicones.
Ferroalloy producers supply material to the steel industry and do
not, themselves, produce the finished steel product. Steel companies have,
however, produced some high carbon ferromanganese in blast furnaces. This
process is not considered part of the ferroalloy industry. Conditions in
the blast furnace are not adequate to produce other types of ferroalloys.
The classification of some materials as ferroalloys is somewhat arbi-
trary. Calcium carbide, for example, is sometimes considered a ferroalloy
because it is frequently produced at ferroalloy plants and in the same type
equipment. Its end use, however, is not the same. Ferrophosphorus is an
alloying material produced in the same type equipment as the ferroalloys,
but it is considered a byproduct of phosphorus manufacturers. This report
concerns itself with the conventional production of ferroalloys in the
27
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submerged electric arc furnace. Ferrophosphorus, calcium carbide, electro-
lytic production of relatively pure metals, vacuum furnace production, and
the aluminosilico-thermic processes are essentially not considered.
5.1 INDUSTRY STATISTICS
The U.S. production and consumption of ferroalloys is among the highest
in the world and probably rivaled only by the Japanese as the world leader.
The industry employs about 8,000 people and has a payroll well in excess of
100 million dollars.
o
Table 8 gives the historical production and consumption of ferroalloys
O Q
in the United States while Tables 9 and 10 give the U.S. steel and foundry
consumption for the three major categories of ferroalloy products. It is
particularly interesting to note that U.S. ferroalloy production has de-
creased in recent years to about 1945 rates, but imports have grown from
8
2.4 percent in 19.45 to over 40 percent of total U.S. consumption. Table 11
gives the total industry power consumption for 1970-1977. Average consump-
tion is, therefore, about 5.66 kw-hr/kg (2.57 kw-hr/lb) of alloy.
8 8
Tables 12 and 13 give some historical data on the expenditure for
environmental protection. Pollution control costs are averaging slightly
less than 4 percent of industry sales. Power consumed for pollution control
is about 6 percent of total power consumed by the industry.
The statistics do not paint a picture of a healthy industry. The
severe pressure from imports has limited the industry's ability to build new
910
facilities to meet the domestic need. The industry claims ' that foreign
producers have been able to ship products into the United States at a price
that doesn't even cover production costs and that some products (e.g..
75 percent FeSi) from developing countries can enter the United States duty
free. The industry fears that unless they get "a fair shake from the trade
g
policies of this country" they may be forced out of business.
The industry reports .few, if any, plans for any new production furnaces
in the near future. The replacement of old, small furnaces by large, more
efficient types and closing of plants or shutting down some furnaces appears
to be the present trend. Airco, Inc., for example, has sold its entire
ferroalloy operations division, and Plant C of this report has been shut
down.
28
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8
TABLE 8. GENERAL STATISTICS ON FERROALLOYS
(FERROMANGANESE, FERROCHROME, FERROSILICON, AND RELATED METALS)
Thousand net tons gross weight
Year
1945
1950
1955
1960
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977 (P)
Imports
39.2
105.2
81.6
143.4
351.4
669.2
342.1
321.1
433.0
372.8
387.8
586.0
716.7
828.2
859.0
993.5
1,013.2
Domestic
Consumption
1,607.1
1,881.9
2,132.9
1,816.3
2,518.5
2,601.1
2,294.2
2,368.3
2,477.2
2,206.5
2,260.8
2,474.7
3,008.4
2,919.6
2,097.7
2,269.6
2,340.7
Imports as
percent cons.
2.4
5.6
3.8
7.9
14.0
25.7
14.9
13.6
17.5
16.9
17.9
23.7
23.8
28.4
40.9
43.8
43.8
Domestic
Production
1,665.7
1,785.6
2,224.6
1,971.8
2,585.1
2,497.9
2,526.2
2,438.1
2,437.1
2,364.2
2,163.4
2,334.7
2,306.4
2,107.9
1,758.7
1,741.6
1,629.6
P = Partial year results extrapolated to full year.
29
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TABLE 9. STEEL AND FOUNDRY PRODUCTION8
Total raw steel Alloy steel
Stainless steel Fdry cstgs. shipped
(Million tons) (Thousand tons)(Thousand tons) (Million tons)
Year Iron Steel
1970
1971
1972
1973
1974
1975
1976
1977 (P)
131.5
120.4
133.2
150.8
145.7
116.6
128.0
125.3
12,824
12,173
13,979
16,163
16,962
15,171
14,308
15,341
1,279
1,263
1,564
1,889
2,150
1,111
1,680
1,862
14.8
14.4
16.3
18.1
16.6
13.2
15.0
16.0
1.7
1.6
1.6
1.9
2.1
1.9
1.8
1.7
TABLE 10. FERROALLOY CONSUMPTION8
1970
1971
1972
1973
1974
1975
1976
1977 (P)
Mn
906.9
820.2
878.1
1,023.8
1,033.4
825.5
838.0
809.5
Cr
(Thousand S.T. )
214.2
198.2
239.4
315.6
359.9
201.3
248.2
257.0
Si
352.0
383.0
461.1
562.9
534.2
393.1
453.7
467.5
30
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8
TABLE 11. POWER CONSUMPTION
Kilowatt hours
1970 10,306,658,159
1971 9,630,993,011
1972 9,599,319,438
1973 10,299,993,808
1974 10,540,057,686
1975 8,224,474,156
1976 8,935,966,337
1977 8,923,241,136
31
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TABLE 12. ENVIRONMENTAL CONTROL COSTS AND INVESTMENT8
Capital expenditures (millions of do!
1970-1974
1975
1976
1977
1975
1976
1977
All expenditures
181
109
65
41
TABLE 13.
Millions of
Pollution
control
25
27
33
Air pollution Water
74
46
28
13
POLLUTION CONTROL COSTS8
dollars Millions of
Industry Pollution
sales control
680 400
772 512
780 548
lars
pollution
2
1
2
11
kwhrs
Industry
total
8,224
8,935
8,923
32
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5.2 FERROALLOY PLANTS IN THE UNITED STATES
1 2
Table 14 gives the current information on ferroalloy plants in the
United States. The list is essentially restricted to plants producing the
primary products associated with ferroalloy. Thus, the list does not
include the plants producing specialty products Ci.e., FeMo, NiCb, etc.);
plants where only CaC2 is produced; or production by the electrolytic,
vacuum, and alumino-thermic processes. Under current conditions with
plants being sold and furnaces being retired, we cannot be certain the
listing is completely accurate. Figure 1 shows the locations of plants
listed.
33
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TABLE 14. SUBMERGED ARC FERROALLOY FURNACES IN THE U.S., MAY 1980
CO
Producer
Alabama Alloys
Chromasco Ltd.
Compania Minera
Autlan, S.A. de C.V.
Foote Mineral Co.
Hanna Mining Co.
Interlake Inc
International Minerals
and Chemicals - TAC
Alloys
Kawecki -Beryl co
KB I, Cabot
MacAlloy Corp.
Northwest Alloys
Location
Woodward, AL
Woodstock, TN
Mobile, AL
Graham, WV
Keokuk, I A
Riddle, OR
Wenatchee, WA
Beverly, OH
Selma, AL
Bridgeport, AL
Kimball, TN
Springfield, OR
Charleston, SC
Addy, WA
Furnace
Types
Open
Open
Sealed
Open
Sealed
Open
Open
Open
Open
Open
Open
Open
Open
Open
Number Total Capacity
Furnaces by Type, MW
1
4
1
3
2
1
4 (one always
in standby)
5
2
1
1
1
2
2
7
42
27
79
35
12
36 (9 MW in
in standby)
70
33
40
20
18
80
45
Normal Products
FeSi
FeCr, FeSi
SiMn
FeSi & Proprietary
Alloys
Silvery iron
FeSi
FeSi, Si Metal
Si, FeCrSi, FeCr
Si Metal
FeSi
FeSi
Si et al .
FeCr
FeSi, Si-
Control Equipment
Baghouse
Aeronetics Scrubber
Scrubber
Baghouse
Scrubber
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
ESP
Baghouse
-------
TABLE 14. (Continued)
en
Producer
Ohio Ferroalloys
Reynolds Metals
Stralloy Inc.
SKW Alloys Inc.
South African Manganese
Amcor Ltd. (SAMANCOR)
Union Carbide Corp.
Furnace
Location Types
Phllo, OH
Powhatan, OH
Montgomery, AL
Sheffield, AL
Steubenvllle, OH
Calvert City, KY
Niagara Falls, NY
Rockwood, TN
Alloy, WV
Ashtabula, OH
Marietta, OH
Portland, OR
Open
Open
Open ""
Open
Open
Open
Open
Open
Open
Open
Mix-sealed
Open
Mix-sealed
Open
Mix-sealed
Number
Furnaces
7
4
3
2
4
6
2
7
10
1
3
2
6
1
2
Total Capacity
by Type, MW
148/156
54
54
28
40
139
45
67/87
182
50
77
45
61/69
8
12
Normal Products
FeSi, FeMn, SiMn
SI Metal
SI Metal
Si Metal
FeCr, FeCrSi
FeSi, FeMn,
SiMn, CrSi
FeSi, FeCrSi
FeSi, FeMn, S1Mn
SI, FeSi, SiMn,
FeMnSi, CaSi
FeSi
FeSi
FeMn, SiMn
FeMn, FeCr
SiMn
FeMn
Control Equipment
Scrubbers and bag-
houses
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse-Scrubber on
one furnace
Baghouse
Scrubbers
Scrubber
Scrubber
Baghouse
Scrubber
-------
Figure 1. Location of submerged-arc furnaces in the United States.
36
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6.0 FERROALLOY MANUFACTURE
This section contains a brief description of ferroalloy manufacturing
processes. More complete descriptions can be found in the open literature.
Ferroalloys are manufactured in submerged-arc furnaces, vacuum furnaces,
induction furnaces, and by the electrolytic and exothermic (alumino-
silico-thermic) processes. The submerged-arc process predominates and is
the main subject of this report.
6.1 SUBMERGED-ARC FURNACE
Almost all furnaces of this type are of the same general design shown
schematically in Figure 2. The furnace shell is typically cylindrical and
constructed of steel. The interior walls are lined with refractories or
carbon bricks. One or more tapholes in the furnace shell are provided for
removing product and slag.
Typically three carbon electrodes extend into the furnace to within a
few meters of the furnace bottom. Vertical movement of these electrodes
is possible and is used to partially control power input to the furnace.
Feed materials are added to the furnace on an as-needed basis so that the
furnace is filled at all times. Power is supplied to the furnace through
the carbon electrodes. Most reactions (smelting) occurs in a limited
region near the tip of the electrodes. The power supplied is sufficient
to produce the alloy in a molten state. The reduction reactions which
occur in the furnace produce large quantities of carbon monoxide (from the
carbon based reductants added) as well as other gases, including moisture
from the charge materials, decomposition products of the feed materials
and intermediate products of reactions. The gases rising through the
furnace charge contain fume from the high temperature region and also
entrain finer size constituents of the charge.
In open-type furnaces (no top cover) the escaping gases burn on the
surface of the charge. These gases are collected and cleaned in a variety
37
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ELECTRODES
REFRACTORY
LINING
CHARGE
MATERIAL
MOLTEN FERROALLOY
CARBON HEARTH
SHELL
CRUCIBLE
TAP HOLE
\ LADLE .g.
iL^J^rdK-gg*
Figure 2. Submerged-arc furnace for ferroalloy production.
38
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of pollution control devices. In covered furnaces no Cor limited) combus-
tion normally occurs under the cover, and the gases are cleaned in scrubbers
and then flared.
Tapping [withdrawal of product] occurs at either preset time intervals
or after a specified power consumption. The molten alloy is collected in
ladles, any finishing reactions completed, and the alloy poured into molds
to cool before being crushed and graded.
6.2 VACUUM AND INDUCTION FURNACES
Vacuum furnaces are used primarily to produce low carbon ferrochrome
from the high carbon alloy produced in the submerged arc furnace although
other type products are also produced. The crushed alloy or other feed
material is placed in a large vacuum chamber and heated to near its melting
point under a vacuum. The carbon in the alloy reacts with oxygen (from
silica or chrome oxide) and is removed as carbon monoxide by steam ejectors.
Chamber heating is by electrical resistance elements.
Induction furnaces produce small tonnages of specialty alloys by
remelting the required materials.
6.3 ELECTROLYTIC PROCESS
Electrolytic processes are used to produce very high purity chromium
and manganese. A solution of the desired metal is prepared, and low-
voltage direct current is passed through the solution. The product is
produced as a deposit (2 cm thick) on the cathode. The feed material for
the process may be alloy from the submerged arc process, high metal content
slags, or ores. Feed preparation for ores may include calcining and leaching,
There is minimal air pollution from the process, but some treatment of the
metal containing wastewaters and sludge is usually required. More detailed
discussion of this process can be found in reference 4.
6.4 EXOTHERMIC PROCESSES
In the exothermic processes, molten alloys are blended with silicon or
aluminum as the reducing agent. These materials react with oxygen in the
alloy and generate considerable heat. For example, to produce low carbon
ferrochrome (LCFeCr) by silicon reduction, the following steps are employed.
39
-------
Chrome ore and lime are fused to form the melt. A precise amount of ferro-
chrome silicon alloy is then added. The reduction reaction is rapid and
produces LCFeCr and a calcium silicate slag. Further refining and reaction
steps may be employed to recover the metal values. For about 5 minutes per
heat, the elevated temperature and strong agitation occurring in the reac-
tion mixture produces particulate emissions with characteristics similar to
those from the submerged arc furnace.
6.5 PHYSICAL CHEMISTRY OF THE SUBMERGED-ARC PROCESS
A detailed discussion of the physical chemistry of ferroalloy production
is beyond the scope of this project. More information can be obtained from
1 13
the cited references. ' A brief overview of the process is presented below.
The raw materials used are, depending on product made, usually quartz
(or some other form of silicon], ores (manganese, chrome, etc.), scrap iron,
and reducing agent (coal, coke). Wood chips, which are added primarily for
porosity within the furnace charge are sometimes added (principally to high
silicon alloys) and can be considered a reductant.
The purpose of the reducing agents is to remove oxygen from the metal
oxides so that the molten metal can accumulate in a pool in the bottom of
the furnace. Before this reaction can take place, the feed material must
be raised to a high temperature. This is accomplished by the conversion of
electrical energy to heat as the electricity flows from the electrodes
through the charge material. Temperatures in the lower levels of the
reaction zone may approach 3650°C (6600°F).
The simplified equation below illustrates the reactions occurring in
the production of 50 percent FeSi.
2 Si02 + Fe203 + 7 C -> 2 FeSi + 7 CO
As can be seen, a large quantity of carbon monoxide is produced in the pro-
cess.
40
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7.0 SUBMERGED ARC FURNACES
Included in this section are descriptions of the different types of
submerged-arc furnaces, some of the advantages and disadvantages of each
type, and a discussion of the potential pollution aspects of each type.
7.1 FURNACE TYPES - ADVANTAGES AND DISADVANTAGES
The basic design of the furnace shell, as described in Section 6, is
very similar for all ferroalloy submerged arc furnaces. Furnace types
referred to in this report, and consistent with, industry terminology, are
categorized primarily by the type of furnace top cover used. There are
four basic types of furnace top covers: Totally open, close hooded, mix-
sealed, and sealed. Each type has unique operating advantages and dis-
advantages, both for the production of alloy and for pollution control.
7.1.1 Totally Open Furnaces
This type furnace is the predominant design in use in the United
States. There is no cover of any kind on the furnace. Gases rising out of
the furnace mix with ambient air and burn on the surface of the raw material
charged to the furnace. The gases are then drawn into a collecting hood
which typically is 2-3 meters [6-9 feet) above the furnace.
The open furnace system offers several advantages. Since the hood is
well out of the way of the furnace top, access to the furnace is virtually
unrestricted. This allows ready access with machinery to stoke the furnace
charge [drive probes into the material to break up any hard crust or bridges
which may form). This is an important advantage when makfng certain types
of alloys (silicon metal, for example) which tend to form solid bridges in
the furnace charge. If a bridge is allowed to form, gases produced by
furnace reactions can become trapped in the lower region of the furnace.
When the bridge breaks or collapses, the rapidly escaping gas can eject raw
material and occasionally molten metal from the furnace. These occurrences
41
-------
are called "blows" by the industry. They obviously present a danger to
equipment and personnel. Five employees of one plant were killed in an
accident of this type (sealed furnace) in 1979.
Another important advantage of the open furnace type is that it allows
the spacing between electrodes to be changed without major modifications to
the furnace overhead system. Electrode spacing is an important consideration
in efficiently producing different families of products. This spacing can
usually be varied enough in an open furnace (with some modifications) to
allow manufacturing of most ferroalloy types. This is an important advantage
in an industry where the demand for various products is variable.
A third advantage is that only one emission control system is required
to collect fumes from the furnace. This means fewer pieces of operating
equipment that must be built, maintained, and monitored.
There are some disadvantages to the open furnace, however. In order
to effectively collect the fumes from the furnace, the hood system must
draw in very large volumes of air. Large air handling systems (ducts, fans,
scrubbers, or baghouses) must be built. Capital and operating costs for
the system can be quite large. Since large volumes of air are drawn into
the hoods, flame temperatures are reduced (below that occurring at near
stoichiometric air-fuel conditions) and may result in incomplete combustion
of some organics. A further disadvantage is that most scrubbers and bag-
houses are designed to produce a cleaned effluent of a certain quality
(i.e., x mg/m ). Thus, for equivalent effluent quality produced, the mass
emissions are larger for the higher air flows.
7.1.2 Close-Hooded Furnaces
In an effort to retain many of the advantages and reduce the dis-
advantages of the totally open furnace, some companies have installed mov-
able doors or panels between the hood and the furnace top to restrict the
air flow. Thus, access to the furnace, for stoking, etc., can be obtained
by opening the doors, and there is little restriction to changing electrode
spacing. With the doors in place, air flow can be restricted without a
decrease in fume capture. The reduced air flow can, however, be both an
advantage and a disadvantage. The lower air flow rate means smaller emis-
sion control equipment (scrubbers, baghouses) is required and, overall mass
42
-------
emissions should decrease, compared to the totally open furnace. Also, the
gas temperature is substantially higher, increasing the probability that
the more refractory organics can be destroyed. One company, Chromium
Mining and Smelting Company (CHROMASCO) has taken advantage of the high gas
temperature by installing a scrubbing system that extracts heat from the
gas and uses it, through steam generation, to produce the furnace draft.
However, some problems have been noted with the system. A disadvantage of
the high temperature that results from restricting the air flow is the
extra precautions that must be taken to protect exposed equipment.
7.1.3 Mix-Sealed Furnaces
In this furnace design, a water-cooled cover is installed directly
on the furnace top. There are doors on the side of this cover to allow
some access for observation but very limited access for stoking. Feed
materials [mix) are added to the furnace through the annular spaces around
the electrodes which pass through the cover. Sufficient mix is kept around
the electrodes so that, as long as a slight negative pressure is maintained
beneath the cover, little furnace gas escapes the furnace cover, and little
air is drawn into the furnace.
An advantage to this design is that the very low gas volumes exiting
the furnace allow the use of much smaller pollution control equipment than
for open furnaces and thus, lower operating expense. Although a secondary
hood over the furnace is required to collect gas and fumes escaping the
cover (primarily from the mix-seals), the relatively low air volume from
this source can be handled in a baghouse which has low capital and operating
cost. The total cost of the two systems, however, may be as much as for a
similar size open furnace. A second advantage is that the furnace gases
can be used, after scrubbing, as plant fuel. This option is seldom exer-
cised in the United States, however, and most gases from the covered type
furnaces are flared. Covered or mix-sealed furnaces are used primarily for
pollution control purposes where there is little danger of violent furnace
"blows."
Disadvantages to the furnace are that two fume collection systems are
required, stoking the furnace is virtually impossible, and that combustion
of the organic matter generated by the furnace is minimal. This latter
43
-------
problem could be a major disadvantage of the nature of the organic matter
generated as shown in later sections.
7.1.4 Sealed Furnaces
Sealed furnaces are similar to the mix-sealed type. The major
difference is that mechanical seals are used around the electrodes and the
feed mix is added to the furnace through sealed chutes. The furnace sealed
in this manner allows virtually no gas and fume to escape from the furnace
cover, and only a minimal secondary hood air flow is required. Also, there
is virtually no air leakage into the furnace and, thus, combustion of
furnace gas does not occur. The cleaned gases are flared.
Reduced escape of gas and fume from the furnace cover and lower cover
temperature [less under cover combustion] are the only identified additional
advantages of the sealed designs. Because of operational inflexibility and
other problems, the industry trend is away from the covered type furnace.
7.2 ANCILLARY EQUIPMENT
After sufficient alloy has been formed in the furnace, it is tapped
(metal withdrawn) through a hole in the side of the furnace. Normally this
hole is plugged with carbon paste. A tap is started by making holes in the
plug (usually with a small cannon). The hole may be enlarged with poles or
oxygen lances. The molten metal flows down a carbon lined trough into the
ladle. Fumes generated in from this area can be quite heavy, especially
during the first few minutes of the tap. Several types of tapping fume
controls are in use and include fixed hoods, hoods that swing into place,.
and mobile hoods. Design of these control systems is difficult since
provision must be made for access to the ladles by overhead cranes. Emis-
sion control in the area is, therefore, usually poorer than for gas and
fume from the furnace.
The filled ladle may have additional material added to produce a
specified product. Very little additional refining or treatment occurs in
the ladle.
The ladle is then carried by overhead crane to the cooling area where
the alloy is poured into carbon lined molds and allowed to solidify. Fumes
produced in this area are noticeable but not substantial. Collection
devices are not used and the fumes rise to the top of the building and exit
through roof monitors..
44
-------
The solidified alloys are removed from the molds, crushed, sized, and
placed in storage bins. Most plants have dust collection equipment over
the crushing operation. Capture of the dust from crushing is usually by
baghouse.
7.3 POLLUTION POTENTIAL
The pollution potential of the submerged arc ferroalloy furnace will
be discussed in terms of organic and particulate matter for the different
furnace types and different emission control options.
Because of the raw materials used (coal, coke, woodchips, etc.), the
chemically reducing atmosphere inside the furnace, and the high temperature,
gases leaving the furnace [before any combustion} theoretically contain
substantial amounts of organic matter, inorganic fumes, and entrained
particulate matter. The amounts of these materials should vary with product
type since this dictates operating temperature and percentage of reductant
used. An indication of the expected variation for particulates can be seen
in Table 15 which summarizes the potential particulate emissions if the
furnaces were uncontrolled.
The actual amount of pollutants generated by the furnace, however, may
also depend on the type of furnace cover used and, possibly, other operating
factors.
7.3.1 Open Furnaces
In an open furnace, the gases burn vigorously on the surface of the
charge as they leave the furnace. This combustion tends to destroy the CO,
H2, and other combustible gases. It also destroys most organic compounds
and converts most metallic components into their oxidized form. Totally
uncontrolled emissions from these furnaces would, therefore, not be expected
to have high concentrations of low molecular weight gases or organics but
could pose problems with respect to particulates and inorganic components.
This is considered in some detail in a previous study and is confirmed by
the analysis presented in Section 12 for furnace B-l. Fume and particulate
matter generated by the furnaces are predominantly submicron as shown by
1 15
test results presented here and elsewhere. '
The amount and types of pollutant discharged and the media in which
they impact the environment may vary with the type of pollution control
45
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TABLE 15. POTENTIAL PARTICULATE EMISSIONS (1971)
Product
Uncontrolled
emission factors,
Ib/ton alloy
Silicon alloys
CaSi
Silicon metal
65-90 percent FeSi
50 percent FeSi
Silvery iron
(15-22% FeSi)
Chrome alloys
FeCrSi
HC FeCr
LC FeCr
Manganese alloys
HC FeMn
LC FeMn
FeMnSi
SiMn
Other
CaC0
1,343
1,200
673
446
116 ,,
831
335
60
335
133
315
219
100
46
-------
equipment. Since gas volumes from open furnaces are very large, most plants
rely on baghouse filtration. There should be little impact from aqueous
effluents when this method is used. However, at least one plant slurries
the dust captured in the baghouse and transports this slurry to the waste-
water ponds. There is a possibility that some metals and organics may leach
out of this dust and impact the final plant wastewater discharge. The major
impacts would be particulate emissions to the air and possible leaching from
solid waste disposal sites. Baghouses are generally considered to capture
99+ percent of the particulate entering. It is not unusual, however, to see
large quantities of dust in the areas surrounding the baghouses. This dust
arises because of leaks in the mechanisms transferring the collected dust to
trucks that remove it from the site. Some of this dust may become resuspended
when there is a significant wind velocity. The collected dusts from the
baghouse are typically landfilled on site or nearby company property. The
possible hazards surrounding this practice are of concern and are discussed
in a separate section of this report.
The collection efficiency of the baghouse for organics is not expected
to be very good and depends on the organic concentration in the gas phase
and baghouse temperature. Theoretical studies have shown that the equili-
brium vapor pressure of benzo(a+e)pyrene can be described by:
Log P = - ^p - Log T + 25.089,
where p is the vapor concentration in nanograms per cubic meter and T is in
degrees Kelvin. The Air Health DMEG value for benzo(a)pyrene (B(a)P) is
20 nanograms/m . Thus, if the baghouse operates at above 17°C (63°F), no
collection of B(a)P would occur if the concentration in the furnace gas was
3
at or below 20 nanograms/m . Actually, most baghouses operate between 100-
150°C so that no collection of B(a)P would occur if its concentration in the
furnace gas was as high as 0.89 (at 100°C) or 71.3 Cat 150°C) milligrams/m .
There is no indication that these concentrations exist in the open furnace
gas. The calculations are presented to show that bag filters have a low
potential for capture of organics generated. It should be noted that many
non-ideal effects, including preferential adsorption on particulate, can
substantially reduce the amount of organic vapor actually passing through
the baghouse.
47
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Scrubbers are used on some open furnaces. This method is not in wide
use primarily because of the increased (compared to baghouses) energy
requirements (higher pressure drop) but also because scrubbers require some
type of wastewater treatment. Average water usage for scrubbers is 20,000
3
liters (5,300 gals.) per Mw-hr of furnace power. A great deal of data on
the wastewater from ferroalloy plants appears in Reference 3. For open
furnaces, suspended solids are the primary water pollutant although low
concentrations of the dissolved metals (manganese, chromium} are also
present, depending on the product being made. The industry seems to have
little difficulty in handling these wastewaters since simple clarification
or solids settling in ponds effectively removes the suspended solids.
There does appear to be some concern with possible leaching of metals from
these solids, however, and this subject will be covered in the section on
solid waste.
The effectiveness of organic removal by scrubbers should theoretically
be higher than that obtained by baghouse since the gas temperature is
significantly lower. The data presented later for the plant tests show
that organic matter collection effectiveness by scrubbers is less, and
sometimes substantially so, than for particulate collection.
7.3.2 Covered Furnaces
Generally, very little combustion occurs under the cover of these
type furnaces. The extent of combustion does vary, however. There is at
least one covered (mix-sealed) furnace in which substantially complete
combustion occurs under the cover (designated in this report as A-l). The
limited combustion which occurs in the covered furnaces means that the
gases going to the pollution control equipment are essentially the same as
generated by the furnace. The gas, therefore, contains high concentration
(20-90 percent) of carbon monoxide, some carbon dioxide, and hydrogen and
various types of organic matter in addition to the fume and particulate.
The high CO content requires that attention be paid to the hazardous
and explosive potential of the exhaust gas. The collection and control
systems are well sealed and work area ventilated. Primarily because of the
explosion hazard, all covered furnaces in the United States use scrubbers to
control the gases and fumes withdrawn from under the furnace cover.
48
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The high energy scrubbers effectively remove particulate matter from
the furnace gases. Medium and low energy [disintegrator} types are less
effective in particulate removal. The particulate matter does contain a
significant amount 0-4 percent indicated by this work} of organic matter,
some of which may be carcinogenic. The gas leaving the scrubber goes to
flares. However, some flares do not burn continuously. From visual obser-
vation during site visits and during test work, it appears that some flares
on mix-sealed furnaces burn less than 75 percent of the time. This can be
due to operational factors Cflare igniters don't work}, to low CO content
in the gas because of high oxygen content in charge materials (manganese
alloys}, or to some undercover combustion. The effectiveness of flares for
destroying the higher molecular weight organics is questionable since test
data show that organics survive even in the gases from open furnaces which
burn vigorously. At present there is no known accurate or reliable method
for sampling emissions from flares.
The scrubber discharge water contains a high concentration of suspended
solids and organic matter. There is a strong but unproven indication that
much of the organic matter is adsorbed on the particulate. Some organics,
phenols for example, are sufficiently water soluble that water treatment is
employed at many plants for their destruction. Wastewater treatment at
most plants consists of solids removal (by settling in ponds or by filtration)
before any chemical treatment of the water. Thus, the solids, and the
organics contained therewith, receive essentially no treatment. Disposal
of the scrubber sludge is either by allowing the settling pond to fill (and
building new ones as required} or dredging the solid out and putting it in
a landfill. We have found no evidence that any of the ponds or landfills
are lined or have impermeable soil conditions. The industry has expressed
the opinion that the sludges are essentially self-sealing. This will be
discussed in the section on solid waste disposal.
The high molecular weight fused aromatic compounds have very low water
solubilities.18 Typical solubility values are 1.4 x 10~ mg/L for coronene,
3.8 x 10"3 mg/L for 3,4-benzopyrene, and 0.26 mg/L for fluoranthene. Studies
19
have shown that a combination of filtration and chlorination are effective
in significantly reducing the concentration of PNAs in water. These data
imply that with effective treatment, wastewater from ferroalloy manufacture
49
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can be very low in PNA content. Chlorination may, however, also produce
other objectionable compounds.
Gas and fumes also escape from the cover of the mix-sealed furnaces.
Most occurs as a result of furnace gases escaping past the mix-seals.
Under normal conditions, small amounts of gas escape the seals and wisps of
fume can be seen rising from the cover. During "blows" or periods when the
mix around the electrodes is low, large volumes of gas escape the seals and
carry fumes and entrained particulate into the secondary emission control
system. In this latter case, the gas escaping the seals is usually burning.
1 2
There are indications from this work and from others ' that significant
amounts of particulate can escape from the covers. All furnaces are equipped
with hoods to collect these gases and particulates. Most of these systems
also capture the particulate in a baghouse. Concern for the pollution
potential from this area is primarily for particulate matter. It is sus-
pected that some organics are contained in these gases and fumes; however,
the total mass should not be high since the gas usually burns during periods
of heavy gas and fume release from the cover.
7.3.3 Ancillary Equipment
A substantial generation of gas and fume occurs at the tap hole and
lip during the initial phase of a tap. These fumes occur as a result of
(1) burning the carbon plug out of the tap hole, (2) fumes rising from the
hot metal, and (3) vaporization of organics in the carbon used as a lip
liner. Further fume generation occurs in this area when the tap hole is
plugged (carbon paste injected into the hole) and when the carbon added to
the lip is heat cured. Most of these emissions are of short duration and
are partially captured by the tap hole emission control system. Fumes not
captured exit the building through the roof monitors. Although the organic
content of the fumes could be at high concentration and could contain
hazardous compounds, the total mass is probably low compared to that in the
furnace gas. Most other fume and dust occurring from transfer, cooling,
grinding, and packaging of the alloy should be primarily metallic components
with analysis similar to the alloy being produced.
50
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8.0 SOLID WASTE DISPOSAL
The Ferroalloy Association estimates20 that about 362,875 tonnes
(400,000 tons] of solid waste Cdusts, sludges, and slag residues) are pro-
duced annually at the current annual production rate of 1.45 million tonnes
(.1.6 million tons) of the various chromium, manganese, and silicon ferro-
alloys. They estimate that about 30 percent of this waste material may be
composed of those designated wastes specifically listed as hazardous by
proposed section 3001 of the Resource Conservation and Recovery Act C&CRA).
20
"Conceivably, all ferroalloy wastes could be classified as hazardous by
the proposed extraction procedure, although, limited testing has shown that
slags, in general, are very insoluble and would be classified as nonhazard-
ous under proposed section 3001 criteria."
The average quantity of waste generated is about 9072 tonnes 00,000
tons) per year per plant but is quite variable and depends on plant size and
product mix. About 40 percent of this waste is generated in Ohio and West
Virginia, 30 percent in Alabama and Tennessee. Smaller quantities are gen-
erated in Oregon, Washington, South Carolina, Iowa, and New York.
The dusts and sludges generated are primarily submicron particles, con-
sisting of oxides of silicon, manganese, chromium, calcium, magnesium, and
other elements in widely varying proportions depending on the product being
made. Slags are vitrified oxides of essentially the same elements. As
shown in other sections of this report, the sludges, particularly from
covered type furnaces, may also contain various types of organic compounds
including polycyclic aromatic hydrocarbons, some of which are known carcin-
ogens.
Currently, these wastes are disposed of by inclusion in dedicated land-
fills or deposition in lagoons. Slags, in particular, may be stocked on
plant property in anticipation of future discovery of recycle methods. Waste
mounds in controlled disposal areas can approach 76.2 meters (250 feet) in
depth while sludge depth in lagoons may be as much as 10.7 meters (35 feet).
51
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The Ferroalloy Association estimates that 85 percent or more of the wastes
are disposed of by these techniques. Less than 15 percent is recycled,
reclaimed, or sold.
To the best of our knowledge, all waste is disposed of in unlined
(nonsealed) areas. Industry data indicate that the sludges and dusts have
saturated hydraulic conductivity "K" values ("permeability") of 10"4 to 10"8
cm/sec, equivalent to the range of medium permeability soils through some
of the best naturally occurring clays. The industry feels, therefore, that
these materials act as their own barriers to rainwater and surface water
intrusion, i.e., that the wastes are "self-sealing."
Estimated current (1980) solid waste disposal costs are $3 to $8 per
ton (907 kg). Industry estimated that an additional cost of $8 to $25 per
ton would be required to meet the requirements of proposed section 3004 of
RCRA. This did not include the cost of upgrading present disposal sites.
Recent (1981) data suggest disposal costs of over $80/ton for any waste
classified as hazardous (Section 3001 of RCRA).
The Ferroalloy Association and EPA (Office of Solid Waste) have been
negotiating for several years as to whether the industry's solid waste
should be classified as hazardous. Calspan Corporation surveyed the indus-
try (as part of a larger study) in the mid 1970's and assessed the hazard
21
potential of the solid wastes. This report concluded that many solid
wastes produced by the industry are hazardous (only metals leaching was
considered) and that disposal practices are not adequate. The industry
22
responded that the study was superficial, lacked an understanding of the
industry, and was, therefore, of little value. The industry particularly
criticized the method used to determine leaching, use of isolated, non-
representative samples, inclusion of ferromanganese production1 by blast
furnace, improper analysis of waste disposal alternatives, and impractical
technical proposals. The industry has submitted their own data to EPA on
23
metals Teachability (Table 16) and on the results of monitor well tests
20
for typical landfills and unlined lagoons (Tables 17, 18). The data from
Table 16 show that leachate from emission control dusts exceed the 10 times
EPA National Interim Primary Drinking Water Criteria for classification as
hazardous for at least one metal when the leaching solution contains only
water or also contains acetic acid (extraction procedure (EP) of 9/12/78
52
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TABLE 16. THE FERROALLOYS ASSOCIATION ENVIRONMENTAL COMMITTEE
SOLID WASTE TASK FORCE LEACHATE TESTING RESULTS
en
oo
Waste from FeMn Production
EPA EP Using H00 Only
Emissions Control Dust (Sx #1)
Emissions Control Dust (Sx #Z)
Slag (3/8" x I/**}
Slag (200 mesh)
EPA EP per 9/12/78 Draft
Emissions Control Dust
Slag - Co. B
EPA EP per 3/6/78 Draft
Slag - Co. A
Slag - Co. E
Waste from FeCr production
EPA EP Using H^O Only
c.
Emissions Control Dust (Sx #1)
Scrubber Dust (Sx #2)
Slag - Co. B
Slag - Co. C
EPA EP per 9/12/78 Draft
Scrubber Dust (Sx #2)
EPA EP per 3/6/78 Draft
Slag - Co. A
Slag - Co. B
Slag - Co. C
As
.10
.01
.04
<.OT
.01
<.02
.05
.05
.001
.01
Leachate concentrations^
Ba Cd Cr Pb
<.10 <.10 (1.4) (2.0)
<.10 (.30) (1.0) (7.6)
<.10 <.10 .40 (14.0)
7.40 <.10 <.10 .30
6.5 .01 .03 .02
4.1 .09 <.01 .02
<.10 <.10 (.65) <.10
<.10 <.10 <.20 <.10
.04 <.01 <.01 <.01
.51 .01 .04 .01
.66 .001 .01 <.01
mg/L
Hg
.001
.001
<.001
.005
<.002
.004
.005
<.001
.003
<.001
Se Ag
.01
<.002
<.005 <.01
<.01 <.001
<.002
<.01 <.001
-------
TABLE 16. (Continued)
Leachate concentrations, mg/L
As Ba Cd Cr Pb Hg Se Ag
Waste from FeCrSi Production
EPA EP Using ti,0 Only
Emissions Control Dust
Slag - Co. C
EPA EP per 9/12/78 Draft
Emissions Control Dust
EPA EP per 3/6/78 Draft
Slag - Co. C
0.001 .04 <.001
<.001 .66
,001
(2.0)
(2.4)
<.001 <.001 <.001
.30
<.001 <.001 <.001
Note: I. C ) around ^i value Indicates ar concentration greater than 10 x DWS.
27 Test data7 based arr HpO only signifies the same ratio of FLO to solids as in EPA EP,
but no acetfc acid is added as per the 3/6 or 9/12/78 draft procedure.
3. Company code in this table is not the same as for the rest of this report.
-------
TABLE 17. DATA FROM A FERROALLOY COMPANY'S MONITORING WELLS
AT A TYPICAL LANDFILL20
Location
Test #1
Upgradient
Groundwater Background
Well #3
Well #4
Downgradient
of Landfill
Well #1
Well #2
Well #5
Test #2
(1 month after #1)
Upgradient
Groundwater Background
Well #3
Well #4
Downgradient
of Landfill
Well #1
Well #2
Well #5
Test #3
(2 months after #1)
Upgradient •
Groundwater Background
Well #3
Well #4
Downgradient
of Landfill
Well #1
Well #2
Well #5
Parameter concentrations mg/L
Ba
.25
.20
.10
<.05
<.05
.05
.15
.01
.05
.05
<.05
.05
.15
.10
.05
Cd
<.005
.03
.01
.10
.005
<.005
.010
.01
<.005
<.005
.005
.010
.01
<.005
.008
Cr Pb
.02 <.03
.02 .08
<.01 .08
.02 .06
.01 .03
.03 .07
.01 .05
<.01 .08
<.01 .10
.01 <.03
.03 .08
.02 .08
.01 .05
.01 .03
<.01 .04
Hg
<.0005
<.0005
<.0005
<.0005
<.0005
<.0005
Note: All data derived from independent laboratory determinations.
55
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TABLE 18. DATA FROM A FERROALLOY COMPANY'S MONITORING WELLS
SURROUNDING AN UNLINED DISPOSAL LAGOON20
Location
Test #1
Lagoon analysi
#1 Well
#2 Well
#3 Well
#4 Well
#5 Well
Test #2
Lagoon analysi
#8 Well
Distance from
Lagoon (in feet)
s
100
500
200
100
1,600
s
375
Parameter
As Ba
. 50 . 042
<.02 .042
.037
.029
.043
.036
.50 .054
.02 .060
concentrations
Pb
.030
.085
.105
.190
.085
.090
.160
ND
, mg/L
Cd
.020
ND
.020
.020
ND
ND
ND
ND
F
3.5
.06
.05
<.05
.06
<.05
4.8
.82
Note: ND means no determinatee amount.
These data derived from independent laboratory determinations.
56
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and 3/6/78 drafts. See also Federal Register, Volume 43, No. 243). Nei-
ther scrubber dust (sludge) nor slags exceeded this criteria. The industry
feels that the test is not representative of actual dust characteristics.
The industry claims the dust forms a hard, monolithic surface layer when
exposed to water, and, therefore, any additional precipitation will run off
rather than being adsorbed and transmitted to groundwater. They also claim
that the dusts are quite alkaline and would, therefore, inhibit leaching
most metals. The data from Table 16 indicates some metals still leach out.
The data in Tables 17 and 18, however, do show that any leachate from at
least two disposal sites has minimal effect on the groundwater quality for
at least five elements of concern.
Previous studies have not addressed the question of the presence of
organic matter. The data developed in this study indicates that dusts from
open type furnaces generally contains less than 0.1 percent organic matter
and that less than 10 percent Cusually less than 3 percent) of this organic
is polycyclic organic matter CPOM). Analysis of the organic matter suggests
possible low concentrations of carcinogens. Scrubber sludges from covered
furnaces, on the other hand, may contain up to 8 percent organic matter.
POM content may be as high as 65 percent of the organics. Detailed anal-
ysis (see later sections) indicate that these sludges are likely to contain
significant concentrations of polynuclear aromatic hydrocarbons (PNA),
including the known carcinogens, benzo(a)pyrene, indeno(l,2,3-cd)pyrene,
and others.
Typical disposal procedures for these sludges is settling in unlined
lagoons which may either be allowed to completely fill with solids or the
solids may be dredged out and landfilled. Since high concentrations of PNA
19
are likely in the scrubber water and sludge and since previous work indi-
cates that as much as 90 percent of this type material can be adsorbed on
suspended particulate, it is likely that the sludges in the lagoons and
landfills, especially that from covered furnaces, contains high concentra-
tions of PNA and may exceed the minimum acute toxicity effluent limits for
solid wastes. Data in the section on Screening Samples strongly indicate
this possibility since a number of the samples are for materials that would
be landfilled without further treatment.
57
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The question then is whether or not current disposal techniques provide
adequate protection from leaching the organic materials into groundwaters.
We first note that the aqueous solubility of PNAs is essentially unaffected
by solution pH. Thus, the fact that the wastes may be alkaline will have
no effect on Teachability, and the use of acetic acid fn the extracting
solution also would be expected to have minimal effect. The possibility
does exist that the PNAs are preferentially adsorbed on the solids, and the
concentration in a leaching solution would be less than the true solubility
in pure water. This can only be confirmed or denied by testing the actual
wastes involved. The possibility also exists that the wastes are "self-
sealing" as indicated by the industry. Since it was beyond the scope of
this work to investigate the above factors, the question cannot be unequivo-
cably answered. It appears, however, that a potential exists for leaching
hazardous organics from the sludges and that, in many instances, the disposal
methods in use may not provide adequate protection against contamination of
groundwaters.
58
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9.0 POM DEGRADATION
In this section, the formation of POM (polycyclic organic matter) in
ferroalloy furnaces is discussed and results of research on possible
degradation or removal mechanisms are presented. Also discussed are the
implications of data obtained in this study for control of POM emissions.
9.1 RATE OF POM FORMATION BY FERROALLOY FURNACES
As a guide for use in evaluating the POM calculations which follow, a
calculation of the total POM emitted by all coke ovens (uncontrolled) in
the United States is presented. Coke ovens are considered by EPA to be
major emitters of POM compounds. Control methods are oriented toward
operational changes that contain the POMs within the ovens and byproduct
plant whenever possible. Approximately 0.91 kg (2 Ibs) of benzene soluble
organics (BSO) are emitted from coke ovens (not including quenching) for
24
each 0.91 metric tons (2000 Ibs) of coal coked. Approximately 0.5-
25
5 percent (wt) of the BSO is POM. Total coal coked in these ovens each
year is about 63.5 x 106 metric tons (70 x 106 tons). Thus, total POM
emissions (uncontrolled) from coke ovens is approximately:
63.5 x 106 Mg coal/yr x 1.0 kg BSO/Mg coal x (0.005-0.05 kg POM/kg BSO)
= 317,500 - 3,175,000 kg/yr (0.7 - 7 x 106 Ibs/yr)
Data from a previous study of a sealed ferroalloy furnace producing
FeMn indicate that the mass of POM generated at full load would be about
24,954 kg/yr (55,014 Ibs/yr) or 1,442 kg/yr (3,179 Ibs/yr) per Mw of
capacity. Since there is about 212 Mw of installed covered (sealed or
mix-sealed) capacity, the total POM generated by covered furnaces assuming
an operating factor of 80 percent is about 244,560 kg/yr (539,170 Ibs/yr)
if all covered furnaces generated POM at this rate.
The POM generation rate of the open and covered furnaces tested in
this study (excluding furnace A-l) were calculated assuming the aromatic
hydrocarbon and halogenated aromatic hydrocarbon categories are all POM
59
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and are the only categories containing POM. Neither assumption is likely
to be entirely correct. The calculations, which follow, indicate that
covered furnaces may generate POM at the rate of 1,230 to 11,080 kg/yr
(2,710 to 24,430 Ibs/yr) per megawatt of furnace power or 208,800 to
1,878,800 kg/yr (460,300 to 4,120,000 Ibs/yr1 for all U.S. furnaces of this
type. Calculated POM generation rates of open furnaces are 100 to 900 kg/yr
(220 to 1,980 Ibs/yr) per megawatt of furnace power or 134,500 to 1,210,500
kg/yr (296,500 to 2,668,700 Ibs/yr} for all U.S. furnaces of this type.
These calculations indicate that covered furnaces, which make up only
14 percent of the industry capacity, may actually generate more POM (61 per-
cent of the total estimated nationwide generation rates) than the open fur-
nace. The total estimated nationwide POM generation rate from all U.S.
furnaces is 343,300 to 3,089,300 kg/yr (756,850 to 6,810,700 Ibs/yr) or
about the same as estimated for coke ovens.
Calculation of POM Generation Rates
A. Open Furnaces
Furnaces included in this calculation are A-2 and B-l.
1. A-2
Furnace power level during test -- 15.8 MW
Stack gas flow rate -- 3,355.4 DSCMM
3
Scrubber water discharge rate -- 2.27 m /min
3
POM in scrubbed gas — 3.7 mg/m (combined aromatic hydrocarbon
and halogenated aromatic categories)
POM in scrubber water -- 3.66 mg/L
POM in gas =
(3.7 x 10"6 kg/m3)(3,355.4 m3/min)(60 min/hr)(24 hr/day)(365 days/yr) *
15.8 MW = 413 kg/yr/MW of capacity
POM in scrubber water
(3.66 x 10~6 kg/L)(l,OOQ l/m3)(2.27 m3/min)(60}(24)(365) * 15.8
= 276.4 kg/yr/MW of capacity
Total A-2 = 413 + 276.4 = 689.4 kg/yr/MW of capacity.
2. B-l
Furnace power during test -- 48.4 MW
Stack gas flow rate — 5,749.8 DSCMM
3
POM in furnace gas -- 4.49 mg/m
60
-------
POM in gas =
(4.49 x 10"6)(5,749.8)(60)(24)(365) -r 48.4 = 280.4 kg/yr/MW of capacity.
Average POM generation rate for open type furnaces (this calculation
assumes that only the open FeMn furnaces generate POM at furnace A-2 rate
and that all others are represented by furnace B-2. We suspect this
results in a low estimate but it is better than a simple average.)
13.3?3 SMn <689'4>+ ^§(280.4, = 302. 8 kg/yr/MW of capacity
Range (1/3 to 3) = 100.9 to 908.4 kg/yr/MW of capacity.
Yearly nationwide POM generation rate range (assuming 80 percent
operating factor).
(100.9)(1,333 MW of capacity)(0. 8) = 134,500 kg/yr
(908.4X1,333 (0.8) = 1,210,500 kg/yr
B. Mix-sealed Furnaces
Furnaces included are B-2, C-l, C-2.
1. B-2
Furnace power -- 48.0 MW
Stack gas flow rate -- 149.97 DSCMM
3
POM in scrubbed gas --446.18 mg/m
Scrubber water discharge rate --2.27 m /min.
POM in scrubber water -- 146 mg/L
Scrubbe
POM in gas =
(446.18 x 10"6)(149.97)(60)(24)(365) -r 48.0 = 732.7 kg/yr/MW of capacity.
POM in scrubber water =
(146 x 10"5)(1000)(2.27)(60)(24)(365) -r 48.0 = 3,629 kg/yr/MW of capacity
Total B-2 = 732.7 + 3,629 = 4,361.7 kg/yr/MW of capacity.
2. C-l
Furnace power -- 15.5 MW
Stack gas flow rate --156.48 DSCMM
Scrubber water discharge rate -- 1.90 m /min
POM in scrubbed gas --197.0 mg/m
POM in scrubber water — 43.8 mg/L
61
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POM in gas =
(197 x 10~6)(156.48)(60)(24)(365) ^ 15.5 = 1,045 kg/yr/MW of capacity.
POM in scrubber water =
(43.8 x 10~6)(1,000)(1.90)(60)(24)(365) * 15.5 = 2,822 kg/yr/MW of
capacity.
Total C-l = 1,045 + 2,822 = 3,867 kg/yr/MW of capacity.
3. C-2
Furnace power -- 16.8 MW
Stack gas flow rate — 173.978 DSCMM
'/n
3
3
Scrubber water flow rate --1.90 m /min
POM in scrubbed gas — 302.86 mg/nT
POM in scrubber water — 20.2 mg/L.
POM in gas =
(302.86 x 10"6)(173.978)(60)(24)(365) -=- 16.8 = 1,648.5 kg/yr/MW of
capacity.
POM in scrubber water =
(20.2 x 10~6)(1,000)(1.90)(60)(24)(365) -=• 16.8 = 1,200.7 kg/yr/MW of
capacity.
Total C-2 = 1,648.5 + 1,200.7 = 2,849.2 kg/yr/MW of capacity.
Average POM generation rate for mix-sealed furnaces =
(4,361.7 + 3,867 + 2,849.2) v 3 = 3,692.6 kg/yr/MW of capacity.
Range (1/3 to 3) = 1,230.9 to 11,077.8 kg/yr/MW of capacity.
Yearly nationwide POM generation rate range from covered type furnaces
(assuming 80 percent operating factor)
(1,230.9)(212)(0.8) = 208,800 kg/yr
(11,077.8X212X0.8) = 1,878,800 kg/yr.
Note that other methods of calculation will likely yield different results
(higher or lower) than given here. For example, the aromatic and halogenated
aromatic hydrocarbon categories make up 80.6 percent [(294.46 -=- 365.3) x 100]
of the total organic matter recovered by the Level 1 analysis of the SASS
train organic module for the C-2 furnace test (Table 83). If one multiplies
this by the 1.7934 kg/hr of organics for the SASS module given in Table 81 and
62
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8,760 hr/yr, one obtains (0.806)(1.7934)(8,760) -=- 16.8 = 753.7 kg/yr/MW of
capacity, substantially less than given previously (POM contained in the dust
collected was included in the previous calculation but would not measurably
affect the comparison now being made). These differences occur because the
total organic recovered from the seven liquid chromatography (LC) fractions
may be greater than or less than the organic determined before LC fraction-
ation. Because it is uncertain which, if either, organic determination is
correct, the calculations used to estimate POM are based on the LC fraction
determination which generally yield the highest POM estimates. This is con-
sistent with the "worst case approximation" philosophy of the Level 1 methodology,
9.2 POM BEHAVIOR IN AQUEOUS SYSTEMS
Some POM generated by ferroalloy furnaces are captured by baghouses and
scrubbers. This section deals with the behavior of POM in the scrubber dis-
charge water and any baghouse dust which is slurried.
Polycyclic organic matter (POM) in aquatic systems may be removed or
transformed by several means. They may evaporate into the air. They may be
broken down by reaction with light. POM tends to adsorb on the surface of
particulate solids present in the water. Thus they may be removed by sedi-
mentation of suspended solids and by adsorption onto previously settled sedi-
ment. Microorganisms and other aquatic life can ingest and transform the POM
present in the water.
To assess the environmental consequences of aqueous discharges of POMs,
not only should the discharge rate be considered, but also those processes
which degrade the pollutants. Laboratory studies have been used to investi-
gate the mechanisms of POM removal.
Two such research programs are discussed below:
Oak Ridge National Laboratory
Research to identify and measure the processes transforming POM is cur-
rently underway at the Environmental Sciences Division of Oak Ridge National
26
Laboratory (ORNL) under a Department of Energy contract. Preliminary measure-
ments have been made of POM removal by several different mechanisms. The ORNL
workers hope to conduct field tests and confirm their models of POM behavior
so that, ultimately, the fate of POM can be predicted from a description of
the aquatic system in question. The following material is based on reports
?~] - ^6
provided by ORNL.
63
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The adsorption of anthracene onto typical sediments was studied.
(Anthracene was chosen as a representative POM which has an intermediate
molecular weight, is not carcinogenic, and is available in a carbon-14 labeled
form.) When anthracene is added to water containing suspended particles, it
is adsorbed on the surface of the particle. In this way, the POM associated
with the particles increases, while the level of dissolved POM in the water
phase decreases. Dead microorganisms and suspended organic material were
found to have a much higher affinity for POM adsorption than do inorganic
particles. The partition coefficient, K., was used as a convenient measure of
the tendency of the POM to adsorb. (It is calculated by dividing the POM
content of the solid by the POM content of the liquid. The larger K., the
more POM will be adsorbed from the water onto the solid surface.) K. for
anthracene onto dead yeast cells was found to be about 20,000 ppm on particu-
late/ppm in water. K, for inorganic clays and silt is much lower by at least
one and as much as two orders of magnitude.
In slow-moving, turbid waters, particulates which have adsorbed POM
settle by gravity. This mechanism has the net effect of removing dissolved
POM from the water and then depositing it on the bottom as sediment. The rate
of this removal can be related to the stream depth, the amount of particulate
present, and the size and density of the suspended solids. In a related
mechanism of POM transport, the sediment layer already at the stream bottom
can adsorb POM directly from the water. As more POMs are adsorbed by the
bottom sediment, the surface layer of sediment will become saturated if POMs
are not removed from the sediment by some other means.
In some steams, microbial degradation will convert POM in the bottom
sediment, and thus result in some equilibrium between adsorption and degra-
dation. The rate of microbial degradation in sediment was found to vary five
or more orders of magnitude for the various POM compounds in sediments from
different sources. In general, the four- and five-ring POM are harder to
transform than the two- and three-ring POM. Also sediments from pristine
areas are not as active in transforming POM as those from previously contami-
nated streams. Contaminated streams have developed microbial populations
capable of transforming POM.
The more volatile two- and three-ring POMs may evaporate from the surface
of aqueous systems. The volatilization rate largely depends on the compound
64
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volatility and the turbulence at the air-water surface. The half-life (i.e.,
the time required to reduce the concentration present by a factor of one-half)
for naphthalene (a two-ring POM) is around 10 hours at 25°C. The half-life
for volatilization increases as the number of rings in the PAH increase, by
roughly a factor of five per additional ring. These half-lives are for well-
mixed waters. Stratification can deplete POM in the upper layers of the water
and may result in longer half-lives under field conditions.
The following predictions were made for anthracene in a slow-moving,
muddy pond about five meters deep. These conclusions are from Reference 27
and should be considered tentative subject to further work.
1. Adsorption to bottom sediment and photolysis by sunlight removes
negligible amounts of POM in this environment. In less turbid, shallower
waters these processes would be more important.
2. Microbial degradation in the sediment is responsible for about
80 percent of the POM degradation under the model assumptions. This contri-
bution is very sensitive to the pond ecology. If water toxicity, excessive
depth, or water treatment prevents microbial growth, then this main contrib-
utor to POM degradation will be absent.
3. Adsorption onto particulates and subsequent sedimentation may account
for about 15 percent of the degradation.
4. Volatilization to the air is predicted to account for about 5 per-
cent of the reduction seen from anthracene.
5. The half-life of anthracene in the water under these conditions is
tentatively predicted to be about a day to a week. Again, this is almost
entirely dependent on microbial degradation being present.
6. Half-lives for four- and five-ring POMs will be longer than for
anthracene because both microbial degradation and volatilization are slower
for the higher ring compounds.
EPA Athens Environmental Research Laboratory
SRI International under contract to EPA's Athens Environmental Research
Laboratory has published their best current procedures for assessing the
environmental effects of a chemical in a freshwater aquatic system. The pro-
cedure includes measurement of the rates of degradation due to volatilization,
oxidation, hydrolysis, photolysis, adsorption to sediments, and microbio-
logical transformation. A computer model has been developed to use the rates
65
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of the individual reactions together with conditions representative of dif-
ferent aquatic systems (sediment content, biological activity, pH, etc.) to
predict the environmental pathways of a chemical. Although some environmental
pathways such as magnification in the food chain and biological transformation
in the sediments are ignored in the model, it is felt that the procedure
represents the state of the art of predicting pollutant behavior in freshwater
37 38
systems. The following is a summary of two reports ' which describe the
procedure.
Because of an interest in pollutants likely to be generated by synthetic
fuel plants, the AERL work used several POM compounds as illustrative com-
pounds for their procedure: p-cresol, benz(a)anthracene, benz(a)pyrene,
quinoline, benzo(f)quinoline, 9H-carbazole, 7H-dibenzo(c,g)carbazole, benzo-
(b)thiophene, and dibenzothiophene. The physical properties, chemical trans-
formations and biodegradations of these compounds were measured. Benzo-
(a)pyrene is believed to be the most representative of these compounds for
discussion of ROMs generated by the ferroalloy industry. The laboratory
studies which were made on benzo(a)pyrene indicate that by far the predominant
removal mechanism is adsorption onto suspended and settled particles present
in the water. The probable fate of the benzo(a)pyrene entering all but the
very cleanest natural waters is rapid absorption onto suspended solids which
will accumulate in the bottom sediments. In this work the biological cultures
which were tested were found not to degrade benzo(a)pyrene, and no biodegra-
dation is accounted for in the model. For a simple two-compartment pond
consisting of a water phase and a sediment phase, the model predicted an
overall half-life of 7.3 hours for benzo(a)pyrene and that 93 percent of the
benzo(a)pyrene would be adsorbed onto the bottom sediments. For a more com-
plex lake environment which includes effects due to changes in depth and
distance from the pollutant source, a similar half-life was predicted with
71 percent of the B(a)P adsorbed onto the sediment.
Research Summary and Application to Ferroalloy Manufacture
As seen, several processes may be operating to transform POM compounds in
freshwater systems. There is a disagreement between researchers for some of
the major removal mechanisms, for example biodegradation. Therefore, pre-
dicting the combined effect of the removal mechanisms is risky at the current
66
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level of knowledge. However, some qualitative conclusions can be drawn although
they should be interpreted under the following qualifications:
All predictions are tentative. Well-controlled laboratory tests
have been made on only a few POM compounds. Data needed for the
modeling of aquatic systems are only now being generated. Field
studies of the laboratory predictions have not yet been done.
There are large uncertainties in many of the physical parameters
needed in modeling studies (e.g., turbulence at the air-water inter-
face, sediment loading, stratification).
The models are very sensitive to factors that are site-specific,
(e.g., depth, turbidity, water velocity, microbial activity).
The two-compartment pond model and the more complex model in the AERL
37 38
work ' might be considered as rough approximation to the processes that
occur in wastewater treatment ponds in the ferroalloy industry. The water-
flow, sediment concentrations, pond depths, pH, etc. used to characterize the
model lakes and ponds are close to the characteristics of the wastewater ponds
in the ferroalloy industry, but are not exactly the same. The following
qualitative conclusions are drawn.
(1) The concentration of POM in the outfall from such a waste treatment
pond will not be determined by solubility of POM in pure water since large
quantities of solids are present in wastewaters from ferroalloy scrubbers.
The POM concentration in the water phase instead will be determined by the
distribution coefficient of the POMs between particulates and water. Hence,
it is expected suspended solid in the outfall will be the main source of
immediate POM discharges.
(2) Over 90 percent of the POM associated with the incoming wastewaters
will be adsorbed onto the particulate present in the wastewaters. The models
predicted desorption of benzo(a)pyrene which had been adsorbed onto bottom
sediment resulting in maintenance of a very low concentration of benzo(a)-
pyrene in solution even after the pond has been abandoned. This long-term
concentration was predicted to equal roughly the concentration in unpolluted
groundwaters.
39
(3) Field data by Sahbad et al. is cited as indicating an approximate
half-life of five to ten years for benzo(a)pyrene which has accumulated in
bottom sediments. Accordingly, large inventories of POM might be expected in
67
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some solid waste sites and slurry ponds. The long-term mobility of POM is not
known.
(4) Neither the potential effects of biomagnification in the food chain
nor the rate of POM biodegradation in ferroalloy sediments are known. Both
effects are critical in determining the lifetime and environmental impact of
the inventory of POM.
9.3 POM BEHAVIOR IN AIR EMISSIONS
Sufficient information exists in the open literature on the possible
effects of known carcinogens (benzo(a)pyrene, for example) that a discussion
of the potential effects of their emissions from process stacks is not required,
However, a discussion of potential reactions in the atmosphere is presented to
illustrate the potential problems with emission of other compounds.
Both the low resolution mass spectrographic (LRMS) analysis and gas
chromatography-mass spectrograph (GC-MS) analysis of samples collected in this
study show that a number of fused ring hydrocarbons (polynuclear aromatic
hydrocarbons, PNAs) probably remain in the furnace gases being emitted from
40
control devices. Previous workers have reported an apparent significant
"excess carxinogenicity" (over that accounted for on the basis of B(a)P and
other carcinogenic PAH) in urban air. In fact, studies of organic particulate
collected in the Los Angeles basin have shown that this material is directly
40
mutagenic and does not require metabolic activation as does benzo(a)pyrene
40
and other promutagens. Research work has shown "that directly active muta-
gens, including nitro derivatives can form on exposure of PAH to gaseous
pollutant." Perylene, a nonmutagen, for example was converted to a directly
active mutagen by exposure to 1 ppm NO^. Thus, it is important in assessing
the pollution potential of ferroalloy emissions to consider not only the known
carcinogens which are emitted but also to consider those compounds which can
be converted to hazardous materials by exposure to environmental pollutants.
Although the air near most ferroalloy plants may not contain the levels of NO-
and HNO.J used in the tests (comparable to Los Angeles basin concentration),
the question of possible atmospheric reactions must be raised and considered
in any future study.
68
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9.4 POM DESTRUCTION
This and other studies cited show that ferroalloy furnaces do generate
significant amounts of polycyclic organic matter, including polynuclear aro-
matics and known carcinogens. The study also provides strong evidence that
the rate of generation of these compounds is considerably higher for covered
(mix-sealed and sealed) furnaces than for the open furnaces. Since the reac-
tions which occur deep in the furnace (reaction zone) should be affected
little, if at all, by the type of furnace cover used, this difference must be
accounted for primarily by the combustion of furnace gases in the open fur-
naces. Using data presented earlier in this section, we can estimate that the
POM generation rate of open furnaces is less than 10 percent of the POM gen-
eration rate of a covered furnace (^g/Mw-hr basis). It is neither surprising
that combustion destroys organics nor that some POM remains after combustion
in an open furnace since these compounds have been found in other combustion
products.
Open furnaces are used to produce most product lines. A prime advantage
is easy access to the furnace to allow stoking which is necessary for some
products. Covered furnaces, on the other hand, are used only for products
that do not require stoking. The gas leaving an open furnace burns vigorously
but the peak flame temperature is frequently moderated by the large volume of
air which is drawn in to cool the gas. Low flame temperature and short resi-
dence time at these temperatures can lead to incomplete combustion of the more
refractory organics. The most effective way to increase the flame temperature
is to reduce the amount of air drawn into the furnace. This can be accom-
plished by tightly hooding the furnace, a method being more frequently used in
the industry to reduce gas volumes to emission control devices. Hoods should
extend to the top of the furnace and panels fit closely to prevent excessive
air infiltration. Hood panels must be retractable to allow access for stoking.
This would obviously create problems for retrofit situations because of increased
structural support required. Also to be considered is modifications to duct
work to withstand the higher temperatures. Gas cooling (radiant cooling
sections or heat exchangers) would be required before the gas entered a bag-
house. Although any heat recovered might be used in other areas of ferroalloy
69
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manufacture (conversion to steam or electricity to run pumps or fans, for
example) the cost of this equipment may not be cost effective at this time.
There are several options, some of which are already in use by the indus-
try, for handling POM generated by covered furnaces. Atmospheric emissions
can be significantly reduced by using high energy scrubbers with efficient
equipment for removing entrained water droplets and particulates. Provisions
should be made to flare the cleaned gas 100 percent of the time or to use it
as supplemental fuel in other plant processes. Since the use. of scrubbers forces
most of the organic into the scrubber water, provisions must be made to handle
the slurry in an environmentally sound manner. The best technology in use to
accomplish this uses solids removal (by clarification and vacuum filtration),
recycling most of the water back to the scrubber, and treating the controlled
blowdown by activated carbon adsorption for organic removal and chlorination
for cyanide destruction. The activated carbon can be reactivated, used as fuel,
or used as a reductant in the furnaces. The sludge should either be land-
filled in an acceptable manner or possibly, pelletized for reuse in the fur-
nace. Technology for the latter has not been demonstrated.
Other options involve burning the furnace gases before particulate cap-
ture occurs. This can be accomplished by providing for combustion under the
furnace cover (see results for furnace A-l). Although this technique does
result in significant reduction in organics, problems were noted with exces-
sive fumes escaping the furnace cover of this furnace. Perhaps a well engi-
neered design could eliminate this problem. This approach has the advantage
that potential emissions to all three media could be significantly reduced by
a single process change. Problems could arise, however, with furnace cover
and ductwork cooling and, for retrofit application, pump and blower capacities
would probably have to be increased. If the gas were cooled, the emissions
could be controlled by a baghouse. Other techniques worthy of consideration
are operating the furnace normally and ducting the dirty gas to a heat recovery
type boiler (like a CO boiler in oil refining application) or converting the
furnace to a tightly hooded open type furnace.
It is emphasized that burning the gas before removing the particulates is
a preferable solution since it simultaneously reduces the organic pollutant
70
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load to all three media and that efficient high temperature combustion offers
the best option for destruction of ROMs and energy recovery. Any engineering
solution will require extensive work beyond the scope of this report.
71
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72
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10. POLLUTION CONTROL ENERGY REQUIREMENTS
After the electric-arc furnaces themselves, the atr pollution control
equipment is by far the largest consumer of energy in ferroalloy manufacture,
To remove particles from the furnace gases requires substantial fan horse-
power. Hooding and gas movement required for control of other particulate
sources such as tapping, crushing, screening, and secondary hooding over
electrodes also is energy consuming. As an industry-wide average, gas
cleaning uses energy equivalent to about 7 percent of the energy consumed
by the furnaces.
Since most of the pollution control energy is expended on moving gas
streams, the total energy requirement is best related to the gas volume
collected multiplied by the pressure drop required by the control device.
This energy is a function of alloy produced, the gas temperature, ductwork
design, and the extent of combustion at the furnace surface. The amount
of gas produced by the furnace is nearly proportional to the furnace
energy consumption for a given product. The amount of entrained (combus-
tion , cooling) air depends on furnace hood design.
The energy requirements for pollution control equipment were obtained
from the literature and several manufacturers.
For control of furnace fumes the energy required varied from 0.01-0.12
kw for pollution control per kw furnace usage. There are two groupings of
energy requirement: a cluster at about 0.02 kw per kw furnace usages for
sealed furnaces and semi-sealed furnaces having no secondary hooding, and
a second cluster at 0.06-0.10 kw per kw furnace usage for open furnaces.
The energy requirements for the closed furnaces are lower because the
exhaust gas flow rate is much lower (by as much as 1/50) since little air
is entrained to burn the gases. However, semi-sealed furnaces which had
secondary hoods to control fume leakage around the electrodes had energy
requirements in the higher cluster- The advantage of lower furnace gas
volume from semi-sealed furnaces is largely negated if secondary hooding
is required.
73
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Control of taphole fumes is usually done by a separate hood with its
own fan. For sealed and semi-sealed furnaces, a separate baghouse is
normally used for cleaning taphole hood exhaust. The energy required is
largely independent of furnace size and ranges between 150 to 30Q kw.
(.For a 30 MW furnace this corresponds to 0.005-0.01 kw per kw furnace
usage increment.)
The energy required for dust control from crushers, screens, etc.,
is dwarfed by the furnace control requirements. In a well-controlled
plant, the energy required for such product handling control is 0.005 kw
per kw furnace usage.
In control systems which use scrubbers, energy is associated with
pumping water, etc. However, the energy expended in moving liquids is
negligible compared to that required to handle furnace gas and fumes. A
value of 0.001-0.003 kw per kw furnace usage is estimated for water
pumping requirements.
The values given above for energy requirements are summarized in
Table 19.
TABLE 19 . ENERGY REQUIREMENTS FOR POLLUTION CONTROL IN
FERROALLOY MANUFACTURE
kw
Energy requirement,
kw of furnace usage
Item Open Sealed
Breakdown by function
Main furnace gases
Taphole control
Product handling
Pumps, etc.
Model plants*
0.04 - 0.11
0.005 - 001
^0.005
Negligible
^0.054
0.01 - 0.03
0.005 - 0.01
O.005
0.001 - 0.003
^0.013
Industry wide average**
1975 0.051
1976 0.061
1977 0.065
*For 30 M furnace based on calculations in EPA-450/2-74-008. Numbers
neglect product handling and are based on average gas flows with no pro-
vision for instantaneous fluctuations in furnace gas flows.
**Based on data in the Ferroalloys Association Statistical Yearbook
1977.8
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ll.Q SCREENING SAMPLES
In the initial phase of this project, RTI personnel inspected nine
plants where ferroalloys are produced. These plants provide a good
cross-section of the industry and included open, mix-sealed, and sealed
submerged arc furnaces, and electrolytic manufacture of chromium and
manganese. Emission control systems for tapping fumes, and primary and
secondary furnace fumes were observed. The collection systems observed
included baghouses, scrubbers, and an electrostatic precipitator.
During these visits a variety of samples were collected purely for
preliminary screening purposes. All samples were of the "grab" type,
and no compositing was done nor was any process-related information
collected. Therefore, the samples must be considered as isolated, and
possibly nonrepresentative of the operation. They do, however, provide
useful information in that they gtve some indication as to which processes
produce significant amounts of organic matter and the POM content of the
sample. This information was considered when selecting plants for
testing. It cannot be overemphasized that since the samples were iso-
lated grab samples, no attempt should be made to use the data to calculate
potential emissions from the source.
The information obtained' is presented in Table 20. The first
column gives the product type being made. All products except CaO and
the electrolytic products were produced in submerged arc furnaces.
Column 2 gives the source from which the sample was taken. The baghouse
dust was typically taken from the load-out hopper. Scrubber discharge
water samples were taken from local sumps at the furnaces. The vacuum
filter solids were collected directly from the filter. The sampling
method used does not allow for subtraction of any organic or suspended
solid in the feed water. It also does not correct for the organic
polymer added to the vacuum filter solids. Column 3 gives the type of
furnace top cover in use. Close-hooded systems had doors extending from
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TABLE 20. SCREENING SAMPLES
Furnace product
Si
Si
Si + 75% FeSi
L.C. SiMn
FeSi Sr.
50, 75% FeSi
50% FeSi
50% FeSi
50% FeSi
50% FeSi
75% FeSi
50% FeSi
50-75% FeSi
18% FeSi
Sample source
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Baghouse
Scrubber
Scrubber
Scrubber
Scrubber
Baghouse
Baghouse
Scrubber
Furnace type
Open
Open
Open
Open
Open
Open
Close-hooded
Close-hooded
Mix-sealed
Mix-sealed
Mix-sealed
Open furnace plus parti cu-
late from electrode area
of mix-sealed furnace
Secondary emissions from
mix-sealed furnace
Sealed
Organics POM, as approxi-
mg/kg Organics mate % organic
Dry solids mg/L found
266 1-3
224
384 <0.1
65
160
171
312
500 12
80,800 333 10-15
41,100 86 25-50
19,900 605 40-60
1,100 1-3
7,000 15-20
28,100 198 20-50
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TABLE 20. (Continued)
Furnace product
18% FeSi
18% FeSi
FeCr
FeCr
FeCr
SiMn
SiMn
H.C. FeMn
CaSiBa
CaC2
CaC2
CaO
SiMn, FeMn and
Electrolytic Cr
Sample source
Tar from 1st
venturi
Vacuum filter
solids
ESP
Tapping fume
baghouse
Scrubber
Scrubber
Tapping fume
baghouse
Scrubber
Baghouse
Scrubber
Secondary
emissions
Scrubber
Scrubber, feed
to sludge beds
Furnace type
Sealed
Sealed
Open
Open
Close-hooded
Open
Open
Open
Open
Mix-sealed
Mix-sealed
Combustion gas was from mix-
sealed furnaces
Open, mix-sealed, and elec-
trolytic
Organics POM, as approxi-
mg/kg Organics mate % organic
Dry solids mg/L found
16,700 l,980a 20-50
12,000 6,100b 40-60
163 1-10
5,600 40-80
900
4,900 12.9 2-4
1,700
10,000 12.2 <0.2
0
22,300 8.33
50
7,900 12.5
19,100 10.4 1-3
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TABLE 20. (Continued)
Furnace product Sample source Furnace type
Electrolytic Mn Baghouse Electric induction
(Ore reduction area)
Electrolytic Mn Slurry
(Mud to tailing pond)
Organics
nig/ kg
Dry solids
320
1,400
Organics
mg/L
198
POM, as approxi-
mate % organic
found
1-10
a - mg/kg of solids as sampled (11.9% solids)
b - mg/kg of solids as sampled (50.77% solids)
00
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the main hood to the top of the furnace. Column 4 gives the analytical
results for GRAV (high boiling point) organics only. This is presented as
mg of GRAV organics per kg of solids collected. For scrubber waters, the
solids were filtered out (0.45 micron filters) and weighed and then both
solids and liquids extracted for organics. Column 5 gives the actual
concentration of GRAV organic in the water sample 0"eluding contribution
from solids). The last column gives the approximate percentage of poly-
cyclic organic material in the GRAV organic found. This was determined
using a sensitized fluorescence technique. The data indicate that the
organic content of baghouse dust from open type furnaces is quite low (<500
mg/kg) and that the organic content of scrubber collected solids from open
furnaces is somewhat higher (500-10,000 mg/kg solids in scrubber water),
although the latter could be due to organics in the feed water. Tapping
fumes from the open furnaces have organic contents of from 1,700 to 5,600
mg/kg solids. Organic content of solids from covered furnaces are much
higher than from other type furnaces with a range of 12,000 to 80,800 mg/kg
solids. The POM analysis indicates that particulates from open furnaces
have quite low POM contents CO.1-10.0 percent of GRAV organic) while the
POM is about 25-60 percent of the GRAV organic from covered furnaces. The
data also suggest that the POM content of particulate in the gas escaping
the furnace cover may be quite high.
Of particular interest was the implication from the data that there is
not only a significant apparent difference in organic generation rates
between open and covered furnaces, but there also appears to be a difference
in the amount of organics generated by covered furnaces producing the same
or different products. This observation was considered in the selection of
furnaces for more detailed testing.
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12.0 PLANT DESCRIPTIONS AND TEST RESULTS
IERL-RTP Level 1 testing was performed at three plants designated A, B,
and C. Two furnaces were tested at each plant. In addition, the final
wastewater discharge from each plant was sampled and analyzed.
The plants and furnaces were selected for testing based on several fac-
tors which included: manufacture of a major ferroalloy product, typical size
furnaces, manufacture of the same product in different type furnaces or
related products in the same type furnace. Known or suspected pollution
potential of the plant was not a prime consideration.
This section of the report is divided into three major subsections,
each dealing with a single plant. Each subsection contains a general plant
description, a description of one furnace tested, the tests conducted on
that furnace and the results obtained. The same information is then given
for the second furnace tested.
At Plant A, a comparison was made of the production of high carbon
ferromanganese (H.C. FeMn) produced in an open furnace and in a mix-sealed
furnace using undercover combustion of process gas. At Plant B a comparison
was made of open and mix-sealed furnaces producing 50 percent ferrosilicon
(50 percent FeSi). The product is half iron and half silicon, the percent
figure refers to the silicon content. At Plant C a comparison was made for
production of 50 percent FeSi and 75 percent FeSi in mix-sealed furnaces.
12.1 PLANT A TESTS
Sampling at Plant A was conducted to compare pollutants from different
furnaces producing high carbon ferromanganese. Furnace A-l is a mix-sealed
furnace that has been modified (holes cut in top cover) to allow air to be
drawn into the furnace. The air drawn in allows virtually complete combustion
of the furnace gases under the furnace cover (at least during the test period).
Furnace A-2 is a typical open furnace design that allows combustion of the
furnace gas as it leaves the furnace. The primary difference in these two
modes of operation is that less air is drawn into furnace A-l, thus allowing
81
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the gases to burn at a higher temperature. Also the volume of gas treated
by the pollution control equipment is substantially less for furnace A-l.
12.1.1 Plant A General Description
This ferroalloy facility is located near a river. The plant produces
SiMn, FeMn, and FeCr in submerged arc furnaces. Refining of some ferroalloys
and production of other material, e.g., Vanadium Carbide, is accomplished in
the Simplex plant, a high, temperature vacuum operation. High purity--99.8
percent—chromium is produced in an electrolytic shop.
Wet scrubbers Cdisintegrators and venturi types) are used to control
emissions from the submerged arc processes. Tapping fumes on one furnace
are controlled by a small baghouse. All process water from the electrolytic
plant waste is collected and oxidized [by ozone) in a Uno>r treatment system.
The treated water is mixed with the furnace wastewater and then flows into
one of several ponds occupying about 100 acres near the river. Once through
cooling water and treated sanitary waters do not enter this system. The
solids settle out and the clarified water overflows into the river. The
settled solids in the pond are dredged out and pumped to a diked impoundment
located behind the plant, well away from the river.
Table 21 lists the submerged arc furnaces, type, and design power rating
for the products listed. Here, as in related descriptions of other plants,
the furnace number designation is not the same as the furnace test number,
i.e., A-l is not furnace 1 of Table 21.
TABLE 21. SURMERGED-ARC FURNACES AT PLANT A
FCE No.
1
2
3
4
5
6
7
8
9
Type
Open
Semi -sea led
Semi -sealed
Semi -sealed
Semi -sealed
Semi -sea led
Open
Semi -sealed
Semi-sealed
Mw Rating,
Approximate
30
7.5
7.5
7.5
12
12
16
7.5
11.4
Product
SiMn
FeMn
FeMn
FeMn
FeCr
FeCr
FeMn
FeMn
FeMn
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Raw materials for the plant are loaded into weigh cars inside a covered
building. The material is transported via skip hoists through a covered duct
to feed bins above the furnaces. No significant amounts of particulate were
observed in these areas.
Two of the furnaces not tested are described below.
Furnace No. 3 - Semi-sealed Producing H.C. FeMn and Operating at 7.9 MW.
Raw materials are fed onto the furnace cover and around the electrodes.
Occasionally the material on the cover is pushed up to the electrode to feed
into the furnace and to maintain the seal. There is a hood system above the
cover which collects gas and particulate leakage and exhausts through a roof
vent without passing through a collector. Fumes generated by this source were
normally light with occasional episodes of moderate to heavy fumes.
The tapping area has a duct approximately 1x2 meters (3 feet by 5 feet)
which collects fumes in the area and exhausts them through the roof directly
to the atmosphere. Capture efficiency of the hoods during the tapping period
was judged to be relatively poor. Tapping occurs about once every 2-2 1/2 hours
and lasts about 15 minutes.
Gas from under the furnace cover is exhausted through two parallel Buf-
falo Forge scrubbers. Gas volume through each scrubber, a multistage centrif-
ugal type, is about 56.6 m /min (2000 ACFM). Gas generated by the furnace
reactions is about 36.8-40 m /min (13-1400 CFM). The carbon monoxide content
of the scrubber discharge is less that 40 volume percent and varies somewhat
with furnace operating conditions (air drawn in through the mix seals and
other openings dilutes the gas and also burns some of the CO to C0?; available
oxygen in Mn ore oxidizes some CO to C0»). Although the cleaned gas is routed
to a flare stack, plant personnel report that it is difficult to keep the
flare lit. Thus, the gases sometimes are not burned.
Furnace No 1 - Open Producing SiMn and Operating at 29 Mw
This furnace is equipped with a hood extending to within about 1.5 meters
(5 feet) of the stoking deck floor. Chain curtains extend down from the hood
to the floor. The chains can be pulled up to allow access for the stoking
equipment. There was a well distributed flame across the furnace charge sur-
face, indicating good combustion. Fume collection by the hood system was
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reasonably good although some fume was observed escaping the system and
exiting through the roof monitor. Furnace gases collected pass through a
twin Venturi scrubber which has two mist eliminators. The scrubber is
equipped with two 1250 hp blowers and handles a total of 5660 m /min (2.5
cm Hg - 57°C) (1 inch H2Q, 135°F). The scrubber pressure drop is 141 cm Hg
(55.57 inches of water) and has a reported dust collection efficiency of 99
percent. The scrubber sludge is collected in two small settling pits where
some of the solids settle. The overflow from the pits goes to the fluid
waste system and then to the settling beds. Tapping fumes from this fur-
nace are collected and particulates removed by a cyclone and baghouse.
All of the slag from H.C. FeMn production is used as raw material for
SiMn production. Slag from SiMn production is sold locally and is used as
road construction material.
Medium carbon products are made by blowing oxygen through the molten
alloy while it is in the ladle. The reaction was said to be quite exothermic.
A 2832 m /min (.100,000 CFM) fume collection system is used to control fumes
generated during the oxygen blowing. RTI personnel did not observe this
operation.
General Information
All of the semi-sealed furnaces at this plant (with the exception of
Nos. 6 and 9 FCES) use pre-baked electrodes. Open furnaces (such as Nos. 1
and 7) use the self-baking type. Electrode consumption on the smaller fur-
naces is 15-17 kg/Mg C30-35 Ibs/ton) of alloy produced. Electrode consump-
tion for SiMn is about 25 kg/Mg (50 Ibs/ton) of alloy produced.
Metal refining is performed in the Simplex plant. This is the largest
ferroalloy vacuum refining operation in the world. The material to be refined
is loaded into the vacuum chambers which are about 5 meters (15 feet) in dia-
meter and 46 meters 050 feet) long. The material can then be heated to
over 1090°C (2000°F) at pressures below 100 microns (
-------
sludge generated in the process from anode dissolution is presently being
stored until a market is developed or a disposal method is found.
12.1.2 Furnace A-l Description
Furnace A-l (Figure 3), a mix-sealed furnace design, was modified by
cutting holes in the furnace cover. This modification was made to relieve
pressure during periods of sudden furnace blows. During normal operations,
air is drawn into the furnace causing virtually complete combustion of the
furnace gases before they exit the furnace. This is confirmed by an Orsat
reading (Table 25) showing less than 1 percent CO in the effluent gas.
Three carbon electrodes, arranged in a delta formation, pass through the
furnace cover and extend well into the furnace. Raw materials are blended in
the mix house and stored in bins above the furnace. This material is fed into
the furnace, as needed, through openings around the electrodes. Fumes, gases,
and particulate escape from the furnace cover and are collected by a hood and
exhausted, uncontrolled, directly to the atmosphere through stacks on the
building roof. The opacity of these stacks is monitored (less than 1 Ringle-
man) and reported to regulatory authorities. The emissions from this area are
substantially greater than is typical in the industry (based on visual com-
parisons by the test crew).
Gases and dust are withdrawn from the furnace and cooled by water sprays
before passing through a high pressure drop Pease-Anthony venturi scrubber.
After passing through a water knock out tank and the gas blower, the gases are
exhausted to the atmosphere. Clarified river water is used in the quench
sprays and the venturi. All condensed and collected scrubber water is col-
lected in a common sump before entering the plant sewer system.
12.1.3 Tes.t Description, Furnace A-l
Samples were taken (see Figure 3 for sampling points) of the cleaned
gases from the primary emission control system, and of the scrubber feed and
discharge water. The sampling point for the gas sample was in a 50.8 cm
(20 inch) internal diameter duct about 3 meters (10 feet) downstream of the
blower and about 1 meter (3 feet) upstream of the gas flow measuring orifice
(a velocity traverse of the duct, demonstrated that the orifice had no effect
85
-------
CO
TO ATMOSPHERE
SECONDARY
EMISSION
HOOD
CARBON
ELECTRODES
TO PRIMARY
EMISSIONS CONTROL
CLARIFIED RIVER WATER
200-300 gpm
WATER
SAMPLE
POINT
300 gpm
VENTURI
FURNACE
A-1
WATER SAMPLE
POINT
500-600 gpm
WATER
KNOCKOUT
TANK
TO SEWER
SUMP
Figure 3. Emission control system on furnace A-1.
TO ATMOSPHERE
SAMPLING POINT
"FOR ORSAT TEST
D. P. ORIFICE
SASS
-4- SAMPLING
POINT
Q
BLOWER, 250 HP
-------
on the flow profile). The sample was collected using the Source Assessment
Sampling System (SASS). A two-liter sample of the scrubber feed water was
collected from a tap near the venturi and a two-liter sample of the scrubber
discharge water was collected at the sump overflow weir thirty minutes after
SASS sampling began. The test was terminated before additional samples
could be taken because of a malfunction in the furnace electrode positioning
equipment which required a furnace shutdown.
Since raw materials are fed to the furnace from storage bins, an "in-
stantaneous" feed rate cannot be determined. Therefore, the feed rate was
determined by counting the number of "trips" made by the preweighed cars to
the storage bins in a 24 hour period when the furnace was operating at 11.8
MW (normal power level). A typical alloy analysis from furnace A-l is
presented in Table 22. In Table 23 details of the mix fed to the furnace
are given. In Table 24 the analysis of the raw materials used in both
furnaces A-l and A-2 is given. Operating at 11.8 MW furnace A-l produces
4654 kg (10,261 Ibs) of HC FeMn alloy and 2909 kg C6413 Ibs) of slag per
hour (specific energy consumption 2.53 kwh/kg--5.58 kwh/lb—alloy; 0.625 kg
slag/kg alloy).
TABLE 22. FURNACE A-l ALLOY ANALYSIS
Component Percent by Weight
Mn 80.00
Fe 11.80
Si 0.50
Cr 0.15
P 0.17
As 0.12
C 6.80
During the test period the furnace was operating at 11.4 MW. The pres-
sure under the furnace cover was -0.011 cm of Hg [-0-06 inches of water) and
the gas temperature at the furnace exit was 482-538°C (900-1000°F). The
venturi was operating with a pressure drop of 13.6 cm of Hg (73 inches of
87
-------
TABLE 23. RAW FEED FOR FURNACE A-l AS 'GIVEN BY THE PLANT
00
O3
Component
Reducing Agent
Buckwheat Coke
Recycled Materials
Std FeMn Fines
Std FeMn Slag
At 11.8
Source
Pile No.
522
912
369
MW OPERATION (4.65 Mg
Kg per
Trip
826
136
136
Kg per
Hour
2511
489
489
ALLOY/HR)
Kg per
Mw-Hr
213
35
35
Kg consumed
Per Mg Alloy
Produced
5408
89
89
Kg consumed
Per Mg of
(Alloy + Slag)
332
55
55
H/H Spills (Conglo-
merate of Ore and
Reducing Agent)
Mn Ores
50% Associated
Wessels
Amapa Pellets
Comilog
Russian
Mor Pellets
Electrodes
Total
23
69
5.9
15
113
129
137
138
123
258
-
454
295
953
1179
227
159
-
4386
1380
897
2898
3587
690
483
67.6
13410
117
76
245
304
58.5
41
5.9
1374
296
192
622
770
148
104
15
2881
182
118
383
474
91
64
9
1773
-------
TABLE 24. MANGANESE ORE ANALYSIS*. FURNACES A-l AND A-2
Component
Associated 50%
Russian
Wessels
Amapa Pellets
Comilog
00
10 Amapa-6SA-LG
Amapa Ore
Mor Pellets
Angolan
Pile No.
113
123
129
137
138
140
186
258
5105
Book
H20
1.51
8.54
1.46
1.68
8.31
5.78
4.78
4.0
6.80
Book
Mn
53.27
47.13
47.09
54.34
51.88
49.74
48.54
65.26
47.86
Fe
9.10
1.33
12.74
6.82
2.54
5.55
5.57
4.58
2.75
Percent by
P S102
0.033
0.161
0.032
0.082
0.112
0.93
0.086
0.075
0.068
4. 22
9.94
5.04
5.89
2.51
3.11
2.89
0.48
6.95
Weight
AL203
0.31
1.71
0.38
6.97
6.07
5.20
5.28
0.055
2.67
CaO
2.03
1.19
4.12
0.35
0.05
0.09
0.07
0.42
0.78
BaO
0.80
1.17
0.35
0.23
0.24
0.20
0.19
-
5.71
K20
0.12
0.40
0.10
0.76
0.63
1.85
1.44
-
l.lp
co2 o2
0.96 7.27
0.85 10.06
2.21 6.09
0.03 4.65
0.06 14.31
13.43
13.09
4.00
0.09 10.78
T102 As MgO
0.04 0.002 0.45
1.40
0.002 0.72
0.47 0.10 0.10
0.24 - 0.06
0.36 0.165 0.06
0.38 - 0.05
0.61
0.47
''As given by plant personnel.
-------
o
water). Total water flow to the quench and venturi was 1.9-2.3 m /min
(500-600 gpm).
Chemicals were added to the SASS system at a remote location to avoid
contamination at the work site. After verifying that the furnace was operat-
ing properly, the probe was inserted into the duct and sampling started.
Approximately one hour later preparations for a furnace shutdown began because
of a malfunction in an electrode positioner. The furnace was not scheduled
for a restart in less than eight hours. Since sufficient sample had been col-
lected the samples were recovered for analysis.
12.1.4 Test Results, Furnace A-l
On-Site Results
A velocity traverse of the exhaust duct at the SASS sampling point
gave the following results:
AP Maximum - 0.45 cm Hg (2.4 in F^O)
AP Minimum - 0.37 cm Hg (2.0 in H20)
AP Average - 0.406 cm Hg (2.174 in H20)
Duct Temperature 52.2°C (126°F)
Duct Area 0.203 m2 (2.18 ft2)
Moisture 12 percent
Gas Velocity 1573 m/min (5160 ft/min)
Flow Rate, Actual 318.6 m3/min (11252 ft3/min)
3 3
Flow Rate, Standard Conditions 255.1 m /min (9010 ft /min)
The results of an Orsat analysis of a gas sample taken, near the SASS
sample point is shown in Table 25. Data taken with the SASS train during the
actual test is given in Table 26.
Particulate
The particulate generated, captured by the scrubber, and emitted to the
atmosphere by furnace A-l is presented in Table 27. It should be noted that
these data apply only to particulate in the primary control system. A sub-
stantial amount of fumes escaped through the furnace cover and were removed by
the secondary control system. These secondary emissions are exhausted uncon-
trolled, directly to the atmosphere. No particulate was captured by the
cyclones (1 micron and greater) indicating that most, if not all, of the par-
ticulate passing through the scrubber is submicron in size. Particulate
90
-------
TABLE 25. ORSAT ANALYSIS, FURNACE A-l
Component
CO
co2
°2
H2
Inerts (N2)
Percent by Volume
0.60
16.7
11.8
0.4
70.5
TABLE 26. SASS TEST DATA, FURNACE A-l
Date of Test
Volume of Gas Sampled
Stack Gas, Temperature
Pressure
Dry Molecular Weight
Wet Molecular Weight
Moisture, Percent
Velocity
Flow Rate
Total Sampling Time
SASS Flow Rate
Percent Isokinetic
4/4/79
,3*
5.082 Nm° (179.446 DSCF*)
(126°F)
(30.09 in Hg)
52.2°C
76.43 cm Hg
31.03
29.52
11.6
26.2 m/sec (86 ft/sec)
255.1 Nm3/min (9010 DSCFM)
O JL.JL.
318.6 AnVVmin (11252 ACFM)
67.5 minutes
0.0753 Nm3/min (2.66 DSCFM)
87.5
*20°C (68°F), 76.0 cm Hg (29.92 in Hg), moisture-free basis.
**Actual (at stack conditions) flow rate.
91
-------
TABLE 27. PARTICIPATES, FURNACE A^l
ro
Air Emissions
Sample Point - In duct downstream of
Volume of Gas Sampled: 5.082 NM3
Sample Weight
Type Collected, mg
Probe 48.3
ly Filter 205.2
l-10p Cyclones 0
Total 253.5
Parti cul ate removed by the scrubber
Sample Point - At scrubber discharge
Sample Weight Solids
Type Collected, mg
Scrubber Inlet 128
Scrubber Discharge 931
Net Scrubber Solids
Total Solids going to the
*
Primary Control System
% Scrubber Efficiency, Solids
scrubber.
Concentration
mg/NM3
9.50
40.38
0
49.88
sump weir and at
Concentration
mg/L
64.7
474.5
409.8
*Substantial emissions observed from secondary emission
aln this and all similar tables, totals
errors.
may differ from
Kg Emitted
per Hour
0.146
0.618
0
0.764
inlet to scrubber
Kg
per Hour
7.3
53.9
46.5
47.3
98.4
control system.
Kg Emitted
per MW-hr
0.0128
0.054
0
0.067
venturi .
Kg
per MW-hr
0.64
4.73
4.10
4.1
the sum of individual values due
Kg Emitted
per Mg Alloy
0.031
0.13
0
0.16
Kg
per Mg Alloy
1.57
11.55
9.98
10.14
to rounding
-------
concentration in the scrubbed gas was 49.88 mg/Nm or 0.764 kg/hr emitted to
the atmosphere. The gas scrubber captured 46.5 kg/hr of particulate matter or
98.4 percent of the dust collected by the primary control system. Total
3
particulate concentration before the scrubber was, therefore, 3090 mg/Nm .
Particulate emitted to the atmosphere from the primary control system is
0.067 kg/Mw-hr, substantially below the 0.23 kg/Mw-hr NSPS limitation. The
NSPS limits pertain to total emissions, however, and it is expected that
inclusion of secondary emissions would substantially raise the furnace emis-
sion factor.
Organic
Given in Table 28 are the amounts of organic generated, captured by the
scrubber, and emitted to the atmosphere from furnace A-l. The concentration
of organic matter in the scrubbed gas (exhausted to the atmosphere) was
3
20.0 mg/Nm or 0.31 kg/hr which is about 40 percent as great as 'the par-
ticulate emissions. The scrubber captured an additional 0.41 kg/hr. Thus,
3
the total organic matter entering the scrubber was 46.8 mg/Nm or 0.72 kg/hr
(0.0628 kg/Mw-hr). The scrubber efficiency of 57.2 percent for the capture of
organics is substantially less than that for particulates (98.4 percent).
Level 1 Organic Analysis
The SASS train catch was analyzed for organic compound categorization as
follows. The particulate catches were separately extracted with methylene
chloride and a TCO and GRAV determined. The extracts were then combined and
fractionated by liquid chromatography (LC) and each fraction analyzed for
total chromatographical organics (TCO)--low boiling point material--and GRAV--
high boiling point material. The infrared spectrum of each fraction was also
determined. A low resolution mass spectrograph (LRMS) analysis was done on LC
fractions 2 and 3 combined. A similar analysis scheme was followed for the
SASS organic module and condensate (both combined).
Aqueous samples (scrubber feed and discharge water) were filtered to
determine suspended solids concentration and the solids and aqueous phases
separately extracted with methylene chloride. A TCO and GRAV was determined
93
-------
TABLE 28. ORGANICS, FURNACE
Air Emissions
Sample Point - In duct downstream of scrubber.
Volume of Gas Sampled: 5.082 M3
Sample Weight
Type Collected, mq
Probe & Filter 9.0
Organic Module 92.8
Total 101.8
Organic Removed by the Scrubber
Sample Point - At inlet to scrubber
Sample Weight Solids
Type Collected, mq
Scrubber Inlet 15
Scrubber Discharge 22
Net Organics Captured
Total Organics going to the
Primary Control System
% Scrubber Efficiency, Organics
Concentration
mg/NM3
1.8
18.3
20.0
and at scrubber
Concentration
ml L
7.6a
11. 2b
3.6
Kg Emitted
per Hour
0.027
0.28
0.31-
discharge sump weir.
Kg
per Hour
0.86
1.27
0.41
0.72
57.2
Kg Emitted
per MW-hr
0.0024
0.025
0.027
Kg
per MW-hr
0.076
0.11
0.036
0.063
Kg Emitted
per Mg Alloy
0.0058
0.060
0.066
Kg
per Mg Alloy
0.19
0.27
0.088
0.15
a57 Percent of Organic adsorbed on solids.
8.2 Percent of organics adsorbed on solids.
-------
on each extract, the extracts for each sample combined and concentrated and
the scrubber discharge water only was analyzed by LC, IR, TCO, GRAV, and LRMS
as above. The LC, IR, and LRMS data are contained in the appendices.
In Tables 29 and 30 the data obtained is summarized. Of the organic
matter captured by the SASS train 91.2 percent was found in the organic module
(Al-X) with the remainder in the probe and filter (particulate catch). All of
the organic found in the particulate catch was GRAV (high boiling point)
material. GRAV material also accounted for 68.8 percent of the total organic
captured by the SASS train. IR and LRMS spectra indicate the material is
predominately high molecular weight aliphatics. No evidence was found for
potential carcinogens.
The data for the organics found in the scrubber water is summarized in
Table 30 (detailed analysis was not performed on feed water and thus was not
subtracted). All of the organic found in the scrubber water was GRAV mate-
rial. Significantly, this material was found to contain almost 1 mg/L of
fused aromatics with molecular weights above 216. The LRMS indicates possible
carcinogens at masses 228, 252, 256, and 302 (benzoanthracene, benzo(a)pyrene,
dimethyl benzoanthracene, and dibenzochrysene isomer, respectively).
The above data indicate little organic matter is emitted from the fur-
nace's primary gas system and that the scrubber effectively captures the
polycyclic aromatic compounds.
12.1.5 Furnace A-2 Description
Furnace A-2 is a companion to furnace A-l both in size and product
(H.C. FeMn). The basic difference in the furnaces is that whereas A-l is a
covered furnace with undercover combustion, A-2 is an open design furnace with
combustion at the furnace surface.
In this type furnace there is no top cover. Three 1.5 meter (60 inch)
diameter carbon electrodes extend into the furnace. Blended raw materials
from storage bins above the furnace are fed into the furnace so that it is
always full. Since there is no furnace cover, gases from the furnace mix with
air (drawn in by the hood system) and burn vigorously at the furnace surface.
The hood, which is about 3-4 meters (9-12 feet) above the furnace surface,
draws in a considerable amount of air while capturing the gas and fumes coming
from the furnace. The collected gases and fumes are then drawn through a twin
95
-------
TABLE 29. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Al-X
3
Total Organics, mg/m
3
TCO, mg/m
GRAV, mg/m3
LCI
2.0
1.85
0.15
LC2
1.0
0.55
0.45
LC3
7.8
0.47
7.33
LC4
3.1
1.54
1.56
LC5
1.7
0.79
0.91
LC6
2.0
0.35
1.65
LC7
1.3
0
1.3
Z
19.0
5.66
13.44
Category
Assigned Intensity - mg/(m )
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
35
QNS
-
-
10/0.25*
10/0.25
10/0.25
10/0.25
-
-
-
-
-
_
_
_
_
_
-
100/7.8
* •
QNS
QNS
-
-
-
-
-
-
-
-
-
100/0.51
.
10/0.05
—
10/0.05
10/0.05
100/0.51
-
-
-
-
-
-
-
-
-
10/0.03
_
10/0.03
_
10/0.03
10/0.03
100/0.33
7.8
0.25
0.25
0.25
0.25
0.54
0.08
0.08
0.08
0.84
(Continued)
*
Quantity Not Sufficient.
The data are presented as assigned intensity (from IR and/or LRMS)/concentration in this and
all similar tables.
-------
TABLE 29. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Al-X (Cont'd)
Category Assigned Intensity - mg/(m ;
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
QNS
_
-
-
QNS*
QNS*
QNS
10/0.05
10/0.05
10/0.05
10/0.05
10/0.05
10/0.05
100/0.51
10/0.03
10/0.03
10/0.03
10/0.03
10/0.03
10/0.03
100/0.33
0.08
0.08
0.08
0.08
0.08
0.08
0.84
Quantity Not Sufficient,
-------
TABLE 30. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Al-SWD
vo
00
Total Organics , mg/L
TCO, mg/L
GRAY, rng/L
LCI
0.15
0
0.15
LC2
0.15
0
0.15
LC3
0.9
0
0.9
LC4
0.9
0
0.9
LC5
0.45
0
0.45
LC6
1.3
0
1.3
LC7
0.6
0
0.6
Z
4.45
0
4.45
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
QNS*
100/0.15
100/0.81
QNS*
-
-
-
-
-
-
10/0.01
100/0.1
10/0.01
100/0.1
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
100/0.1
-
-
-
-
-
-
-
-
-
10/0.04
-
10/0.04
-
10/0.04
10/0.04
100/0.4
*
QNS
0.96
0.01
0.1
0.01
0.14
0.01
0.05
0.01
0.05
0.05
0.5
-------
TABLE 30. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Al-SWD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
QNS
QNS
0.09
QNS*
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
100/0.4
QNS*
0.05
0.05
0.05
0.05
0.05
0.05
0.50
Quantity Not Sufficient.
-------
venturi flooded disc type scrubber, Figure 4, mist eliminators and exhausted
by two 1250 hp fans through a 2.44 meters (8 feet) diameter, 38.1 meters (125
feet) tall stack.
A major difference in the emission control system, as compared to furnace
A-l, is that the hood system collects all furnace gas and fumes. The A-l
furnace has two emission control systems, primary and secondary (for col-
lection of furnace cover fumes). The data comparison, see 12.1.9, indicates
that a substantial fraction of the fume generated by furnace A-l escaped into
the secondary collection system.
12.1.6 Test Description, Furnace A-2
v
Samples were taken (see Figure 4 for sampling points) of the cleaned
gas and of the scrubber discharge water. Since the same service water is used
for all scrubbers, the feed water analysis for furnace A-l was used. The
sample point for the gas sample was about midway up the scrubber discharge
stack. A velocity traverse showed an even flow profile. The sample was
collected using the SASS system (the lOu cyclone was not used due to a serious
leak). A four-liter water sample was collected from the discharge of each
mist eliminator (scrubber discharge point-1 liter of each collected every 30
minutes during the test). The test was stopped after 85 minutes when the
furnace was shut down because of a problem at the power station.
Raw material feed rate was determined by counting "trips" by the pre-
weighed feed cars in a twenty-four hour period of normal operation at 14.8 Mw.
Details of the mix fed to the furnace are given in Table 31, and Table 24
gives the raw material analysis (supplied by the company).
Operating at 14.8 Mw, furnace A-2 produces 6,278 kg (13,840 Ibs) of H.C.
FeMn alloy and 3,924 kg (8,650 Ibs) of slag per hour. The alloy analysis is
similar to that given in Table 22.
During the test period the furnace was operating at 15.8 Mw. The gas
temperature in the duct leading from the hood to the scrubbers was 93-116°C
(200-240°F) at the point it leaves the furnace building. Significantly higher
temperatures 204-538°C (400-1000°F) are occasionally measured at this point
during furnace "blows" - periods when bridges of fused material suddenly
collapse into the furnace and release gases trapped in the furnace. Furnace
"blows" are extremely dangerous since the rapidly escaping gas can eject raw
100
-------
GAS FROM
FURNACE HOOD
MAKEUP
WATER
SASS
SAMPLING
POINT
60 FT ABOVE
GROUND
FLOODED
DISC
VENTURI
INLET FROM
PARALLEL
SYSTEM
SCRUBBER DISCHARGE WATER
Figure 4. Furnace A-2 emission control system.
-------
TABLE 31. RAW FEED FOR FURNACE A-2 AS GIVEN BY THE COMPANY
o
PO
Component
14
Source
Pile No.
.8 Mw (6.28
Kg per
Trip
Mg - ALLOY/hr)
Kg per
Hour
Kg per
MW-Hr
Kg consumed
Per Mg Alloy
Produced
Kg consumed
Per Mg of
(Alloy + Slag)
Reducing Agent
Buckwheat Coke
Recycle Materials
Std FeMn Fines
Std FeMn Slag
Mill Scale
Mn Ores
Angolan
Indian
Amapa
GSA Amapa
Mor Pellets
Electrodes
Total
522
748
2,807
190
448
271
912
369
237
5,105
141
186
140
258
-
136
272
45
318
227
1,814
590
272
-.
510
1,021
170
1,191
850
6,804
2,211
1,021
101
16,685
34
69
11
80
58
460
149
69
7
1,127
82
162
27
190
136
1,085
352
162
16
2,660
50
98
16
115
82
658
214
98
10
1,612
-------
material and molten metal. Each venturi scrubber was operating at a pressure
drop of 8.7 cm Hg (46.5 inches of
Each of the two 1250 horsepower
exhaust fans were operating at about 68 percent of maximum (~850 hp). Total
scrubber discharge flow rate was estimated by plant personnel to be about 2.3
3
m /min (600 gpm).
After verifying that the furnace was operating normally, the SASS probe
was inserted into the stack and sampling begun. One hour and 15 minutes later
the sampling crew was advised that the furnace was to be shut down because of
a problem at the power house. Since plant personnel could provide no estimate
of the outage time, the test was stopped and the samples recovered.
12.1.7 Test Results, Furnace A-2
A velocity traverse of the exhaust stack was performed just prior to
the SASS test and the following results were obtained:
0.12 cm Hg (0.65 inches H90)
AP Maximum
AP Minimum
AP Average
Stack Temperature
Stack Area
Moisture
Gas Velocity
Flow Rate, Actual
Flow Rate, Standard Conditions
0.093 cm Hg
0.107 cm Hg
32°C
4.67 m2
7 percent
788.2 m/min
3
3,676.6 m/min
3,196.4 m /min
(0.50 inches H£0)
(0.574 inches H20
(90°F)
(50.3 ft2)
(2,586 ft/min)
(129,837 ft3/min)
(112,879 ft3/min)
Data taken with the SASS train during the actual test is given in Table 32.
TABLE 32. SASS TEST DATA, FURNACE A-2
Date of Test
Volume of Gas Sampled
Stack Gas, Temperature
Stack Gas, pressure
(Continued)
4/5/79
8.2687 Nm3 (292.005 DSCF)*
32°C (90°F)
75.44 cm Hg (29.7 inches Hg)
103
-------
Table 32 (Continued)
Dry Molecular Weight 29.1
Wet Molecular Weight 28.31
Moisture 7 percent
Velocity 13.53 m/sec (44.4 ft/sec)
Flow Rate, Actual 3791.7 A m3/min (133,902 ACFM)
Flow Rate, Standard Condition 3355.4 Mm /min (118,495 DSCFM)
Total Sampling Time 82.7 minutes
SASS Flow Rate 0.1 Nm3/min 3.53 DSCFM
Percent Isokinetic 117
*20°C (68°F), 76.0 cm Hg (29.92 inches Hg)
Particulate
In Table 33, the amounts of particulate generated, captured by the scrub-
ber, and emitted to the atmosphere from furnace A-2 are given. In contrast to
furnace A-l, these data apply to all particulate generated by the furnace (not
including tapping, etc.) since a furnace cover, requiring a primary and secon-
dary control system, is not used.
No particulate was captured by the cyclones (1 micron and greater) indi-
cating that most, if not all of the particulate passing through the scrubber
was submicron in size. Particulate concentration in the scrubbed gas was 27.7
mg/m or 5.32 kg emitted per hour to the atmosphere. The gas scrubber cap-
tured an additional 169.6 kg/hr of particulate matter or 96.96 percent of the
dust generated by the furnace. Particulate concentration in the gas stream
o
before the scrubber was, therefore, 911.9 mg/m . Particulate emitted to the
atmosphere is 0.337 kg/Mw-hr or 46.5 percent greater than would be allowed by
NSPS of 0.23 kg/Mw-hr.
Organic
Given in Table 34 are details of the organics generated, captured by the
scrubber, and emitted to the atmosphere from furnace A-2. The concentration
o
of organic matter in the scrubbed gas (atmospheric emission) was 23.98 mg/m
or 4.6 kg/hr which is 86.5 percent as great as the particulate emission. The
104
-------
TARI F "n PARTTPIII ATFS. FURNACE A-2
o
en
Air Emissions
Sample Point - In discharge stack
Volume of Gas Sampled: 8.2686 NM3
Sample
Type Col
Probe
ly Filters
Cyclones
Total
Particulate Removed by the
Sample Point - Discharge
Sample Wei
Type Col
Service Water
Scrubber Discharge 10
Net Scrubber Solids
Total Solids
% Scrubber Efficienc
Weight
lected, mg
29.9
199.4
0
229.3
Scrubber
pipes on
ght Solids
lected, mg
128
,140
y, Solids
after scrubber.
Concentration
mg/NM3
3.62
24.12
0
27.73
East and West scrubbers
Concentration
mg/L
64.7
1309.2
1244.5
Kg Emitted
jDer Hour
0.694
4.63
0
5.32
, and service
Kg
per Hour
8.8
178.4
169.6
174.9
96.96
Kg Emitted
per MW-hr
0.0439
0.293
0
0.337
water line.
Kg
per MW-hr
0.56
11.29
10.73
11.07
Kg Emitted
per Mg Alloy
0.10
0.69
0
0.79
Kg
per Mg
1.31
26.52
25.21
26.0
Alloy
-------
TABLE 34. ORGANICS, FURNACE A-2
Air Emissions
_ -. ._ _• -••- - •—• - — '
Sample Point - In discharge stack after scrubber.
Volume of Gas Sampled: 8.2666 NM3
Sample Weight
Type Collected, mg
Probe and Filter 15.2
Organic Module 183.1
Total 198.3
Organic Captured by the Scrubber
Sample Point - Discharge pipes on
Sample Weight Solids
Type Collected, mg
Scrubber Inlet 15
Scrubber Discharge 70.0
Net Organics Captured
Total Organics
°L Scrubber Efficiency, Orqanics
Concentration
mg/NM3
1.84
22.14
23.98
East and West scrubbers
Concentration
mg/L
7.6a
14. lb
6.5
Kg Emitted
per Hour
0.35
4.25
4.60
and service
Kg
per Hour
1.04
1.92
0.89
5.49
16.15
Kg Emitted
per MW-hr
0.022
0.27
0.29
water line.
per MW-hr
0.066
0.12
0.056
0.35
a57 Percent of organic adsorbed on solids.
44 Percent of organic adsorbed on solids.
Kg Emitted
per Mg Alloy
0.05
0.63
0.68
per Hg Alloy
0.15
0.29
0.13
0.82
-------
scrubber captured an additional 0.89 kg per hour. Thus, the total organic
matter entering the scrubber was 28.6 mg/Nm3 or 5.4S kg/hr (0.35 kg/Mw-hr).
The scrubber efficiency of 16.15 percent for organics removal is substantially
less than the 96.96 percent found for particulate capture.
Level 1 Organic Analysis
The SASS train catch was analyzed for organic compound categorization as
follows: the particulate catches were separately extracted with methylene
chloride and TCOs and GRAVs determined. These extracts were then combined and
fractionated by LC. An IR, TCO, and GRAV were run on each fraction. An LRMS
was run on LC fractions 2 and 3 (combined). A similar scheme was followed for
the SASS organic module and condensate (combined before extraction). The
scrubber discharge water was filtered to determine suspended solids concen-
tration and the solids and aqueous phases separately extracted. A TCO and
GRAV was determined on each extract, the extracts combined and concentrated
before analysis by LC as above. The LC, IR, and LRMS data are contained in
the appendices.
In Tables 35 and 36 the data obtained are summarized. Of the organic
matter captured by the SASS train 92.3 percent was found in the organic module
(A2-X) with the remainder in the probe and filter (particulate catch). The
organic found in the particulate catch was 98.7 percent GRAV material. GRAV
material also accounted for 83.7 percent of the total organic captured by the
SASS train. A large fraction of this material is in LC fraction 2 which is
consistent with the compound categorization which shows predominant categories
of aliphatic and aromatic hydrocarbons. The LRMS spectra of LC fractions 2
and 3 (combined) contains (among other masses) a major peak at M/e of 302
(possibly dibenzochrysene isomer) and a minor peak at M/e 276 (possibly indeno-
(1,2,3-cd)pyrene) both known carcinogens.
The data for the organics found in the scrubber discharge water are
summarized in Table 36. The total organic found was 98.6 percent GRAV mate-
rial and was predominately normal and halogenated aliphatic and aromatic
hydrocarbons. LRMS indicates the material is predominately (>80 percent)
fused aromatic compounds with molecular weights above 216. High intensity
peaks in the LRMS were found at M/es of 228, 252, 266, 276, 278, and 302 which
indicates the presence of known carcinogens benzoanthracene (or chrysene),
107
-------
TABLE 35. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A2-X
o
00
3
Total Organics, mg/in
3
TCO, mg/m
GRAV, mg/m3
LCI
1.0
0.7
0.3
LC2
5.7
0.2
5.5
LC3
0.9
0.4
0.5
LC4
1.6
1.2
0.4
LC5
1.1
1.0
0.1
LC6
4.3
0.7
3.6
LC7
1.5
0
1.5
Z
16.1
4.1
12.0
Category
'1
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient.
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/0.2
100/0.2
**
100/0.2
100/0. 2**
-
-
.-
-
-
_
_
_
A#
100/0.2
100/0.2**
-
LOO/2.8
LOO/2.8
100/0.4
100/0.5
35
QNS
-
-
-
-
LOO/0. 2**
-
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
100/0.2
-
-
-
-
-
-
-
-
-
10/0.11
10/0.11
_
100/1.1
10/0.11
100/1.1
-
-
-
-
-
-
-
-
-
10/0.04
10/0.04
__
LOO/0 .4
10/0.04
100/0.4
3.4
0.2
3.5
0.2
0.2
-
0.02
0.02
0.02
0.17
0.02
0.17
0.02
1.42
0.17
1.7
Possible Contamination.
-------
TABLE 35. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A2-X
i
Category Assigned Intensity - rag/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
_
-
-
-
-
-
-
QNS*
QNS*
QNS*
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
100/0'.2
10/0.11
10/0.11
10/0.11
10/0.11
10/0.11
10/0.11
100/1.1
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
100/0.4
0.17
0.17
0.17
0.17
0.17
0.17
1.7
Quantity Not Sufficient.
o
to
-------
TABLE 36. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A2-SWD
Total Organics, mg/L
TCO, mg/L
GRAY, mg/L
LCI
3.4
0.2
3.2
LC2
3.9
0.1
3.8
LC3
2.9
0
2.9
LC4
1.2
0
1.2
LC5
0.7
0
0.7
LC6
O.Q
0
0.9
LC7
n s
0
0.5
I
13.6
0.3
15.3
Category
Assigned Intensity - mg/ L,
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/1.7
100/1.7
-
-
-
-
-
_
—
—
—
-
-
-
-
-
-
100/1.26
100/1.26
100/1.26
10/0.13
-
-
_
—
-
—
-
-
-
-
-
-
-
100/0.57
100/0.57
10/0.06
100/0.57
-
_
_
_
-
-
-
-
-
& A
100/0.57
-
-
-
-
10/0.07
10/0.07
10/0.07
LOO/0.67
10/0.07
10/0.07
10/0.07
10/0.07
10/0.07
-
-
-
-
-
-
-
-
-
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
QNS
QNS
1.7
2.96
1.83
1.83
0.26
0.64
0.11
0.71
0.11
0.11
0.11
0.11
0.11
0.04
0.04
0.61
(Continued)
*
Quantity Not Sufficient,
Possible Contaminant.
-------
TABLE 36. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A2-SWD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
• **
100/0.57
-
-
-
-
-
-
_
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
QNS
*
QNS
0.04
0.04
0.04
0.04
0.04
0.04
0.61
Quantity Not Sufficient,
Possible Contaminant,
-------
benzo(a)pyrenes dibenzofluorene, indenoO,2,3-cd)pyrene, dibenzanthracene,
and dibenzochrysene isomer, respectively.
These data indicate that carcinogenic compounds possibly are being emit-
ted to the atmosphere from the furnace and that although the scrubber is
reasonably ineffective for organic compound removal, it is trapping many of
the possibly carcinogenic, high molecular weight compounds.
12.1.8 Plant A Final Wastewater Discharge
All wastewater from the plant flows into about 100 acres of ponds
where solids settle before the water is discharged to the river. The solids
are occasionally dredged out and landfilled on company property. A grab
sample of the pond effluent (17.03 m /min, 4500 gpm) was taken the same day
furnace A-2 was tested. The sample was filtered for suspended solids deter-
mination, extracted and subjected to LC, IR, TCO, GRAV, and LRMS analysis.
The overall results for solids and organics are summarized in Table 37, and
the Level 1 organic analysis is summarized in Table 38. The LC, IRS and LRMS
data are in the appendices.
The organic compounds found are predominately high molecular weight
aliphatics. No evidence was found for carcinogenic compounds.
12.1.9 Plant A Summary
Sampling was conducted to compare the two furnaces, one using under-
cover combustion (A-l) and one of open design (A-2), producing high carbon
ferromanganese. The results, Table 39, indicate that furnace A-l more effec-
tively destroys organic compounds. However, a definitive conclusion cannot
be drawn because secondary emissions from furnace A-l, which were substantial,
were not sampled. Assuming (see Table 2 for basis of assumption) that both
furnaces generate particulate at the same rate (11.07 kg/Mw-hr), emissions
from furnace A-l secondary control system would be 6.92 kg/Mw-hr (62.5 percent
of total dust generated) or 78.9 kg/hr. However, since organics are only 1.5
percent of the particulate mass generated by furnace A-l and 3.1 percent of
the particulate for furnace A-2, there is evidence that less organic is
emitted from furnace A-l (on a kg/Mw-hr basis).
Detailed analysis indicated carcinogenic compounds were not being emitted
to the atmosphere from furnace A-l. Potential presence of carcinogenic com-
pounds was found in the scrubber water, however, and in emissions to the air
112
-------
TABLE 37. PLANT A FINAL EFFLUENT
Sample Point - Near plant effluent discharge point.
Total Plant Discharge Flow Rate: 17.034 m3/min (4500 gpm)
Component
Suspended Solids
*
Organics
Weight
Collected, mg
36
13.3
Concentration
mg/L
9.4
6.65
Kg Emitted
per Hour
9.6
6.8
22 Percent of the organic is adsorbed on the suspended solids.
93.6 Percent of the organic is concentrated in LC fraction 3.
IR and LRMS indicate the organic has no aromatic structure and is predominately high
molecular weight aliphatic compound.
-------
TABLE 3a ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A-PE
Total Organics, mg/L
TCO, mg/L
GRAV, mg/L
LCI
0
0
0
LC2
0.25
0
0.25
LC3
20.4
0
20.4
LC4
0.35
0
0.35
LC5
0
0
0
LC6
0.6
0
0.6
LC7
0.25
0
0.25
E
21.8
0
21.8
Category
Assigned Intensity - mg/L
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
-
-
-
-
-
-
-
-
-
_
_
_
_
_
_
100/0.25
100/4.7
100/4.7
10/0.5
10/0.5
100/4.7
10/0.5
-
-
-
_
_
_
_
_
_
&&
100/4.7
QNS
QNS
-
-
-
-
-
-
-
-
-
10/0. nos
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
QNS
4.7
4.95
0.5
0.5
4.7
0.5
n.nos
0.005
0.005
0.005
0.005
4. 70S
(Continued)
ft
Quantity Not Sufficient
Possible contamination.
-------
TABLE 38. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. A-PE (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulf oxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
*
QNS
-
-
-
-
-
-
-
QNS
QNS
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
QNS
0.005
0.005
0.005
0.005
0.005
0.005
0.005
Quantity Not Sufficient,
-------
TABLE 39. EMISSION COMPARISON, FURNACES A-l AND A-2
Emissions to Atmosphere
Furnace No.
A-l
A-2
A-l
A-2
Component
Particulate
Particulate
Organ ics
Organics
kg/hr
0.76
5.32
0.31
4.60
kg/Mw-hr
0.067
0.337
0.027
0.29
kg/Mg Alloy
0.16
0.79
0.066
0.68
Total Generated3
kg/hr
47.3
174.9
0.72
5.49
kg/Mw-hr
4.1
11.07
0.063
0.35
kg/Mg Alloy
10.14
26.0
0.15
0.82
Sum of component in scrubber discharge gas and scrubber water. It does not include
secondary emissions from furnace A-l. Hood design for furnace A-2 collects essentially
all of the furnace gas and fume.
-------
and in the scrubber water from furnace A-2. No evidence for carcinogenic com-
pounds was found in the final plant wastewater discharge. This, of course,
raises the question as to whether the carcinogenic compounds indicated in the
scrubber water were destroyed or whether they accumulated in the sludge (sub-
sequently dredged out and landfilled by the company).
A major difference in the emission control systems for the two furnaces
is the volume of air that is scrubbed. Furnace A-l scrubbed gas volume is
o
only 255.1 Nm /min (9010 DSCFM) (does not include secondary emission control
system) while 3196.4 Nm /min (112,879 DSCFM) are scrubbed in the A-2 furnace
system. Fan horse power requirements are 250 for furnace A-l and 2500 for
furnace A-2.
12.2 PLANT B TESTS
Sampling at Plant B was conducted to compare different type furnaces pro-
ducing 50 percent ferrosilicon (50 percent FeSi). Furnace B-l is a typical
open furnace design that allows combustion of furnaces gases as they leave the
furnace. Furnace B-2 is a tightly sealed, mix-sealed type furnace. Essen-
tially no combustion of the furnace gas occurs in furnace B-2. There are two
primary differences in the operation of the two furnaces. One is the dif-
ference in combustion of furnaces gases noted above. The second is in the
type of pollution control equipment and gas volume treated by this equipment.
Furnace B-l is serviced by a baghouse while a high pressure drop venturi
scrubber is used on furnace B-2. The gas volume from furnace B-l is sub-
stantially greater than that from furnace B-2 because a large amount of air is
drawn in during combustion.
12.2.1 Plant B General Description
The plant is located near Lake Erie. Unclarified lake water is used
for furnace cooling and gas scrubbing. Treated wastewater from the plant is
discharged to the lake.
All raw materials (coal, coke, limestone, gravel, iron scrap, quartz, and
wood chips) are stored in the open on the ground (no concrete pads). Products
are normally stored inside although a few small piles are on concrete pads
outside. All solid wastes from the plant are landfilled on plant property.
117
-------
This includes wood and iron scrap as well as slag and sludges from gas clean-
ing. Final wastewater treatment occurs on plant property in about 20 acres of
ponds. Treatment includes solid settling and alkaline chlorination for cya-
nide and phenol destruction. Solids are dredged from the pond and landfilled.
In Table 40 below are some details on the furnaces. The furnace numbers
are not consistent with test number, i.e., test B-l is not on furnace number 1.
TABLE 40 . SUBMERGED ARC FURNACES
Furnace No. Type
1 Mix-sealed
2 Mix-sealed
3 Mix-sealed
4 Mix-sealed
5 Open
Mw Rating
18
22
22
45
45
Pollution Control
Scrubber and Baghouse
Individual Scrubbers
Baghouse for Secon-
dary Dust Common for
Nos. 2 and 3.
Scrubber-Baghouse for
Secondary Dust Com-
mon with Furnace No. 5
Baghouse
Baghouse
Product
50% FeSi
CaC2
CaC2
50% FeSi
50%FeSi
All operating mix-sealed furnaces have wet scrubbers to clean the primary
undercover furnace gas. The cleaned gas, about 80 percent CO, is collected in
a common header. The collected gas is used as fuel in the lime kiln (converts
limestone to CaO for use in CaC2 production). About 170 m /min (6000 CFM) and
28 m3/min (1000 CFM) of the gas is produced in FeSi furnace No. 4 and CaC2
furnaces Nos. 2 and 3, respectively. The lime kiln uses only about 127 m3/min
(4500 CFM). The 43 m3/min (1500 CFM) excess gas from furnace No. 4 is flared.
All secondary dusts (above mix-seals, packing, grinding, etc.) are collected
in baghouses. Gas produced in open furnace No. 5 is also cleaned in a bag-
house (common with secondary dust from mix-seals of furnace No. 4). All dust
collected is slurried with water in small buildings near each baghouse. The
slurry is treated in clarifier-thickeners with the thickener underflow going
to the treatment ponds referred to above.
118
-------
Calcium Carbide Furnaces
The calcium carbide furnaces are housed in a common building. Both are
mix-sealed type and have secondary fume hoods above the mix-seals. These
hoods go to a common baghouse, rated at 5100 m3/min (180,000 ACFM) at 107°C
(225°F), using Nomex bags. Primary undercover furnace gases are cleaned by
Buffalo Forge scrubbers, (rated at 57 m3/min (2000 ACFM) 54°C (130°F) - re-
cycle water, 1.7 m /min (450 gpm) blowdown, collection efficiency reported to
be 99 percent) two for each furnace - one operating, one spare. Hoods, about
2.4 m x 2.4 m (81 x 8'), are used to capture tapping fumes. Fume collection
in all areas was good. Collection of tap fumes was the poorest but we esti-
mate about 80 percent capture in this area.
Raw materials, 3,175 kg/hr (7,000 Ibs/hr) lime, 1,814 kg/hr (4,000 Ibs/hr)
coke are delivered to each furnace cover by chutes positioned around the three
hollow center self-baking electrodes. Lime fines are blown into the furnaces
through the hollow center electrodes by recycled CO gas.
The calcium carbide furnaces are tapped continuously. Circular casting
wheels are used. Combined production of the furnaces is about 6,800 kg/hr
(15,000 Ibs/hr).
Lime Kiln
Carbon monoxide gas produced in the furnaces is used as a fuel in the
calcination of limestone. Kiln temperature is about 1,260°C (2,300°F). The
exhaust gas, containing about 4 percent oxygen and 1 to 1 1/2 percent combus-
tible gases is cleaned in a Pease Anthony wet scrubber. The operation was
clean and well operated.
Wastewater System
Wastewaters originate from the various wet scrubbers and slurrying of
collected baghouse dust. All water from furnace 4 goes to a single clarifier
where the solids are thickened. The clarifier overflow is returned to the
process for reuse. Thickened sludge from the clarifier is pumped to the west
settling pond. Carbide furnace scrubber water, lime kiln scrubber water, and
carbide baghouse slurry are collected and pumped to the east settling pond.
Solids settle out in the two ponds and are dredged and pumped to the landfill
site. The water leaving these ponds is chlorinated at an appropriate pH for
119
-------
cyanide and phenol destruction. The CaC- furnaces produce most of the plants
raw cyanide load and most of the phenol comes from the FeSi furnaces.
12.2.2 Furnace B-l Description
Furnace B-l, Figure 5, is an open design, loosely hooded furnace pro-
ducing 50 percent FeSi. The fume hood extends to within about 2-3 meters (6-9
feet) of the furnace and collects all gases and fumes generated by the fur-
nace. There are doors on the hood that can be closed to reduce the amount of
air drawn into the system but they are frequently, if not usually, open.
Tapping fumes are controlled by a small hood immediately above the tap hole
and a large, mobile hood that can be positioned to cover the ladle and the tap
hole lip. Fume capture in all areas was good although some fume does escape
the tapping hood system. Tapping occurs about every 70 minutes and lasts
about 15 minutes. Gases exhausted to the baghouse (from the furnace hood)
first pass through a cyclone for heavy solids removal and then through a
radiant cooling section (a series of large diameter U-shaped pipes).
Power is supplied to the furnace through three submerged 1.52 meter
(60 inch) diameter Soderberg carbon electrodes arranged in a triangular pat-
tern. Pre-mixed feed materials are gravity fed into the furnace from overhead
storage bins. The furnace operations are highly instrumented and a signifi-
cant amount of the operation is under computer control. The furnace typically
operates at about 52.5 Mw and produces about 245 Mg (270 tons) of product per
24 hours of operation. There is no slag (in the normal usage of the word)
produced in this operation. There is a "Dross" produced (less than 2 percent
of total production) composed of A1203, CaO, SiC, SiO- and other unreacted mix
compounds.
Gases collected from the furnace exit the building at a temperature of
about 355°C (670°F) and are cooled (noted above) before going to the baghouse.
The baghouse contains 14 compartments which are cleaned in sequence. It is
designed to handle 13,450 m3/inin at 204°C (475,000 ACFM at 400°F). Thirty
percent of the gas flow to the baghouse is from the secondary fume control
system of furnace B-2. Gas from furnace B-2 joins the gas from furnace B-l
just before entering the baghouse.
120
-------
BUILDING
BAGHOUSE
FROM FURNACE
B-2 SECONDARY
EMISSIONS
SLURRY TO WASTEWATER POND
Figure 6. Emission control system furnace B-1.
-------
12.2.3 Test Description, Furnace B-l
The source assessment sampling system (SASS) was used to sample the
gas and fume collected by the main hood system on furnace 8-1. The sample
point (see Fig'ire 5) was in the duct about 15 meters (50 feet) upstream of the
cyclone (used to remove large particles before the gas goes through the radi-
ant cooling section). Therefore, this sample is a measure of the furnace
gases before any emission control. The baghcuso discharge was not sampled
because a representative, and meaningful sample could not be obtained.
Prior to the SASS test a velocity profile was determined on the 3.048
meter (10 feet) duct with the following results.
AP Maximum - 0.28 cm Hg (1.5 inches water)
AP Minimum - 0.22 cm Hg (1.2 inches water)
AP Average - 0.24 cm Hg (1.31 inches water)
Duct Temperature - 348°C (658°F)
Duct Area 7.29 m2 (78.5 ft2)
Moisture 1 percent
Gas Velocity 1,708 m/min (5,604 ft/min)
Flow Rate, Actual 12,467 m3/min (440,255 ft3/min)
3 3
Flow Rate, Standard Condition 5,750 m /inin (203,052 ft /min)
An Orsat analysis of the gas taken during the SASS test is presented in
Table 41.
TABLE 41. ORSAT ANALYSIS, FURNACE B-l
Component Percent by Volume
CO 0.0
C00 2.8
L.
Inerts (N.) 79.0
Data taken with the SASS train during the actual test are given in Table
42.
122
-------
TABLE 42. SASS TEST DATA, FURNACE B-l
Date of Test
Volume of Gas Sampled
Stack Gas, Temperature
Pressure
Dry Molecular Weight
Wet Molecular Weight
Moisture, Percent
Velocity
Flow Rate
Total Sampling Time
SASS Flow Rate
Percent Isokinetic
(470.415 DSCF)
658°F
29.82 inches Hg
4/25/79
13.321 Nm3
348° C
75.74 cm Hg
29.18
28.96
2.0
23.5 m/sec (93.4 feet/sec)
12,467 m3/min (440,255 ACFM)
5,750 Nm3/min (203,052 DSCFM)
135 minutes
0.0987 Nm3/min(3.48 DSCFM)
100.7
Raw materials are fed to the furnace from storage b~ins above the furnace.
Pre-weighed and blended mix is delivered to these bins v'a "trip" cars. Given
in Table 43 are the raw mix components and average feed rate from midnight
until 2.00 p.m. on the day of the test (testing occurred from 11:15 a.m. until
2:15 p.m.). The average analysis of the alloy produced is given in Table 44.
The furnace was operating at an average load of 48.4 Mw and produced about
9.54 Mg (10.52 tons) of 50 percent FeSi alloy per hour during the test period.
12.2.4 Test Results, Furnace B-l
Particulates
In Table 45, details of the particulate generated by furnace B-l are
given. These data include all particulate directly from the furnace but do
not include fumes from tapping, etc. It should be noted that these are not
emissions to the atmosphere since the sample point was before the emission
control equipment.
The particulate concentration in the gas was 1,364 mg/Nm . Of this,
58.6 percent was captured by the Slu filters (submicron dust and fume). Total
123
-------
no
Component
Reducing Agent
Rosa Pea Coal
Porosity Agents
Wood Chips
Wood Chips
Recycle Material
Briquett Culls
Si Ores
Sidley Special
Gravel
Sm. Ind. Min. Qtz.
Fe Ores
Regular Steel
Low Cr Steel
Electrode
Total
Pile No.
4,521
9,050
9,555
. 5,687
3,101
3,607
6,382
6,173
-
AT 48.4 Mw
Kg/Trip
506
165
165
12
587
357
220
270
_
2,295
(9.54 Mg ALLOY/HR)
Kg/Hour
5,207
1,698
1,703
247
6,037
3,672
2,268
2,776
153
23,761
Kg/Mw-Hr
108
35
35
5
125
76
47
57
3
490
Kg Consumed Per
Mg Alloy Produced
545
177
180
26
632
384
237
290
16
2,486
-------
TABLE 44. AVERAGE PRODUCT ANALYSIS, FURNACE B-l
All
Fe - 49.02
Si 49.2
Mn 0.87
Ca 0.04
Sr 0.0
B 0.0
Values in Percent
Cr
Al
C
Mg
P
Ca
0.17
0.44
0.0
0.0
0.0
0.03
125
-------
TABLE 45. PARTICIPATE LEVELS BEFORE CONTROL EQUIPMENT, FURNACE B-l
ro
01
Sample Point - In duct before any pollution control equipment.
Volume of Gas Sampled: 13.321 NM3
Particulate
Sample
Type
Probe
10p Cyclone
3u Cyclone
lv Cyclone
-------
participate generated by the furnace was 470.6 kg/hr or 9.72 Kg/Mw-hr or 49.2
kg/Mg alloy produced. A baghouse collection efficiency of at least 95.4
percent would be required to meet NSPS of 0.45 kg/Mw-hr for 50 percent FeSi
furnaces. (The above calculation does not include tapping fumes which are
included in the NSPS requirement of 0.45 kg/Mw-hr paniculate emission). Put
another way, a baghouse collection efficiency of 99.9 percent would allow 0.35
kg/Mw-hr of particulate to be emitted by tapping operations and still be in
compliance with NSPS requirements.
Organics
Details of the organic generated by furnace B-l are included in Table 45.
The concentration of organic matter in the gas was 34.68 mg/Nm3. The organic
module contained 77.5 percent of this organic matter. Since the duct tem-
perature was above 300°C at the sample point, and the SASS cyclones were
operated at about 204°C, it is not surprising that little organic was adsorbed
on the dust. One could speculate that little of this organic matter is trapped
by the baghouse since it operates at about 150°C (300°F) - the actual baghouse
temperature was not measured during the test since the plant sensor was not
operating.
Level 1 Inorganic Analysis
The SASS particulate catches (probe, l-3y cyclone and filter combined,
and 3-1 Oy and >10y cyclones combined) and the first impinger were analyzed by
spark source mass spectroscopy (SSMS) and by atomic adsorption spectroscopy (AAS)
The AAS results are presented in Table 46. A summation of the SSMS data
obtained is given in Table 47, and the individual sample SSMS data are given
in Tables 48-52. The original SSMS analysis data are given in the Appendix D.
The data in Tables 47-52 are given as concentration of the elements in the
o
furnace gas at the sampling point in yg/m . The data given in Appendix D are
the concentration of the elements in the sample collected.
Level 1 Organic Analysis
The SASS train catch was analyzed for organic compound categorization as
follows:
127
-------
TABLE 4fi FIIRNAf.F R-1 . Ha. As. Sba ANALYSIS BY AAS
Sample Type
Probe Solids
3,1 Oy Cyclones
-------
TABLE 47. FURNACE B-l, SSMS ANALYSIS SUMMARY
ro
10
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
yg/Nm
Concentration
^1 41. 3
^185.1
83.6
>1 ,700*
<7.6
NR
4.7
0.2
0.2
0.02
0.2
0.04
0.48
0.5
Kg generated
per Mw-hr
<\ ,007
^1,319
596
12,100
<54
34
1.4
1.4
0.14
1.4
0.29
3.4
3.6
Element
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
yg/Nm3
Concentration
<0.18
<1.3
0.5
2.4
4.3
5.1
>126*
37
6,555*
8.2
9.6
26.6
363.9
2,255*
STD
<255
972
Kg generated
per Mw-hr
<1.3
<9.3
3.6
17
31
36
>898
260
>46,7QO
58
68
190
2,594
>16,100
<1,810
6,930
Major component of at least one sample.
(Continued)
Blanks indicate the element was below detection limits.
-------
TABLE 47. (CoDt'dJ
CO
o
Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
yg/Nm3
Concentration
<57.2
1.6
7.1
2.3
>747*
119
2,075
48.1
>122.3*
210.6
473
MC*
MC*
>562*
<42.3
MC*
>187*
>810*
Kg generated
per Mw-hr
<408
11
51
16
>5,300
848
14,800
340
>872 '
1,501
3,370
MC
MC
>4,000
<301
MC
H.330
>5,770
Element
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryl 1 i urn
Lithium
Hydrogen
yg/Nm
Concentration
14.6
>317.7*
< 25.4
MC*
>52*
>130*
>880*
MC*
MC*
>23,142
> 1,000*
>359.7*
>969*
NR**
NR**
NR**
30.3
<0.19
161.9
NR**
Kg generated
per Mw-hr
104
>2,265
<181
MC
>3,300
>927
>6,30C
MC
MC
> 164, 900
>7,000
>2,5BO
>6,900
216
<1.35
1,154
Major component-of at least one sample.
**
Not reported.
-------
TARI F 4ft
ANAI YSTS FURNACE R-l . PROBE SOLIDS
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
Conc>3
yg/Nm
10.2
2
13
MC
3.9
NR
1
10.2
0.08
0.1
0.2
Element
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Cone . 3
yg/Nm
0.008
10.6
0.1
1
2
1
120
17
98.1
0.8
2.0
3.9
6.4
185
STD
58.8
21
Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Conc.3
yg/Nm
10
0.3
2
1
146
39.2
24
10
95.3
18
67.3
MC
MC
MC
2
MC
>21
MC
Element
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Cone.-
yg/Nm
6.2
241
0.06
MC
>252
MC
>126
MC
MC
>20
MC
>53.2
MC
NR
NR
NR
4.2
0.08
6.4
NR
STD - Internal Standard
NR - Not Reported
MC - Major Component
-------
00
f\5
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
Cone.,
yg/Nrrr
0.2
2
5.6
MC
0.7
NR
0.7
0.2
0.02
0.2
0.04
0.4
0.4
0.9
Element
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Conc.q
vig/Nnr
£ 0.01
^ 0.4
0.2
0.9
2*
3.8
MC*
17
MC
0.4
3.4
2.7
31.5
65.2
STD
47.2
29.2
Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Cone.,
jjg/Nm
18
0.9
4.3
1
MC
6.3
11
4.9
27
3.6
54*
MC
MC
151
0.2
MC
^166
MC
Element
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Conc-3
yg/Nm
5.4
76.5
0.2
MC
>200
121
>101
MC
MC
>16
MC
>40.5
144
NR
NR
NR
]
<0.02
0.4
NR
Heterogeneous STD - Internal Standard NR - Not Reported MC - Major Component
-------
SOLIDS
CJ
CO
Conc.o
Element yg/Nm
Uranium <0.8
Thorium <0.9
Bismuth 65
Lead MC
Thallium 3
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten 3
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
Element
Terbium
Gadolinium
Europium
Samarium
Neodymium
Parseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Cone.,
yg/Nm
0.3
0.2
0.5
0.3
0.3
6
3
455
7
4
20
326
MC
STD
77
20
Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Conc.3
yg/Nm
29
0.4
0.7
0.3
421
94.5
40
33
MC
189
352
MC
MC
11
< 0.09
MC
MC
799
Element
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Cone.,
yg/Nm
3
MC
1 0.09
MC
MC
MC
>653
MC
MC
>105
MC
>266
1825
NR
NR
NR
25
< 0.09
15
NR
STD - Internal Standard NR - Not Reported MC - Major Component
-------
CO
Cone . 3
Element yg/Nm
Uranium 5! 40
Thorium 23,000
1,000
MC
NR
NR
NR
140
NR
Heterogeneous STD - Internal Standard NR - Not Reported MC - Major Component
-------
TARI F KO
ANAI YSTS FIIRNAPF R-l . IMPINGED 1 SOLIDS
CO
en
Cone.-
Element vg/Nm
Uranium £0.1
Thorium < 0.2
Bismuth
Lead 0.38
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
Conc.o
Element vg/Nm
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium 2.1
Cesium
Iodine 0.2
Tellurium
Antimony
Tin 4.63
Indium STD
Cadmium
Silver 2.1
Palladium
Rhodium
Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromi ne
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Cone.-,
vg/Nm
£0.2
0.1
0.03
0.01
0.43
0.2
1.3
0.06
0.09
£0.03
1.2
< 0.06
Element
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Cone.-
yg/Nm
0.2
10.02
MC
MC
8.39
MC
0.35
MC
0.98
^0.2
MC
MC
NR
NR
NR
0.09
0.06
NR
STD - Internal Standard NR - Not Reported MC - Major Component
-------
Probe solids (Bl-PW) - extracted, GRAV, LC, IR.
Particulate filter and l-3|j cyclone catch - extracted, GRAV not
sufficient for LC.
>3u cyclone catch - extracted, GRAV - not sufficient for LC.
Organic module (Bl-X) - extracted, TCO, GRAV, LC, IR, LRMS.
The data obtained are summarized in Tables 53 and 54. The LC, IR, and
LRMS data are in the appendices. Of the organic matter captured by the SASS
train 77.5 percent was found in the organic module. The probe solids contain
20.7 percent of the total organic captured. All of the organic found on the
particulates is GRAV material (Level 1 does not require a TCO on these samples)
The organic module catch was also 76.5 percent GRAV material.
The compound categorization of the probe solids organics does not show a
predominate concentration of any category. Major categories found were ethers,
alcohols, ketones, amines, sulfonic acids, and esters. The concentrations are
well below applicable DMEG values.
The compound categorization of the organic module is similar to that
found for the particulates except that substantial concentrations of ali-
phatics, silicones, and fused aromatic hydrocarbons were also found. The LRMS
data indicate the possible presence of the carcinogenic compounds benzanthra-
cene, chrysene, and benzopyrene (M/es of 228, 252).
12.2.5 Furnace B-2 Description
Furnace B-2, Figure 6, is a mix-sealed furnace producing 50% FeSi. The
unit is a companion to B-l in size and product. The B-2 furnace is relatively
tightly sealed to prevent any appreciable quantity of air being drawn into the
furnace gas collection system. As a result, the gas produced by the furnace
is about 80 percent CO and most of it is used as fuel in the lime kiln. Fur-
nace power level is about 48 Mw and about 245 Mg (270 tons) of product is made
per 24 hours of operation.
The furnace cover fits tightly and "mud" is packed around the opening to
prevent air ingression. Feed materials are fed from the overhead storage bins
onto the furnace cover so that it provides a partial gas seal of the feed
openings around the electrodes. Some furnace fumes escape from around the
electrodes during normal operations and can be substantial during furnace
"blows." The gas escaping the cover is frequently burning during periods of
136
-------
TABLE 53- ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Bl-PW
3
Total Organics, mg/m
TCO, mg/m3
GRAV, mg/m3
LCI
0.1
0
0.1
LC2
0.06
0
0.06
LC3
0.06
0
0.06'
LC4
0.45
0
0.45
LC5
0.24
0
0.24
LC6
1.47
0
1.47
LC7
0.06
0
0.06
I
2.4
0
2.4
Category
Assigned Intensity - mg/(m )
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
*
QNS
-
LOO/0.026
LO/0.003
LO/0.003
LO/0.003
-
-
Kit
100/0.026
-
-
-
-
-
-
-
-
-
-
10/0.002
10/0.002
10/0.002
10/0.002
-
-
-
-
-
-
**
LOO/0.02
-
-
-
-
-
-
10/0.01
10/0.01
10/0.01
100/0.09
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
**
100/0.09
-
100/0.09
-
-
-
-
-
-
10/0.005
LOO/0.05
10/0.005
10/0.005
10/0.005
10/0.00!
10/0.00!
10/0.00!
10/0.00!
100/0.05
-
-
-
-
-
-
-
-
-
10/0.03
10/0.03
-
100/0.26
10/0.03
100/0.26
-
-
-
-
-
-
-
-
-
10/0.002
-
10/0.002
-
10/0.002
10/0.002
100/0.02
0.026
0.005
0.005
0.015
0.012
0.015
0.166
0.015
0.047
0.015
0.047
0.015
0.377
0.377
0.42
(Continued)
*
Quantity Not Sufficient,
**
Possible Contamination.
-------
TABLE 53, ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO, Bl-PW, (Cont'd)
Category Assigned Intensity - mg/ ra3)
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
QNS*
_
—
-
-
-
-
-
**
100/0.02
-
-
-
-
-
itft
100/0.02
**
LOO/0.09
-
-
-
-
-
-
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
10/0.005
100/0.05
100/0.26
10/0.03
100/0.26
10/0.03
10/0.03
10/0.03
100/0.26
10/0.002
10/0.002
10/0.002
10/0.002
10/0.002
10/0.002
100/0.02
0.377
0.037
0.267
0.037
0.037
0.037
0.35
Quantity Not Sufficient,
Possible Contamination.
CO
oo
-------
TABLE 54- ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Bl-X
to
3
Total Organics, mg/m
3
TCO, mg/m
GRAV, mg/m3
LCI
2.9
2.3
0.6
LC2
2.5
0.7
1.8
LC3
4.1
0.7
3.4
LC4
1.2
0.4
0.8
LC5
1.2
0.8-
0.4
LC6
0.8
0.1
0.7
LC7
0.7
0
0.7
I
13.4
5.0
8.4
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient.
**
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/0.58
100/0.58
**
.00/0.58
**
.00/0.58
xw
.00/0.58
-
-
-
-
-
-
-
-
-
-
-
-
100/0.63
100/0.63
100/0.63
100/0.63
-
-
-
-
-
-
-
-
-
-
-
-
-
100/1.03
100/1.03
100/1.03
100/1.03
-
-
-
-
-
-
-
-
-
-
QNS
-
-
-
-
-
_
10/0.023
10/0.023
10/0.023
.00/0.23
10/0.023
10/0.023
10/0.023
10/0.023
10/0.023
LOO/0.23
-
-
-
-
-
_
_
—
-
10/0.021
-
10/0.021
-
00/0.21
10/0.021
10/0.021
-
-
-
-
-
_
_
_
-
10/0.02!
-
10/0.02!
-
10/0.02:
10/0.02:
100/0.23
0.58
1.21
2.24
2.24
2.24
1.03
0.023
0.023
0.023
0.274
0.023
0.067
0.023
0.256
0.067
0.481
Possible Contamination.
-------
TABLE 54. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Bl-X, (Cont'd)
Category
Assigned Intensity - mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulf oxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
—
-
-
-
-
-
-
_
-
-
-
-
-
-
_
-
-
-
-
-
-
10/0.023
10/0.023
10/0.023
100/0.23
100/0.23
10/0.023
10/0.023
100/0.21
10/0.021
10/0.021
10/0.021
100/0.21
10/0.021
10/0.021
10/0.023
10/0.023
10/0.023
10/0.023
10/0.023
10/0.023
100/0.23
0.256
0.067
0.067
0.274
0.4.63
0.067
0.274
Quantity Not Sufficient,
-------
TO BAGHOUSE
rs r\
FURNACE
TO GAS MAIN
RECYCLE WATER
210 gpm
VENTURI
COBLOWER
KNOCKOUT SEPARATOR
Figure 6. Emission control system, furnace B-2.
A WATER SAMPLES
• SASS SAMPLE
TO FLARE
t
X
BYPASS STACK
MAKEUP
WATER
-500 gpm
CLEARWATER
TO RECYCLE
500 gpm
SLURRY TO
POND
-------
heavy funding. There is a hood above the furnace cover to collect these fumes
and fumes released during furnace outages, when the seal is broken, and when
electrode length is being determined. These collected secondary fumes go to
the baghouse which collects particulate generated by furnace B-l.
The primary fume collection system draws gas and fumes from beneath the
furnace cover. Gases are withdrawn from the furnace at two points, 180 degrees
apart. Two high pressure drop venturi scrubbers (one on each side) clean the
gas. A water knockout and separation follow the scrubbers. About 4-12
liters (1-3 gallons) per hour of kerosene is injected into the gas stream at
the fans (CO blowers) to assist in keeping the fan blades clean. The cleaned
furnace gas is forced into the gas main (maintained at about 89 cm of Hg (2=5
PSIG). Most of this gas (^75 percent) goes to the lime kiln.. The excess goes
through a bypass stack to a flare. All water from the scrubbers is collected
in a common sump and flows to a clarifier. Underflow from the clarifier flows
to a wastewater pond. Overflow (essentially free of suspended solids) is
recycled to the scrubbers. Makeup water (clarified lake water) is added to
the clarifier overflow.
12.2.6 Test Description, Furnace B-2
Samples were taken (see Figure 6 for sampling points) of the cleaned
gases from the scrubbers and of the scrubber feed and discharge water. The
sampling point for the gas sample was in the 35.56 cm (14 inches) ID gas main
bypass duct just before the pressure control damper. The sample was taken
with the SASS train. A special probe was used for access through the 2 cm
(0.75 inch) port. Pitot tubes were not used because of the small port, thus
velocity measurements were not made. Gas flow rate was supplied by the com-
pany (estimated accurate to ± 30 percent). Since the stack was under pressure,
the probe was equipped with a pressure gauge and valve to prevent pressurizing
the SASS system. Provisions were also made to introduce nitrogen into the
probe to flush all air out of the system before the high CO content stack gas
was admitted to the system. The cyclones were not used (since they tend to
leak, they represent an explosion hazard) and the probe was connected directly
to the
-------
the venturi. About one-third of the sample was collected at the end of each
hour of SASS sampling. A total of 8 liters was taken of the combined scrubber
discharge water at the lift station to the clarifier (about one-third collect-
ed after each hour of SASS sampling).
Raw material consumption (average during normal operation 12 hours pre-
ceding the sampling) and composition are given in Table 55. Operating at 48.0
Mw, the furnace produces about 9.7 Mg (10.7 tons) of 50 percent FeSi product
per hour. The average product analysis is given in Table 56.
During the test period the furnace operated at 48.0 Mw. The scrubbers
were each operating with a 15 cm of Hg (81 inches of water) pressure drop.
Each of the 100 hp CO blowers (240 V-310 AMP) was operating at about 280 amperes,
Water flow to each scrubber system was 0.34 m (90 gpm) to the venturi and 0.8
3 3
m (210 gpm) to the water knockout (total 2.3 m (600 gpm) for both scrubbers).
Gas main pressure was 86.4 cm of Hg (2.49 PSIG).
The probe was inserted into the duct during a furnace outage shortly
before testing began. After verifying that the furnace was operating normal-
ly, sampling was initiated. A net sampling time of 165.9 minutes was obtained
in the 220 minute sample period. Sampling was terminated when a SASS system
pump failed.
12.2.7 Test Results, Furnace B-2
On-Site Results
Neither a velocity traverse nor Orsat analysis was obtained because of
safety restrictions and lack of Pitot tubes on the modified SASS probe. Gas
3
flow reported by the company was: total gas flow from furnace, 170 m /min
(6000 ACFM); 42.5 m3/min (1500 ACFM) through the bypass. The reported gas
composition was 85 percent CO, 15 percent C0£.
Data taken with the SASS train (and company supplied data) during the
test are given in Table 57.
Particulate
The amounts of particulate generated by, captured by scrubbers, and
escaping the scrubbers of furnace B-2 are given in Table 58. It should be
noted that these data apply only to particulates in the primary control system.
It should also be noted that these data are for the scrubbed gas (B-l data was
143
-------
TABLE 55. RAW MATERIAL FEED FOR FURNACE B-2
Component
Reducing Agent
Jewel Coal
Cleveland Coke
Cleveland Coke
Miscellaneous
Borax
Si Ores
Ind. Min. Quartz
Sidley Spec.
Gravel
Sidley Reg.
Gravel
Sm Ind Min Qtz
Fe Ores
6700 Tin Can
LO CR Steel
Electrode
Total
Pile
4,519
5,326
5,325
9,690
3,508
3,101
3,202
3,607
6,700
6,173
-
AT 48.0
Kg/Trip
509
89
137
5
347
409
355
244
197
587
_
2,878
Mw (9.71
Kg/Hr
3,902
684
1,046
35
2,654
3,131
2,717
1,862
1,508
4,496
136
22,171
Mg ALLOY/HR)
Kg/Mw-Hr
81
14
22
1
55
65
57
39
31
94
3
462
Kg Consumed
Per Mg of Alloy Produced
403
70
108
4
275
324
282
194
156
466
14
2,294
-------
TABLE 56. AVERAGE PRODUCT ANALYSIS, FURNACE B-2
Component
Si
Fe
Mn
Ca
Cr
Al
Percent (Wt)
46.7
51.7
0.05
0.03
0.06
0.7
TABLE 57. SASS
Component
Ce
Mg
P
Cu
Sr
B
TEST DATA, FURNACE B-2
Percent (Wt)
0
0
0
0.04
0
0
Date of Test
Volume of Gas Sampled
Stack Gas, Temperature
Pressure
Dry Molecular Weight
Wet Molecular Weight
Moisture, Percent
Velocity (calc.)
Flow Rate in Bypass
Flow Rate, Total
Total Sampling Time
SASS Flow Rate
Percent Isokinetic
*20°C (68°F), 76.0 cm Hg (29.92 in Hg)
5/1/79
14.4018 Nm3
51.7°C
86.4 cm Hg
30.4
28.66
14
7.16 meters/sec
37.49 Nm3/min
42.48 m3/min
149.97 Nm3/min
169.9 m /min
165.9 minutes
0.0866 Nm /min
100.6
(508.595 DSCF)*
(125°F)
(34.01 in Hg
(abs))
(23.5 FPS)
(1324 DSCFM)
(1500 ACFM)
(5296 DSCFM)
(6000 ACFM)
3.06 SCFM
145
-------
TABI F 58. PARTICIJLATFS. FURNACE B-2
Particulate not captured by the scrubber
Sample Point - Bypass stack after
Volume of Gas Sampled: 14.4018 NM
Sample Weight
Type Collected, mg
Probe 493.3
-------
before emission control) and that for this furnace only one-fourth of the
total gas flow is actually discharged to the atmosphere, and this is flared
(three-fourths of the gas goes to the lime kiln).
Particulate concentration in the scrubbed gas was 248.8 mg/Nm or 2.24
kg/hr escaping the scrubber. The scrubber captured an additional 445.4 kg/hr
of particulate matter or 99.5 percent of the particulate collected by the
primary emission control system. Particulate concentration before the scrub-
ber was, therefore, 49,750 mg/Nm . Total particulate escaping the scrubber
was 0.05 kg/Mw-hr, substantially less than the NSPS requirement of 0.45
kg/Mw-hr for all furnace emissions.
Organics
Given in Table 59 are details of the organics at various points in the
furnace B-2 primary emission control system. The same consideration applies
as described under particulates. The calculated concentration of organic
matter generated by the furnace and remaining in the scrubbed gas was 283.7
3
mg/Nm or 2.55 kg/hr (injected kerosene subtracted out. Because of inaccuracy
in the kerosene flow rate determination, the assumption was made for this
calculation only that all TCO components trapped by the SASS train were due to
injected kerosene.) This value is 14 percent greater than the concentration
of particulate emissions. The scrubber captured an additional 74.2 kg organic/hr
or 96.7 percent of the total organics going to the control system. Thus, the
total organic entering the scrubbers was 8530 mg/Nm or 76.7 kg/hr (1.60
kg/Mw-hr).
Level 1 Organic Analysis
The SASS train catch was analyzed for organic compound categorization as
follows. The particulate catch, including solids trapped in the probe, was
combined and extracted, TCO and GRAV determined, the extract fractionated by
LC and TCO, GRAV and IR run on all fractions. LC fractions 2 and 3 combined
were analyzed by LRMS. The aqueous condensate (115 ml) was extracted and the
extract plus the module rinse was used to extract the XAD-2 resin. A TCO and
GRAV was determined, LC fractionation done and TCO, GRAV and IR done on each
fraction. An LRMS was done on LC fractions 2 and 3 combined. Kerosene, which
was injected to the gas blowers, was analyzed for TCO and GRAV and fractionated
147
-------
TABLE 59. ORGANICS, FURNACE.B-2
00
Organics not captured by the scrubbers
Sample Point - Bypass stack after venturi scrubbers.
Volume of Gas Sampled: 14.4018 NM3
Sample Weight
Type Collected, mg
Probe and Filter 1,366
Organic Module 10,420
Injected Kerosene (all tco)
Net Organic
Organics captured by the scrubbers
Sample Point - At inlet to venturi and
Sample Weight Solids
Type Collected, met
Scrubber Inlet 14
Scrubber Discharge 1102.0
Net Scrubber Organics
Total Organics going to the
Primary Control System
% Scrubber Efficiency
Concentration
mg/NM3
94.85
723.52
534.65
283.72
at scrubber
Concentration
mg/L
6.6
551.0
544.4
Kga
per Hour
0.85
(0.22)
6.5
(1.63)
4 8
(1.2)
2.55
(0.64)
discharge clarifier
Kg
per Hour
0.89
75.1
74.2
76.7
96.67
Kg
per MW-hr
0.018
(0.0044)
0.14
(0.03)
0.10
(0.03)
0.05
(0.01)
-
lift station.
per MW-hr
0.019
1.56
1.55
1.60
aScrubber exhaust gas is split, one-fourth goes to a bypass flare, three-fourths to gas
ment for other process uses. Numbers in parentheses
(not counting destruction bv the flare).
are the amounts actually exhausted
Kg
per Mg Alloy
0.09
(0.02)
0.67
(0.17)
0.49
(0.12)
0.26
(0.07)
Kg
per Mg
0.09
7.7
7.6
7.89-
combustion
Alloy
equip
to the environ-
-------
by LC. TCO and GRAV were done on each fraction. The sample was TOO per-
cent TCO.
Scrubber feed and discharge waters were filtered for suspended solids
determination and each phase separately extracted and TCO and GRAV determined.
Only the scrubber discharge sample was subjected to LC fractionation and
further analysis as above. LRMS analysis was performed on LC fractions 2 and
3 separately.
The data obtained are summarized in Tables 60-63. (No attempt was made
to eliminate contribution of injected kerosene.) Of the organic matter cap-
tured by the SASS train, 66.6 percent (88.4 percent including the kerosene)
was found in the organic module. All of the organic found in the probe and
filter solids before LC fractionation was GRAV (high boiling point). GRAV
material accounted for 100 percent (26 percent when the kerosene is included)
of the organic found in the organic module before LC fractionation. IR and
LRMS spectra indicate the organic captured by the SASS train is predominately
aliphatic and aromatic hydrocarbons. The concentrations of aromatic hydro-
carbons, particularly fused aromatics (PNAs) is quite high and could exceed
DMEG values if destruction by the flare does not occur. The LRMS spectra for
LC fractions 2 and 3 of the SASS particulates show strong evidence of fused
aromatics with molecular weights greater than 216. Significant intensities
(related to concentration) were found at masses 252, 266, 276, 292, and 302
which suggest the presence of the known carcinogens benzo(a)pyrene, dibenzo-
fluorene, indeno(l,2,3-cd)pyrene, methyl dibenzanthracene, and dibenzochrysene
isomers, respectively. No evidence of carcinogenic compounds was found in the
SASS organic module. However, this may be due to the fact that the fractions
analyzed were predominately TCO. The GRAV component, which usually contains
most carcinogenic PNAs, being in low concentration, would have been assigned
low relative intensities and, thus, not be reported.
The data for the organics found in the scrubber discharge water are
summarized in Table 63. The organic in the scrubber water was 83 percent GRAV
material. Significantly, the data indicate that as much as 30 mg/L of this
material may be fused aromatics with molecular weights above 216. The LRMS
indicates significant concentrations at masses 228, 252, 266, 276, and 302
which suggest the presence of the known carcinogens chrysene, benzo(a)pyrene,
149
-------
TABLE 60. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-PART
Ol
o
3
Total Organics , mg/m
3
TCO, mg/m
GRAY, mg/m3
LCI
11.8
11.8
0
LC2
3.5
0.9
2.6
LC3
30.5
2.2
28.3
LC4
11.9
1.5
10.4
LC5
2.3
0
2.3
LC6
7.1
0
7.1
LC7
0.4
0
0.4
£
67.4
16.4
51.0
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient,
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/5.9
100/5.9
-
-
-
-
• -
-
-
-
-
-
-
-
-
-
-
100/2.9
10/0.29
10/0.29
-
-
-
-
-
-
-
-
-
-
-
-
-
-
100/9.8
100/9.8
10/0.98
100/9.8
—
-
-
-
-
-
-
-
-
-
-
-
-
-
100/3.2
10/0.32
10/0.32
100/3.2
10/0.32
10/0.32
10/0.32
10/0.32
10/0.32
-
-
100/3. 2**
-• —•*•-
QNS
QNS
-
-
-
-
-
-
—
-
-
-
-
10/0.014
-
10/0.014
10/0.014
100/0.14
5.9
8.8
10.09
10.09
4.18
1.3
0.32
3.2
0.32
0.32
0.32
0.334
0.32
0.014
0.014
3.34
Possible Contamination.
-------
TABLE 60. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-PART
Category Assigned Intensity
mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
QNS
*
QNS
10/0.014
10/0.014
10/0.014
100/0.14
10/0.014
10/0.014
10/0.014
0.014
0.014
0.014
0.14
0.014
0.014
0.014
Quantity Not Sufficient,
-------
TABLE 6L ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-X
en
l\3
3
Total Organics, mg/m
3
TCO, mg/m
GRAY, mg/m3
LCI
699.0
699.0
0
LC2
159.3
153.2
6.1
LC3
84.0
81.7
2.3
LC4
14.6
12.7
1.9
LC5
9.0
7.6
1.4
LC6
4.6
0.5
4.1
LC7
1.4
0
1.4
E
971.9
954.7
17.2
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient.
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons °
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
LOO/174.8
LOO/174.8
&*
LOO/174.8
&&
LOO/174.8
-
-
-
-
-
-
-
-
-
-
-
-
-
100/11.1
100/11.1
100/11.1
100/11.1
-
-
-
-
-
-
-
-
-
-
-
-
-
100/27.1
100/27.1
10/2.71
100/27.1
-
-
-
-
-
-
-
-
-
-
-
-
-
-
10/0.52
10/0.52
10/0.52
100/5.2
10/0.52
10/0.52
10/0.52
10/0.52
10/0.52
-
100/5.2""
QNS
QNS
QNS
174.8
185.9
213.0
213.0
14.33
27.62
0.52
5.2
0.52
0.52
0.52
0.52
0.52
5.2
Possible Contamination.
-------
TABLE 61. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-X (Cont'd)
Category
Assigned Intensity - mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
QNS
QNS
QNS
Quantity Not Sufficient.
en
Co
-------
TABLE 62. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-K
on
Total Organics,mg^mL
TCO, mg/mL
GRAV, mg/mL
LCI
725.0
725.0
0
LC2
56.4
56.4
0
LC3
11.4
11.4
0
LC4
9.4
9.4
0
LC5
2.4
2.4
0
LC6
0.2
0.2
0
LC7
0
0
0
E
804.8
804.8
0
Category
Assigned Intensity - mg
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nltroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/659
10/65.9
-
-
-
-
.-
-
-
-
-
-
-
-
-
-
QNS
QNS
QNS
QNS
QNS
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
659
65.9
(Continued)
*
Quantity Not Sufficient
-------
TABLE 62. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-K (Cont'd)
Category Assigned Intensity - mg
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
QNS
*
QNS
*
QNS
*
QNS
*
QNS
Quantity Not Sufficient.
en
en
-------
TABLE 63. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-SWD
C71
CTl
Total Organics, mg/L
TCO, mg/L
GRAV, mg/L
LCI
133.5
25.0
108.5
LC2
133.5
8.5
125.0
LC3
122.5
1.5
121.0
LC4
75.0
6.0
69.0
LC5
30.0
11.0
19.0
LC6
62.5
19.5
43.0
LC7
8.0
0
8.0
I
565.0
71.5
493.5
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient,
AA
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/66.75
LOO/66.75
-
-
-
-
-
-
-
-
-
-
_
-
-
100/43.1
100/43.1
100/43.1
10/4.31
-
-
-
-
-
-
-
-
__
_
_
_
-
100/29.9
100/29.9
10/2.99
100/29.9
-
-
-
-
-
-
-
_
„_
AA
100/29.9
_
-
—
-
10/1.15
100/11.5
10/1.15
100/11.5
10/1.15
10/1.15
10/1.15
100/11.5
100/11.5
_
AA
100/11 .5
—
—
-
-
-
-
10/0.57
LOO/5.7
10/0.57
10/0.57
10/0.57
LOO/5.7
LOO. 5. 7
10/0.57
30/0. 57
inn/st7
QNS*
QNS*
66.75
109.85
73.0
73.0
8.45
41.4
1.72
17.2
1.72
1.72
1.72
17.2
17.2
n sy
n. S7
L~l 1
Possible Contamination.
-------
TABLE 63, ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B2-SWD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
—
-
-
-
-
-
-
_
-
-
-
-
-
-
-
-
-
-
-
-
**
100/11.5
10/0.57
10/0.57
10/0.57
10/0.57
10/0.57
10/0.57
10/0.57
*
QNS
QNS
0.57
0.57
0.57
0.57
0.57
0.57
12.07
Quantity Not Sufficient.
Possible Contamination.
en
-------
dibenzofluorene, indenoQ,2,3-cd)pyrene, and dibenzochrysene isomer, respect-
ively.
In summary5 the test results on furnace B-2 show that the scrubbers are
effective for control of particulates generated and capture over 96 percent of
the organics generated (primary control system only). The data also indicate
that a significant amount of fused aromatic hydrocarbons are generated by the
furnace. Analysis of this material indicates the possibility of substantial
amounts of carcinogens. Although the scrubbers capture a large fraction of
these materials, a significant concentration of potential carcinogens is
indicated in the scrubbed gas.
12.2.8 Plant B Final Wastewater Discharge
All wastewater from the plant flows into about 20 acres of ponds where
solids settle out and the clarified water is chlorinated. Solids are dredged
out of the ponds as required and landfilled on company property. A grab
2
sample of the final pond effluent, 7.57 M /min (2000 gpm), was taken the same
day furnace B-2 was tested. The sample was filtered for suspended solids
determination, extracted and subjected to LC5 IR, TCO, GRAV, and LRMS analy-
sis. The overall results for solids and organics are summarized in Table 64,
and the Level 1 organic analysis is summarized in Table 65. There was no
indication of fused ring aromatic compounds or carcinogenic compounds.
12.2.9 Plant B Summary
Testing was conducted at this plant to compare two furnaces of dif-
ferent design producing the same product (50 percent FeSi). Furnace B-l is of
open design which allows vigorous combustion of the furnace gases. Furnace B-
2, a tightly sealed, mix-sealed type furnace, operates with essentially no
combustion of the furnace gases. The results, Table 66, indicate that furnace
B-l more effectively destroys organic compounds. Also, since little fume was
observed from the top cover of furnace B-2, the above indication is virtually
certain.
Detailed analysis indicates carcinogenic compounds in all furnace streams
sampled. Furnace B-l seems to generate fewer types of carcinogenic compounds
and a lower total mass of the compounds than does furnace B-2. Although
furnace B-2 scrubbers capture a large fraction of the organics generated, a
158
-------
TABLE 64. PLANT B FINAL EFFLUENT
Sample Point - Discharge from final pond (just upstream of final discharge sample point)
Total Plant Discharge Flow Rate: 7.571 m3/min (2000 gpm)
Component
Suspended Solids
*
Organics
Weight
Collected, mg
9
24
Concentration
mg/l
2.3
12
Kg Emitted
per Hour
1
5.5
in
«£>
*
Zero percent of the organic is adsorbed on the solids.
The organic is concentrated in LC fractions 3 and 6.
Only high molecular weight aliphatic compounds are indicated by IR and LRMS.
-------
TABLE 65. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B-PE
CTl
o
Total Organics , mg/L
TCO, mg/L
GRAV, mg/L
LCI
0.2
0.2
0
LC2
0
0
0
LC3
1.9
0
1.9
LC4
1.05
0
1.05
LC5
0.35
0
0.35
LC6
2.95
0.35
2.60
LC7
0.35
0
0.35
E
6.8
0.55
6.25
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient.
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
1 ' *
QNS
35
QNS
-
-
10/0.08
10/0.08
10/0.08
10/0.08
100/0.79
-
-
-
-
-
-
-
**
100/0.79
-
-
-
-
100/0.22
10/0.02
10/0.02
100/0.22
10/0.02
10/0.02
10/0.02
10/0.02
10/0.02
-
-
^&
100/0.22
—
-
-
-
-
-
10/0.01
LOO/0.1
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
-
-
-
-
-
-
-
-
-
10/0.14
-
10/0.14
-
10/0.14
10/0.14
10/0.14
-
-
-
-
-
-
-
-
-
100/0.09
-
10/0.009
-
10/0.009
10/0.009
loo/n OQ
0.08
0.08
0.30
0.10
0.03
1.11
0.03
0.26
0.03
0.179
0.03
0.159
0.159
1 ?S
Possible Contamination.
-------
TABLE 65. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. B-PE (Cont'd)
Category Assigned Intensity -
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
QNS*
QNS*
_
-
-
-
-
-
-
_
-
-
-
-
-
100/0.22
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
10/0.01
100/0.1
10/0.01
10/0.14
10/0.14
100/1.4
10/0.14
10/0.14
10/0.14
10/0.009
10/0.009
10/0.009
10/0.009
10/0.009
10/0.009
100/0.09
0.159
0.159
0.159
0.159
0.159
0.159
0.55
Quantity Not Sufficient.
Possible Contamination
-------
TABI.F 66. PATA COMPARISON, FURNACES B-l AND B-_2_
Furnace No.
Component
Remaining in Cleaned das
kg/hr kg/Mw-hr kg/Mg Alloy
Total Generated
kg/hr kg/Mw-hr kg/Mg Alloy
B-l
B-2
B-l
B-2
Parti cul ate
Participate
Organic
Organic
2.24
2.55
0.05
0.05
0.23
0.26
470.6
447.7
11.96
76.7
9.72
9.3
0.25
1.60
49.2
46
1.25
7.89
CT>
ro
No data for furnace B-l since baghouse collection efficiency not determined. Only 25 percent
of stated value for furnace B-2 goes to the flare since the gas is used as fuel in another process (not
typical for the industry). Some destruction of organics by the flare is expected.
Sum of comoonent in scrubber discharge gas and scrubber water for furnace B-2. It does not
include secondary fumes from furnace B-2. Hood design for furnace B-l essentially collects all of the
furnace fumes.
-------
significant amount may be present in the scrubbed gas. No evidence was found
for carcinogenic organic compounds in the plant final wastewater discharge.
This strongly suggests that the solids removed from the wastewater ponds and
landfilled on plant property contain a significant amount of organic matter,
including known carcinogens.
A major difference in the emission control systems, besides the gas
combustion difference, is the volume of air that is collected and cleaned.
Gas volume from furnace B-l is 12,467 Nm3/min (440,255 ft3/min) while 150 Nm3/
3
min (5296 ft /min) is scrubbed by the primary emission control system of fur-
's
nace B-2. (Secondary emission control system gas flow rate is about 2500 Nm /
3
min (88,000 ft /min).) Fan horsepower requirements are 2800 for furnace B-l
and 1400 for furnace B-2 (1200 for secondary emission control and 200 for the
CO blowers).
12.3 PLANT C TESTS
Sampling at Plant C was conducted to compare similar furnaces producing
different products. Both furnaces are of mix-sealed design and, although not
as tightly sealed as furnace B-2, allow limited undercover combustion of the
furnace gases. The furnaces are of comparable size and the emission control
systems are virtually identical. Furnace C-l was producing 75 percent ferro-
silicon (FeSi), a product containing 25 percent iron and 75 percent silicon.
Furnace C-2 was producing 50 percent ferrosilicon, the same product type
produced by furnaces B-l and B-2. Both materials are major product lines of
the ferroalloy industry.
12.3.1 Plant C General Description
This plant was shut down some months after testing was completed. The
description applies to the plant at the time it was tested. The plant was
started up in 1939 and currently has four mix-sealed furnaces. Three of the
four furnaces at this plant were in operation making either 50 percent FeSi or
75 percent FeSi. A specialty grade ferroalloy (SMZ) is also made at the
plant. The furnace numbers and furnace test numbers are not consistent, i.e.,
test C-l and C-2 were not done on furnace numbers 1 and 2.
Furnace No. 1, a mix-sealed furnace of about 17 MVA produces 50 percent
FeSi or 75 percent FeSi. Prebaked electrodes, 0.89 m (35 inches) O.D., are
used.
163
-------
Furnace No. 3, a mix-sealed furnace of about 17 MVA. Produces 50 percent
FeSi. Prebaked electrodes, 0.89 m (35 inches) O.D., are used.
Furnace No. 4. a mix-sealed furnace of about 22 MVA. Was not operating
due to economic conditions. It uses 1.02 m (40 inches) prebaked electrodes.
Furnace No. 5, a mix-sealed furnace of about 20 MVA. Produces 75 percent
FeSi. Self-baking electrodes, 1.07 m (42 inches) are used.
The two fume collection ducts on each furnace cover pass down through the
operating floor. The gas in each duct is cleaned in a Buffalo Forge scrubber
of about 57 m /min (2,000 ACFM) capacity. The cleaned gaseous discharge from
each scrubber goes to a separate flare stack.
The eight flare stacks at Plant C (two per furnace) all have igniters
which spark periodically and ignite a natural gas pilot. Depending on the
heating value of the flare gas at the time, the flare may or may not ignite.
The unlit stack emissions vary from a grayish smoke to a pure white steam
plume. The carbon monoxide content of the gases going to the flare was
reported by plant personnel to average around 50 to 55 volume percent.
All the furnaces have secondary hooding to collect any fumes leaking from
around the electrodes. The secondary hoods and the furnace taphole controls
are ducted to a single baghouse.
The capture efficiency of the secondary hooding varied from furnace to
furnace. One furnace, which was blowing much fume past the electrode seals,
still appeared to have a capture efficiency of over 90 percent, while another
furnace had a somewhat lower capture efficiency, about 80 percent.
Taphole particulate control consists of an approximately 1 meter (3 feet)
square duct near the taphole and a hydraulically operated cylindrical "cap"
which is positioned over the ladle during tapping to divert the fumes to the
mentioned duct. The fumes collected by the tapping control hoods go to the
baghouse together with collected fumes from the secondary control hoods.
Casting at this plant is from ladles into square chills by overhead crane.
The baghouse is relatively new and incorporates improvements over earlier
o
baghouses built by the company. It is designed to handle 18,400 m /min (650,000
ACFM). There are 13 compartments with 500-0.2 by 6.4 m (8 inches x 21 feet)
Nomex bags per compartment. There are two 2,000 HP fans on the baghouse, but
normally only one operates unless the plant is operating at full load making
large amounts of 75 percent FeSi (75 percent FeSi generates more dust than 50
164
-------
percent FeSi). The normal gas temperature is 66-93°C (150-200°F) at the
baghouse.
Housekeeping around the baghouse was excellent. The dust collected in
the baghouse is dumped into cement trucks, water is added, and the slurry is
dumped into a pit dedicated for the service. The area is hosed down once per
shift to clean up any dust spills.
The water discharge from the scrubbers is chlorinated (lime is added for
pH control) and sent to settling pond No. 5. The settling pond is about 11 m
(34 feet) deep and covers 13 acres. It is almost full after being in service
25 to 30 years.
The overflow from Pond No. 5 runs into a second settling pond of 17 acres
which was constructed about seven years ago. Effluent is pumped from the
second settling pond to a clarifier flocculator where lime and flocculant are
added. The overflow from the clarifier flocculator is chlorinated and is
collected in two small settling ponds (1 acre each) before mixing with all
plant wastewater in a third pond. All wastewater is discharged over a single
weir into a slough on the river. Land is available at the plant and a new
settling pond may be constructed to replace Pond No. 5. All the scrubber
water is once-through river water; there is no recirculation of scrubber
water.
There is, in addition to the main settling ponds, a pair of ponds in
series which are used to settle water from gravel washing. The incoming
gravel is washed to remove fine sand which is settled in the first pond and
reclaimed every year or two.
Raw materials storage (coke, ore, gravel and wood chips) is in the open,
on concrete pads, between the plant and the settling ponds.
12.3.2 Furnace C-l Description
Furnace C-l, Figure 7, is a mix-sealed furnace producing 75 % FeSi.
The furnace was designed to operate at about 16 Mw. Power is supplied to the
furnace through three 1.07 m (42 inches) diameter self-baking carbon elec-
trodes arranged in typical delta formation. The furnace cover does not pro-
duce a tight gas seal. Air can be drawn into the furnace through openings at
the doors (warped) and other areas around the cover. Air is probably also
drawn into the furnace through the mix-seals, especially when the mix level is
165
-------
TO BAGHOUSE
FLARE TIP
FLARE TIP
RIVER
WATER
SAMPLING
POINT
K.O.
POT
BUFFALO
FORGE
SCRUBBER
i »i
'•••
X
SAMPLIN
POINT
.'••.'•'.••iv--!
+. '.. .: -:;;V..-;.:.;:\:::J; '.::, '..-V.V..
V ;-V;;V:;>::-:-;>. ;:,:^'.-.^
:'vh-";v'-^^ •^•:;':^:
.'_';
,--••-. ••••1
SUMP T° SEWER SUMP
Figure T- Emission control system, furnaces C-1 and C-2.
^* TO SEWER
-------
low. The inspirated air allows the furnace gas to be partially combusted
under the furnace cover.
Raw materials (mix) are premixed and delivered to storage bins above the
furnace in "trip" cars. Mix is fed to the furnace on an as needed basis
through nine chutes (three for each electrode) onto the furnace cover and it
provides a partial gas seal at the electrodes. Additional amounts of coal and
stone (gravel) can be directly added onto the furnace cover if needed to
stabilize operations.
Furnace controls are essentially all manual. Recording of operating data
is also manual. It became obvious during the time spent at the plant that
stability of operations depended heavily on individual operator skill.
The furnace is tapped (alloy withdrawn) at about 23 Mw-hr intervals.
About 2.7 Mg (3 tons) of alloy are recovered from each tap. Slag is not pro-
duced by the furnace.
Fumes from the furnace cover (secondary fumes) are collected by a hood and
are captured in a baghouse (secondary fumes and tapping fumes from all fur-
naces go to the same baghouse). Furnace gases are withdrawn from beneath the
cover through two parallel scrubbing systems (50 percent of gas through each
system) located 180° apart. Water is sprayed into the gas duct just as the
gases leave the furnace. The cooled gases pass through a Buffalo Forge type
o
scrubber (design 57 m /min - 2000 ACFM each) and a water knockout pot before
entering the flare stack. Although the stacks are equipped with auto-
igniters, the flares do not burn continuously.
Water flow rate to each scrubber is about 0.95 m /min (250 gpm). The
scrubbers operate once-through (no recirculation). All collected and con-
densed water from each scrubber collects in a local sump before discharging to
the plant sewer system.
12.3.3 Test Description, Furnace C-l
Samples were taken (see Figure 7 for location of sampling points) of
the cleaned gases (scrubber discharge gas) from the primary emission control
system, and of the scrubber feed and discharge waters. The sampling point for
the gas sample was in the 50.8 cm (20 inches) internal diameter duct leading
to the flare. The sample was collected using the complete SASS train (adapted
167
-------
so that nitrogen flushing of the system was possible before sampling and
during filter changes).
Water samples were collected during the SASS test run. Eight liters
(2 gallons) of scrubber feed water were taken from a tap near the furnace.
Eight liters of scrubber discharge water were taken from the local sump for
the scrubber and stack being tested. About one-third of each sample was taken
at the end of each hour of SASS testing.
Since an "instantaneous" feed rate cannot be determined because mix is
fed from storage bins, the furnace feed rate was determined by averaging the
mix delivered in the 12-hour period before and during the test. Average fur-
nace power was 15.5 Mw and average production of alloy was 1.91 Mg/hr (2.1
tons/hr). Given in Table 67 is the raw material feed recipe for furnace C-l.
The product alloy averaged 74.5 percent silicon during the test period. A
velocity traverse was made of the gas duct (through the same port to be used
in the SASS test) prior to the test during a period when the furnace was not
operating (the emission control system, however, was operating at normal
levels). The SASS probe was inserted into the duct during this brief outage.
After verifying that the furnace was operating properly, sampling was begun.
Sampling was interrupted twice to make filter changes. A net sampling time of
216 minutes was obtained in the 300 minute sampling period. The test was ter-
minated voluntarily.
12.3.4 Test Results, Furnace C-l
On-site Results
The velocity traverse data for the duct is shown in Table 68.
An Orsat analysis of the gas taken during the SASS test is shown in
Table 69.
Data taken with the SASS train during the actual test is given in Table 70.
Particulates
Given in Table 71 are the amounts of particulate generated, captured by
the scrubber, and escaping the scrubber of furnace C-l. It should be noted
that these data apply only to particulate from the primary emission control
system. Some fumes were observed escaping the furnace cover (through the
mix-seals) but these were not judged to be substantial. These fumes, which
168
-------
cr>
Component kg per Trip
Si Ore
Washed SOU Stone 907
Reducing Agent
Quinwood N-Coal 289
Rosa P Coal 159
Fe Component
A-l Steel 141
Other
Wood Chips 635
Electrode - No Data
Total 2,131
15.5 Mw (1.91 Mg ALLOY/HR)
kg per Hour
3,297
1,052
577
511
2,308
7,745
kg per Mw-Hr
213
68
37
33
149
501
kg Consumed
Per Mg of
Alloy Produced
1,731
552
303
269
1,212
4,066
-------
TABLE 68. VELOCITY TRAVERSE, FURNACE C-l STACK
Distance, cm AP, mmHg
1.0 0.54
3.3 0.54
6.1 0,54
8.9 0.58
12.7 0.60
18.0 0.62
Average vP = 0.53 mmHg
Gas Velocity 594 m/min.
Flow Rate at Stack Conditions
Flow Rate at Standard Conditions
TABLE 69 ORSAT
Component
co2
CO
°2
Non-condensible
Distance, cm
32.8
33.0
41. 9
44.7
47.5
49.8
Temperature 51.7°C
120,4 m3/min.
93.6 m/min.
ANALYSIS, FURNACE C-l
Percent by Volume
10.4
28.2
1.4
60.0
AP, mmHg
0.60
0.56
0.52
0.49
0.45
0.37
Dry basis.
170
-------
JABLE ?n. SASS TEST DATA. FURNACE C-l
Date of Test
Volume of Gas Sampled
Stack Gas Temperature
Pressure, Absolute
Dry Molecular Weight
Wet Molecular Weight
Moisture, percent
Velocity
Flow Rate > each stack
Total Sampling Time
SASS Flow Rate
Percent Isokinetic
6/13/79
19.749 Nm3
68.3°C
75.3 cm Hg
29.72
27.08
22.5
9.78 m/sec
78.24Nm3/min
118.7 m3/min
216 minutes
0.0915 Nm3/min
122
(697.431 DSCF)
(155°F)
(29.64 in Hg)
(32.1 F/sec)
(2,763 DSCFM)
(4,193 ACFM)
(3.23 DSCFM)
+20°C (68°F), 76.0 cm Hg (29.92 in Hg).
171
-------
ro
Particulate not captured by the scrubber
Sample Point - In stack after Buffalo
Volume of Gas Sampled: 19.749 NM3
Sample Weight
Type Collected, mg
Probe 1,893.0
lOy Cyclone 7,585.7
3y Cyclone 707.5
ly Cyclone 68.4
-------
sometimes burn as they leave the cover, are collected and captured in a bag-
house which handles most secondary fumes in the plant. About 37 percent of
the particulate captured by the SASS train was less than 1 micron in size.
Over 46 percent was greater than 10 microns in size. There is a particularly
dramatic variation in particle size noted in this sample which can also be
seen in most other SASS samples taken. That is, the mass captured in each
succeedingly smaller size fraction decreases dramatically, but the mass cap-
tured in the less than 1 micron size fraction is sharply larger (factor of
about 90) than that captured in the 1-3 micron range. This does not appear to
be related to scrubber design or efficiency for a particular size fraction
since the same trend was found in particulates from furnace B-l, where gas was
sampled before entering the control device.
Particulate concentration in the scrubbed gas was 825.1 mg/Nm or 7.75
kg/hr (0.5 kg/Mw-hr) to be emitted to the atmosphere after passing through the
flare. (Stack opacity appeared to exceed 40 percent most of the time.) The
gas scrubber captured an additional 189 kg/hr of particulate matter or 96.1
percent of the primary dust generated. Total particulate concentration in the
gas before the scrubber was, therefore, 20,950 mg/Nm or 12.7 kg/Mw-hr.
Emissions from the stacks (assuming no destruction of particulate by the
flares) of 0.5 kg/Mw-hr would exceed NSPS (0.45 kg/Mw-hr) for all furnace
emissions (primary and secondary).
Organics
Given in Table 72 are the amounts of the organic generated, captured by
the scrubber, and escaping the scrubber of furnace C-l. The concentration of
organic matter in the scrubbed gas (total SASS catch) going to the flares was
487.4 mg/Nm or 4.58 kg/hr. (Inspection of the SASS train XAD-2 resin after
the test indicated it was overloaded, thus, the above figures may actually be
too low.) The amount of organics not captured by the scrubber (but possibly
destroyed by the flares) are, therefore, about 59 percent as large as the
amount of particulate not captured by the scrubber. The scrubbers captured 15
kg/hr or 76.7 percent of the organics going to the primary control system.
The total organic matter entering the scrubbers was, therefore, 2,090 mg/Nm .
Over 95 percent of the organic captured by the SASS train was found in
the organic module. Only 23.1 mg/Nm was found on the particulate matter.
173
-------
Organics not captured by the scrubber
Sample Point - In stack after Buffalo
Volume of Gas Sampled: 19.749 NM3
Sample Weight
Type Collected, mg
Probe9 Filter
and Cyclones 456.2
Organic Module 9170
Total
Organics captured by the scrubber
Sample Point - Scrubber feed water and
Sample Weight Solids
Type Collected, mg
Scrubber Inlet 6.0
Scrubber Discharge 267.7
Net Scrubber Organics
Total Organics Going to the
Primary Control System
% Scrubber Efficiency, Organics
Forge scrubber.
Concentration
mg/NM3
23.10
464.3
487.4
scrubber discharge
Concentration
mg/L
1.5
133.9
132.4
Kg
per Hour
0.217
4.36
4.58
sump weir.
. Kg
per Hour
0.17
15.2
15.0
19.6
76.66
Kg
per MW-hr
0.014
0.28
0.30
Kg
per MW-hr
0.011
0.980
0.97
1.27
Kg
per Mg Alloy
0.11
2.3
2.4
Kg
per Mg Alloy
0.089
8.0
7.9
10.3
-------
Organic content of the dust going to the flares was thus, about 2.8 percent.
The organic content of the dust could be higher, however, since the SASS probe
and cyclones were operated at about 204°C (400°F) (normal operating tempera-
ture for SASS system and used for all tests except B-2) substantially above
the stack temperature of 68°C (155°F), and could have distilled the organics
from the dust into the organic module. Organics found in the scrubber discharge
water were 8 percent of the particulate captured. In this case some organic
not associated with the dust may have been captured. Therefore, the actual
organic content of particulate going to the flares is probably between 2.8 and
8.0 percent.
Level 1 Organic Analysis-
The SASS train catch was analyzed for organic compound categorization as
follows. The entire particulate catch (probe, cyclones, and filters) was
extracted; analyzed for TCO and GRAV; fractionated by LC; TOO, GRAV, and IR
run on each fraction; and LRMS run on LC fraction 2 and 3 combined. The
aqueous condensate was extracted and the extract combined with the module
rinse which was then used to extract the XAD-2 resin. The final extract was
then analyzed for TCO, GRAV, fractionated by LC with subsequent analysis as
for the particulates.
Scrubber feed and discharge waters were filtered to determine suspended
solids, the solid and aqueous phases from each sample separately extracted. A
TCO and GRAV was determined on each extract, the extracts for each sample
combined and concentrated and analyzed for TCO and GRAV. No LC workup was
performed on the scrubber feed water since the organic content was low. The
scrubber discharge sample was analyzed by LC; TCO, GRAV and IR on each frac-
tion; and LRMS on LC fractions 2 and 3, separately. The LC, IR, and LRMS
results are contained in the appendices.
Summarized in Tables 73, 74, and 75 are the data obtained. Of the 23.1
3
mg/Nm organic found in the SASS particulate catch, 97 percent was GRAV mate-
rial . Of the 464.3 mg/Nm captured by the organic module, 39 percent was
GRAV material. Of the 133.9 mg/L organic in the scrubber water, 83 percent
was GRAV material.
The data in Table 73 show that organics in the particulate catch con-
tained appreciable quantities of aromatic hydrocarbons, halogenated aromatics
and heterocyclic oxygen compounds with lesser amounts of nitrogen compounds,
175
-------
TABLE ?a ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Cl-PART
CTl
3
Total Organics, mg/m
TCO, mg/m
GRAV, mg/m3
LCI
0.14
0.14
0
LC2
1.3
0.07
1.21
LC3
5.9
0
5.9
LC4
3.5
0
3.5
LC5
2.2
0
2.2
LC6
3.8
0
3.8
LC7
0.5
0
0.5
I
17.4
0.21
17.19
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
LOO/0.13
LO/0.01
' -
-
-
-
-
-
-
-
-
_
_
-
-
-
-
.00/0.4
100/0.4
100/0.4
10/0.04
-
-
-
-
-
-
_
-
-
-
-
-
100/1.9
100/1.9
10/0.19
100/1.9
-
-
-
-
-
_
-
-
-
-
-
-
-
10/0.08
100/0.78
10/0.08
100/0.78
10/0.08
10/0.08
10/0.08
100/0.78
100/0. 7R
-
-
—
-
-
-
-
-
10/0.03
10/0.03
10/0.0.3
10/0.03
10/0.03
100/0. 98
ino/n.2R
100/0.28
100/0.28
100/0.28
-
-
-
-
-
-
-
-
-
10/0.1
-
in/n i
10/0.1
10/0.1
100/1.0
QNS
0.13
0.41
2.3
2.3
0.31
2.68
0.11
0.81
0.11
0.21
0.11
1 16
1 06
0.38
0.38
1.28
-------
TABLE 7? ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Cl-PART (Cont'd)
Category Assigned Intensity - mg/(ml
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
100/0.28
10/0.03
10/0.03
10/0.03
10/0.03
10/0.03
100/0.28
10/0.1
10/0.1
10/0.1
10/0.1
100/1.0
10/0.1
100/1.0
QNS
0.38
0.13
0.13
0.13
1.03
0.13
1.28
Quantity Not Sufficient.
-------
TABLE 74. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO, Cl-X
••vl
CO
3
Total Organics, mg/m
3
TCO, mg/m
GRAY, mg/m3
LCI
264.0
262.7
1.3
LC2
81.0
59.5
21.5
LC3
31.0
5.70
25.3
LC4
30.4
19.0
11.4
LC5
17.7
8.9
8.8
LC6
62.0
19.0
43
LC7
5.1
0
5.1
E
491.2
374.7
116.5
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient.
* *
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/66.0
100/66.0
100/66J)
100/66^0
-
-
-
-
_
_
_
—
-
-
-
-
-
100/16.2
100/16.2
100/16.2
100/16.2
-
-
-
_
_
_
-
-
-
-
-
100/28.0
-
-
.
-
10/0.80
10/0.80
10/0.80
100/8.0
10/0.80
10/0.80
10/0.80
10/0.80
10/0.80
-
-
100/8.0**
£_.
QNS
-
-
-
-
-
-
-
-
_
10/0.94
100/9.4
-
100/9.4
100/9.4
10/0,94
*
QNS
66.0
82.2
110.2
82.2
17.0
0.8
0.8
8.0
0.8
1.74
0.8
10.2
0.8
9.4
9.4
8.94
Possible Contamination.
-------
TABLE 74. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Cl-X (Cont'd)
Category
Assigned Intensity - mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
—
-
-
-
-
-
-
_
-
-
-
-
-
100/16. 2'
QNS
10/3.0
100/8.0*
QNS
100/9.4
10/0.94
10/0.94
10/0.94
100/9.4
100/9.4
10/0.94
QNS
9.4
0.94
0.94
0.94
9.4
9.4
28.14
Quantity Not Sufficient.
Possible Contamination.
-------
TABLE 75. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Cl-SWD
oo
o
Total Organics, mg/ L
TCO, mg/L
GRAY, mg^
LCI
23.0
4.0
19.0
LC2
25.8
1.8
24.0
LC3
47.8
1.1
46.7
LC4
22.8
2.2
20.6
LC5
15.6
4.5
11.1
LC6
15.3
0.2
.15.1
LC7
2.9
0
2.9
£
153.2
13.8
139.4
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient,
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/5.8
100/5.8
**
100/5.8
A*
100/5.8
—
—
—
—
—
—
—
—
—
—
—
—
—
100/8.3
100/8.3
100/8.3
10/0.83
—
—
—
—
—
—
—
—
—
—
—
—
—
100/7.8
100/7.8
10/0.78
100/7.8
—
—
100/7.8**
—
—
—
—
—
**
100/7.8
—
—
—
—
10/0.35
100/3.5
10/0.35
100/3.5
10/0.35
10/0.35
10/0.35
100/3.5
100/3.5
—
—
*i
100/3.5
—
—
—
—
—
—
10/0.35
10/0.35
10/0.35
10/0.35
10/0.35
100/3.5
100/3.5
10/0.35
10/0.35
100/3.5
—
—
—
—
—
—
—
—
—
10/0.51
—
100/5.1
—
10/0.51
10/0.51
10/0.51
—
—
—
—
—
—
—
—
—
10/0.1
—
100/1.0
—
10/0.1
10/0.1
10/0.1
5.8
14.1
21.9
21.9
1.96
11.3
0.7
3.85
8.5
1.31
0.7
13.1
7.0
0.96
0.96
15.41
Possible Contamination.
-------
TABLE 75. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. Cl-SWD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
**
100/7.8
—
—
—
—
—
—
**
100/3.5
10/0.35
10/0.35
10/0.35
10/0.35
10/0.35
10/0.35
10/0.35
10/0.51
10/0.51
10/0.51
10/0.51
100/5.1
10/0.51
10/0.51
10/0.1
10/0.1
10/0.1
10/0.1
100/1.0
10/0.1
10/0.1
0.96
0.96
0.96
0.96
6.45
0.96
12.26
Quantity Not Sufficient,
Possible Contamination.
OD
-------
sulfur compounds, ketones, and esters. The LRMS indicates that the aromatic
and halogenated aromatic hydrocarbons are predominately fused aromatics with
molecular weights above 216. Major LRMS intensities (related to concentra-
tion) were found at masses 252 and 276, indicating possibly high concentra-
tions of the known carcinogens benzo(a)pyrene and indeno(l,2,3-cd)pyrene,
respectively. Minor LRMS intensities were found at masses 266 and 302 which
could correspond to the carcinogens dibenzofluorene and dibenzochrysene isomer,
respectively. A total of 15 different masses were found between mass 178 and
402 that correspond to fused aromatics.
The data in Table 74 show that the organic trapped in the SASS organic
module contained high concentrations of many different compound categories.
Most notable, however, are aliphatic and aromatic hydrocarbons. Aromatic
3
hydrocarbon levels (192.4 mg/Nm ) would be very high if emitted to the atmos-
phere. However, some flaring of this gas does occur and is expected to destroy
some of the organics.
The LRMS analysis indicates that most of the aromatic hydrocarbons trapped
in the organic module are fused aromatics with molecular weights above 216.
Ten different masses indicating fused aromatics ranging from mass 152 to 376
were found. Major intensities were found at masses 252 and 276, which indi-
cate possibly high concentrations of the carcinogens benzo(a)pyrene and indeno-
(1,2,3-cd)pyrene.
The data in Table 75 show that the organic content of the scrubber water
is distributed among many compound categories. Aromatic hydrocarbons (includ-
ing halogenated types) are the largest categories, totalling 43.8 mg/L.
The LRMS analysis of the scrubber water sample fractions shows 12 dif-
ferent masses (in the 178-326 Mw range) associated with fused aromatic hydro-
carbon. Major intensities were found at masses 252, 266, and 276 which indi-
cate the possible presence of significant amounts of the carcinogens benzo-
(a)pyrene, dibenzofluorene, and indeno(l,2,3-cd)pyrene, respectively. Minor
peaks were found at masses 228, 202, and 302 indicating the possible presence
of the carcinogens chrysene, methyl dibenzanthracene, and dibenzochrysene
isomer, respectively.
12.3.5 Furnace C-2 Description
Furnace C-2, a mix-sealed furnace, is designed to operate at about 17
MVA. Prebaked carbon electrodes, three in triangular formation, with diameters
182
-------
of 0.89 m (J35 inches] are used. The product made in the furnace is 50 percent
FeSi. Raw material feed mechanisms, emission control systems, and general
operation of the furnace are virtually identical to that for furnace C-l.
12.3.6 Test Description, Furnace C-2
Samples were taken from the same locations as sampled on furnace C-l
(see Figure 7). The SASS train was used to sample the cleaned gas (scrubber
discharge) from the primary emission control system. A velocity traverse of
the 50.8 cm (20 inches) duct was made prior to the SASS test (furnace off but
emission control systems operating normally). An 8 liter (2 gallons) sample
of the scrubber discharge water was taken (at the scrubber local sump) during
the SASS test, approximately one-third collected at the end of each hour of
testing. The test was voluntarily terminated after three hours. Total sam-
pling time was 139 minutes.
Raw material consumption was determined by averaging the "trip" weights
in the eight-hour shift preceding the test. Details of the feed mix are given
in Table 76. Operating at 16.8 Mw, the furnace produces 2.72 Mg (3.0 tons) of
alloy per operating hour. No slag is produced. A typical product analysis
shows: 50.5 percent Si, 49.4 percent Fe, 0.1 percent Al.
During the SASS test, the furnace was operating at 16.8 Mw. Water flow
o
to each scrubbers was 0.95 m /min (250 gpm).
12.3.7 Test Results, Furnace C-2
On-site Results
The velocity traverse data for the duct is shown in Table 77.
183
-------
TABLE 76. RAW MATERIAL CONSUMPTION FOR FURNACE C-2
oo
Component
Si Components
Washed Southern
Stone
Reducing Agents
Petroleum Coke
Rosa Nut Coal
Rosa Pea Coal
Fe Component
A-l Steel
Other
Wood Chips
kg per Trip
1,089
45
302
239
615
227
16.8 Mw (2.72 Mg ALLOY/HR)
kg per Hour kg per Mw-Hr
3,429 204
134 9
950 57
753 45
1,936 115
714 43
kg Consumed
Per Mg of
Alloy Produced
1,260
53
349
276
712
262
Electrode - No Data
Total 2,516
7,925
472
2,912
-------
TABLE 77. VELOCITY TRAVERSE, FURNACE C-2 STACK
Distance, cm
1.0
3.3
6.1
8.9
12.7
18.0
AP , mmHg
0.56
0.65
0.65
0.56
0.52
0.47
Distance, cm
32.8
33.0
41.9
44.7
47.5
49.8
AP, mmHg
0.45
0.54
0.45
0.56
0.34
0.49
Average AP = 0.52 mmHg
Gas Velocity 567 m/min.
Flow Rate at Stack Conditions
Temperature 41.7°C
115.4 m /min.
Flow Rate at Standard Conditions 98.5 m /min.
An Orsat analysis of the gas taken during the SASS test is shown in Table 78,
TABLE 78. ORSAT ANALYSIS, FURNACE C-2
Component
Percent by Volume
co2
CO
°2
Non-condensibles
+Dry basis.
13.0
24.5
0.0
62.5
Data taken with the SASS train during the actual test is given in Table 79.
185
-------
TABLE 79. SASS TEST DATA, FURNACE C-2
Date of Test
Volume of Gas Sampled
Stack Gas Temperature
Pressure, Absolute
Dry Molecular Weight
Wet Molecular Weight
Moisture, Percent
Velocity
Flow Rate, Each Stack
Total Sampling Time
SASS Flow Rate
Percent Isokinetic
6/19/79
11.944 Nm
3+
50.6°C
75.7 cm Hg
30.08
28.51
13.0
9.11 m/sec
86.99 Nm3/min
110.80 m3/min
139.0 minutes
0.0859 Nm3/min
104.8
(421.779 DSCF)
(123°F)
(29.82 in Hg)
(29.9 F/sec)
(3072 DSCFM)
(3913 ACFM)
(3.03 DSCFM)
20°C (68°F), 76.0 cm Hg (29.92 in Hg)
Particulates
Given in Table 80 are the amounts of particulate generated, captured by
the scrubber, and escaping the scrubber of furnace C-2. It should be noted
that these data apply only to particulates from the primary emission control
system. Some fumes were observed escaping the furnace cover (through the mix
seals) and at times were quite substantial. 'These fumes, which sometimes are
burning, are collected and captured in a baghouse which handles most secondary
fumes in the plant. About 32 percent of the particulate matter captured by
the SASS train was less than 1 micron in size. Over 28 percent of the
particulate matter was captured in the >10 micron size fraction cyclone.
Particulate trapped in the >10 micron cyclone and probe accounted for 67
percent of the particulate captured. Less than one percent of the particulate
matter was found in the 1-10 micron size range.
186
-------
TABLE 80. PARTICULATES., FURNACE C-2.
00
Participate not captured by the scrubbers
Sample Point - In stack after Buffalo Forge scrubber.
Volume of Gas Sampled: 11.944NM3
Sample
Type
Probe
10y Cyclone
3y Cyclone
ly Cyclone
-------
Particulate concentration in the scrubbed gas was 1241.6 mg/Nm or 12.96
kg/hr (0.77 kg/Mw-hr) going to the flare, (Stack opacity appeared to exceed
40 percent most of the time.) The gas scrubbers captured an additional 174.9
kg/hr of particulate matter or 93 percent of the primary dust generated.
Total particulate concentration in the gas before the scrubber was, therefore,
3
18,000 mg/Nm or 11.2 kg/Mw-hr. Emissions from the stacks, assuming no destruc-
tion of particulate by the flares (0.77 kg/Mw-hr), would exceed NSPS (0.45
kg/Mw-hr) for all furnace emissions (primary and secondary).
Organics
Given in Table 8 are the amounts of organic generated, captured by the
scrubbers, and escaping the scrubbers of furnace C-2. The concentration of
organic matter in the scrubbed gas (total SASS catch) going to the flares was
195.6 mg/Nm or 2.04 kg/hr. The amount of organic escaping the scrubbers is,
therefore, about 15.8 percent as large as the amount of particulate escaping
the scrubbers. The scrubbers captured 7.9 kg/hr or 79.5 percent of the total
organics going to the primary emission control system. The total organic
matter entering the scrubber was, therefore, 950 mg/Nm or 0.59 kg/Mw-hr.
About 88 percent of the organic captured by the SASS train was found in
3
the organic module. Only 23.8 mg/Nm was found on the particulate matter.
Organic content of the dust going to the flares was, therefore, about 2 percent,
The organic content of the dust could be higher, however, since the SASS probe
and cyclones operated at 204°C (400°F), substantially above the stack tempera-
ture of 50.6°C (123°F). Organics found in the scrubber discharge water were
4.5 percent of the particulate captured. Recognizing that not all of the
organic captured by the scrubbers was associated with the particulate captured,
the actual organic content of particulate going to the flares is probably
between 2 and 4.5 percent. Some destruction of this organic material would
occur when the gas was flared.
Level 1 Organic Analysis
The SASS train catch was analyzed for organic compound categorization as
follows. The entire particulate catch (probe, cyclones, and filters) was
combined and extracted; analyzed for TCO and GRAV; fractionated by LC; TCO,
GRAV, and IR run on all fractions; and LRMS run on LC fractions 2 and 3,
188
-------
00
Organics not captured by the scrubbers
Sample Point - In stack after Buffalo Forge scrubber.
Volume of Gas Sampled: 11.944 NM3
Sample Weight Concentration
3
Type Collected, mg mg/NM
Probe, Filter
and Cyclones 284.7
Organic Module 2052
Total
Organics captured by the scrubbers
Sample Point - Scrubber feed water
Sample Weight Solids
Type Collected, mg
Scrubber Inlet 6.0
Scrubber Discharge 142.3
Net Scrubber Organics
Total Organics going to the
Primary Control System
% Scrubber Efficiency, Organics
23.84
171.8
195.6
and scrubber discharge
Concentration
mg/L
1.5
71.1
69.6
Kg
per Hour
0.25
1.79
2.04
sump weir.
Kg
per Hour
0.17
8.07
7.90
9.95
79.47
Kg
per MW-hr
0.015
0.11
0.12
Kg
per MW-hr
0.010
0.48
0.470
0.59
Kg
per Mg Alloy
0.091
0.66
0.75
Kg
per Mg Alloy
0.062
2.96
2.90
3.65
-------
separately. The aqueous condensate was extracted and the extract combined
with the module rinse which was used to extract the XAD-2 resin. The extract
was then analyzed as above, except that an LRMS was run on LC fractions 2 and
3 combined. The scrubber water discharge sample was filtered to determine
suspended solids and the solid and liquid phases separately extracted. These
extracts were then combined and concentrated. Analysis procedure was the same
as above except that an LRMS was run only on LC fraction 3. The LC, IR, and
LRMS data are in the appendices.
Summarized in Tables 82, 83, and 84 are the data obtained. Of the 23.8
3
mg/Nm organic found in the particulate catch, 98 percent was GRAV material.
GRAV material accounted for 73 percent of the 171.8 mg/Nm organic material
found in the organic module. Of the 71.1 mg/L found in the scrubber discharge
water 94 percent was GRAV material.
The data in Table 82 show that the organics in the SASS particulate catch
are predominately aromatic and halogenated aromatic hydrocarbons. Lesser
amounts of aliphatic and heterocyclic oxygen compounds were found. The LRMS
analysis of LC fraction 2 indicates that organics in this fraction are pre-
dominately fused aromatics with molecular weights less than 216. A minor LRMS
peak was found at mass 228 which could be the carcinogen chrysene. The LRMS
analysis of LC fraction 3 indicates the fraction is predominately fused aro-
matics with molecular weights above 216. Major LRMS intensities (related to
concentration) were found at masses 252, 276, and 302, which indicate the
possible presence of significant amounts of the carcinogens benzo(a)pyrene,
indeno(l,2,3-cd)pyrene, and dibenzochrysene isomer, respectively. A minor
peak was also found at mass 228 which could be chrysene. A total of 13 dif-
ferent masses were found between mass 178 and 376 that correspond to fused
aromatics.
Table 83 shows that the organic trapped in the SASS organic module had
high concentrations of aliphatic and aromatic hydrocarbons with lesser amounts
o
of most other compound categories. Aromatic hydrocarbon levels (294.46 mg/Nm ,
would be quite high if emitted to the atmosphere. However, some flaring of
this gas does occur and is expected to destroy some of the organics.
The LRMS analysis of the SASS organic module LC fractions 2 and 3 com-
bined indicates the material is predominately fused aromatics with molecular
weights above 216. Major LRMS intensities were found at masses 252 and 276
190
-------
TABLE 82. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-PART
3
Total Organics , mg/m
3
TCO, mg/m
GRAY, mg/m3
LCI
2.3
0.3
2.0
LC2
2.1
—
2.1
LC3
8.0
0
8.0
LC4
4.3
0.03
4.27
LC5
2.5
0.3
2.2
LC6
0.9
0
0.9
LC7
0.2
0
0.2
E
20.3
0.6
19.7
Category
Assigned Intensity
- mg/(nO
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
LOO/0.58
LOO/0.58
LOO/0.585
LOO/0.58
100/2.1
—
100/2.58
100/2.58
10/0. 25?
100/2.58
—
—
—
—
—
—
—
—
—
—
*
QNS
*
QNS
*
QNS
QNS
0.58
0.58
5.24
3.16
0.258
2.58
(Continued)
*
Quantity Not Sufficient,
Possible Contamination.
-------
TABLE 82 ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-PART (Cont'd)
Category
Assigned Intensity - mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
—
—
—
—
—
—
—
• ' *
QNS
—
—
—
—
—
—
—
QNS
QNS
*
QNS
*
QNS
Quantity Not Sufficient.
-------
TABLE 83. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-X
to
Total Organics, mg/m
3
TCO, mg/m
GRAV, mg/m3
LCI
291.6
284.7
6.9
LC2
53.7
36.3
17.4
LC3
8.0
2.4
5.6
LC4
3.8
1.0
2.8
LC5
1.4
0
1.4
LC6
4.5
0.4
4.1
LC7
2.1
0
2.1
E
365.3
324.8
40.5
Category
Assigned Intensity - mg/(m )
(Continued)
*
Quantity Not Sufficient,
**
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
10/24.3
10/24.3
X*
100/243
—
—
—
—
—
—
—
—
—
—
—
—
—
—
10/2.44
100/24.4
100/24.4
10/2.44
—
—
—
—
—
—
—
—
—
—
—
—
—
100/1.33
100/1.33
100/1.33
100/1.33
—
—
—
—
—
—
—
—
—
A&
100/1.33
—
—
—
—
100/0.81
10/0.081
10/0.081
100/0.81
10/0.081
10/0.081
10/0.081
10/0.081
10/0.081
—
—
**
100/0.81
QNS
—
—
—
—
—
—
—
—
—
10/0.15
—
10/0.15
—
10/0.15
10/0.15
100/1 .S
QNS
24.3
26.74
268.73
25.73
4.58
1.411
0.081
0.081
0.081
0.231
0.081
0.231
0.081
0.15
0.15
3.64
Possible Contamination.
-------
TABLE 83. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-X (Cont'd)
Category
Assigned Intensity - mg/(m )
Amines
Alkyl S Compounds
Sulfuric Acids
Sulf oxides
Amides
Carboxylic Acids
Esters
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
**
100/1.33
—
—
—
—
—
—
**
100/0.81
*
QNS
10/0.15
10/0.15
10/0.15
10/0.15
10/0.15
10/0.15
100/1.5
QNS*
0.15
0.15
0.15
0.15
0.15
0.15
3.64
Quantity Not Sufficient.
.Possible Contamination.
-------
TABLE 84. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-SWD
cn
Total Organics , mg/L
TCO, mg/L
GRAV, mg/L
LCI
1.4
0.4
1.0
LC2
1.7
0.8
0.9
LC3
49.5
3.0
46.5
LC4
11.8
0
11.8
LC5
4.7
0.6
4.1
LC6
1.5
0
1.5
LC7
2.9
0
2.9
I
73.5
4.8
68.7
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient,
**
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ke tones
QNS
—
100/0.4
100/0.4
100/0.4
10/0.04
—
—
**
100/0.4
—
—
—
—
—
—
—
—
—
—
100/9.7
100/9.7
10/0.97
100/9.7
—
—
—
—
—
—
—
—
—
100/9.7*'
—
—
—
—
10/0.26
100/2.6
10/0.26
100/2.6
10/0.26
10/0.26
10/0.26
100/2.6
100/2.6
—
—
—
—
—
—
—
—
—
10/0.06
10/0.06
10/0.06
10/0.06
LOO/0.59
LOO/0.59
LOO/0.59
LOO/0.59
10/0.06
LOO/0.59
QNS
5f
QNS
0
0.4
10.1
10.1
1.27
1.23
0.32
3.06
0.32
0.32
0.85
3.19
3.19
0.59
0.06
10.29
Possible Contamination.
-------
TABLE 84. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C2-SWD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxid^s
Amides
Carbuxylic Acids
Esters
QNS
—
—
—
—
—
—
—
—
—
—
—
—
—
100/9. T
—
—
—
—
—
—
100/0.59
10/0.06
10/0.06
10/0.06
10/0.06
10/0.06
100/0.59
*
QNS
QNS*
0.59
0.06
0.06
0.06
0.06
0.06
10.29
Quantity Not Sufficient.
Possible Contamination.
01
-------
which indicates the possible presence of the carcinogens benzo(a)pyrene and
indeno(l,2,3-cd)-pyrene, respectively. Minor intensities were found at masses
228, 266, and 302 which could be the carcinogens chrysene, dibenzofluorene,
and dibenzochrysene isomer, respectively. A total of 12 different masses in
the range 178-350 were found indicating fused aromatic hydrocarbons.
The data in Table 84 show that the organic compounds in the scrubber
water are distributed among many compound categories. Aromatic hydrocarbons,
including halogenated types, are the largest categories, totalling 20.2 mg/L.
Other significant categories are ether, heterocyclic nitrogen and sulfur
compounds, ketones, and esters.
The LRMS analysis of the scrubber water LC fraction 3 indicates this
fraction is predominately fused aromatics with molecular weights above 216.
Major intensities were found at masses 252, 276, and 302 which indicates the
possible presence of significant amounts of benzo(a)pyrene, indeno(l,2,3-cd)-
pyrene, and dibenzochrysene isomer, respectively. Minor intensities were also
found at masses 228 and 266, indicating the possible presence of the carcinogens
chrysene and dibenzofluorene, respectively. A total of 15 different masses in
the range 178-376 were found indicating the presence of fused aromatics.
GC-MS Analysis
Gas chromatography-mass spectrographic (GC-MS) or direct inlet probe
analyses were run on two of the samples from furnace C-2 for exact compound
identification. Quantitative data was desired from these analyses but prob-
lems in both analyses prevented this. The samples analyzed by these tech-
niques were the scrubber water discharge extract (direct inlet probe) and the
SASS train organic module extract (GC-MS). Both analyses were performed on
the original extract before LC fractionation.
The scrubber water discharge sample was analyzed by EPA at the IERL-RTP
laboratory using a capillary inlet "pseudo probe" which should model the
direct injection probe mass spectrographic analysis up to mass 350. The
results of this analysis are given in Table 85. Although the results are not
as definitive as one would like, they are in substantial agreement with the
Level 1 LRMS analysis. Carcinogenic compounds were identified at masses 234
(benz(a)anthraceiie), 252 (benzo(a)pyrene), and 302 (dibenzo(ai + ah)pyrene,
the latter two in signficant concentration.
197
-------
TABLE 85. DIP-MS ANALYSIS OF FURNACE C-2 SCRUBBER WATER
Elution Time,
Min.
4.4
6.4
10.8
11.8
17.4
20.7
(Continued)
Molecular Weight
Parent Ion
202
234
228
202
259
252
252
282
276
302?
Compound(s)
Identified
Pyrene and/or Fluoranthene and a
Mixture of Several Possible
Anthracene Compounds, such as
Dehydro- trans, dimethyl ethano-
Anthracene, benz(a)
Anthracene, etc; also possible
presence of triphenylene
Fluoranthene and/or Pyrene
259
Dinitrodiphenylamine (Possible)
Benzo(a)pyrene and/or Perylene
and or 10, 11 Benzfluoranthene
Perylene, 10, 11-benzfluoranthene
Possibly ll-Phenyl-9, 10 Ethano-
9, 10 - Dihydroanthracene
C,g or PA Rin9 Compound likely:
Benzo(ghi)perylene
^15/16 Benz°Pyran» Possibly with a
Naphthalene Group
Relative
Intensity
64.5
5.0
5.0
5.0
100
1.0
100
100
7.9
100
100
Composition
C16H10
C18H12
r18H12
L18H12
C16H10
C12H9°4N3
C20H12
C20H12
C22H18
C22H12
?
-------
TABLE fiS. (Cont'd)
Elution Time,
Win.
21.0
23.3
24.1
28.8
Molecular Weight
Parent Ion
302
304
316
300
* 302
* 300
Compound (s)
Identified
As Above
Di phenyl acenaphthal ene
C23-Methyl -Phenol (?)
CHO Compound, C2Q_26
Dibenzo(ai + ah)pyrene
Coronene
Relative
Intensity
100
14.2
13.4
100
Composition
C24H16
C23H?0?
?
Possible assignments based on parent plus p-2 intensity.
-------
The scrubber water discharge sample extract was also analyzed by the
Department of Energy's Pittsburgh Energy Technology Center. The results,
obtained by high resolution mass spectrographic analysis, are given in Table 86.
All of the 16 masses representing the 30 compounds included in the mass spectral
screening program for the EPA Level 1 Assessment Plan were detected. The
percent relative intensity given is semiquantitative at best and is, there-
fore, not used in calculating POM generation rates. The significant aspect of
this data is that it provides corroborating evidence that mix-sealed furnaces
(at least this particular one) generate a variety of compounds of environ-
mental concern and that these materials are captured to some unknown extent by
the pollution control equipment.
The SASS train organic module extract sample was analyzed by Stewart
Laboratories, Inc. The sample was analyzed on a Finnigan model 4023 GC/MS
system using a Finnigan 9610 GC, Wang CO Nova Computer (DCC-116) and Incos
data system with 32 K memory and 16-bit word central processing unit.
Two types of GC columns were used: a 1 percent Dexsil 300 on 100/200
mesh supelcoport 1.83 m (6 feet) x 2 mm (0.079 inch) ID glass which was tem-
perature programmed—initial temperature 150°C, held 2 minutes; programmed at
4°C/min to 300°C; and a 1.5 percent SP-301 (liquid crystal) on 100/200 mesh
supelcoport 1.83 m (6 feet) x 2 mm (0.079 inch) ID glass which was temperature
programmed —initial temperature 260°C, held 2 minutes; programmed to 290°C at
4°C/minute.
Although the results, presented in Tables 87 and 88, provide excellent
identification of the compounds present, quantitation was not possible because
of a problem with the sample (The dilution response was not linear and seemed
to indicate the presence of very fine suspended solids in the original sample.)
Therefore, a comparison of relative response factors is the only indication of
relative concentrations available. This measure appears under the columns •
headed RIC.
Positive compound identifications are based on a matching of gas chroma-
tographic retention times with those of known standards as well as matching of
mass spectra with known standards and a computerized library search of the
26,500 entry NIH/EPA mass spectra library. Tentative identifications are
based on computer matching of mass spectra with the NIH/EPA reference library.
200
-------
TABLE 86. HIGH RESOLUTION MASS SPECTROGRAPHIC ANALYSIS
OF FURNACE C-2 SCRUBBER DISCHARGE WATER EXTRACT
ro
o
Mass
Calculated
166.
178.
179.
202.
216.
228.
252.
254.
256.
267.
0783
0783
0735
0783
0939
0939
0939
1095
1252
1048
Measured
166.
178.
179.
202.
216.
228.
252.
254.
256.
267.
0759
0780
0804
0775
0910
0928
0931
0944
1076
1049
Percent Relative
AMMU* Intensity
2 7.
0 43.
7 1.
1 100.
3 10.
1 25.
1 51.
15 4.
18 1.
5 1.
8
9
2**
0
9
7
5
7
5
5
Formula
C
13
14
13
16
17
18
20
20
20
20
H N
10
10
9 1
10
12
12
12
14
16
13 1
Possible Compounds
Fluorene
Anthracene
Phenanthrene
Acridine
Pyrene
Fluoranthene
Benzo(a)f 1 uorene
Benzo(b)f luorene
Chrysene
Triphenylene
Benzo( a) anthracene
Benzo(c)phenanthrene
Benzo(b)f 1 uoranthene
Benzo( j )f 1 uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Cholanthrene [Benz(j)aceanthrylene
7,12-Dimethylbenz(a)anthracene
Dibenzo(c,g)carbazole
*Difference between measured and calculated mass in millimass units
**Corrected for C-.,. contribution.
-------
TABLE 86. (Continued)
Mass
Calculated Measured
268. 1252
276.0939
278.1095
279.1090
300.0939
302.1095
ro
o xn-i
ro Ul
268.0978
276.0936
278.1082
279.1048
300.0932
302.1067
fference between
AMMU*
27
0
1
4
1
3
measured and
Percent Relative
Intensity Formula
2.3
14.9
3.8
0.2**
0.9
1.1
calculated mass
C
21
22
22
21
24
24
H N
16
12
14
13 1
12
14
Possible Compounds
3-Methyl chol anthrene
Benzo(ghi)perylene
Dibenz(a,b)anthracene
Dibenz(a, j)acridine
Dibenz(a,b)acridine
Coronene
Dibenzo(a,b)pyrene
Dibenzo(a , i )pyrene
Dibenzo(b,def)chrysene
in millimass units.
**Corrected for C,_ contribution.
-------
IAB1ELR7 RESULTS FROM 1 % DEXSIL 300 COLUMN, SAMPLE C2-X
ro
O
OJ
Compound
Fluorene*
Unidentified
Unidentified
Phenanthrene
Anthracene
9-methyl phenanthrene*
Cyclopenta(def)phenanthrene*
Fluoranthene
Unidentified PAH
Pyrene
Benzo(a)fluorene*
Methyl Pyrene*
and/or Benzo(b)fluorene*
Unidentified PAH
Unidentified PAH
Benzo(ghi )f 1 uoranthene*
Diisooctyl Phthalate
*
Scan
No.
45
75
170
200
200
284
293
409
422
444
516
547
617
630
663
686
Ret.
Time
1:30
2:30
5:40
6:40
6:40
9:28
9:44
13:38
14:04
14:48
17:12
18:14
20:34
21:00
22:06
22:52
Base
m/e
166
166
184
178
178
192
190
202
202
202
216
216
234
226
226
149
Best Computer Match
Name
Fluorene
Phenanthrene
Anthracene
9-methyl phenanthrene
Cyclopenta(def)-
phenanthrene
Fluoranthene
Pyrene
Benzo(a)fluorene
Benzo(ghi )fl uoranthene
Purity
903
929
890
774
829
961
959
797
828
784
Ht
974
989
993
814
908
987
988
823
909
859
Refit
913
935 .
890 }
931
847
968
965
864
835
828
RIC
686080
176384
132863
334336
13743
99199
251648
52287
261119
5000
1212
2975
16016
81152
34687
Indicates a compound tentatively identified by matching spectra with NIH/EPA mass spectra
reference library.
(Continued)
-------
ro
s
Compound
Unidentified
Benzo(j)fluoranthene*
and/or benz(e)acephenanthrylene*
Unidentified PAH
Benzo(a)pyrene ,
Benzo(e)pyrene
Perylene
Indeno(l ,2,3-cd)pyrene
Benzo(ghi)perylene
Anthanthrene*
Coronene
Scan
No.
772
851
868
895
913
1064
1097
1113
1292
Ret.
Time
25:44
28:22
28:56
29:50
30:26
35:28
36:34
37:06
43:04
Base
m/e
152
252
252
252
252
276
276
276
300
Best Computer Match
Name Puri ty
Acenaphtylene 872
912
909
Benzo(k)fluoranthene 842
Perylene 854
905
894
769
Fit
961
960
857
926
943
826
Refit
939 ,
939 '
985
958
941
867
RIC
22272
32032
1480
22400
4004
9951
29599
7560
9423
k
Indicates a compound tentatively identified by matching spectra with NIH/EPA mass spectra reference
library.
-------
TABLE 88. RESULTS FROM 1.5 % SP301 LIQUID CRYSTAL COLUMN, SAMPLE C2-X
IN5
O
cn
Compound
Unidentified PAH
Benzo(ghi)fluoranthene*
Benz(a)anthracene
Chrysene
Unidentified
Benzo( j )f 1 uoranthene*
and/or benz(e)acephenanthrylene*
Benzo(e)pyrene
Benzo(k)fl uoranthene
Perylene
Benzo(a)pyrene
Scan
No.
28
40
44
57
92
121
134
141
168
217
Base
m/e
226
226
228
228
240
252
252
252
252
252
Best Computer Match
Name Purity Fit
Benzo(ghi)fluoranthene 953 977
BenzoM)fl uoranthene 940 990
Benz(e)acephenanthrylene 930 985
Supelco literature reference match
Refit RIC
69888
969 149504
69632
53248
4480
l\\ } 33280
5256
3656
4208
10864
Indicates a compound tentatively identified by matching spectra with NIH/EPA mass spectra reference
library.
-------
Listed in Table 89 are the 13 positively identified and 10 tentatively
identified polynuclear aromatic hydrocarbon in the furnace C-2 SASS organic
module catch.
Also included in this table is the normalized relative concentration in the
sample, the estimated maximum concentration in the cleaned gas (after scrub-
bing but before flaring) of the primary control system of furnace C-2, and the
42
DMEG values for the compounds.
The normalized relative concentrations and estimated concentration in the
cleaned gas were calculated as follows. The first assumption made is that
since the same sample was analyzed on both columns the RIC value obtained for
identical compounds should be the same in both cases. Since this is not the
case (possibly due to sample size variation, response of the instrument or or
other factors), the RICs in Table 88 were multiplied by the ratio of RICs for
the sum of benzo(a)- and benzo(e)pyrene obtained in the two analyses (22,400 -r
(5,256 + 10,864) = 1.39). The next step was to sum all the RICs given in
Table 87 and the modified RICs from Table 88 for compounds not given in Table 87,
The individual compound RICs were then divided by the RIC sum to obtain the
normalized relative sample concentration (this only sums to 83 percent in
Table 89 because the unidentified PAHs are not included). These relativ.e
sample concentrations were then multiplied by the estimated concentration of
aromatic hydrocarbons (268.73 mg/m ) given in Table 83.
In this calculation, the RICs were adjusted based on the benzo(a)- and
benzo(e)pyrene figures. If other compounds found in both Tables 87 and 88
were used to make this modification, a slight difference in the final result
would be obtained. It must also be understood that this method of estimating
the concentration of PAHs in the cleaned scrubber gas is not considered to be
very accurate and should be considered only as giving the order of magnitude
of the different compounds in the unflared gas.
The positive identification includes four known carcinogens, benzo(a)-
anthracene, chrysene, benzo(a)pyrene, and indeno(l,2,3-cd)pyrene. Benz(a)-
anthracene may exceed the DMEG limit by a factor of over 200. Benzo(a)pyrene
may exceed the DMEG value by a factor of 105. The tentative identifications
include one known carcinogen (benzo(j)fluoranthene) which may slightly exceed
the DMEG value.
206
-------
TABLE 89. ESTIMATED CONCENTRATIONS OF IDENTIFIED PAHs
ro
o
—i
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(k)fluoranthene
Perylene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Benzo(ghi)perylene
Coronene
Fluorene*
9-Methyl phenanthrene*
Carcinogen
Mass Rating
178
178
202
202
228 +
228 +_
252
252
252
252 +++
276 +
276
300
166
192
Normalized
Relative Sample
Concentration
6.8
6.8
10.2
10.6
3.9
3.0
0.30
0.06
0.16
0.61
0.41
1.20
0.38
27.9
0.56
Estimated Concentrations
in Onflared Gas
mg/Nm
18.3
18.3
27.4
28.5
10.5
8.1
0.81
0.16
0.43
1.64
1.10
3.2
1.0
75.0
1.5
DMEG42
Air Health 3
Limit, fflg/Nm
1.6
56
90
230
0.045
2.2
3.0
1.6
2 x 10"5
1.6
-
-
-
-
+_weakly carcinogenic, + carcinogenic, ++ and +++ strongly carcinogenic, - not carcinogenic,
* Tentative identification.
(Continued)
-------
TABLE 89. (Cont'd)
Compound
Cyclopenta(def) phenan-
threne*
Benzo(a)fluorene*
Methyl Pyrene*
Benzo(b)fluorene*
Benzo(ghi)fluor-
anthene*
Benzo(j)fluoranthene*
o Benzo(e)acephen-
00 anthrylene*
Anthanthrene*
Carcinogen
Mass Rating
190
216
216
216
226
252 ++
252 ?
276
Normalized
Relative Sample
Concentration
4.0
0.20
0.025
0.025
3.3
1.3
1.3
0.31
Estimated Concentrations
in Unflared Gas
mg/Nm3 DMEG
Air Health 3
Limit, m,g/Nm
10.7
0.54
0.07
0.07
8.9
3.5 6.5
3.5
0.83
+_ Weakly carcinogenic, + carcinogenic, ++ and +++ strongly carcinogenic, - not carcinogenic.
tentative identification.
-------
12.3.8 Plant C Final Wastewater Discharge
All process wastewater flows to a common sump where lime and chlorine
are added. The water then flows to pond No. 5 (which is full of solids) and
then through a series of ponds where solids settle out and additional lime and
chlorine are added. The ponds are allowed to fill up and new ones built as
needed. The treated process discharge then flows into a small pond where it
joins other plant wastewaters (sanitary and furnace cooling). Two samples
were taken: a grab sample of the pond No. 5 outlet, which is essentially the
combined partially treated total process discharge (since no settling occurs
in pond No. 5); and a grab sample of the treated process discharge just before
it enters the final pond and before mixing with other wastewaters. Total flow
3
at both locations was estimated to be 5.68 m /min (1500 gpm). Both samples
were filtered for suspended solids determination, the solids and liquid phases
separately extracted, TCO and GRAV run on each extract, the extracts for each
sample combined and concentrated and subjected to TCO, GRAV, LC, TCO, GRAV,
and IR. LRMS analysis was done on LC fractions 2 and 3 of each sample.
Summarized in Table 90 are the overall results for solids and organics, and
summarized in Tables 91 and 92 are the level 1 organic analyses. The LC, IR,
and LRMS data are in the appendices.
TABLE 90. PLANT C EFFLUENTS
Untreated Plant Wastewater
Sample Point - Pond 5 outlet (some chlorine added, essentially no
solids removal).
Estimated Flow Rate: 5.68 m /min (1500 gpm)
Weight Concentration kg
Component Collected, mg mg/L per day
Suspended Solids 4,256 1100 9000
Organics 313.8 81.0 660
Treated Plant Wastewater
Sample Point - At entrance to final equilization pond (after
chlorination and solids removal).
209
-------
Table 90 (Continued)
Component
Suspended Solids
Organics
Weight
Collected, mg
66.0
19.5
Concentration
mg/L
17.8
8.0
kg
per Day
145
65
For the pond No. 5 outlet water, about 99 percent of the organic was
found to be associated (adsorbed) with the solids. A variety of compound
categories, Table 91, were found in the waste. Aromatic hydrocarbons (includ-
ing halogenated types) make up the largest categories found (total 34 mg/L).
LRMS analysis indicates a substantial concentration of fused aromatics with
molecular weights between 223 and 376. Indications of at least 16 different
fused aromatics were found. Major intensities were found at masses 252, 266,
276, and 302 which indicates the possible presence of substantial concentra-
tions of the carcinogens benzo(a)pyrene, dibenzofluorene, indenopyrene, and
dibenzochrysene isomer, respectively. Minor intensities were also found at
masses 228 (chrysene), 242 (methyl chrysene), and 292 (methyl dibenzoanthra-
cene), all carcinogens.
For the treated process wastewater, about 25 percent of the organic
matter is associated with the solids. Organics in the wastewater were fairly
evenly divided (Table 92) over all compound categories. Aromatic hydrocarbons
accounted for only about 0.15 mg/L of the total organic. LRMS analysis gave
evidence of fused aromatics at masses 228 (chrysene) and 252 (benzo(a)pyrene),
both carcinogens.
12.3.9 Plant C Summary
Sampling was conducted at this plant to compare two similar mix-sealed
furnaces producing different products. Furnace C-l was producing 75 percent
FeSi and furnace C-2 was producing 50 percent FeSi. The results, Table 93,
indicate that the furnaces produce equivalent amounts of particulate matter on
a kg/hr or kg/Mw-hr basis and that the scrubbers on furnace C-l are more
efficient. The particulate in the scrubbed gases of both furnaces would
exceed NSPS limits of 0.45 kg/ Mw-hr. The amount (per Mw) of organic gen-
erated by furnace C-l is more than double that of furnace C-2. This may be
210
-------
TABLE -91. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C-P50
ro
Total Organics, mg/ L.
TCO, mg/ L
GRAV, mg/ L
LCI
6.45
1.1
5.35
LC2
11.0
2.9
8.1
LC3
37.0
1.0
36.0
LC4
9.7
0.8
8.9
LC5
7.7
1.5
5.2
LC6
14.8
2.6
12.2
LC7
0.85
0
0.85
I
87.6
10.0
77.6
Category
Assigned Intensity - mg/L,
(Continued)
A
Quantity Not Sufficient
**
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Silicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
100/1.6
100/1.6
*x
100/1.6
**
100/1.6
—
—
—
—
—
—
—
—
—
—
—
—
—
100/3.5
100/3.5
100/3.5
10/0.35
—
—
—
—
—
—
—
—
—
—
—
—
—
100/11.9
100/11.9
10/1.19
100/11.9
—
—
—
—
—
—
—
—
—
—
—
—
—
—
10/0.13
LOO/1.3
10/0.13
10/0.13
100/1.3
10/0.13
10/0.13
100/1.3
100/1.3
100/1.3*"
—
100/1. 3XX
—
—
—
—
—
—
10/0.1
100/1.0
10/0.1
10/0.1
10/0.1
100/1.0
100/1.0
100/1.0
10/0.1
100/1.0
—
—
—
—
—
—
—
—
—
10/0.26
—
100/2.6
—
100/2.6
10/0.26
100/2.6
—
—
—
—
—
—
—
—
—
10/0.02
—
10/0.02
—
100/0.2
10/0.02
10/0.02
1.6
5.1
17.0
17.0
1.67
13.2
0.23
1.13
1.4
0.51
0.23
4.92
2.3
5.1
0.38
4.92
Possible Contamination.
-------
TABLE 91. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C-P50 (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
—
—
—
—
—
—
—
—
—
—
—
—
—
--
—
—
—
—
—
—
—
**
100/1.3
—
—
—
—
—
—
100/1.0
10/0.1
10/0.1
10/0.1
10/0.1
10/0.1
100/1.0
100/2.6
10/0.26
10/0.26
10/0.26
10/0.26
100/2.6
10/0.26
100/0.2
10/0.02
10/0.02
10/0.02
10/0.02
100/0.2
10/0.02
5.1
0.38
0.38
0.38
0.38
2.9
1.28
Quantity Not Sufficient.
**
Possible Contamination
ro
-------
TABLE 92. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C-TPD
CO
Total Organics, mg/L.
TCO, roR/L
GRAV, mg/L
LCI
0.2
0.2
0
LC2
0.25
0
0.25
LC3
1.6
0.8
0.8
LC4
1.05
0
1.05
LC5
0.7
0.35
0.35
LC6
4.3
0.3
4.0
LC7
0.45
0
0.45
I
8.55
1.65
6.9
Category
Assigned Intensity - mg/L
(Continued)
*
Quantity Not Sufficient,
Aliphatic Hydrocarbons
Halogenated Aliphatics
Aromatic Hydrocarbons
Halogenated Aromatics
Sllicones
Heterocyclic 0 Compounds
Nitroaromatics
Ethers
Aldehydes
Phosphates
Nitriles
Heterocyclic N Compounds
Heterocyclic S Compounds
Alcohols
Phenols
Ketones
LOO/0.1
LOO/0.1
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
100/0.08
10/0.008
10/0.008
10/0.008
—
—
—
—
—
—
—
—
—
100/0.08
—
—
10/0.067
10/0.067
10/0.067
10/0.067
—
—
—
—
—
—
—
—
100/0.67
—
—
—
—
10/0.12
10/0.12
10/0.12
10/0.12
10/0.12
10/0.12
10/0.12
10/0.12
10/0.12
—
—
—
—
—
—
—
—
—
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
—
—
—
—
—
—
—
—
—
10/0.2
—
10/0.2
—
10/0.2
10/0.2
10/0.2
—
—
—
—
—
—
—
—
—
10/0.015
—
10/0.015
—
10/0.015
10/0.015
100/0.15
0.1
0.18
0.075
0.075
0.195
0.187
0.16
0.16
0.16
0.375
0.16
0.375
0.16
0.255
0.255
1.14
**
Possible Contamination.
-------
TABLE 92. ORGANIC EXTRACT SUMMARY TABLE, SAMPLE NO. C-TPD (Cont'd)
Category Assigned Intensity - mg/L
Amines
Alkyl S Compounds
Sulfuric Acids
Sulfoxides
Amides
Carboxylic Acids
Esters
-
—
—
—
—
—
—
—
—
—
—
—
—
**
100/0.08
—
—
—
—
—
—
**
100/0.67
—
—
—
—
—
—
—
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.04
10/0.2
10/0.2
10/0.2
100/2.0
10/0.2
10/0.2
10/0.2
10/0.015
10/0. Olf
10/0. Oli
10/0. Olf
10/0.015
10/0.015
100/0.15
0.255
0.255
0.255
2.055
0.255
0.255
1.14
Quantity Not Sufficient.
Possible Contamination.
-------
Furnace No.
C-l
C-2
C-l
C-2
Component
Parti cul ate
Participate
Organic
Organic
Remaining in
kg/hr kg/Mw-hr
7.75
12.96
4.58
2.04
0.50
0.77
0.30
0.12
Cleaned Gasa
kg/Mg Alloy
4.1
4.75
2.4
,0.75
Total Generated
kg/hr kg/Mw-hr kg/Mg Alloy
196.7
187.9
19.6
9.9
12.7
11.2
1.27
0.59
103.0
68.9
10.3
3.6
After scrubber but before flare.
j
Sum of component in scrubber discharge gas and scrubber water.
secondary fumes from furnace covers, etc.
The data do not include
en
-------
related to the higher proportion of coal or wood chips used in furnace C-l.
The scrubbers on neither furnace provide good control of particulate or organic
matter. The particulate matter going to the flares of furnace C-l is between
2.8 and 8.0 percent organic matter while the organic content of furnace C-2
unfTared particulates is between 2 and 4.5 percent.
Detailed analysis indicates that very high levels of carcinogens, includ-
ing benzo(a)pyrene may be emitted to the atmosphere from both furnaces. GC-MS
analysis of the scrubbed but unflared gas from furnace C-2 gave positive
identification of 13 polynuclear aromatic hydrocarbons (PAHs) and tentative
identification for 10 additional PAH. These include five known carcinogens
including benz(a)anthracene and benzo(a)pyrene. Estimated concentrations of
these two carcinogens are greater than DMEG levels by factors of 233 and 8 x
A
10 , respectively. The analyses also indicates that carcinogens are contained
in the scrubber discharge water and are probably adsorbed on the particulate
matter. There is a high probability, therefore, that the sludge ponds at the
plant site (unlined) also contain substantial amounts of fused aromatics and
carcinogens. There is some evidence that the plant final wastewater discharge
may also contain low concentrations of one or more carcinogens.
216
-------
REFERENCES
1. Dealy, J. 0. and Killin, A. M. "Engineering and Cost Study of the Ferro-
alloy Industry," EPA-450/2-74-008, May 1974.
2. Background Information for Standards of Performance: Electric Submerged
Arc Furnaces for Production of Ferroalloys, Volume 1: Proposed Standards
EPA-450/ 2-74-018a. Volume 2: Test Data Summary. EPA 450/2-74-018b, Octo-
ber 1974.
3. Development Document for Effluent Limitations Guidelines and New Source
Performance Standards for the Smelting and Slag Processing Segment of the
Ferroalloy Manufacturing Point Source Category, EPA 440/1-74-008a, February
1974.
4. Development Document for Interim Final Effluent Limitations Guidelines
and Proposed New Source Performance Standards for the Electrolytic Ferroalloy
Segment of the Ferroalloy Manufacturing Point Source Category, EPA 440/l-75-038a,
February 1975.
5. Development Document for Interim Final Effluent Limitations Guidelines
and Proposed New Source Performance Standards for the Calcium Carbide Segment
of the Ferroalloy Manufacturing Point Source Category, EPA 440/1-75-038,
February 1975.
6. Rudolph, J. L., Harris, J. C., Grosser, Z. H., and Levins, D. L., "Ferro-
alloy Process Emissions Measurement," EPA 600/2-79-045.
7. Lentzen, D. E., Wagoner, D. E., Estes, E. D., and Gutknecht, W. F.,
"IERL-RTP Procedures Manual: Level 1 Environmental Assessment—Second Edition,"
EPA 600/7-78-201.
8. "Statistical Yearbook 1977." The Ferroalloy Association.
9. "Ferroalloys: Will Foreign Competitors Lock Domestic Out of the Market-
place?" 33 Metal Producing, November 1978, p. 49.
10. Watson, G. A., "The Future of the Ferroalloy Industry," presented at the
36th Electric Arc Furnace Conference, Toronto, Canada, December 6, 1978.
11. "Airco, Inc. Will Sell Ferroalloys Business to Several Parties," Chemical
Week, May 16, 1979, p. 17.
12. Private communication from the Ferroalloy Association and Information
collected by plant visits.
13. Durrer, R. and Volkert, G., "The Metallurgy of Ferroalloys - Revised
Edition, 1972.
14. "An Accident Killed Five Supervisors at a Strike-bound Ferromanganese
Plant." Chemical Engineering, January 29, 1979.
217
-------
REFERENCES (Continued)
15. Person, R. A., "Control of Emissions from Ferroalloy Furnace Processing,"
Electric Furnace Proceeding, 1969, p. 81.
16. Pupp, C. et al., "Equilibrium Vapour Concentrations of Some Polycyclic
Aromatic Hydrocarbons, As/L and SeO. and the Collection Efficiencies of these
Air Pollutants," Atmospheric Environment, Volume 8, 1974, p. 915.
17. Adams, J. W., "Flare Sampling - A Feasibility Study," Report prepared for
U.S. EPA under Contract No. 68-02-2150, T.D. 20901.
18. MacKay, D. and Shiu, W. Y., "Aqueous Solubility of Polynuclear Aromatic
Hydrocarbons," Journal of Chemical and Engineering Data, Volume 22, No. 4,
1977 p. 399.
19. Harrison, R. M., et al., "Effect of Water Chlorination upon Levels of
Some Polynuclear Aromatic Hydrocarbons in Water," Environmental Science and
Technology, Volume 10, No. 12, November 1976, p. 1155.
20. Communication from G. A. Watson, TFA, to Stuart Haus, MITRE Corporation,
June 27, 1979.
21. "Assessment of Industrial Hazardous Waste Practice in the Metal Smelting
and Refining Industry/' Volume III, EPA report SW-145C.3, Calspan Corporation.
22. Thomas Gaye, TFA, to Alexandra Tarnay (EPA Office of Solid Waste-
Washington, DC), June 7, 1977.
23. G. A. Watson, TFA, to Alan S. Corson (EPA-6ffice of Solid Waste-
Washington, DC), January 9, 1979.
24. Trenholm, A. R., Beck, L. L. , and R. V. Hendriks, "Hazardous Organic
Emissions from Slot Type Coke Oven Batteries," Presented at the 71st AlChE
meeting, Miami, November 1978.
25. Unpublished RTI data.
26. Research sponsored by the Division of Biomedical and Environmental Research
U.S. Department of Energy under contract W-7405-eng-26 with Union Carbide
Corporation.
27. Southworth, G. R., "Transport and Transformations of Anthracene in Natural
Waters: Process Rate Studies," Publication No. 1175, Environmental Sciences
Division, Oak Ridge National Laboratory, Oak Ridge (1977).
28. Herbes, S. E., L. R. Schwall, and G. A. Williams, "Rate of Microbial
Transformation of Polycyclic Aromatic Hydrocarbons: A Chromatographic Quanti-
fication Procedure," Appl. and Env. Microbiol. Vol. 34, No. 2, pp. 244-246
(August 1977).
29. Herbes, S. E., G. R. Southworth, and C. W. Gehrs, "Organic Contaminants
in Aqueous Coal Conversion Effluents: Environmental Consequences and Research
218
-------
REFERENCES (Continued)
Priorities," reprint from Trace Substances i_n Environmental Health-X; 1976; A
Symposium, University of Missouri, Columbia, MO (1976).
30. Southworth, G. R., J. J. Beauchamp, and P. K. Schmieder, "Bioaccumulation
Potential of Polycyclic Aromatic Hydrocarbons in Daphnia Pulex," Water Research,
Vol. 12, pp. 973-977 (1978).
31. Herbes, S. E., and L. R. Schwall, "Microbial Transformation of Polycyclic
Aromatic Hydrocarbons in Pristine and Petroleum-Contaminated Sediments,"
Appl. and Env. Microbiol.. Vol. 35, No. 2, pp. 306-316 (February 1978).
32. Southworth, G. R., J. J. Beauchamp, and P. K. Schmieder, "Bioaccumulation
Potential and Acute Toxicity of Synthetic Fuels Effluents in Freshwater Biota:
Azaarenes," Env. Sci. & Tech.. Vol. 12, pp. 1062-1066 (September 1978).
33. Southworth, G. R., "The Role of Volatilization in Removing Polycyclic
Aromatic Hydrocarbons from Aquatic Environments," Pub. No. 1176, Environmental
Sciences Division, Oak Ridge Laboratory, Oak Ridge, TN.
34. Herbes, S. E., "Partitioning of Polycyclic Aromatic Hydrocarbons Between
Dissolved and Particulate Phases in Natural Waters," Water Res., Vol. 11,
pp. 493-496 (1977).
35. Griest, W. H., and S. E. Herbes, "Characterization of Environmental
Distribution of Polycyclic Aromatic Hydrocarbons in Sediment and Water in the
Vicinity of a Coal Coking Plant," presented at the Div. of Env. Chem., ACS,
Anaheim, CA (March 18-22, 1978).
36. Herbes, S. E., L. R. Schwa11, and C. P. Allen, "Microbial Transformations
of Polycyclic Aromatic Hydrocarbons in River Sediments in the Vicinity of a
Coal Coking Plant," presented at the Div. Env. Chem., AC, Anaheim, CA
(March 12-17, 1978).
37. Smith, J. H., et al., "Environmental Pathways of Selected Chemicals in
Freshwater Systems: Part 1-Background and Experimental Procedures,"
EPA 600/7-77-113, October 1977.
38. IBID, Part II - Laboratory Studies, EPA 600/7-78-074, May 1978.
39. Shabad, L. M., "The Carcinogenic Hydrocarbon Benzo(a)pyrene in the Soil,"
Journal of the National Cancer Institute, Volume 47, p. 1179, 1971.
40. Pitt, J. N., Jr., et al., "Atmospheric Reactions of Polycyclic Aromatic
Hydrocarbons: Facile Formation of Mutagenic Nitro Derivatives," Science,
November 1978.
41. Smith. E. M., and Levins, P. L., "Sensitized Fluorescence for the Detec-
tion of Polycyclic Aromatic Hydrocarbons," EPA-600/7-78-182, September 1978.
219
-------
REFERENCES (Continued)
42. Kingsbury, G. L. , Sims, R. C. , and White, J. B., "Multimedia Environ-
mental Goals for Environmental Assessment-MEG Charts and Background Infor-
mation Summaries," Volume Ill-Categories 1-12, EPA-600/7-79-176a, August 1979
& Volume IV-Categories 13-26, EPA-600/7-79-176b, August 1979.
220
-------
APPENDIX A
INFRARED ANALYSIS REPORTS
-------
TABLE A-l. IR REPORT—SAMPLE NO. A1X. CUT LC-1
- Quantity Not Sufficient -
TABLE A-2. IR REPORT—SAMPLE NO. A1X. CUT LC-2
Wave Number (cm ) Intensity Assignment Comment
2920 S Sat'd C-H
2850 M Sat'd C-H
TABLE A-3. IR REPORT—SAMPLE NO. A1X. CUT LC-3. 4 & 5
- Quantity Not Sufficient -
TABLE A-4.
Wave Number (cm )
2936
2866
1731
1457
1379
1277
1175
1112
714
IR REPORT— SAMPLE
Intensity
S
M
S
M
M
S
w
M
W
NO. A1X. CUT LC-6
Assignment Comment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ketone, Phosphate
Ester
Phosphate
Alkyl
A-2
-------
TABLE A-5. IR REPORT—SAMPLE NO. A1X, CUT LC-7
Wave Number (cm~ )
2936
2866
1739
1457
1379
1254
1175
TABLE A-6.
Intensity
S
M
S
M
M
M
M
IR REPORT—SAMPLE NO.
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ketone
Ester
A1SWD. CUT LC-1. 2.
Comment
3. & 4
- Quantity Not Sufficient -
TABLE A-7. IR REPORT—SAMPLE NO. A1SWD. CUT LC-5
Wave Number (cnf )
2934, 2967
2857
1729
1450
1264
1018-1100
804
749
Intensity
S
M
M
W
S
S
S
W
Assignment
Sat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Ketone, Phosphate
Phosphate, Ether
Phosphate
Alkyl , Phosphate
Comment
Broad
A-3
-------
TABLE A-8. IR REPORT—SAMPLE NO. A1SWD, CUT LC-6
Wave Number (cm" )
2868, 2967
2934
1740
1456
1379
1140-1240
1083
749
Intensity
M
S
S
W
w
M
W
W
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ester, Si li cone
Ketone
Si li cone
Alkyl
Comment
Broad
TABLE A-9. IR REPORT—SAMPLE NO. A1SWD. CUT LC-7
- Quantity Not Sufficient -
TABLE A-10.
Wave Number (cm )
2933, 2972
2862
1733
1465
1279
1120
TABLE A-ll.
IR REPORT— SAMPLE NO. A-FE, CUT
Intensity
S
M
S
M
S
M
Assignment
Sat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Ketone, C-F
C-F, Sat'd C-H
IR REPORT— SAMPLE NO. A-FE, CUT
LC-1
Comment
. Poss.
Contamination
LC-2
- Quantity Not Sufficient -
-------
TABLE A-12. IR REPORT—SAMPLE NO. A-FE. CUT LC-3
Wave Number (cm )
2928, 2966
2857
1739
1460
1262
1087
1021
797
687
TABLE A-13.
Intensity
S
W
S
W
S
S
S
S
W
IR REPORT— SAMPLE
Assignment
Sat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Ketone, Si li cone
Silicone, C-F
Silicone, C-F
Alkyl, Silicone
Alkyl, C-C1
NO. A-FE. CUT LC-4
Comment
Poss.
Contamination
& 5
- Quantity Not Sufficient -
TABLE A-14. IR REPORT—SAMPLE NO. A-FE. CUT LC-6
Wave Number (cm )
2828
2857
Intensity
S
M
Assignment
Sat'd C-H
Sat'd C-H
Comment
TABLE A-15. IR REPORT—SAMPLE NO. A-FE. CUT LC-7
- Quantity Not Sufficient -
A-5
-------
TABLE A-16. IR REPORT—SAMPLE NO. A2X, CUT LC-1
Wave Number (cm ) Intensity Assignment Comment
3201
3068
2928
2858, 2959
1457
1379
1199
815
737
M
W
S
M
M
W
M
M
M
0-H
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, Alcohol
Sat'd C-H
Aromatic C-H,
Alcohol, Phenol
Subst. Aromatic
Alkyl, C-C1,
Alcohol
Poss.
Contamination
Broad
TABLE A-17. IR REPORT—SAMPLE NO. A2X, CUT LC-2. 3, & 4
- Quantity Not Sufficient -
TABLE A-18. IR REPORT—SAMPLE NO. A2X, CUT LC-5
Wave Number (cm )
2928, 2959
2873
1738
1252
1175
1020
800
Intensity
S
M
S
M
W
M
M
Assignment Comment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Ketone, Ester
Si li cone
Sat'd C-H, Ester
Sili cone
Alkyl , Sili cone
A-6
-------
TABLE A-19. IR REPORT—SAMPLE NO. A2XA CUT LC-6
Wave Number (cm )
3374
2944
2865
1730
1370, 1456
1260
1174
1072
838
720
Intensity
S
S
M
S
M
S
S
M
W
W
Assignment
0-H
Sat'd C-H
Sat'd C-H
Ester, Ketone
Sat'd C-H, Alcohol
Alcohol
Ester
Alcohol
Alkyl
Alkyl, Alcohol
Comment
Broad
Doublet
Doublet
TABLE A-20. IR REPORT—SAMPLE NO. A2X. CUT LC-7
Wave Number
3500
2936
2865
1738
1464, 1378
1245
1182
Wave Number
2934
2868
842
749
711
(cnf ) Intensity
W
M
M
S
W
M
M
TABLE A-21 . IR REPORT— SAMPLE
(cm~ ) Intensity
S
M
W
S
W
Assignment
0-H
Sat'd C-H
Sat'd C-H
Ester, Ketone
Sat'd C-H
Ester, Ketone
Alcohol
Ester, Alcohol
NO. A2SWD, CUT
Assignment
Sat'd C-H
Sat'd C-H
Alkyl
Alkyl, C-C1
C-C1
Comment
Broad
Broad
LC-1
Comment
-------
TABLE A-22. IR REPORT--SAMPI F NO. A2SWH. CUT LC-2
Wave Number (cnf )
3060
2972
2868
1439
1264
1182
842
815
749
TABLE A-23.
Wave Number (cm )
3060
2934, 2967
2868
1740
1461, 1379
1138-1275
1138
815, 946
Intensity
M
W
W
M
W
W
M
M
S
IR REPORT— SAMPLE
Intensity
W
M
W
S
W
M
W
W
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H/
Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic
C-C1
NO. A2SWD. CUT
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ester, Ketone
Sat'd C-H
Ester, Ketone
Aromatic C-H
Subst. Olefin/
Comment
5
LC-3
Comment
Poss.
Contamination
Broad
749
Aromatic
Subst. Aromatic.
C-C1
A-8
-------
TABLE A-24. IR REPORT—SAMPLE NO. A2SWD. CUT LC-4
Wave Number
2939
1187
974
749
(cm ) Intensity
M
M
M
S
Assignment
Sat'd C-H
Sat'd C-H,
Ether
Alkyl
Alkyl, C-CL
TABLE A-25. IR REPORT-SAMPLE NO. A2SWD, CUT
Wave Number
2934
2868, 2967
1275
749
(cm" ) Intensity
S
M
W
S
TABLE A-26. IR REPORT— SAMPLE
Assignment
Sat'd C-H
Sat'd C-H
Sat'd C-H
Alkyl, C-C1
Comment
Broad
Broad
Broad
LC-5
Comment
NO. A2SWD, CUT LC-6 & 7
- Quantity Not Sufficient -
TABLE A-27. IR REPORT—SAMPLE NO. B1PW, CUT LC-1
- Quantity Not Sufficient -
TABLE A-28. IR REPORT— SAMPLE NO. B1PW, CUT LC-2
Wave Number (cm~ )
2967
1254
1081
847
698, 752
Intensity
W
W
S
M
W
Assignment Comment
Sat'd C-H
Sat'd C-H
Ether Poss.
Contamination
Alkyl
Alkyl, C-C1
A-9
-------
TABLE A-29. IR REPORT—SAMPLE NO. B1PW, CUT LC-3
Wave Number (cnf )
Intensity
Assignment
Comment
3460
2732, 2866, 2959
1739
1606
1379, 1465
1081-1183
964
847
752
W
S
S
W
M
S
W
M
M
N-H, 0-H
Sat'd C-H
Ester
Amine
Sat'd C-H
Ester, Amine,
Alcohol
Alkyl
Ami ne
Alkyl, C-C1,
Ami ne
Poss.
Contamination
Broad
Poss.
Contamination
Doublet
Broad
TABLE A-30. IR REPORT—SAMPLE NO. B1PW, CUT LC-4
Wave Number (cm" )
Intensity
Assignment
Comment
3450
2936, 2967
2873
1739
1582
1379, 1465
1277
1128
1074
964
846
745
W
S
M
S
W
M
S
M
M
W
W
W
N-H, 0-H
Sat'd C-H
Sat'd C-H
Ketone
Amine
Sat'd C-H
Ketone, Alcohol
Amine,. Alcohol
Amine, Alcohol,
Ether
Alkyl
Ami ne
Alkyl, Ami ne,
Alcohol
Broad
Poss.
Contamination
Doublet
A-10
-------
TABLE A-31. IR REPORT—SAMPLE NO. B1PW. CUT LC-5
Wave Number
2928, 2967
2865
1730
1375, 1455
1268
1213
1127
1080
Wave Number
3460
3295
2857, 2936
1738
1605
1378, 1464
(cm~ ) Intensity
S
M
S
W
S
M
M
M
TABLE A-32. IR REPORT— SAMPL
(cnf ) Intensity
M
W
S
S
W
M
Assignment
Sat'd C-H
Sat'd C-H
Ester, Ketone
Sat'd C-H
Ketone
Ester
Ether
Ether
.E NO. B1PW, CUT
Assignment
N-H, 0-H
N-H, 0-H
Sat'd C-H
Ester, Ketone
Ami ne
Sat'd C-H,
Alcohol
Comment
LC-6
Comment
Broad
Shoulder
1080-1252 S Alcohol, Sulfonic
Acid, Amine,
Ester, Ketone
845 W Amine
751 W Alkyl, Amine,
Alcohol
712 W Alkyl, Amine,
Alcohol
A-ll
-------
TABLE A-35. IR REPORT—SAMPLE NO. BIX, CUT LC-2
Wave Number (cnf )
3067
2975
2912
1260
1072
845
Intensity
W
M
W
s
s
M
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Silicone, C-F
C-F, Silicone
Subst. Aromatic,
Comment
Multiplet
Broad
806
Olefinic C-H
Subst. Aromatic.
Olefinic C-H
TABLE A-36. IR REPORT—SAMPLE NO. BIX. CUT LC-3
Wave Number (cm~ )
3077
2967
2912
1260
1080
842
Intensity
W
M
W
S
S
M
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Silicone, C-F,
Silicone, C-F
Subst. Aromatic,
Comment
Multiplet
Broad
806
Olefinic C-H
Subst. Aromatic.
Olefinic C-H
TABLE A-37. IR REPORT—SAMPLE NO. BIX, CUT LC-4
- Quantity Not Sufficient -
A-12
-------
TARI F fl-^ft TR RFPORT SAMPI F NH Rl V- TUT I f.-
Wave Number (cm ) Intensity Assignment Comment
2967 M Sat'd C-H
2873 W Sat'd C-H
1722 (1600-1722) M Ketone, Amide Broad
1260 S Phosphate, Ketone
1088, 1033 S Phosphate, Broad
Sulfoxide Doublet
806 S Phosphate
TflRI F fl-?Q TR RFPnRT--SAMPI F NO R1X. HIT I T-fi
Wave Number (cm" )
3398
2936, 2967
1652 (1620-1720)
1550
1456
1393
1260
1088
806
712
TAR| F
Wave Number (cm )
2865, 2928
1739
1457, 1371
1136
Intensity
S
W
S
W
W
M
M
M
M
W
A-4D TR RFPDRT — SAMPI
Intensity
M
S
W
M
Assignment
0-H, N-H
Sat'd C-H
Amide, Amine
Amine
Sat'd C-H
Alcohol
Amide, Alcohol
Alcohol , Amine
Sat'd C-H
Alcohol , Amine
F Nf) RlX. HIT
Assignment
Sat'd C-H
Ester, Ketone
Sat'd C-H
Ester, Alkyl
Comment
Very Broad
Broad
Broad
I r-7
Comment
Broad
A-13
-------
TABLE A-41. IR REPORT—SAMPLE NO. B2PW. F. CUT LC-]
Wave Number (cm" )
2928
2857
1456
1378
TABLE A-42
Wave Number (cm~ )
2928
2857
1456
1378
TABLE A-43.
Wave Number (cm )
3053
2928
2865
1604
1456
1378
814, 884
Intensity
S
M
W
W
IR REPORT— SAMPLE
Intensity
S
M
W
W
IR REPORT— SAMPLE
Intensity
M
S
M
M
M
W
M
Assignment
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, C-F
NO. B2PW. F. CUT
Assignment
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, C-F
NO. B2PW. F. CUT
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H
Sat'd C-H, C-F
Subst. Aromatic,
Comment
LC-2
Comment
LC-3
Comment
751
Olefin
Alkyl, Subst.
Aromatic, C-C1
A-14
-------
TABLE A-44. IR REPORT—SAMPLE NO. B2PW, F. CUT LC-4
Wave Number (cm )
2936, 2959
2865
1730
1464
1378
1276
1127
1072
743
TABLE A-45.
Intensity
S
M
S
M
W
S
M
M
W
IR REPORT— SAMPLE
Assignment Comment
Sat'd C-H
Sat'd C-H
Ketone Poss.
Contamination
Sat'd C-H
Sat'd C-H, C-F
Si li cone, Ketone
Ether
Ether, Si li cone,
Alkyl
NO. B2PW. F. CUT LC-5 & 6
- Quantity Not Sufficient -
TABLE A-46. IR REPORT—SAMPLE NO. B2PW. F. CUT LC-7
Wave Number (cm )
2928, 2967
2857
1730
1456
1284
1127
1072
Intensity
M
W
S
W
M
W
W
Assignment Comment
Sat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Ketone
Sat'd C-H
Sulf oxide
A-15
-------
TABLE A-47. IR REPORT—SAMPLE NO. B2X, CUT LC-1
Wave Number (cnf )
3053
2857, 2928, 2959
1511, 1597
1378, 1464
1268
955, 1010
818
783
TABLE
Wave Number (cm )
3053
2857, 2928, 2959
1604
1456
1370
1260
1190
1080
829
775
751
Intensity
W
s
W
M
W
W
W
M
Assignment Comment
Unsat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H
Alkyl, C-F
Aromatic C-H
Olefin, Subst.
Aromatic
Subst. Aromatic,
Alkyl. C-C1
A-48. IR REPORT— SAMPLE NO. B2X, CUT LC-2
Intensity
M
S
W
M
W
W
W
W
M
M
M
Assignment Comment
Unsat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H-
Sat'd C-H
Alkyl, C-F,
Si li cone
Aromatic C-H, Alkyl,
C-F
Aromatic C-H, C-F,
Si li cone
Subst. Aromatic,
Olefin
Subst. Aromatic,
Alkyl, C-C1
Subst. Aromatic,
Alkyl, C-C1
A-16
-------
TARI F A-4Q. TR RFPORT—SAMPLE NO. B2X. CUT LC-3
Wave Number (cm~ )
3053
2959
2858, 2928
1457
1375
1277
1191
831
753, 784
TABLE
Wave Number (cm~ )
2928
2866, 2959
1723
1465
1285
1128
TABLE A-51.
Intensity
M
W
S
M
W
W
W
W
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, C-F
Sat'd C-H, C-F
Sat'd C-H, Aromatic
C-H, C-F
Subst. Aromatic,
Olefin
Subst. Aromatic,
Alkyl, C-C1
A-50. IR REPORT— SAMPLE NO. B2X, CUT LC-4
Intensity
S
M
S
M
M
M
IR REPORT— SAMPLE NO.
Assignment Comment
Sat'd C-H
Sat'd C-H Poss.
Contamination
Ketone
Sat'd C-H
Sat'd C-H, Ketone
Sat'd C-H, Ether
B2X, CUT LC-5-7
- Quantity Not Sufficient -
A-17
-------
Wave Number (cnf )
2868, 2934
749
TABLE A-53.
Wave Number (cm" )
3060
2972
2923
1910
1603
1456
1258
1187
946, 1034
815, 881
749
Intensity
S
M
IR REPORT-SAMPLE
Intensity
S
M
S
w
M
M
W
W
W
M
S
Assignment Comment
Sat'd C-H
Alkyl, C-C1
NO. B2SWD, CUT LC-2
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic Overtone
Aromatic C=C
Sat'd C-H
Sat'd C-H
Sat'd C-H, Aromatic
C-H
Aromatic C-H
Subst. Aromatic
Subst. Aromatic,
C-C1
TABLE A-54. IR REPORT—SAMPLE NO. B2SWD, CUT LC-3
Wave Number (cm )
3060
2967
1724
1450
1275
810, 881
Intensity
M
M
M
M
W
W
Assignment
Unsat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Ketone
Subst. Olefin/
Comment
Poss.
Contamination
749
Aromatic
Subst. Aromatic,
C-C1
A-1R
-------
TABLE A-55. IR REPORT—SAMPLE NO. B2SWD, CUT LC-4
Wave Number (cm~ )
3060
2934, 2967
2873
1740
1461
1384
1181-1269
1138
749
TABLE A-56.
Wave Number (cm )
3043
2934
2868
1707
1598
1461
1357
1149-1264
1018, 1149
799
Intensity
W
S
W
S
M
W
M
W
S
IR REPORT—SAMPLE
Intensity
W
S
M
M
S
M
M
M
W
W
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ester, Ether,
Ketone
Aromatic C-H,
Sat'd C-H
Subst. Aromatic
Alkyl
NO. B2SWD, CUT
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone
Aromatic C=C
Sat'd C-H
Sat'd C-H
Ketone, Ether
Aromatic C-H
Subst. Olefin/
Comment
Broad
9
LC-5
Comment
Broad
755
Aromatic
Subst. Aromatic
A-19
-------
TABLE A-57. IR REPORT—SAMPLE NO. B2SWD. CUT LC-6 & 7
- Quantity Not Sufficient -
TABLE A-58. IR REPORT—SAMPLE NO. B-PE, CUT LC-1 & 2
- Quantity Not Sufficient -
TABLE A-59. IR REPORT-SAMPLE NO. B-PE, CUT LC-3
Wave Number
2933, 2966
2862
1739
1460
1378
1082, 1136,
961
748
(cnf ) Intensity
S
M
S
M
W
1290 M
W
w
Assignment
Sat'd C-H
Sat'd C-H
Ketone
Sat'd C-H
Sat'd C-H
Ether, Ketone
Alkyl
Alkyl, C-C1
Comment
Poss.
Contamination
TABLE A-60. IR REPORT— SAMPLE NO. B-PE, CUT LC-4
Wave Number
2933, 2966
2862
1739
1246
1136, 1175
1076
753
(cnf ) Intensity
S
M
S
W
M
W
W
Assignment
Sat'-d C-H
Sat'd C-H
Ester, Ketone
Si li cone, Ester,
Ether, Sat'd C-H,
Ketone
Ester, Ether
Ether, Si li cone
Alkyl
Comment
A-20
-------
TABLE A-61. IR REPORT-SAMPLE NO. B-PE. CUT LC-5
Wave Number
2966
2862, 2933
1734
1175
1021, 1087
753
Wave Number
2939, 2955
2846
1027
758
(cm) Intensity
M
M
S
M
W
W
TABLE A-62. IR REPORT-SAMPLE
(cnf ) Intensity
M
W
S
W
Assignment Comment
Sat'd C-H
Sat'd C-H
Ester
Ether, Ester
Ether
Alkyl
NO. B-PE, CUT LC-6
Assignment Comment
Sat'd C-H
Sat'd C-H
Sulfoxide
Alkyl
TABLE A-63. IR REPORT— SAMPLE NO. B-PE, CUT LC-7
Wave Number
2966
2868
1734
1252
1175
1016
753
(cm~ ) Intensity
M
W
S
M
W
W
W
Assignment Comment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Ester, Ketone,
Phosphate
Ester
Phosphate
Alkyl
A-21
-------
TABLE A-64. IR REPORT—SAMPLE NO. B2K, CUT LC-1
Wave Number (cm~ )
2928
2857, 2959
Intensity
S
M
Assignment
Sat'd C-H
Sat'd C-H
Comment
TABLE A-65. IR REPORT—SAMPLE NO. B2K. CUT LC-2. 3. 4. 5. & 6
- Quantity Not Sufficient -
TABLE A-66. IR REPORT—SAMPLE NO. B2K. CUT LC-7
Wave Number (cm~ ) Intensity Assignment Comment
2936, 2967 S Sat'd C-H
2873 M Sat'd C-H
1730 S Ester, Ketone
1260 S Ester, Phosphate
Silicone
1127 M Sat'd C-H
1027 S Sulfoxide, Phosphate,
Silicone
806 S Phosphate, Alkyl
A-22
-------
JABLE A-67. IR REPORT--SAMPLE NO. C1SWD. CUT LC-1
Wave Number (cm" )
3060
2923
2868
1456
1275
1187
881
815
749
Intensity
M
S
M
M
W
W
W
M
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd/Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic,
C-C1
TABLE A-68. IR REPORT—SAMPLE NO. C1SUD. CUT LC-2
Wave Number (cm" )
3060
2923-2972
1598
1258
1182
886
842
815
749
711
Intensity
S
M
W
W
W
W
M
M
S
M
Assignment
Unsat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H
Sat'd/Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic,
C-C1
Subst. Aromatic,
Comment
Broad
C-C1
A-23
-------
Wave Number (cm" )
3060
2939, 2961
2868
1729
1620
1461
1390
1275
1182
881
815
749
Intensity
M
M
W
M
W
M
W
M
W
M
M
S
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Aldehyde,
Ester
Aromatic C=C
Sat'd C-H
Aldehyde
Sat'd C-H, Ketone
Sat'd/Aromatic C-H,
Ester
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic,
C-C1
Comment
Poss.
Contamination
TABLE A-70. IR REPORT—SAMPLE NO. C1SWD, CUT LC-4
Wave Number (cm~ )
3060
2934, 2967
2868
1729
1598
1461
1379
1138-1275
1029, 1078
821, 886
749
Intensity
W
S
M
S
M
M
W
M
W
W
S
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Ester
Aromatic C=C
Sat'd C-H
Sat'd C-H
Ketone, Ester,
Aromatic
Ether, Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic/
Comment
•
Poss.
Contamination
Broad
C-C1
A-24
-------
TARI F A-71. IR REPORT—SAMPLE NO. C1SWD. CUT LC-5
1
Wave Number (cm" )
3043
2967
2868
1696
1598
1456
1160-1275
749
TABLE A-72.
Wave Number (cm )
3060
2934-2978
1652
1603
1456
1373
1275
1034
826
749
Intensity
W
M
W
W
M
M
M
S
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone
Aromatic C=C
Sat'd C-H
Ketone, Aromatic
Subst. Aromatic,
C-C1
IR REPORT— SAMPLE NO. C1SWD, CUT
Intensity
W
M
S
M
M
W
M
W
W
S
Assignment
Unsat'd C-H
Sat'd C-H
Amide, Olefin
Aromatic C=C,
Olefin
Sat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Aromatic,
C-C1
Comment
Broad
LC-6
Comment
A-25
-------
Wave Number (cm" )
2972
1653
1598
1368
1275
749
Intensity
M
M
w
W
W
S
Assignment
Sat1 d C-H
Amide, Olefin
Aromatic C=C,
Olefin
Sat'd C-H
Sat'd C-H
Subst. Aromatic,
C-C1
Comment
Broad
Broad
Broad
TABLE A-74^ IR REPORT—SAMPLE NO. C-P50. CUT LC-1
Wave Number (cm" )
3056
2955
2931
2859
1457
1379
1115, 1187
828, 876
Intensity
W
M
S
W
M
W
W
W
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd/Aromatic C-H
Subst. Olefin/
Aromatic
750 Subst. Aromatic,
C-C1
A-26
-------
TARI.F A-75. IR RFPnRT--SAMPLF NO. C-P5Q. CUT LC-2
Wave Number (cnf )
3050
2925
1601
1451
1379
1301
1265
1181
1037
953
881
816, 840
738
714
Intensity
M
W
W
M
W
W
W
W
W
W
M
S
S
M
Assignment Comment
Unsat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H
Sat'd C-H
Olefinic C-H
Sat'd C-H
Aromatic,
Sat'd C-H
Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic,
C-C1
Subst. Aromatic,
C-C1
A-27
-------
TABLE A-76. IR REPORT-SAMPLE NO. C-P50, CUT LC-3
Wave Number (cm" )
3050
2925
2859 , 2967
1457
1385
1181
1031
947
881
840
750
620
Intensity
S
M
W
S
W
M
W
W
M
M
S
W
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat1 d C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic C-H
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic Doublet
Subst. Aromatic,
C-C1
C-C1
TABLE A-77. IR REPORT—SAMPLE NO. C-P50, CUT LC-4
Wave Number (cm" )
3422
3056
2931
2871, 2967
1702
1601
1451
1277, 1324, 1378
1199, 1241
882
816
750
Intensity
M
M
M
W
M
M
S
W
W
W
M
S
Assignment Comment
0-H, N-H Broad
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Aldehyde
Amine, Aromatic C=C
Alcohol, Sat'd C-H
Aldehyde, Ketone
Aldehyde, Ketone
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic, Amine
Subst. Aromatic,
Alcohol , Amine
-------
TABI.F A-7S. IR RFPORT--SAMPLF NO. C-P50. CUT LC-5
Wave Number (cm" )
3398
3056
2871, 2961
2937
1738
1600
1457
1379
1241
965
840
750
612, 702
Intensity
M
W
W
S
s
S
s
W
s
W
M
M
W
Assignment Comment
N-H, 0-H Broad
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Ester
Aromatic C=C,
Amine
Sat'd C-H, Alcohol
Sat'd C-H, 0-H
Ketone, Ester,
Ether
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic, Amine
Subst. Aromatic,
Alcohol
Alcohol
A-29
-------
TARI F A-79 TR RFPORT--SAMPLE NO. C-P50. CUT LC-6
Wave Number (cnf )
3308
3068
2937
2859, 2967
1708
1601
1457
1271
1079
828
Intensity
S
W
M
W
S
S
S
S
W
M
Assignment
N-H, 0-H
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Acid, Ketone
Aromatic C=C,
Ami ne
Sat'd C-H,
Alcohol
Amine, Acid
Amine, Alcohol ,
Aromatic C-H
01 ef i n i c/Aromati c
C-H
Comment
Multiplet
756 S Subst. Aromatic,
Alcohol, Amine
696 M Alcohol, Alkyl
A-30
-------
TARI F A-RD TR RFPDRT--SAMPLE NO. P.-P5Q. CUT LC-7
Wave Number (cm~ )
3400
2847
1654
1451
1409
1115
1019
690
TABLE A-81.
Wave Number (cnf )
2928
2857
TABLE A-82.
Wave Number (cm~ )
3053
2865, 2967
2928
1456
884
814
744
Intensity
S
W
S
W
W
W
S
S
IR REPORT— SAMPLE
Intensity
S
M
IR REPORT— SAMPLE
Intensity
S
M
S
S
W
M
S
Assignment
N-H, 0-H
Sat'd C-H
Ami de
Sat'd C-H
Amide, Alcohol
Amine, Alcohol
Alcohol
Alcohol, Alkyl
NO. C1PART, CUT LC-1
Assignment
Sat'd C-H
Sat'd C-H
NO. C1PART, CUT LC-2
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Subst. Aromatic,
Olefin
Subst. Aromatic
Subst. Aromatic,
Comment
Broad
Comment
Comment
Alkyl, C-C1
A-31
-------
Wave Number (cm~ )
3053
2920
2857
1597
1456
1198
884
751
Intensity
S
M
W
M
S
M
S
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic C=C
Sat'd C-H
Aromatic C-H Broad
Subst. Aromatic Multiplet
Subst. Aromatic
Alkyl, C-C1
TABLE A-84. IR REPORT—SAMPLE NO. C1PART. CUT LC-4
Wave Number (cm~ )
3053
2850, 2912
1180
814, 877
744
Intensity
M
W
S
M
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Ether, Aromatic,
Alkyl
Subst. Aromatic
Subst. Aromatic,
Alkyl
A-32
-------
TABLE A-85. IR REPORT—SAMPLE NO. C1PART, CUT LC-5
Wave Number (cm~ )
3421
3053
2865, 2959
2928
1738
1604
1378, 1456
1150 - 1300
1080
845, 963
751
TABLE A-86.
Wave Number (cm~ )
2936
2865
1738
16.05, 1651
1378, 1456
1150 - 1300
1080
751
TABLE A-87.
Intensity
W
W
M
S
s
W
M
S
M
W
M
IR REPORT— SAMPLE
Intensity
M
M
S
W
M
M
W
W
IR REPORT-SAMPLE
Assignment
0-H, N-H
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Ester
Aromatic C=C,
Ami ne
Sat'd C-H
Ketone, Ester,
Alcohol, Phenol
Aromatic C-H
Subst. Aromatic
Subst. Aromatic,
Amine, Alkyl
NO. C1PART, CUT LC-6
Assignment
Sat'd C-H
Sat'd C-H
Ester, Ketone
Amide, Olefin
Sat'd C-H
Ketone, Ester
Sat'd C-H
Alkyl
NO. C1PART, CUT LC-7
Comment
Broad
Comment
Broad
- Quantity Not Sufficient -
A-33
-------
Wave Number (cnf )
3053
2740, 2857, 2928
1934
1597
1511
1476
1425
1386
1010, 1080, 1127, 1268
830
783
728
Intensity
S
S
W
M
M
M
M
M
W
M
M
M
Assignment Comment
Unsat'd C-H
Sat'd C-H
Aromatic Overtone
Aromatic C=C
Aromatic C=C
Sat'd C-H
Sat'd/Olefin C-H
Sat'd C-H
Aromatic C-H
Subst. Aromatic
Subst. Aromatic,
Alkyl, C-C1
Subst. Aromatic,
Alkyl, Olefin,
C-C1
TABLE A-89. IR REPORT—SAMPLE NO. C1X, CUT LC-2
Wave Number (cm~ )
3061
2967, 2865
2928
1808, 1934
1730
'1604
1425, 1456
1080, 1190
830
775
Intensity
S
W
M
W
M
M
S
M
S
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Aromatic Overtone
Ester Poss.
Contamination
Aromatic C-H
Sat'd/Olefin C-H,
Si li cone
Si li cone, Ester
Subst. Aromatic
Subst. Aromatic,
736
Alkyl, C-C1
Subst. Aromatic,
Alkyl, Olefin,
C-C1
-------
TABLE A-90. IR REPORT—SAMPLE NO. C1X. CUT LC-3
- Quantity Not Sufficient -
TABLE A-91. IR REPORT—SAMPLE NO. C1X, CUT LC-4
Wave Number (cm~ )
2866, 2959
2936
1739
1457, 1379
1136 - 1285
1081
Intensity
W
M
S
W
M
W
Assignment Comment
Sat1 d C-H
Sat'd C-H
Ester, Ketone Poss.
Contamination
Sat'd C-H
Ester, Ether,
Ketone
Si li cone
TABLE A-92. IR REPORT-SAMPLE NO. C1X, CUT LC-5, 7
- Quantity Not Sufficient -
TABLE A-93. IR REPORT—SAMPLE NO. C1X, CUT LC-6
Wave Number (cm )
3312
3061
2936
2866
1707
1606
1378, 1449
1000 - 1300
Intensity
S
W
S
M
S
M
M
M
Assignment
0-H, N-H
Unsat'd C-H
• Sat'd C-H
Sat'd C-H
Acid, Amide
Amine, Amide
Sat'd C-H
Alcohol , Phenol ,
Comment
Broad
760
M
Amine
Subst. Aromatic,
Alkyl, Alcohol,
Amine
Broad
-------
TABLE A-94. IR REPORT—SAMPLE NO. C2SWD. CUT LC-1
- Quantity Not Sufficient -
TABLE A-95.
Wave Number (cm" )
3058
2968
1451
1260
1186
1096
1027
800
742
TABLE A-96.
Wave Number (cm )
3052
2931, 2962
2862
1736
1599
1451
1381
1038 - 1287
742 - 843
IR REPORT— SAMPLE
Intensity
W
W
W
s
W
s
M
S
M
IR REPORT— SAMPLE
Intensity
S
M
W
S
M
S
W
M
S
NO. C2SWD, CUT LC-2
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, Ether
Sat'd/ Aromatic
C-H
Aromatic C-H,
Ether
Ether, Aromatic
C-H
01 ef in/Aromatic
C-H
Subst. Aromatic,
C-C1
NO. C2SWD, CUT LC-3
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ketone, Ester
Aromatic C-H
Sat'd C-H,
Aromatic C-H
Sat'd C-H
Ester, Ketone
Subst. Aromatic,
C-C1
Comment
Poss.
Contamination
Comment
Poss.
Contamination
Multiplet
Multiplet
615
M
C-C1
A-36
-------
TABLF A-97. TR REPORT—SAMPI.F NO. C2SWD. CUT LC-4
Wave Number (cnf )
3056
1451
1325
1241
882
840
750
TABLE A-98.
Wave Number (cm )
3404
3056
2931
2865
2224
1738
1600
1451
1379
1175, 1282
953
840, 882
756
Intensity
W
W
W
W
W
M
S
IR REPORT—SAMPLE
Intensity
M
M
W
M
W
S
S
S
W
S
W
M
S
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H, Ether
Subst. Olefin/
Aromatic
Subst. Olefin/
Aromatic
Subst. Aromatic
NO. C2SWD. CUT LC-5
Assignment
N-H, 0-H
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Nitrite
Ketone, Ester
Olefin, Aromatic
C=C, Amine
Alcohol, Sat'd C-H,
Aromatic C=C
Sat'd C-H
Ester, Alcohol ,
Ketone, Amine
Olefinic/Aromatic
C-H
Olefinic/Aromatic
C-H
Subst. Aromatic
Comment
Broad
Comment
Broad
A-37
-------
.E A-99. IR REPORT-SAMPLE NO. C2SWD. CUT LC-6
- Quantity Not Sufficient -
TABLE A-100.
Wave Number (cm~ )
2928
2857
748
TABLE A-101.
Wave Number (cm~ )
2928, 2966
2868
1734
1284
1191
961
748
IR REPORT—SAMPLE
Intensity
S
M
M
IR REPORT— SAMPLE
Intensity
S
M
S
M
M
W
M
NO. C-PE. CUT LC-1
Assignment
Sat'd C-H
Sat'd C-H
Alkyl, C-C1
NO. C-PE, CUT LC-2
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H, Ketone
Sat'd C-H, Ester
Alcohol
Alkyl, C-C1
Comment
Comment
Poss.
Contamination
A-38
-------
TABLE A-102. IR REPORT—SAMPLE NO. C-PE. CUT LC-3
Wave Number (cnf )
2831, 2961
2862
1745
1460
1383
1279
1082, 1175
967
753
TABLE A-103.
Wave Number (cnf )
2933, 2966
2868
1262
1175
748
TABLE A-104.
Wave Number (cm )
2939, 2966
2862
1262
764
748
Intensity
S
M
S
M
W
S
S
M
W
IR REPORT— SAMPLE
Intensity
S
M
W
W
M
IR REPORT— SAMPLE
Intensity
S
M
W
S
S
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Sat'd C-H, Ketone
Ester, Sat'd C-H
Alkyl
Alkyl, C-C1
NO. C-PE, CUT LC-4
Assignment
Sat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Alkyl
NO. C-PE, CUT LC-5
Assignment
Sat'd C-H
Sat'd C-H
Sat'd C-H
Alkyl
Alkyl
Comment
Poss.
Contamination
Comment
Comment
A-39
-------
Wave Number (cnf )
2950
2862
1021
764
TABLE A-106.
Wave Number (cnf )
2933, 2966
2862
1740
1264
1138, 1176
1083
957
749
TABLE A-107.
Wave Number (cnf )
3053
2928
2857
1456
845
736
Intensity
S
M
W
S
IR REPORT— SAMPLE
Intensity
M
W
S
M
M
W
W
W
IR REPORT— SAMPLE
i
Intensity
W
S
M
M
M
S
Assignment Comment
Sat'd C-H
Sat'd C-H
Sulfoxide
Alkyl
NO. C-PE, CUT LC-7
Assignment Comment
Sat'd C-H
Sard C-H
Ketone, Ester
Ketone
Ester
Alkyl
Alkyl
Alkyl
NO. C2PART, CUT LC-1
Assignment Comment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Sat'd C-H
Subst. Aromatic Doublet
Alkyl, Subst.
Aromatic, C-C1
TABLE A-108. IR REPORT—SAMPLE NO. C2PART, CUT LC-2
- Quantity Not Sufficient -
A-40
-------
TABLE A-109. IR REPORT-SAMPLE NO. C2PART, CUT LC-3
Wave Number (cnf )
3053
2857, 2928
1918
1598
1441
1183
878
839
753
Intensity
S
W
W
M
M
M
M
M
S
Assignment Comment
Unsat'd C-H
Sat'd C-H
Aromatic Overtone
Aromatic C-H
Sat'd/Olefinic C-H
Aromatic/Sat 'd C-H Multiplet
Subst. Aromatic
Subst. Aromatic
Subst. Aromatic,
Alkyl, C-C1
TABLE A-110. IR REPORT—SAMPLE NO. C2PART, CUT LC-4. 5. 6, & 7
- Quantity Not Sufficient -
TABLE A-111. IR REPORT-SAMPLE NO. C2X, CUT LC-1
Wave Number (cm )
3061
962, 1010, 1080, 1127
728, 775, 830
TABLE A-112.
Wave Number (cm )
3045
775, 814
736
Intensity
M
M
S
IR REPORT-SAMPLE
Intensity
M
M
S
Assignment
Unsat'd C-H
Aromatic C-H
Subst. Aromatic,
C-C1
NO. C2X, CUT LC-2
Assignment
Unsat'd C-H
Subst. Aromatic
Subst. Aromatic,
Comment
Comment
C-C1
H-41
-------
Wave Number (cm" )
3053
2936, 2959
2857
1738
1464
1378
1135-1292
Intensity
W
S
M
S
M
M
M
Assignment
Unsat'd C-H
Sat'd C-H
Sat'd C-H
Ester, Ketone
Sat'd C-H
Sat'd C-H
Ketone, Si li cone,
Comment
Poss.
Contamination
Multiplet
1080
M
Ester, Sat'd/
Aromatic C-H
Aromatic C-H,
Si licone
822, 963
744
VI
M
Subst. Aromatic
Subst. Aromatic,
AlkyT, C-C1
TABLE A-114. IR REPORT—SAMPLE NO. C2X, CUT LC-4
Wave Number (cnf )
2936, 2967
2865
1738
1456
1378
1135-1252
1080
735
TABLE A-115.
Intensity
M
M
S
w
w
M
M
W
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ether, Ester,
Ketone, Si li cone
Ether, Si li cone
Alkyl, C-C1
Comment
Multiplet
IR REPORT— SAMPLE NO. C2X, CUT LC-5
- Quantity Not Sufficient -
A-42
-------
TABLE A-116. IR REPORT—SAMPLE NO. C2X. CUT LC-6
Wave Number (cm" )
2936
2865
1738
1456
1378
1174-1244
TABLE A-117.
Intensity
M
W
S
W
W
M
IR REPORT— SAMPLE
Assignment
Sat'd C-H
Sat'd C-H
Ketone, Ester
Sat'd C-H
Sat'd C-H
Ketone, Ester
NO. C2X, CUT LC-7
Comment
Multiplet
- Quantity Not Sufficient -
A-43
-------
APPENDIX B
LOW RESOLUTION MASS SPECTROGRAPH REPORTS
-------
TABLE B-l
Intensity
Major Categories
TOO
Sub-Categories,
10
10
10
100
100
Other
. LRMS REPORT— SAMPLE NO.
Category
Aliphatics
Specific Compounds
Probably Fragment
Probably Fragment
Aliphatic with Two Sites
of Unsaturation
Probably Fragment
Probably Fragment
A1X. LC CUT 2 & 3 CO
MW Range m/e
149-283
149
183
236
255
283
MBINED
Composition
C11H17
C13H27
C17H32
C18H39
C20H43
IR shows no evidence of aromatic structures.
B-2
-------
TABLE B-2. LRMS REPORT-SAMPLE NO. AT-SUP, LC CUT 2
Intensity
Major Categories
10
100
Sub-Categories,
100
10
10
100
100
10
10
100
10
10
Category MW Range
Fused Aromatics, MW <216 202
Fused Aromatics, MW >216 252-314
Specific Compounds
Phthalate Fragment
Pyrene, Fluoranthene
Probably Fragment
Probably Fragment
Benzopyrene, Benzo-
fluoranthene
Dimethyl benzanthracene
Probably Fragment
Probably Fragment
Methyl Coronene
m/e
149
202
213
243
252
256
258
279
299
314
Composition
C8H5°3
C16H10
C20H12
C20H16
C20H18
C9CH1/1
Other
Quantity not sufficient for IR.
B-3
-------
TABLE B-3. LRMS REPORT—SAMP'F NO. A1-SWD. LC CUT "*
Intensity Category MW Range m/e Composition
Major Categories
10 Fused Aromatics, MW <216 202
100 Fused Aromatics, MW >216 228-302
10 Ester/Ketone
Sub-Categories, Specific Compounds
100 Phthalate Fragment 149 C8H5°3
100 Probably Fragment 167
10 Pyrene, Fluoranthene 202 ^16^10
10 Probably Fragment 213
10 Benzanthracene, Chrysene 228 ^18^12
100 Probably Fragment 243
10 Benzopyrene, Benzofluo-
ranthene 252 ^20^12
10 Dimethyl Benzanthracene 256 C20^16
10 258 C2QH18
100 Probably Fragment 279
10 Probably Fragment 287
10 Probably Fragment 299
10 Dibenzochrysene Isomer 302 C24H14
10 Methyl Coronene 314 C25H14
Other
Quantity not sufficient for IR.
B-4
-------
TARI F R-4. LRMS RFPORT--SAMPLE NO. A2-X. 1C CUT 2 & 3
Intensity
Major Categories
100
100
Sub-Categories,
100
10
10
10
10
100
10
10
10
10
10
100
100
100
100
10
Other
Quantity not
Category MW Range
Fused Aromatics, MW >216 276-338
Alkyl Fragments 255-613
Specific Compounds
Probably Fragment
Probably Fragment
Anthanthrene, Indenopyrene
Probably Fragment
Coronene
Dibenzochrysene Isomer
Probably Fragment
Benzanthanthrene
Probably Fragment
Probably Fragment
Probably Fragment
Probably Fragment
Probably Fragment
Probably Fragment
Probably Fragment
sufficient for IR.
m/e Composition
255 C H
1 P ^Q
257 r H
1ft dl
276 C22H12
283 C2QH43
300 C24H12
302 C24H14
311 C24H23;
C23H35
326 C26H14
338
339
543
557
571
585
599
613
B-5
-------
Intensity
Major Categories
10
100
Sub-Categories,
100
100
100
100
100
10
100
10
100
100
10
10
10
10
Category MW Range
Fused Aromatic, MW <216 202
Fused Aromatics, MW >216 228-452
Specific Compounds
Pyrene, Fluoranthene
Benzanthracene, Chrysene
Methyl Chrysene
Benzopyrene, Benzofluoranthene
Dibenzofluorene
Methyl Cholanthrene
Anthanthracene, Indenopyrene
Dibenzanthracene
Dibenzochrysene Isomer
Benzanthanthrene
Dinaphthanthracene
Dinaphthopyrene
m/e
202
228
242
252
266
268
276
278
302
326
378
402
428
452
Composition
C16H10
C18H12
C19H14
C20H12
C21H14
C21H16
C22H12
wrt/^rln n
22 14
C24H14
(sr\t~ H-B A
26 14
C30H18
C32H18
Other
IR showed no evidence of other functional groups.
B-6
-------
JTABLE R-fi LRMS RFPDRT--SAMPLE NO. A2-SWD. LC CUT 3
Intensity
Major Categories
10
100
10
Sub-Categories,
10
10
100
10
100
100
10
100
100
10
100
10
10
10
10
Category MW Range
Fused Aromatics, MW <216 202
Fused Aromatics, MW >216 228-452
Esters/Ketones 202-452
Specific Compounds
Pyrene, Fluoranthene
Benzanthracene, Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Dibenzanthracene
Methyl Dibenzanthracene
Dibenzochrysene Isomer
Benzanthanthrene
Dibenzochrysene Isomer
Dibenzanthanthrene Isomer
Dinaphthanthracene
Dinaphthopyrene
m/e
202
228
252
266
276
278
292
302
326
328
376
378
402
428
452
Composition
C16H10
C18H12
C20H12
C21H14
C22H12
C22H14
C23H16
C24H14
C26H14
C26H16
C30H16
C30H18
C32H18
B-7
-------
TABLE B-7. LRMS REPORT—SAMPLE NO. A-PE. LC CUT 2
Intensity Category MW Range m/e Composition
Major Categories
TOO Aliphatics 236-278
Sub-Categories, Specific Compounds
TOO C17H32 AliPhatic Compound 236 ci7H32
TOO Probably Fragment 243 ciaH27
10 Probably Fragment 255 cieH35
10 Probably Fragment 257 cH
in r M
L20M34 Aliphatic Compound 278
Other
Quantity not sufficient for IR.
B-8
-------
TARLF R-R. LRMS RFPDRT--SAMPLE N0_ A-PF. I C. CUT 3
Intensity
Major Categories
100
10
Sub-Categories,
100
100
100
10
10
100
10
10
100
100
100
100
100
100
Other
IR showed no
Category MW Range
Aliphatic 236-604
Ketones (Contaminant)
Specific Compounds
Probably Fragment
Phthalate Fragment
^17^32 Aliphatic Compound
Probably Fragment
^19^34 Aliphatic Compound
C-,gH3g Aliphatic Compound
Probably Fragment
^23^36 Aliphatic Compound
aromatic structures.
m/e
129
149
236
239
262
264
279
312
369
551
576
577
602
604
Composition
C8H5°3
C17H32
C19H34
C19H36
C23H36
B-9
-------
TABLE B-9. LRMS REPORT—SAMPLE NO. B1-X. LC CUT 2
Intensity Category MW Range m/e Composition
Major Categories
10
10
100
Sub-Categories,
10
10
Fused Aromatics, MW <216 202
Fused Aromatics, MW >216 228
Aliphatics >554
Specific Compounds
Pyrene, Fluoranthene 202 C16H10
Benzanthracene, Chrysene 228 ^i«H12
The following major fragment peaks were noted: 553, 503, 479
429S 420, 417, 405, 369, 355, 343, 327, 295, 281, 221, 207,
147, 135.
B-10
-------
TABLE B-10. LRMS REPORT—SAMPLE NO. Bl-X. LC CUT 3
Intensity Category MW Range m/e Composition
Major Categories
10 Fused Aromatics, MW <216 202
10 Fused Aromatics, MW >216 228-252
100 Aliphatics/Aralkyls >702
Sub-Categories, Specific Compounds
10 Pyrene, Fluoranthene 202 C16H10
10 Benzanthracene, Chrysene 228 C1RH12
100 Benzopyrene, Benzofluo-
ranthene 252 C20H12
This spectrum was extremely complex. Major peaks were noted at the
following masses: 135, 145, 197, 221, 235, 259, 295, 327, 331, 343,
346, 390, 405, 417, 420, 451, 467, 479.
The most notable pattern was observed in the m/e 529-701 region
701 627 553
692 618 544
677 603 529
Long chain aliphatics or aralkyls.
B-ll
-------
TARI.E B-11 LRMS REPORT SAMPLE NO. B2-PART. LC CUT 2 & 3 COMBINED
Intensity Category MW Range m/e Composition
Major Categories
10
TOO
Sub-Categories,
10
10
10
100
10
10
100
100
100
10
10
10
10
10
10
10
Fused Aromatics, MW <216 202
Fused Aromatics, MW >216 252-426
Specific Compounds
Pyrene, Fluoranthene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Methyl Anthanthrene
Dibenzochrysene Isomer
Anthrafluorene
Benzanthanthrene
Dibenzanthanthrene Isomer
Dibenzopentacene
Dibenzocoronene Isomer
Dibenzanthanthrene Isomer
Dibenzocoronene Isomer
Dinaphthopyrene
202
252
266
276
290
292
302
316
326
350
352
374
376
400
402
426
C16H10
C20H12
C21H14
C22H12
C23H14
C23H16
C24H14
C25H16
C26H14
C28H14
C28H16
C30H14
C30H16
C32H16
C32H18
B-12
-------
TARI F R-1?. LRMS RFPQRT--SAMPLE NO. B2-X. 1C CUT 2 & 3 COMBINED
Intensity Category MW Range m/e Composition
Major Categories
100 Fused Aromatics, MW <216 152-202
10 Fused Aromatic, MW >216 216
Sub-Categories, Specific Compounds
10 Aralkyl Compound 152 cnH?0
10 Probably Fragment 165 C12H21
100 Phenanthracene, Anthracene 178 ci4Hio
10 Probably Fragment 189 C14H21
10 Methyl Anthracene 192 ci4H24
100 Pyrene, Fluoranthene 202 C16H10
10 Benzofluorene, Methyl
Pyrene 216 CH
B-13
-------
TABLE B-13. LRMS REPORT—SAMPLE NO. B2-SWD. LC CUT 2
Intensity Category MW Range m/e Composition
Major Categories
10 Fused Aromatics, MW <216 202
100 Fused Aromatics, MW >216 216-328
100 Aliphatics 290-374
Sub-Categories, Specific Compounds
10 Pyrene, Fluoranthene 202 C16H10
10 Benzofluorene, Methyl
Pyrene 216 C17H12
10 Anthanthrene, Indenopyrene 276 ^22^12
100 Coronene 300 C24H12
100 Dibenzochrysene Isomer 302 C24H14
100 Dibenzochrysene Isomer 328 c?6^16
Peaks are present at intervals of 14 mass units within the
following ranges:
100 290-374
100 316-372
100 342-370
Aliphatics or Aralkyl Compounds
Other
IR showed no evidence of other functional groups.
B-14
-------
TABLE B-14. LRMS REPORT—SAMPLE NO. B2-SWD. LC CUT 3
Intensity Category MW Range m/e Composition
Major Categories
10
100
100
10
Sub-Categories,
10
10
10
100
100
100
100
100
100
100
100
100
100
Fused Aromatics, MW <216 202
Fused Aromatics , MW >216 228-376
Aliphatics 202-430
Ester/Ketone
Specific Compounds
Phthalate Ester Fragment
Pyrene, Fluoranthene
Benzanthracene, Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Coronene
Dibenzochrysene Isomer
Anthrafluorene
Benzanthanthrene
Pyrenofluorene
Dibenzanthanthrene Isomer
Dibenzanthanthrene Isomer
149
202
228
252
266
276
300
302
316
326
340
350
376
C8H5°3
C16H10
C18H12
C20H12
C21H14
C22H12
C24H12
C24H14
C25H16
C26H14
C27H16
C28H14
C30H16
Peaks are present at intervals of 14 mass units within the following
ranges: 280-308; 290-318; 292-320; 302-316; 326-382; 350-406; 352-394;
376-418; 400-428; 402-430. Aliphatic or Aralkyl Compounds.
Other
IR shows presence of carbonyl groups.
B-15
-------
TABLE B-15. LRMS REPORT-SAMPLE NO. B-PE. LC CUT 3
Intensity
Category
MW Range
m/e Composition
Major Categories
100 Aliphatics
10 Ester
Sub-Categories, Specific Compounds
10 Possible Molecular Ion,
Aliphatic
10 Possible Molecular Ion,
Aliphatic
The following fragmentations were noted:
100
100
100
100
to 390
Phthalate Peak
10
10
10
100
100
100
Other
370
390
112
129
147
149
167
189
212
241
259
279
IR showed no aromaticity.
B-16
-------
TABLE B-16. LRMS REPORT--SAMPLE NO. C1-PART. LC CUT 2 & 3
Intensity
Major Categories
10
TOO
Sub-Categories,
10
10
100
10
100
10
10
10
100
10
10
10
10
10
10
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 252-402
Specific Compounds
Phenanthracene, Anthracene
Pyrene, Fluoranthene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthracene, Indenopyrene
Methyl Anthanthracene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
Pyrenofluorene
Dibenzanthanthrene Isomer
Dibenzocoronene Isomer
Dibenzanthanthrene Isomer
Dibenzocoronene Isomer
Dinaphthopyrene
m/e
178
202
252
266
276
290
300
302
326
340
350
374
376
400
402
Composition
C14H10
C16H10
C20H12
C21H14
C22H12
C23H14
C24H12
C24H14
C26H14
C27H16
C28H14
C30H14
C30H16
C32H16
C32H18
B-17
-------
TARI F R-17 I RMS RFPDRT--SAMPI F NO C1-X. 1C HIT 2 & 3 COMBINEEL
Intensity
Major Categories
10
100
10
Sub-Categories,
10
10
10
100
100
10
10
100
100
10
Category MW Range
Fused Aromatics, MW <216 152-202
Fused Aromatics, MW >216 252-376
Esters 152-376
Specific Compounds
Aralkyl Compound
Phenanthracene, Anthracene
Pyrene, Fluoranthene
Benzopyrene, Benzofluo-
ranthene
Anthanthrene, Indenopyrene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
Dibenzanthanthrene Isomer
Dibenzanthanthrene Isomer
m/e
152
178
202
252
276
300
302
326
350
376
Composition
C11H20
C14H10
C16H10
C20H12
C22H12
C24H12
C24H14
C26H14
C28H14
C30H16
B-18
-------
TABLE B-18. LRMS REPORT—SAMPLE NO. C1-SWD. 1C CUT 2
Intensity
Major Categories
10
100
10
Sub-Categories,
10
100
10
10
10
100
100
100
10
10
10
100
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 216-326
Aliphatics 278-360
Specific Compounds
Phenanthrene, Anthracene
Pyrene, Fluoranthene
Methyl Pyrene
Benzofluoranthene Isomer
Benzanthracene, Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Methyl Dibenzanthracene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
m/e
178
202
216
226
228
252
266
276
292
300
302
326
Composition
C14H10
C16H10
C17H12
C18H10
C18H12
C20H12
C21H14
C22H12
C23H16
C24H12
C24H14
C26H14
Even mass peaks appeared as clusters within the following range:
352-360, 340-346, 326-332, 314-316, 306-310, 290-296, 278-282.
Other
IR showed presence of no other functional group.
B-19
-------
TABLE B-19. LRMS REPORT—SAMPLE NO. Cl-SWD. LC CUT 3
Intensity
Major Categories
10
100
10
Sub-Categories,
100
10
10
100
100
10
10
100
100
100
10
100
10
10
10
10
10
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 226-352
Ester/Ketone
Specific Compounds
Phthalate Peak
Phenanthrene, Anthracene
Pyrene, Fluoranthene
Benzofluoranthene Isomer
Benzanthracene, Chrysene
Methyl Benzofluoranthene
Methyl Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Methyl Anthanthrene
Dibenzochrysene Isomer
Methyl Benzocholanthrene
Dibenzochrysene Isomer
Methyl Dibenzochrysene
Dibenzopentacene
Dibenzanthanthrene
Dinaphthanthracene
m/e
149
178
202
226
228
240
242
252
266
276
290
302
318
328
342
352
376
378
Composition
C8H5°3
C14H10
C16H10
C18H10
C18H12
C19H12
C19H14
C20H12
C21H14
C22H12
C23H14
C24H14
C25H18
C26H16
C27H18
C28H16
C30H16
C30H18
(Continued)
B-20
-------
Table B-19 (continued)
Intensity Category MW Range m/e Composition
Other
Major fragment peaks were observed at the following masses:
112, 113, 129, 167, 217.
TABLE B-20. LRMS REPORT—SAMPLE NO. C2-PART. 1C CUT 2
Intensity Category MW Range m/e Composition
Major Categories
100 Fused Aromatics, MW <216 178-202
10 Fused Aromatics, MW >216 216-228
Sub-Categories, Specific Compounds
10 Phenanthracene, Anthracene ' 178 ci4Hin
100 Pyrene, Fluoranthene 202 C16H10
10 Benzofluorene, Methyl
Pyrene 216 C]7H12
10 Benzofluoranthene Isomer 226 ^18H10
10 Benzanthracene, Chrysene 228 C18H12
B-21
-------
Intensity
Major Categories
10
100
Sub-Categories,
10
10
10
10
100
100
100
100
100
10
10
10
10
Other
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 226-376
Specific Compounds
Phenanthracene, Anthracene
Pyrene, Fluoranthene
Benzofluoranthene Isomer
Benzanthracene, Chrysene
Benzopyrene, Benzofluo-
ranthene
Anthanthrene, Indenopyrene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
Dibenzanthanthrene Isomer
Dibenzopentacene
Dibenzocoronene Isomer
Dibenzanthanthrene Isomer
m/e
178
202
226
228
252
276
300
302
326
350
352
374
376
Composition
C14H10
C16H10
C18H10
C18H12
C20H12
C22H12
C24H12
C24H14
C26H14
C28H14
C28H16
C30H14
C'30H16
IR shows no evidence of other functional groups, only aralkyl structures.
B-22
-------
TABLE B-22. LRMS REPORT—SAMPLE NO. C2-X. LC CUT 2 & 3 COMBINED
Intensity
Major Categories
10
100
10
Sub-Categories,
100
100
10
10
100
10
100
10
10
10
100
10
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 226-350
Esters, Ketones 178-350
Specific Compounds
Phenanthracene, Anthracene
Pyrene, Fluoranthene
Benzofluoranthene Isomer
Benzanthracene, Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
Dibenzanthanthrene Isomer
m/e
178
202
226
228
252
266
276
282
300
302
326
350
Composition
C14H10
C16H10
C18H10
C18H12
C20H12
C21H14
C22H12
C21H30'
C22H18
C24H12
C24H14
C26H14
C28H14
B-23
-------
Intensity
Major Categories
10
100
Sub-Categories,
10
100
10
100
10
10
100
10
100
100
100
100
10
10
10
Other
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 216-376
Ketones/Esters
Specific Compounds
Phenanthrene, Anthracene
Pyrene, Fluoranthene
Methyl Pyrene
Benzof 1 uoranthene
Benzanthracene, Chrysene
Methyl Benzof 1 uoranthene
Benzopyrene, Benzof 1 uo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Coronene
Dibenzochrysene Isomer
Benzanthanthrene
Dibenzanthanthrene Isomer
Dibenzopentacene
Dibenzanthanthrene Isomer
m/e
178
202
216
226
228
240
252
266
276
300
302
326
350
352
376
Composition
C14H10
C16H10
C17H12
C18H10
C18H12
C19H12
C20H12
C21H14
C22H12
C24H12
C24H14
C26H14
C28H14
C28H16
C30H16
IR showed evidence of carbonyl function.
B-24
-------
TABLE B-24. LRMS REPORT-SAMPLE NO. C-P50, LC CUT 2
Intensity
Major Categories
10
10
100
Sub-Categories,
10
100
10
100
10
10
100
100
100
10
10
10
10
10
10
(Continued)
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 252-276
Aliphatics 280-350
Specific Compounds
Phenanthrene, Anthracene
Pyrene, Fluoranthene
Benzopyrene, Benzofluo-
ranthene
Anthanthrene, Indenopyrene
Saturated Aliphatic
Saturated Aliphatic
Saturated Aliphatic
Aliphatic, One Site of
Unsaturation
Aliphatic, One Site of
Unsaturation
Aliphatic, One Site of
Unsaturation
Aliphatic, One Site of
Unsaturation
Aliphatic, One Site of
Unsaturation
Aliphatic, One Site of
Unsaturation
Aliphatic, Two Sites of
Unsaturation
Aliphatic, Two Sites of
Unsaturation
m/e
178
202
252
276
282
296
310
280
294
308
322
336
350
292
306
Composition
C14H10
C16H10
C20H12
C22H12
C20H42
C21H44
C22H46
C20H40
C21H42
C22H44
C23H46
C24H48
C25H50
C21H40
C22H42
B-25
-------
Table B-24 (continued)
Intensity Category MW Range m/e Composition
10 Aliphatic, Two Sites of
Unsaturation 320 C23H44
10 Aliphatic, Two Sites of
Unsaturation 334 C24H46
10 Aliphatic, Two Sites of
Unsaturation 348 C25H48
B-26
-------
TABLE B-25. LRMS REPORT—SAMPLE NO. C-P50. LC CUT 3
Intensity
Major Categories
10
100
Sub-Categories,
10
10
10
10
10
10
100
100
100
10
100
100
10
100
10
10
Other
Category MW Range
Fused Aromatics, MW <216 178-202
Fused Aromatics, MW >216 226-376
Specific Compounds
Phenanthrene, Anthracene
Pyrene, Fluoranthene
Benzofluoranthene Isomer
Chrysene
Methyl, Benzofluo-
ranthene
Methyl Chrysene
Benzopyrene, Benzofluo-
ranthene
Dibenzofluorene
Anthanthrene, Indenopyrene
Methyl Dibenzanthracene
Coronene
Dibenzochrysene Isomer
Anthrafluorene
Benzanthanthrene
Dibenzanthanthrene Isomer
Dibenzanthanthrene Isomer
m/e
178
202
226
228
240
242
252
266
276
292
300
302
316
326
350
376
Composition
C14H10
C16H10
C18H10
C18H12
C19H12
C19H14
C20H12
C21H14
C22H12
C23H16
C24H12
C24H14
C25H16
C26H14
C28H14
C30H16
IR showed evidence of no other functional group.
B-27
-------
F R-?fi. I RMS RFPORT—SAMPLE NO. C-TPD. IP. CUT 2
Intensity Category MW Range m/e Composition
Major Categories
10
100
100
100
Sub-Categories,
10
100
10
100
100
100
Fused Aromatics, MW <216 202
Fused Aromatics , MW >216 216-252
Aliphatics >279
Ketone/Ester/Ether >279
Specific Compounds
Phthalate Fragment 149
Pyrenes Fluoranthene 202
Methyl Pyrene 216
Benzofluoranthene Isomer 226
Benzanthracene, Chrysene 228
Benzopyrene, Benzofluo-
ranthene 252
C5H8°3
C16H10
C17H12
C18H10
C18H12
C20H12
Strong fragment peaks appear at the following masses: 55, 57, 70,
71, 83, 100, 101, 112, 129, 147, 241, 259, 279.
Other
Although IR does not indicate aromaticity, peaks at half mass units in
LRMS suggest presence of aromatic compounds.
B-28
-------
TABLE B-27. . LRMS REPORT—SAMPLE NO. C-TPD. 1C CUT 3
Intensity Category MW Range m/e Composition
Major Categories
100 Aliphatics to 602
100 Ketones/Ester/Ether to 602
Sub-Categories^ Specific Compounds
100 Long Chain Ketone/Ester or
Other 236
10 Long Chain Ketone/Ester or
Other 264
10 Long Chain Ketone/Ester or
Other 300
10 Long Chain Ketone/Ester or
Other 302
10 Long Chain Ketone/Ester or
Other 350
100 Long Chain Ketone/Ester or
Other 368
100 Long Chain Ketone/Ester or
Other 374
10-100 Fragment Peaks appear at the following masses:
313, 307, 279, 243, 167, 149, 129, 113, 112
100 Peaks appear in clusters 14 mass units apart from
m/e 466 to 602.
Other
No evidence of aromaticity.
B-29
-------
APPENDIX C
LC ANALYSIS REPORTS
Notice
The reader will notice that some of the data given in this appendix does
not match that given in the tables in the main body of the report.
The first block of data in the LC analysis reports gives the Total Sample,
Calculated; Total Sample; Amount Taken for LC; and the Amount Recovered after
LC. The second line, Total Sample, is the total amount of organic found in
the sample extracted and is corrected for amounts withdrawn for TCO, GRAV, and
preliminary IRs. It was necessary in some cases to calculate best estimate
Total Sample from this data for two reasons. In Tables C-6 and C-8, the
entire sample had not been extracted. Therefore, the Total Sample data was
multiplied by the ratio of Total Sample Collected to Amount of Sample Extracted
to obtain the calculated Total Sample. In Tables C-3, 5, 8, 15, 18, 19, and
20, corrections were made for errors in sample handling. For these samples
about 4 liters were filtered for suspended solids determinations. All of this
solid was extracted with methylene chloride and a TCO and GRAV determined.
Only 2 liters of the filtered water was extracted. The two extracts were
combined and fractionated. Obviously the sample fractionated contains a
higher proportion of organics from the solids than contained in the original
sample. Using the volumes of the samples filtered for solids determination,
the volume of filtered water extracted, the TCO and GRAV data for the solids
extraction, and the TCO and GRAV data for the combined samples (given in the
tables as Total Sample), a value for the TCO and GRAV was calculated that
represents the analysis that would have been obtained if the samples had been
combined properly. This value is given under Total Sampling, Calculated.
For these samples, the Total Sample, Calculated, value is used wherever
the total amount of organic in the sample is given. Although the numbers
obtained are not direct analytical data, they should be very close to the true
value and are certainly better than the numbers actually obtained by analysis.
The LC fractionation data given on the lower half of the LC analysis
report sheets are the actual data obtained in the analysis and are corrected
back to the Total Sample (not Total Sample, Calc.) where indicated. Where the
difference between Total Sample and Total Sample, Calc. is substantial
(Tables C-5, 8, 15, 18, and 19), the LC fraction concentration data was multi-
plied by the ratio of the two Total Sample concentrations before entering the
data into the Organic Summary Tables in the report.
-------
TABLE C- 1 . LC ANALYSIS REPORT, SAMPLE NO. A1X
Sample Site Plant A, FCE 1
Sample Acquisition Date 4/4/79
Type of Source FeMn, Undercover Combustion, Scrubber Stack Discharge
Test Number A-l Sample ID Number A1X
Sample Description XAD-2 Resin. Module Rinse, Condensate
Original Sample Volume or Mass 122.95 gms XAD-2. 1335 ma CHoC&o from Rinses. 126 mi M
Analyst Responsible J. Lvtle. C. Foust.. J. Lodge ,
Calculations and Report Reviewed by R. Handy, VI. Westbrook ,
Total Samples Calc.
2
Total Sample
Taken for LC3
4
Recovered
TCO
mg
31.8
GRAV
mg
61.0
15.9 30.5
28.2
34.1
TCO + GRAV
Total mg
92.8
46.1
62.3
Concentration
mg/ (m3, X, or X»)6
18.26 mg/m3
9.07
12.3 .
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
^i
e
03
5
in me
Corrected.
4.7
1.4
1.2
3.9
2.0
0.9
0
1
^
•u
o
9.4
2.8
2.4
7.8
4.0
1.8
0
28.2
Found In
Fraction
1 .3
1.2
18.6
4.0
2.2
4.2
3.4
34.9
GRAV
-£
0}
£3
0.8
0
0
0
0
0
0
in m
Corrected
0.5
1.2
18.6
4.0
2.2
4.?
3.4
34.1
9
«5
%
t—
1.0
2.4
37.2
8.0
4.4
8.4
6.8
68.2
>
< Ql
S*
4- ~
10.4
5.2
39.6
15.8
8.4
10.2
6.8
96.4
0 **
Concentrat1
3 mg/
(m , X, or
2.0
1.0
7.8
3.1
1.7
2.0
1.3
19.0
3.
Calculated total quantity in
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate
Quantity in entire sample,
determined before LC
5.
6.
C-2
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C- 2. LC ANALYSIS REPORT, SAMPLE NO. A1SWD
Sample Acquisition Date 4/4/79
Sample Site Plant A. FCE 1
Type of Source FeMn, Undercover Combustion, Scrubber Discharge Water
Test Number A1 Sample ID Number A1SWD
Sample Description Scrubber Discharge Hater, Venturi on Primary Emissions
Original Sample Volume or Mass 1962 ML
Analyst Responsible J. Natske, J. Lytle. C. Foust,
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC
A
Recovered
TCO
mg
0
*
0
*
0
GRAV
mg
22.0
15.0
6.0
TCO H- GRAV
Total mg
22.0
15.0
6.0
Concentration
mg/ OH?, L, or *)g)6
11.2 mq/£
7.6
3.1
Cone. TCO was zero before LC.
Fraction
1
2
3
4
5
6
7
Sum
C C
•i- O
•^
T3 4->
c u
3 03
O 1-
U_ LL.
TCO
.*:
c
ra
5
•
in me
Corrected
*-5
4->
O
0
0
0
0
0
0
0
0
Found in
Fraction
1.0
0.2
1.2
1.2
0.6
1.8
0.8
GRAV
^.
c
fO
CO
0.8
0
0
0
0
0
0
' in m
Corrected
0.2
0.2
1.2
1.2
0.6
1.8
0.8
6.0
g
*5
4-1
O
1—
0.3
0.3
1.8
1.8
0.9
2.6
1.2
. 8.9
< Cft
C£. =
O
+ 'fl
4-1
O 0
<_> 1—
1—
0.3
0.3
1.8
1.8
0.9
2.6
1.2
8.9
U3
§ s
4-1 i.
ft} ^ O
S- CT
4-> £ -
C _i
OJ
-------
TABLE C-3 . LC ANALYSIS REPORT, SAMPLE NO. A-PE
Sample Site Plant A
Sample Acquisition Date 4/5/79
Type of Source Ferroalloy. FeMn, SiMn, Electrolytic Cr
Test Number A Sample ID Number A-Pi
Sample Description Plant Final Discharge. Aqueous
Original Sample Volume or Mass 2000 ML
Analyst Responsible J. Natske, C. Foust. J. Lytle
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC
4
Recovered
TCO
mg
0
0
0
0
6RAV
mg
13.3
16.0
13.6
37.0
TCO H- GRAY
Total mg
13.3
16.0
13.6
37.0
Concentration
mg/ ^3, L, or K8)6
6.65 mgA
8.0 mg/£
6 . 8 mg A
18.5 mgA
Fraction
1
2
3
4
5
6
7
Sum
Found 1n
Fraction
TCO
c
a
03
in me
Corrected,
1
o
0
Found in
Fraction
0
0.4
34.6*
0.6
0
1.0
0.4
GRAV
«:
0.8
0
0
0
0
0
0
in m
Corrected
0
0.4
34.6
0.6
0
1.0
0.4
37.0
g
o
0
0.5
40.7
0.7
0
1.2
0.5
43.6
i—
4- «3
4-3
O 0
i—
0
0.5
40.7
0.7
0
1.2
0.5
43.6
1C
c >&>
O ^f
4J e
C _1
0)
{^ **
C P9<
^3 >«£*'
-------
TABLE C-4 . LC ANALYSIS REPORT, SAMPLE NO. A2-X
Sample Site Plant A
Sample Acquisition Date 4/5/79
Type of Source FeMn, Open Furnace, Scrubber Stack Discharge
Test Number A2 Sample ID Number A2-X
Sample Description XAD-2 Resin. Module Rinse
Original Sample Volume or Mass 123.3 gms XAD-2. 865 ma Module Rinse
Analyst Responsible J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
A
Recovered
TCO
mg
32.1
16.1
33.8
GRAV
mg
151.0
75.5
49.5
TCO + GRAV
Total mg
183.1
91.6
83.3
Concentration
mg/ (m3, X, or K»)6
22.14 mg/m3
11.1
10.1
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
-*
c
0
5.4
1.4
3.0
9.8
8.2
6.0
0
33.8
Found in
Fraction
2.3
23.0
2.2
1-.6
0.6
14.6
6.0
GRAV
.^
c
«
m
0.8
0
0
o
0
0
0
' in m
Corrected
1 .5
23.0
2.2
1,6
0.6
14.6
6.6
49.5
T
*5
-M
O
3.0
46.0
4.4
3.2
1 .2
29.2
12.0
99.0
>
rf- CTi
2 i
CJ
+ 'n
4->
O 0
^
8.4
47.4
7.4
13.0
9.4
35.2
12.0
132.8
vo_^
C >ff>
O 2K
Concentrat
3 mg/
(m , K, or
1.0
5.7
0.9
1.6
1 .1
4.3
1.5
16.1
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 5.
C-5
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C- 5. LC ANALYSIS REPORT, SAMPLE NO. A2-SWD
Sample Site Plant A
Sample Acquisition Date 4/5/79
Type of Source FeMn, Open Furnace. Scrubber Water Discharge
Test Number A-2 Sample ID Number A2-SWD
Sample Description Discharge Water from Flooded Disc Venturi __
Original Sample Volume or Mass 2000 ma Extracted, 7745 ma Total for Solids
Analyst Responsible J. Natske. C. Foust. J. L.ytle
Calculations and Report Reviewed by
R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
0.4
1.0
0.7
0.7
GRAV
mg
27.8
69.0
44.9
43.1
TCO + GRAV
Total mg
28.2
70.0
45.6
43.8
Concentration
mg/ (W?, L, or X$)6
14.1 mg/x,
35.0
27.8
26.9 .
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
c
re
5
in me
Corrected.
0.5
0.2
n
n
n
n
n
0,7
o
t—
0.8
0.3
0
0
n
0
0
1,1
Found in
Fraction
11 .3
12.4
9.4
4.0
2.4
2 8
1 .6
GRAV
c
0.8
0
o
n
n
o
0
in m
•
Corrected
10.5
12.4
9.4
4.0
2.4
2 8
1 .6
43,1
g
o
16.1
19.0
14.4
fi 1
3 7
4 3
2.5
66.1
Ct £i
CD
o "o
1—
16.9
19.3
14.4
6.1
3 7
4 3
2.5
67,2
o ^>
i. 01
c _i
0)
8.5
9.6
7.2
3.1
1 .8
2 2
1 .3
38.6
Calculated total quantity 1n
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate
Quantity in entire sample,
determined before LC
3.
5.
6.
C-6
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C- 6. LC ANALYSIS REPORT, SAMPLE NO. Bl-PW
Sample Site Plant B
Sample Acquisition Date 4/25/79
Type of Source 50% FeSi, Open Furnace, Stack before Emission Control
Test Number B-1 Sample ID Number Bl-PW
Sample Description SASS System Probe Wash
Original Sample Volume or Mass 3.733 gms - 2.8097 Extracted
Analyst Responsible J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
A
Recovered
TCO
mg
-
-
-
GRAV
mg
95.7
72.0
48.0
16.1
TCO + GRAV
Total mg
95.7
72.0
48.0
16.1
Concentration
mg/ (m , K, or KH)
7.18 mg/m3
5.41
3.6
1.2
Fraction
1
2
3
4
5
6
7
Sum
c c
•<- o
«^-
•o -w
s o
3 03
0 S-
U- U_
TCO
.*
c
«
03
in me
Corrected
1
&
•M
O
c c
•<- 0
T3 ^M
C U
3 (Q
0 S-
LL. U.
1.3
0.4
0.4
3.0
1 .6
9.8
0.4
GRAV
.*
c
< O>
ex £
O
+ (0
4->
O O
0 f-
1.0
0.8
0.8
6.0
3.2
19.6
0.8
32.2
U3
c >sr>
o ^c
Concentrat
3 mg/
(m , K, or
0.1
0.06
0.06
0.45
0.24
1.47
0.06
2.4
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 5.
r-7
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-7 . LC ANALYSIS REPORT, SAMPLE NO. Bl-X
Sample Site Plant B
Type of Source
Test Number B-l
Sample Acquisition Date 4/?5/79
50% FeSi. Open Furnace. Stack before Emission Control
Sample ID Number Ri-x
Sample Description XAD-2 Resin and Module Rinse
Original Sample Volume or Mass 85.32 gms XAD-2. 340 m Module Rinse
Analyst Responsible J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
84'. 0
25.2
19.9
GRAV
mg
274.0
82.2
33.8
TCO + GRAV
Total mg
358.0
170.4
53.7
Concentration
mg/ (m3,XK, orXft*)6
26.87mgY:nd
12.8
4.0
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
.^
c
«3
S
in me
Corrected.
9.4
2.7
3.0
1.5
3,1
0.?
0
19.9
•55
4->
0
31.3
9.0
10.0
5.0
10.3
0.7
0
66.3
Found in
Fraction
3.0
7.4
13.4
3.2
1.8
3.0
2.8
GRAV
.^
e
(T3
ca
0.8
0
0
0
0
0
0
in m
Corrected
2.2
7.4
13.4
3.2
1.8
3.0
2.8
33.8
g
.5
•u
o
1—
7.3
24.7
44.7
10.7
6.0
10.0
9.3
112.7
>
§*
+ 15
J->
0 0
O h-
38.6
33.7
54.7
15.7
16.3
10.7
9.3
179.0
<*o
§ 5
Concentrati
3 mg/
(m , 1, or
2.9
2.5
4.1
1.2 .
1.2
0.8
0.7
13.4
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6.
C-8
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-8 . LC ANALYSIS REPORT, SAMPLE NO. B2-PART
Sample Site Plant B
Sample Acquisition Date 5/1/79
Type of Source 50% FeSi, Mix-sealed Furnace, Stack Discharge after Venturi
Test Number B2 Sample ID Number B2-PART
Sample Description Probe Wash and Particle Filters (No Cylcones Used)
Original Sample Volume or Mass 0.4933 gms in Probe Wash, 3.0903 gms on filters
Analyst Responsible 0.4933 gm PH, 2.1823 gms Filter Extracted. J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
A
Recovered '
TCO
mg
0
0
0
8.8
GRAV
mg
1366
1020
51.0
27.4
TCO + GRAV
Total mg
1366
1020
51.0
36.2
Concentration
mg/ (m3, K, or W)6
94.85 mg/m3
70.8
3.5
2.5 .
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
.*
c
1C
S
in me
Corrected
6.3
0-5
1.2
0.8
0
0
0
8.8
1
^
.<->
o
1—
126
10.0
24.0
16.0
0
0
0
176
Found in
Fraction
0
1.4
15.2
5.6
1.2
3.8
0.2
GRAV
1
CQ
0.8
0
0
0
0
0
0
in m
Corrected
0
1.4
15.2
5.6
1.2
3.8
0.2
27.4
g
«5
••->
o •
h-
0
28
304
112
24
76
4.0
548
>
-------
TABLE C-9 . LC ANALYSIS-REPORT, SAMPLE NO. B2-X
B
Sample Acquisition Date 5/1/79
Sample Site _
Type of Source 50% FeSi, Mix-sealed Furnace, Stack Discharge after Venturi
Test Number B-2 Sample ID Number B2-X
Sample Description XAD-2 Resin. Module Rinse. Condensate
Original Sample Volume or Mass 99.29 gms XAD-2. 690 m& CHgCAg, 175 m£ H?0
Analyst Responsible J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy, W. Hestbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
7700
231
412.5
GRAV
mg
2720
81.6
7.4
TCO + GRAV
Total mg
10,420
312.6
419.9
Concentration
mg/ (m3, K, or Xg)6
723.5 mg/m3
21.7
29.1 .
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
-^
c
*
r»-
03
in mg
Corrected
302
6.6.,?
35,3
5,5
3,3
o,p
0
n?.5
«5
4-1
O
0.067
2.207
1.177
183.3
no
6.7
0
13.751
Found in
Fraction
n
2.6
i.n
O.R
0.6
1.8
0.6
GRAV
.*
c
CCL =
CD
•+• '(O
4-)
O 0
<_3 1—
1—
in nfi7
?3?Q?.
i n?in.
?in
nn
fifi
?n
?QQ?
U3
c :BD
o »<
Concentrati
3 mg/
(m , K, or
fiQQ n
7 IRQ 1
i P4 n
14 6
Q o
7 a. fi
n i
-------
TABLE C-10. LC ANALYSIS REPORT, SAMPLE NO. B2-K
Sample Site Plant B
Type of Source
Test Number
Sample Acquisition Date 5/1/79
50% FeSi Mix-sealed Furnace
B-2
Sample ID Number B2-K
Sample Description Kerosene, Injected to Scrubber Blower (Entrained in Stack)
Original Sample Volume or Mass 1 liter, Analysis is for 2 ma
Analyst Responsible J. Lodge. J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample , mg/mfc
Taken for LC3
4
Recovered
TCO
mg
663
331.5
402.4
GRAV
mg
109.4
54.7
0
TCO + GRAV
Total mg
772.4
386.2
402.4
Concentration
mg/ (m , L, or kg)
-
Suspected Error
Fraction
1
2
0
4
5
6
7
Sum
Found in
Fraction
TCO
.*
c
03
03
in me
Corrected
362.5
28.2
5.7
4.7
1.2
0.1
0
402.4
!
^
4->
0
725.0
56.4
11.4
9.4
2.4
0.2
0
804.8
Found in
Fraction
0
0
0
0
0
0
0
0
GRAV
.*:
c
«
0.8
0
0
o
0
0
0
in m
Corrected
0
0
0
0
0
0
0
0
g
«5
4_>
O
t—
0
0
0
0
0
0
0
0
>
rf" CTi
£ £
O
•+• «
•M
0 0
0 H-
h-
/Zb.U
56.4
11.4
9.4
2.4
0.2
0
804.8
1C
c "a»
O -*
Concentrat
3 nig/
(m , L, or
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5
Quantity in entire sample,
determined before LC 5.
c-n
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-ll. LC ANALYSIS REPORT, SAMPLE NO. B2-SWD
Sample Site Plant B
Sample Acquisition Date 5/1/79
Type of Source 50% FeSi. Mix-Sealed Furnace, Scrubber Hater Discharge
Test Number B2 Sample ID Number B2-SWD
Sample Description Scrubber Hater from Primary Emission Control
Original Sample Volume or Mass 2000 ma Extracted, 3982 ma for Solids
Analyst Responsible J. Natske, J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, N. Westbrook
Total Sample, Calc.
2
Total Sample
Taken for LC
4
Recovered
TCO
mg
183
18.3
14.3
GRAV
mg
919
91.9
98.7
TCO + GRAV
Total mg
1,102,
110.2
113.0
Concentration
mg/ ($, L, or B$*6
551 .0 mg/fc
55.1
56.5
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
-*
c
«3
s
in me
Corrected
5.0
1,7
0,3
1,P
?,?
3,9
0
14-3
^5
4-1
£
50.0
17
3
12
22
39
0
143
Found in
Fraction
22.5
25
?4.?
13.8
3.8
8.6
1.6
GRAV
.^
c
03
S
0.8
0
0
0
0
0
0
in m
Corrected
21.7
25.0
?4.?
13.8
? R
8 fi
1 6
98.7
g
•=5
3
i—
217
250
242
138
38
86
16
987
>
%*
•+• 'fl
•M
O 0
O 1—
1—
267
267
245
•150
60
125
16
1130
W3
c *5
O JC
•M S-
fl •*•» o
i. C1
-M S -
C _J
0)
(J J.
C fX
0 »S
u >«*•
133.5
133.5
122.5
75
30
62.5
8
565
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6.
C-12
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-T2.' LC ANALYSIS REPORT, SAMPLE NO. B-PE
Sample Site Plant B
Sample Acquisition Date 5/1/79
Type of Source Ferroalloy. 50% FeSi, CaC
Test Number
B
Sample ID Number B-PE
Sample Description Plant Final Effluent
Original Sample Volume or Mass 2000 m Extracted, 3983 m for Solids
Analyst Responsible J. Natske, J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
3.0
2.6
0.9
GRAV
mg
21.0
17.9
10.6
TCO + GRAV
Total mg
24.0
20.5
11.5
Concentration
mg/ (Jj3, L, or Kg)6
12 mg/i
10.3
5.8
t
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
c
m
in me
Corrected
n "\
n
n
n
n
n.fi
0
0 9
o
n 4
n
n
n
n
n.7
n
i i
Found in
Fraction
n R
n
? 9
i R
n fi
4 4
n fi
GRAV
c
03
03
n R
n
n
n
n
n
n
in m
Corrected
n
n
1 9
1 R
n fi
4 4
n fi
g
4-1
O
1—
n
n
1 R
9 1
n 7
R 9
n 7
19 R
^
3. £
0
O 0
<_> i—
t—
n 4
n
"} R
? i
n 7
•i 9
n 7
i? fi
c >ijn
o -»
•*-> i.
^ "^s. O 1
S- CT>
•ME" I
c _i !
Ol
o
C c^^
o >S
n ?
n
1 Q
i n^
n ^R
? QR
n ?R
fi R
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined oefore LC 6.
C-13
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-13. LC ANALYSIS-REPORT, SAMPLE NO. Cl-PART
Sample Site Plant C
Sample Acquisition Date 6/13/79
Type of Source 75% FeSi Mix-sealed Furnace, Stack after Scrubbers
Test Number C-l Sample ID Number Cl-PART
Sample Description Probe Rinse, Filters, and Cyclones
Original Sample Volume or Mass 16.2946 gms Solids
Analyst Responsible J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy. W. Hestbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
13.2
2.0
0.6
GRAV
mg
443.0
66.5
51.0
TCO + GRAV
Total mg
456.2
68.5
51.6
Concentration
mg/ (m, K, or K8)
23.1 mg/m3
3.5
2.6
i
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
.*
c
(d
CD
in me
Corrected.
0.4
U.2
0
0
0
0
0
0.6
!
«-5
-M
o
h—
2.7
1.3
0
0
0
0
0
4.0
Found in
Fraction
0.8
3.8
17.4
10.4
6.6
11.4
1.4
GRAV
.*:
c
fl
r—
CO
0.8
0
0
0
0
0
0
in m
Corrected
0
3.8
17.4
10.4
6.6
11 4
1.4
51.0
g
*s
•M
o
0
25.3
116.0
69.3
44.0
76.0
9.3
339.9
rf" m
5 S"
SC £
«J
+ 13
=W
0 0
<_3 t—
1—
2.7
26.6
116.0
69.3
44.0
76.0
9.3
343.9
U3
§ 5
Concentrati
3 nig/
(m , X, or
0.14
1.3
5.9
3.5
2.2
3.8
0.5
17.4
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 5.
C-14
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-14. LC ANALYSIS REPORT, SAMPLE NO. Cl-X
Sample Site Plant C
Sample Acquisition Date 6/13/79
Type of Source 75% FeSi Mix-sealed Furnace. Stack Discharge after Scrubber
Test Number C-1 _ Sample ID Number Cl-X _
Sample Description XAD-2 Resin, Module Rinse and Condensate
Original Sample Volume or Mass 83.5 gms XAD-2. 2151 mi CH0C^^. 2499 ma FLO
Analyst Responsible J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
5570
44.6
GRAV
mg
3600
28.8
59.21 18.4
TCO + GRAV
Total mg
9170
73.4
77.6
Concentration
mg/ (m3, U or &C)6
464.3 mg/m3
3.7
3.9
Fraction
1
2
3
4
5
6
7
Sum
TCO in mg
Found in
Fraction
a.
c
ra
s
Corrected
41.5
9.4
0.9
3.0
1.4
^5
4-1
o
(—
5.188.0
1.175.0
GRAV in mg
Found in
Fraction
1.0
3.4
112.5 4.0
375. 0! 1.8
175.0! 1.4
-*
c
03
S
0.8
0
n
0
n
3.0l 375.0 ! 6.8 i 0
0
0 1 0.8 0
Corrected
0.2
3.4
4.n
1 8
1 4
fi.fi
0.8
*5
+j
o
'<—
25. n
d?R.n
c;nn n
??R n
17^ n
RRn.n
inn.n
59.217.400.5 ! lia.4 pr3nn.n
li
0
-f- "to
4->
O 0
0 1—
Concentration
o nig/ fi
(ni ,XK, or K#)°
cL?~n n ?R4.n
ijfinn n si n !
fii? * TI n
finn d "?n 4
?Rn n 17 7
•\}??c, n F.9 n
inn d t; i
q,7nn ^ dQi ?
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6.
C-15
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-15. LC ANALYSIS-REPORT, SAMPLE NO. Cl-SWD
Sample Site Plant C
Sample Acquisition Date 6/13/79
Type of Source 75% FeSi, Mix-sealed Furnace, Scrubber Discharge Water
Test Number _C-1 Sample ID Number Cl-SWD
Sample Description Hater Discharged from Scrubber on Primary Emission
Original Sample Volume or Mass 2000 ma Extracted, 3305 ml, for Solids
Analyst Responsible J. Natske. J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
2
Total Sample
Taken for LC3
4
Recovered
TCO
mg
45.0
74.3
18.6
11.4
GRAV
mg
222.7
368.0
92.0
115.1
TCO + GRAV
Total mg
267.7
442.3
110.6
126.5
Concentration
mg/ (i$, L, or P$)6
133.9 mg/£
221.1
55.3
63.3 .
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
rQ
S
in me
Corrected.
3.3
1.5
0.9
1.8
3.7
0.2
0
1.4
-M
0
13.7
6.0
3.6
7.2
14.8
0.8
0
45.6
Found in
Fraction
16.5
19.8
38.6
17.0
9.2
12.4
2.4
GRAV
C
en
0.8
0
o.
0
0
0
0
in m
Corrected
15.7
19.8
38.6
17. C
9.?
12.4
2.4
115.1
g
55
o
1—
62.8
79.2
154.4
68.0
36.8
49.6
9.6
460.4
as E
0
•+> *«
o o
t—
76.0
85.2
158.0
75.2
51.6
50.4
9.6
506.0
s'i
«3 -*^ O
S- CD
•*-"£"
C _J
0)
38
42.6
79.0
37.6
25.8
25.2
4.8
253.0
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 5.
C-16
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-16. LC ANALYSIS REPORT, SAMPLE NO. C2-PART
Sample Site Plant C Sample Acquisition Date 6/19/79
Type of Source 50% FeSi. Mix-sealed Furnace, Scrubber Discharge Stack
Test Number C-2 Sample ID Number C2-PART
Sample Description Probe Wash. Filters, and Cyclones
Original Sample Volume or Mass 14.8282 gms
Analyst Responsible J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy, W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
4.7
1.4
2.2
GRAV
mg
280.0
84.0
70.6
TCO H- GRAV
Total mg
284.7
85.4
72.8
Concentration
mg/ (m3, 1, or K)g)6
23.8 mg/m3
7.2
6.1.
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
C
CD
in me
Corrected
i n
—
n
0 1
i i
n
n
2 2
0
1—
3 3
-
n
0 3
3 7
n
0
7.3
Found in
Fraction
8 0
7 4
28.6
1& 4
8 0
3 4
0.6
GRAV
C
ra
/-n
0 8
0
0
0
n
n
0
in m
Corrected
7.2
7.4
28.6
15 4
8.0
3.4
0.6
g
0
t—
24.1
24.7
95.3
51 .3
26.7
11.3
2.0
235.4
__,
St. £
-M
O 0
o H—
*~
27.4
24.7
95.3
51 .3
30.4
11.3
2.n
242.7
o a*
Concentrat
3 mg/
(m , K, or
2.3
2.1
s.n
4.3
?.5
n.9
n.2
20.3
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 5.
C-17
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-17. LC ANALYSIS-REPORT, SAMPLE NO. C2-X
Sample Site Plant C
Sample Acquisition Date 6/19/79
Type of Source 50% FeSi. Mix-sealed Furnace, Scrubber Discharge Stack
Test Number C-2 Sample ID Number C2-X
Sample Description XAD-2 Resin. Module Rinse, Condensate
Original Sample Volume or Mass 95.69 gms XAD, 1650 ma CH2C£?> 1010 m£ HgO
Analyst Responsible J. Lytle, C. Foust
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
2
Total Sample
Taken for LC3
4,
Recovered
TCO
mg
552.0
13.2
119.4
GRAV
mg
1500
36.0
11.6
TCO + GRAV
Total mg
2052
49.2
131.0
Concentration
mg/ (m , £s or $6)
171.8 mg/m3
4.1
ll.Q
i
Fraction
2
3
4
5
6
7
Sum
TCO in mg
Found in
Fraction
^
c
«=C CTl
C£. &
U3
H- 15
-t->
0 0
0 1—
Concentration
o mg/ fi
(mj, JL, or)(^)b
83.3 13.483.3 PQl.fi
208.3
66.7
33.3
16.7
50. n
25.0
11.6! 483.3
641 fi W 7
PR qi R n
d^ Ri 1 R
Ifi 7! Id
Rd ?i 4 R
?R_nl ? i
djSfiP.Rl ^^ ^J
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
C-18
-------
TABLE C-18. LC ANALYSIS REPORT, SAMPLE NO. C2-SWD
Sample Site Plant C
Sample Acquisition Date 6/19/79
Type of Source 50% FeSi Mix-sealed Furnace, Scrubber Discharge Water
Test Number C-2 Sample ID Number C2-SWD
Sample Description Scrubber Water Discharge, Primary Emission Control
Original Sample Volume or Mass 2000 ma Water Extracted, 3900 rru for Solids
Analyst Responsible J. Natske, J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
8.5
16.6
5.0
5.7
GRAV
mg
133.8
261.0
78.3
80.4
TCO + GRAV
Total mg
142.3
277.6
83.3
86.1
Concentration
mg/ (rf, L, or X$)6
71.1 mg/a
138.8
41.7
43.1
Fraction
1
2
3
4
5
6
7
Sum
Found In
Fraction
TCO
^.
c
O
1—
1 .3
3.3
12.0
0
2.3
0
0
18.9
Found 1n
Fraction
2.0
1.0
54.4
13.8
4 8
1.8
3.4
GRAV
•£
fO
S
0.8
0
o
0
n
0
0
in m
Corrected
1 .2
1 .0
54.4
13.8
4.8
1 .8
3.4
g
r-5
03
4->
0
1—
4.0
3.3
181.3
46.0
16.0
6.0
11.3
267.9
>
< C7>
G£ £
O
+ fO
+->
O 0
^
5.3
6.6
193.3
46. C
18.'
6.C
n.:
286.?
U3 ]
C «i
0 aX
— ' V.
TJ — . O
i. CT i
^£J i
<
3 S
. 2.651
3.3
96.65
23. n
9.15
3.0
! 5.65
3 143.4
1. Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5
2. Quantity in entire sample,
determined before LC 5.
C-19
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample si;e
and concentrations
-------
TABLE C-19. LC ANALYSIS REPORT, SAMPLE NO. C-P50
Sample Site Plant C
Sample Acquisition Date 6/19/79
Type of Source
Test Number C
50-75% FeSi, Mix-sealed Furnaces, Wastewater
Sample ID Number C-P50
Sample Description Partially Chlorinated Scrubber Discharge Waters
Original Sample Volume or Mass 2000 mi, Water Extracted, 3873 ma for Solids
Analyst Responsible J. Natske. J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy, VI. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC3
4
Recovered
TCO
mg
22.6
43.8
13.1
11.6
GRAV
mg
139.4
270.0
81.0
90.2
TCO + GRAV
Total mg
162.0
313.8
94.1
101.8
Concentration
mg/ (aril, L, or Kg)6
81 mg/£
156.9
47.1
50.9 '
Fraction
1
2
3
4
5
6
7
Sum
Found in
Fraction
TCO
.^
c
(9
03
in me
Corrected
1 3
3,4
1,?
0,9
1 8
3,0
0
11 6
1
•5*
4-1
O
1—
4.3
11.3
4.0
3.0
6.0
10.0
0
38.6
Found in
Fraction
7.0
9.4
41.8
10.4
7.2
14.2
1.0
GRAV
.^
c
a
5
0 8
n
0
n
n
0
0
in m
Corrected
6 2
Q.4
dl .R
in.d
7 ?
14.2
1 .0
90,?
g
•=5
4->
O
20 5
31 .3
1 3Q 3
34.7
24 0
47.3
3 3
ann.fi..
>
3E
p- «•
+ a
•M
0 0
O 1—
25 CL
d? fi
Id3 3
37 7
3D n
57 3
33
33Q ?
U3
•iJ ^
« ^>« O
s- en
•M £ -
C _J
OJ
O "
1 "S
1 ? R
?1 3
71 fie;
1ft RR
15
?R fi^
1 fiR
IfiQ fi
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6.
C-20
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
TABLE C-2Q LC ANALYSIS REPORT, SAMPLE NO. C-TPD
Sample Site Plant C
Sample Acquisition Date 6/19/79
Type of Source 50-75% FeSi. Mix-sealed Furnaces
Test Number C
Sample ID Number C-TPD
Sample Description Treated (Chlorination + Settling) Process Discharge Hater
Original Sample Volume or Mass 2000 ma Water Extracted, 37Q5 mi for Solids
Analyst Responsible J. Natske. J. Lytle. C. Foust
Calculations and Report Reviewed by R. Handy. W. Westbrook
Total Sample, Calc.
Total Sample
Taken for LC
4
Recovered
TCO
mg
4.5
5.5
4.7
2.8
GRAV
mg
11.5
14.0
11.9
11.8
TCO + GRAV
Total mg
16.0
19.5
16.6
14.6
Concentration
mg/ OW3, L, orM6
8.0 mg/i
9.75
8.3
7.3
Fraction
1
2
3
4
5
6-
7
Sum
Found in
Fraction
TCO
.*
• c
it3
S
in me
Corrected.
0.3
q
1.4
0
0.6
0.5
0
2.8
!
«-5
-i->
o
0.4
0
1.6
0
0.7
0.6
0
3.3
Found in
Fraction
0.5
0.4
1 .4
1.8
0.6
6.8
0.8
GRAV
^.
c
fO
a
0,8
0
o
0
0
0
0
in m
Corrected
0
0.4
1.4
1.8
0.6
6.8
0.8
11.8
g
«s
+->
0
_Q_
0.5
1.6
2.1
0.7
8.0
0.9
13.8
>
0 0
0 I—
1—
0.4
0.5
3.?
?.l
1 .4
R.fi
o.q
17.1
U3
C >*
O 3&
*-> W
iT3 ^ O
i~ CT
4-> £ -
C _l
OJ
U
C C*K
o sg
u -^
n.?
0.?5
i .fi
1 .05
n.7
4.3
0.45
! 8.55
Calculated total quantity in 3.
original sample correcting
for amounts withdrawn for TCO, 4.
GRAV and error in water sample
analysis, where appropriate 5.
Quantity in entire sample,
determined before LC 6.
C-21
Portion of whole sample used
for LC, actual mg
Quantity recovered from LC column,
actual mg
Total mg computed back to total
sample
Supply values for both sample size
and concentrations
-------
APPENDIX D
SPARK SOURCE MASS SPECTROGRAPH ORIGINAL DATA
-------
Reply to
COMMERCIAL TESTING & ENGINEERING CO.
GENERAL OFFICES: 228 NORTH LA SALLE STREET, CHICAGO, ILLINOIS 60601 • AREA CODE 3t2 726-8434
INSTRUMENTAL ANALYSIS DIVISION. 490 ORCHARD STREET, GOLDEN, COLORADO 80401, PHONE: 303-278-9521
To: Mr. Kenneth H. Davis, Jr.
Chemistry and Life Sciences Div.
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
Date: October 4, 1979
Analyst: J. Oldham
P n Wn
P.O. No.:
Sample No.: #]_
pfiot 6 **<•'<>*
IAD No.: 97-D198-087-04
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
. Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
CONC.
1°-6
8
45
MC
14
NR
4
74
MC
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
22
860
0.2
MC
>900
MC
>450
MC
MC
>73
MC
>190
MC
NR
NR
NR
15
0.3
23
NR
NR - Not Reported
All elements not detected <
MC — Major Component
INT — Interference
0.1
Approved:
-------
Reply to
COMMERCIAL TESTING & ENGINEERING CO.
GENERAL OFFICES: 338 NORTH LA SALLE STREET, CHICAGO, ILLINOIS 80801 • AREA CODE 313 736-8434
INSTRUMENTAL ANALYSIS DIVISION, 490 ORCHARD STREET, GOLDEN, COLORADO 80401, PHONE: 303-278-9521
To: Mr. Kenneth H. Davis, Jr.
Chemistry and Life Sciences Di
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 277
ft*.#A>#C 6 Si ~ 1
P. O. NO.. SfiSS CyfLC^P/tXt'Cut./
Sample No.: #2
,2k
09
#*£, > 3 «
»;<*.«
Date: October 4, 1979
Analyst: J. Oldham
IAD No.: 97-D198-087-04
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmi urn
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
CONC.
1
8
25
MC
3
NR
3
0.9
<0.1
0.8
0.2
2
2
4
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
i
CONC.
<0.6
<2
0.9
4
*8
17
*MC
76
MC
2
15 •
12
140
290
STD
210
130
^Heteroae
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttri urn
Strontium
Rubidium
Bromi ne
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
?neous
CONC.
81
4
19
6
MC
28
50
22
120
16
*240
MC
MC
670
1
MC
>740
MC
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
24
340
1
MC
>890
540
>450
MC
MC
>72
MC
>180
=640
NR
NR
NR
5
<0.1
2
NR
STD — Internal Standard
NR — Not Reported
All elements not detected <
0.1 PPm
D-3
Approved:
-------
Reply to
COMMERCIAL TESTING & ENGINEERING CO.
GENERAL OFFICES: 228 NORTH LA SALLE STREET, CHICAGO, ILLINOIS 60601 • AREA CODE 312 728-8434
INSTRUMENTAL ANALYSIS DIVISION, 490 ORCHARD STREET, GOLDEN, COLORADO 80401, PHONE: 303-278-9521
To: Mr. Kenneth H. Davis, Jr.
Chemistry and Life Sciences Div.
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
P. O, No.: SJss CycJ.e#£ +
Sample No.: #3
Date: October 4, 1979
Analyst: J. Old ham
^ < 3
IAD No.: 97-D298-087-04
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
Uranium <0.9
Thorium <1
Bismuth 76
Lead MC
Thallium 3
Mercury NR
Gold
Platinum
Iridium
Osmi urn
Rhenium
Tungsten 3
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
CTrt I^.AA___| Pi 1 1
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
•Tin
Indium
Cadmium
Silver
Palladium
Rhodi um
CONC.
0.4
0.2
0.6
0.3
0.3
7
3
530
8
5
23
380
MC
STD
90
23
D24
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttri um
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
34
0.5
0.8
0.4
490
110
47
38
MC
220
410
MC
MC
13
<0.1
MC
MC
930
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryl 1 i um
Lithium
Hydrogen
CONC.
4
MC
±0.1
MC
MC
MC
>760
MC
MC
>122
MC
>310
=960
NR
NR
NR
29
<0.1
17
NR
NR — Not Reported
All elements not detected <
MC — Major Component
INT — Interference
0.1 ppm
Approved:
-------
Reply to
COMMERCIAL TESTING & ENGINEERING CO.
GENERAL OFFICES: 238 NORTH LA SALLE STREET, CHICAGO, ILLINOIS 80601 • AREA CODE 31S 7S6-8434
INSTRUMENTAL ANALYSIS DIVISION, 490 ORCHARD STREET, GOLDEN, COLORADO 80401, PHONE: 303-278-9521
To: Mr. Kenneth A. Davis, Jr. ^C\
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, N.C. 27709
/^a.rt/i//tc
P. O. No.: 6925
Sample No.: #4 Liquid
* £- U* /
c /i? """ *
"•"oG^a^A,*
k
'•OB
Ss-
Date: October 17, 1979
Analyst: J. Qldham
IAD No.: 97-D198-087-04
CONCENTRATION IN yg/ml
ELEMENT CONC.
Uranium <4
Thorium <5
Bismuth
Lead 46
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
ELEMENT CONC.
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymium
Cerium
Lanthanum
Barium 170
Cesium
Iodine
Tellurium
Antimony
Tin * 57
Indium STD
Cadmium f.2
Silver 26
Palladium
Rhodium
*Heterogeneous D-5
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC. ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
5 Chlorine
0.5 Sulfur
54 Phosphorus
Silicon
Aluminum
Magnesium
Sodium
MC Fluorine
MC ' Oxygen
12 Nitrogen
<_1 Carbon
* MC Boron
* MC Beryllium
0.3 Lithium
Hydrogen
CONC.
MC
<0.7
MC
MC
MC
MC
MC
* MC
>630
29
MC
NR
NR
NR
4
NR
STD — Internal Standard
NR - Not Reported
All elements not detected <
MC — Major Component
INT — Interference
0.5
/n it
Approved:///^
-------
COMMERCIAL TESTING & ENGINEERING CO.
GENERAL OFFICES: 998 NORTH LA SALLE STREET, CHICAGO, ILLINOIS 80801 • AREA CODE 318 738-8434
Reply tO INSTRUMENTAL ANALYSIS DIVISION, 490 ORCHARD STREET, GOLDEN, COLORADO 80401, PHONE: 303-278-9521
To: Mr. Kenneth A. Davis, Jr. f
Research Triangle Institute Jfm
P.O. Box 12194
Research Triangle Park, N.C. 27709
fa.qj'j-ce ^3- 1
6/9 S5 fitiS? //^ /»/><£ ^/f et-T^tfi
P O. No.: 6925 ^Sa
Sample No.: #4 Solid
ELEMENT CONC.
Uranium • <5
Thorium <6
Bismuth
Lead 13
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmi urn
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
t-'VS foU.fvt) ''*> /s*ffV&CSS.
CONCENTRATION
ELEMENT CONC.
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymi urn
Cerium
Lanthanum
Barium 74
Cesium
Iodine ' 8
Tellurium
Antimony
Tin 160
Indium STD
Cadmium
Silver 72
Palladium
Rhodi urn
D-6
Ik
Date: October 17, 1979
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-81-038
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE Level ^ Environmental Assessment of
Electric Submerged-Arc Furnaces Producing Ferro-
alloys
5. REPORT DATE
March 1981
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
C.W. Westbrook and D. P. Daugherty
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
CAHA1B and CBGB1C
11. CONTRACT/GRANT NO.
68-02-2630, Task 4
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 6/78-12/80
14. SPONSORING AGENCY CODE
EPA/600/13
15.SUPPLEMENTARY NOTES IERL-RTP project officer is Robert C. McCrillis, Mail Drop 62,
919/541-2733.
16. ABSTRACT
The report gives results of an EPA/IERL-RTP Level 1 multimedia environ-
mental assessment of the ferroalloy industry. It contains general industry statistics
and results of sampling and analysis at three plants (six furnaces total). It indicates
that the potential for serious environmental problems exists in some segments of the
industry, but it does not prove that the pollution problems are occurring. Specifi-
cally, the pollution potential for covered (mix-sealed and sealed) furnaces is sub-
stantially higher than for open furnaces, primarily due to the high concentration of
organics in gases generated by the former. Covered furnaces generate polycyclic
organic material (POM) at the rate of about 1,230-11,080 kg/yr per MW of furnace
capacity (or 208,800-1,878,800 kg/yr for all U.S. covered furnaces). Open furna-
ces generate POM at about 100-900 kg/yr per MW furnace capacity (or 134,500-
1,210,500 kg/yr for all U.S. open furnaces). No growth is expected in the use of
covered furnaces, comprising only 14% of the industry's production capacity. The
estimated nationwide POM generation rates (before emission control devices) are in
the same order of magnitude as those of slot-type coke ovens, which EPA considers
to be major emitters; however, the control devices used on all U.S. ferroalloy fur-
naces remove most of this material from the gas stream.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Polycyclic Organic Mat-
ter
c. COSATI Field/Group
I3B
Pollution Carcinogens
Iron and Steel Industry
Assessments
Electric Arc Furnaces
Ferroalloys
Polycyclic Compounds
Organic Compounds
MET
11F
14B
13A,13I
07C
19. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS {This Report)
Unclassified
21. NO. OF PAGES
332
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
333
------- |