United States Solid Waste and EPA530-R-99-022
Environmental Protection Emergency Response NTIS: PB99-155 970
Agency (5305W) April 1998
&EPA identification and
Description of
Mineral Processing
Sectors; Technical
Background
Document; Final
Printed on paper that contains at least 30 percent postconsumer fiber
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50272-101
REPORT DOCUMENTATION | 1. Report No.
PAGE |
I EPA530-R-99-022
12.
13. Recipient's Accession No.
j PB99-155970
4. Title and Subtitle
Identification and Description of Mineral Processing Sectors and Waste Streams; Technical Background
Document; Final
6.
5. Report Date
April 1998
7. Authors)
8. Performing Organization Rept No.
9. Performing Organization Name and Address
US. EPA
OFFICE OF SOLID WASTE
401M STREET, SW
WASHINGTON, DC 20460
12. Sponsoring Organization Name and Address
10. Project/Task/Work Unit No.
11. Contract © or Grant (G) No.
(0)
13. Type of Report & Period Covered
I Technical Background Document
114.
15. Supplementary Notes
16. Abstract (Limit: 200 words)
Presents methodology and data sources used to identity the mineral processing sectors and waste streams. Provides individual commodity
reviews, which include a commodity section describing its uses and giving pertinent statistics, a detailed process description with process flow
diagrams, and a process waste stream section that identifies individual waste streams. Appendices include detailed explanations ot
methodology used to estimate annual waste generation rates for the individual waste streams, work sheet for waste stream assessment,
definitions for classifying mineral processing waste streams, recycling work sheets for individual mineral processing waste streams, listing of
waste streams generated by mineral production activities by commodity, mineral processing sectors generating hazardous wastes, mineral
processing sectors not generating hazardous wastes, and a list of commenters.
17. Document Analysis a. Descriptors
b. Identifiers/Open-Ended Terms
C.COSAT1 Field Group
IK, Availability Statement
RELEASE UNLIMITED
I 19. Security Class (This Report) 121. No. of Pages
| UNCLASSIFIED |
I I
120. Security Class (This Page) |
I UNCLASSIFIED I
(SeeANSl-Z39.1S)
OPTIONAL FORM 272 (4-77)
(Formerly NTIS-35)
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This technical background document, Identification and Description of Mineral
Processing Sectors and Waste Streams, was submitted for public review to EPA's RCRA Docket
# F-95-PH4A-FFFFF. It provides supplementary information and support for the January 25,
1996 Supplemental Proposed Rule, Land Disposal Restrictions—Supplemental Proposal to
Phase IV: Clarification ofBevill Exclusion for Mining Wastes, Changes to the Definition of Solid
Waste for Mineral Processing Wastes, Treatment Standards for Characteristic Mineral
Processing Wastes, and Associated Issues (61 FR 2338), The Agency has received comments
from the public on this document and has listed these comments and Agency responses in the
final section of the document. The Agency finalizes this document as of May 1, 1998 and
submits it to RCRA Docket # F-98-2P4F-FFFFF to provide supplementary information and
support for the May 1, 1998 Final Rule, Land Disposal Restrictions Phase IV: Final Rule
Promulgating Treatment Standards for Metal Wastes and Mineral Processing Wastes; Mineral
Processing Secondary Materials and Bevill Exclusion Issues; Treatment Standards for
Hazardous Soils, and Exclusion of Recycled Wood Preserving Wastewaters.
DISCLAIMER
This document is intended solely to provide information to the public and the regulated
community regarding the wastes that are potentially subject to the requirements of this rule. This
information was also utilized by the Agency to assist in evaluating the potential impacts on the
industry associated with complying with the rule. While the guidance contained in this
document may assist the industry, public and federal and state regulators in applying statutory
and regulatory requirements of RCRA, the guidance is not a substitute for those legal
requirements; nor is it a regulation itself. Thus, it does not impose legally-binding requirements
on any party, including EPA, States or the regulated community. Based on the circumstances,
the conclusions in this document may not apply to a particular situation, and EPA and State -
decision makers retain the discretion to adopt approaches on a case-by-case basis that differ from
this guidance where determined to be appropriate based on the facts of the case and applicable
statutes and regulations.
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TABLE OF CONTENTS
Section Page
I. EXECUTIVE SUMMARY 1
II. METHODS AND DATA SOURCES 25
A. Identify Mineral Commodity Sectors of Interest 26
B. Conduct Exhaustive Information Search 26
C. Prepare Mineral Commodity Analysis Reports 39
D. Identify Mineral Processing Waste Streams Potentially Affected by the Phase IV LDRs 54
E. Identify Mineral Processing Facilities Potentially Affected by the Phase IV LDRs 58
F. Caveats and Limitations 58
III. MINERAL COMMODITIES 69
A. Individual Mineral Commodity Reviews 69
1. Alumina and Aluminum 71
2. Antimony 95
3. Arsenic , Ill
4. Beryllium , 115
5. Bismuth .' 143
6, Boron 153
7. Bromine from Brines 165
8. Cadmium 173
9. Calcium Metal 185
10. Cesium and Rubidium 191
11. Chromium, Ferrochrome, and Ferrochrome-Silicon 207
12, Coal Gas 221
13. Copper 233
14. Elemental Phosphorus 281
15. Fluorspar and Hydrofluoric Acid 305
16. Gemstones 313
17. Germanium 317
18. Gold and Silver 331
19. Iodine ! 353
20. Iron and Steel 359
21. Lead 371
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TABLE OF CONTENTS (CONTINUED)
Section Page
22. Lightweight Aggregate 409
23. Lithium and Lithium Carbonate 427
24. Magnesium and Magnesia from Brines 435
25. Manganese, Manganese Dioxide, Ferromanganese, and Silicomanganese 451
26. Mercury 473
27. Molybdenum, Ferromolybdenum, and Ammonium Molybdate 483
28. Phosphoric Acid 497
29. Platinum Group Metals 513
30. Pyrobitumens, Mineral Waxes, and Natural Asphalts 525
31. Rare Earths 533
32. Rhenium 555
33. Rutile (Synthetic) 563
34. Scandium 569
35. Selenium ; 581
36. Silicon and Ferrosilicon : 591
37. Soda Ash 599
38. Sodium Sulfate 611
39. Strontium 617
40. Sulfur 623
41. Tantalum, Columbium, and Ferrocolumbium 633
42. Tellurium 649
43. Tin 657
44. Titanium and Titanium Dioxide 665
45. Tungsten 695
46. Uranium 711
47. Vanadium 729
48. Zinc 743
49. Zirconium and Hafnium 771
IV. SUMMARY OF FINDINGS 783
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TABLE OF CONTENTS (CONTINUED)
Section Page
APPENDICES 821
A. Detailed Explanations of Methodology Used to Estimate Annual Waste Generation
Rates for Individual Waste Streams 823
B, Work Sheet for Waste Stream Assessment of Recycling, Recovery, and Reuse Potential 849
C, Definitions for Classifying Mineral Processing Waste Streams 853
D, Recycling Work Sheets for Individual Mineral Processing Waste Streams 857
E. Listing of Waste Streams Generated by Mineral Production Activities by Commodity 1009
F. Mineral Processing Sectors Generating Hazardous Wastes 1021
G, Mineral Processing Sectors Not Generating Hazardous Wastes 1025
H. List of Commenters •..,..,.... 1029
ill
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I. EXECUTIVE SUMMARY
The purpose of this executive summary is to describe EPA's review of mineral commodities that may
generate hazardous wastes as defined by RCRA Subtitle C. These wastes and the facilities and commodity sectors
that generate them may be affected by the establishment of Land Disposal Restrictions for mineral processing wastes.
Through a series of rulemakings (see Background below) EPA has established and applied criteria to determine
which mineral processing wastes are no longer exempt from Subtitle C regulation. These wastes are termed "newly
identified" mineral processing wastes.
Any newly identified mineral processing waste that exhibits one or more of the four characteristics of a
hazardous waste if disposed on the land must be made subject to the Land Disposal Restrictions (LDRs).
Accordingly, EPA has promulgated treatment standards (Best Demonstrated Available Technology, or BOAT) for
newly identified mineral processing wastes.
EPA reviewed the 36 industrial sectors (commodities) and 97 different general categories of wastes
identified in a previously published Advanced Notice of Public Rule Making (ANPRM) (October 21, 1991). EPA
also reviewed a listing of more than 100 mineral commodities prepared by the U.S. Bureau of Mines (Bureau of
Mines' 1987 Minerals Year Book, 1989-1995 Mineral Commodities Summary, and 1985 Mineral Facts and
Problems). This information, in addition to data collected in previous EPA studies, was used to compile a
comprehensive list of mineral commodity sectors. In the process, the Agency identified a total of 62 mineral
commodities that could generate mineral processing waste streams that could potentially exhibit one of the
characteristics of a RCRA hazardous waste.
The Agency used publicly available information to prepare a draft technical background document (TBD)
on the production of particular mineral commodities and associated operations that generate mineral processing
wastes. This draft was made available for public comment in January 1996 (docket No. F-95-PH4A-FFFFF).
Numerous public comments were submitted to the Agency addressing the draft TBD. In addition, although the
Agency did not request further comments on the draft TBD in a subsequent Federal Register notice articulating
modifications to the proposed Phase 4 LDR rule (62 FR 26041), several comments were submitted that included
process information or other data that were relevant to the TBD; these comments may be found in docket No. F-97-
2P4P-FFFFF. This final TBD addresses and provides EPA's responses to all of these comments and information
contained therein, where appropriate.
The Agency cautions that this document should not be construed to be an exclusive list of mineral
processing and associated waste streams; other types of mineral processing wastes may exist." Moreover, the
omission or inclusion of a waste stream in this background document does not relieve the generator from the
responsibility for correctly determining whether each of its particular wastes is covered by the Bevill mining waste
exclusion. This report has been extensively revised from the previous draft and should be used as guidance for EPA.
A, METHODS AND DATA SOURCES
1. Background
Under the provisions of the Mining Waste Exclusion of the Resource Conservation and Recovery Act
(RCRA), solid waste from the extraction, beneficiation, and processing of ores and minerals is exempt from
regulation as hazardous waste under Subtitle C of RCRA, as amended. The Mining Waste Exclusion was established
in response to §3001(b)(3) of the statute (also known as the "Bevill Amendment"), which was added in the 1980
Solid Waste Disposal Act Amendments. The Bevill Amendment precluded EPA from regulating these wastes (as
well as several other "special wastes") until the Agency performed a study and submitted a Report to Congress, as
directed by §8002, and determined either to promulgate regulations under Subtitle C or that such regulations were
unwarranted, (i.e., that the Exclusion should continue), as directed by §3001(b)(3)(C) of the statute. In response to
the Bevill Amendment, EPA modified its final hazardous waste regulations in November 1980 to reflect this new
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exemption, and issued a preliminary and very broad interpretation of the scope of its coverage ("solid waste from the
exploration, mining, milling, smelting and refining of ores and minerals" (45 FR 76618, November 19, 1980)).
In 1984, the Agency was sued for failing to complete the required Report to Congress and regulatory
determination in conformance with the statutory deadline (Concerned Citizens ofAdamstown v. EPA, No. 84-3041.
D.D.C., August 21, 1985). In responding to this lawsuit, EPA explained that it planned to propose a narrower
interpretation of the scope of the Exclusion, and proposed to the Court two schedules: one for completing the §8002
studies of mineral extraction and beneficiation wastes and submitting the associated Report to Congress, and one for
proposing and promulgating a reinterpretation for mineral processing wastes. In so doing, the Agency, in effect, split
the wastes that might be eligible for exclusion from regulation into two groups: mining (extraction and beneficiation)
wastes and mineral processing wastes. The Court agreed to this approach and established a schedule for completing
the two initiatives.
The Report to Congress on mining wastes was published on December 31, 1985, and on July 3, 1986 (51
FR 24496) EPA published the regulatory determination for these wastes, which stated that, in the Agency's
judgment, Subtitle C regulation of these wastes was unwarranted. In keeping with its agreement, EPA also proposed
to narrow the scope of the Mining Waste Exclusion for mineral processing wastes on October 2, 1985 (50 FR
40292). In this proposal, however, the Agency did not specify the criteria that it used to distinguish the mineral
processing wastes that qualified for the Exclusion from those that did not.
In response to the proposed rule, many companies and industry associations "nominated" wastes that they
believed should be retained within the Exclusion. Faced with an inability at that time to articulate criteria that could
be used to distinguish exempt from non-exempt wastes and the approaching Court-ordered deadline for final action,
EPA withdrew its proposal on October 9, 1986 (51 FR 36233); the Agency was promptly sued by a coalition of
environmental/public interest groups. In July 1988, the Court in Environmental Defense Fund v. EPA held that
EPA's withdrawal of the 1985 proposal was arbitrary and capricious, and ordered the Agency to define the specific
mineral processing wastes that were eligible for the Mining Waste Exclusion. The Court also directed the Agency to
restrict the scope of the Exclusion to include only "large volume, low hazard" wastes, based upon the legislative
history of the special wastes concept.
During the three years that followed this decision, EPA proposed and promulgated several rules that
redefined the boundaries of the Exclusion for mineral processing wastes. These rulemaking notices included explicit
criteria for defining mineral beneficiation and processing, and large volume and low hazard, as well as evaluations of
which specific mineral industry wastes were in conformance with these criteria and thus, eligible for special waste
status. This rulemaking process was completed with the publication of final rules on September 1, 1989 (54 FR
36592) and January 23, 1990 (54 FR 2322). EPA's evaluations led to the finding that only 20 specific mineral
processing wastes fulfilled the newly promulgated special wastes criteria; all other mineral processing wastes were
removed from the Mining Waste Exclusion. The 20 special wastes were studied in a comprehensive Report to
Congress published on July 30, 1990. Subsequently, EPA ruled, after considering public comment and performing
additional analysis, that Subtitle C regulation was unwarranted for these 20 waste streams.
How LDR Relates to Mineral Processing Wastes
As a consequence of the rulemaking process described above, all but 20 mineral processing wastes have
been removed from the Mining Waste Exclusion. These newly non-exempt wastes have the same regulatory status
as any other industrial solid waste. That is, if they exhibit characteristics of hazardous waste or are listed as
hazardous wastes, they must be managed in accordance with RCRA Subtitle C or equivalent state standards.
Existing waste characterization data suggest that some of these wastes may exhibit the characteristic of toxicity for
metals (waste codes D004-D011), corrosivity (D002), and/or reactivity (D003).
EPA considers these wastes to be "newly identified" because they were brought into the RCRA Subtitle C
system after the date of enactment of the Hazardous and Solid Waste Act (HSWA) Amendments on November 8,
1984. EPA declined to include newly identified wastes within the scope of the Land Disposal Restrictions (LDRs)
for Subtitle C characteristic hazardous wastes ("Third Third" Rule) published on June 1, 1990, deciding instead to
promulgate additional treatment standards (Best Demonstrated Available Technology, or BOAT) in several phases
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that were to be completed in 1997. The rationale for this decision is articulated at 55 FR 22667. In brief, at that
time. EPA had not performed the technical analyses necessary to determine whether the treatment standards being
promulgated for characteristic hazardous wastes were feasible for the newly non-exempt mineral processing wastes.
The issue was further complicated by the fact that the list of non-exempt wastes was not final at that time, because
the regulatory determination for the 20 wastes studied in the 1990 Report to Congress had not yet been promulgated.
The boundaries of the Exclusion have now been firmly established, and the Agency is ready to characterize and
establish treatment standards for all newly identified hazardous mineral processing wastes.
More recent work performed by OSW's Waste Treatment Branch (WTB) on the composition and other
characteristics of the mineral processing wastes that have been removed from the Exclusion suggests that some of
these wastes may pose unique treatability and/or capacity problems. Accordingly, there was a need for EPA to
perform further data collection and analysis activities in order to develop BDAT treatment standards that are both
adequately protective and achievable,
2. Scope of the Report
In order to provide the necessary foundation to both develop a fully comprehensive inventory of mineral
commodity sectors, facilities, and waste streams that may be affected by the LDRs program and identify applicable
treatment technologies, EPA conducted an extensive effort to collect information. Specifically, EPA: (1) conducted
electronic literature searches; (2) reviewed documents, including the 1989 mineral processing survey instruments
(NSSWMPF), public comments on the 1991 ANPRM, and various articles and conference proceedings; (3) reviewed
documents prepared by the Office of Solid Waste, various Agency contractors, state regulatory authorities, and the
Bureau of Mines (BOM); (4) reviewed the "Mineral Commodity Summaries" prepared by the BOM; and (5)
contacted BOM Commodity Specialists. Information collected included detailed process descriptions and
identification of waste streams. In addition, in preparing this final Technical Background Document, EPA carefully
considered and, where appropriate, incorporated or otherwise addressed new information and suggested corrections
to the draft document offered in public comment on the Agency's proposed rules (61 FR 2338, 62 FR 26041) and
supporting documents. These comments were submitted to, and may be found in, docket Nos. F-95-PH4A-FFFFF
and F-97-2P4P-FFFFF, respectively. The specific methodology that EPA employed for this effort is described in
detail in Section 3, Methods and Data Sources, below.
Based on this information, EPA prepared 49 separate analyses covering the 62 commodity groups presented
in Exhibit 1-1. Each analysis includes me following:
* A commodity summary describing the uses and salient statistics of the particular mineral commodity;
• A process description section with detailed, current process information and process flow diagram(s);
and
• A process waste stream section that identifies — to the maximum extent practicable — individual waste
streams, sorted by the nature of the operation (i.e., extraction/beneficiation or mineral processing).1
Within this section, EPA also identified:
waste stream sources and form (i.e., wastewater (<1 percent solids and total organic content), 1-10
percent solids, and >10% solids);
Bevill-Exclusion status of the waste stream (i.e., extraction/beneficiation waste stream, mineral
processing waste stream, or nonruniquely associated waste stream);
1 EPA strongly cautions that the process information and identified waste streams presented in the commodity analysis
reports should not be construed to be the authoritative list of processes and waste streams. These reports represent a best effort,
and clearly do not include every potential process and waste stream. Furthermore, the omission of an actual waste stream (and
thus its not being classified as either an extraction/beneficiation or mineral processing waste in this report) does not relieve the
generator from its responsibility of correctly determining whether the particular waste is covered by the Mining Waste Exclusion.
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waste stream characteristics (total constituent concentration data, and statements regarding whether
the waste stream exhibits or is expected to exhibit one of the RCRA hazardous waste
characteristics of toxicity, ignitability, corrosivity, or reactivity);
annual generation rates (reported or estimated);
management practices (e.g., tank treatment and subsequent NPDES discharge, land disposal, or in-
process recycling); and
whether the waste stream is being (or could potentially be) recycled, and thus be classified as
either as a sludge, by-product, or spent material.
The list provided in this report represents EPA's best effort to date, and generators continue to be
responsible for determining whether any wastes omitted from these lists are non-exempted and subject to Subtitle C
controls.
3. Methodology and Major Data Sources
EPA researched and obtained information characterizing the mineral processing operations and wastes
associated with the mineral commodities listed in Exhibit 1-1. This information was used by EPA both to update
existing data characterizing mineral processing wastes obtained through past Agency efforts and to obtain
characterization information on newly identified waste streams not previously researched.
To provide the necessary foundation to both (1) develop a fully comprehensive inventory of mineral
commodity sectors, facilities, and waste streams that may be affected by the LDRs program and (2) identify
applicable treatment technologies, EPA embarked on an information collection program. Specifically, to capitalize
on information collected through past efforts, as well as to collect more recent data, we conducted the following
activities:
• Reviewed mineral processing survey instruments (NSSWMPF) and public comments (submitted in
response to the 1991 ANPRM) for process-related information (e.g., process flow diagrams, waste
characterization data, and waste management information) contained in our in-house files.
• Reviewed numerous documents provided by EPA (e.g., contractor reports and various Bureau of
Mines reports) for process-related information.
• Reviewed the 1993, 1994, and 1995 "Mineral Commodity Summaries" prepared by the Bureau of
Mines (BOM) for salient statistics on commodity production.2
« Reviewed and summarized damage case information presented in the "Mining Sites on the
National Priorities List, NPL Site Summary Reports" to support work on assessing the
appropriateness of the Toxicity Characteristic Leaching Procedure (TCLP) for mineral processing
wastes.
« Contacted the BOM (now USGS) Commodity Specialists associated with the commodity sectors of
interest to (1) obtain current information on mining companies, processes, and waste streams, and
(2) identify other potential sources of information.
« Retrieved applicable and relevant documents from the BOM's FAXBACK document retrieval
system. Documents retrieved included monthly updates to salient statistics, bulletins, and
technology review papers.
" Following elimination of the U.S. Bureau of Mines in 1995, responsibility for certain mineral commodity-related activities
was transferred to the U.S. Geological Survey (USGS).
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* Conducted an electronic query of the 1991 Biennial Reporting System (BRS) for waste generation
and management information on 34 mineral processing-related Standard Industrial Classification
(SIC) numbers,
* Conducted an electronic literature search for information related to mineral processing and waste
treatment technologies contained in numerous technical on-line databases, including: NTIS,
Compendex Plus, METADEX, Aluminum Industry Abstracts, ENVIROLINE, Pollution Abstracts,
Environmental Bibliography, and GEOREF.
EPA searched for relevant information (published since 1990) on the mineral commodities listed in Exhibit
1-1. We chose 1990 as the cutoff year so as not to duplicate past information collection activities conducted by EPA
and EPA contractors, and to obtain information on mineral processes "retooled" since clarification of the Bevill
Amendment to cover truly "high volume, low hazard" wastes.
In preparing the commodity sector reports, EPA used its established definitions and techniques for establishing
which operations and waste streams might be subject to LDR standards. EPA decisions concerning whether
individual wastes are within the scope of the RCRA Mining Waste Exclusion were based upon a number of different
factors. The Agency examined these factors in sequence, in such a way as to yield unambiguous and consistent
decisions from sector to sector. The step-wise methodology used for this analysis is presented below:
1. Ascertain whether the material is considered a solid waste under RCRA.
2. Establish whether the waste and the operation that generates it are uniquely associated with mineral
production.
3. Determine whether the waste is generated by a mineral extraction, beneficiation, or processing
step.
4. Determine whether the waste is generated by a primary mineral processing step, and, more
generally, whether or not primary mineral processing occurs in the sector/within a process type.
5. Check to see whether the waste, if a processing waste, is one of the 20 special wastes from mineral
processing.
This analytical sequence results in one of three outcomes: 1) the material is not a solid waste and hence, not subject
to RCRA; 2) the material is a solid waste but is exempt from RCRA Subtitle C because of the Mining Waste
Exclusion; or 3) the material is a solid waste that is not exempt from RCRA Subtitle C and is subject to regulation as
a hazardous waste if it is listed as a hazardous waste or it exhibits any of the characteristics of hazardous waste.3
3 RCRA Subtitle C regulations define toxicity as one of the four characteristics of a hazardous waste. EPA uses the Toxicity
Characteristic Leaching Procedure (TCLP) to assess whether a solid waste is a hazardous waste due to toxicity. In today's final
rule, EPA is reinstating the application of the TCLP to mineral processing wastes in response to a Court remand. For further
discussion, see the preamble to today's final rule.
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EXHIBIT 1-1
MINERAL COMMODITIES OF POTENTIAL INTEREST
1) Alumina
2) Aluminum
3) Ammonium Molybdate
4) Antimony
5) Arsenic Acid
6) Asphalt (natural)
7) Beryllium
8) Bismuth
9) Boron
10) Bromine (from brines)
11) Cadmium
12) Calcium Metal
13) Cerium, Lanthanides, and Rare Earth metals
14) Cesium/Rubidium
15) Chromium
16) Coal Gas
17) Copper
18) Elemental Phosphorus
19) Ferrochrome
20) Ferrochrome-Silicon
21) Ferrocolumbium
22) Ferromanganese
23) Ferromolybdenum
24) Ferrosilicon
25) Gemstones
26) Germanium
27) Gold and Silver
28) Hydrofluoric Acid
29) Iodine (from brines)
30) Iron and Steel
31) Lead
32) Lightweight Aggregate
33) Lithium (from ores)
34) Lithium Carbonate
35) Magnesia (from brines)
36) Magnesium
37) Manganese and MnO2
38) Mercury
39) Mineral Waxes
40) Molybdenum
41) Phosphoric Acid
42) Platinum Group Metals
43) Pyrobitumens
44) Rhenium
45) Scandium
46) Selenium
47) Silicomangaaese
48) Silicon
49) Soda Ash
50) Sodium Sulfate
51) Strontium
52) Sulfur
53) Synthetic Rutile
54) Tantalum/Columbium
55) Tellurium
56) Tin
57) Titanium/TiO2
58) Tungsten
59) Uranium
60) Vanadium
61) Zinc
62) Zirconium/Hafnium
NOTE: This list represents EPA's best efforts at identifying mineral commodities that may generate
mineral processing wastes. Omission or inclusion on this list does not relieve the generator of
the responsibility for appropriately managing wastes that would be subject to RCRA Subtitle C
requirements.
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EPA used waste stream characterization data obtained from numerous sources to document whether a
particular waste stream exhibits one (or more) of the characteristics of a RCRA hazardous waste (i.e., toxicity,
corrosivity, ignitability, and reactivity). Due to the paucity of waste characterization data (particularly, TCLP data),
EPA used total constituent data (if available) or engineering judgment to determine whether a particular waste
exhibits one of the characteristics of a RCRA hazardous waste (i.e., toxicity, corrosivity, ignitability, and reactivity).
When data were available, EPA used actual waste generation rates reported by facilities in various Agency
survey instruments and background documents. To account for the general lack of data for many of the mineral
commodity sectors and waste streams, the Agency developed a step-wise method for estimating mineral processing
waste stream generation rates when actual data were unavailable. Specifically, EPA developed an "expected value"
estimate for each waste generation rate using draft industry profiles, supporting information, process flow diagrams,
and professional judgment. From the "expected value" estimate, EPA developed upper and lower bound estimates,
which reflect the degree of uncertainty in our data and understanding of a particular sector, process, and/or waste in
question. The precise methodology employed for determining waste generation rates varied depending on the
quantity and quality of available information.
To determine waste stream management practices, EPA reviewed process descriptions and process flow
diagrams obtained from numerous sources, including Kirk-Othmer (several editions). EPA's Effluent Guideline
Documents (see sector reports for specific references), EPA survey instruments, and the literature. Because the
available process descriptions and process flow diagrams varied considerably in both quality and detail, EPA often
needed to interpret the information to determine how specific waste streams are managed. For example, process
descriptions and process flow charts found through the Agency's electronic literature search process often focus on
the production process of the mineral product and omit any description or identification of how or where waste
streams are managed. In such cases, the Agency has used professional judgment to determine how and where
specific waste streams are managed. Specifically, EPA considered (I) how similar waste streams are managed at
mineral processing facilities for which die Agency has management practice information, (2) the waste form and
whether it is amenable to tank treatment, (3) generation rates, and (4) proximity of the point of waste generation to
the incoming raw materials, intermediates, and finished products, to predict the most likely waste management
practice.
As was the case for the other types of waste stream-specific information discussed above, EPA was unable
to locate published information showing that many of the identified mineral processing waste streams were being
recycled. Therefore, the Agency developed a work sheet to assist EPA staff in making consistent determinations of
whether the mineral processing waste streams could potentially be recycled, reused, or recovered. This work sheet,
shown in Appendix C, was designed to capture the various types of information that could allow one, when using
professional judgment, to determine whether a particular waste stream could be recycled or whether it contains
material of value. If EPA determined that the waste stream is or could be fully/partially recycled, it initially used the
definitions provided in 40 CFR §§ 260.10 and 261.1 to categorize each waste stream as either a by-product, sludge,
or spent material. In today's final rule, however, these distinctions have been eliminated in die context of the
primary minerals industry. This final document nonetheless contains references to mis former classification scheme,
because it is used extensively in other analyses (e.g., the Regulatory Impact Analysis) that EPA has prepared in
support of today's rule.
EPA, through the process of researching and preparing mineral commodity analysis reports for the mineral
commodities, identified a total of 553 waste streams that are believed to be generated at facilities involved in mineral
production operations. The Agency then evaluated each of the 553 waste streams to remove waste streams that
would not be affected by the Phase IV LDRs. Specifically, EPA removed the following materials:
• All of the extraction and beneficiation waste streams;
« The "Special 20" Bevill-Exempt mineral processing waste streams;
• Waste streams that are known to be fully recycled in process; and
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» All of the mineral processing waste streams that do not or are unlikely to exhibit one or more
of the RCRA characteristics of a hazardous waste (based on either actual analytical data or
professional judgment).
Finally, as noted above, EPA made a number of corrections and other modifications to the draft TBD in
response to new information provided in written comments received in response to the two proposed rules and the
draft TBD.
As a result of this evaluation process, EPA narrowed the potential universe of waste streams that could
potentially be affected by the Phase IV LDRs to the 133 hazardous mineral processing waste streams presented in
Exhibit 1-2.
4. Caveats and Limitations of Data Analysis
The results and information presented in this report are based primarily on a review of publicly available
information. The accuracy and representativeness of the collected information are only as good as die source
documents. As a result of this limited data quality review, EPA notes that in some instances, Extraction Procedure
(EP) leachate data reported by various sources are greater than 1/20^ of the associated total constituent
concentrations. Generally, one would expect, based on the design of the EP testing procedure, die total constituent
concentrations to be at least 20-times die EP concentrations. This apparent discrepancy, however, can potentially be
explained if the EP results were obtained from total constituent analyses of liquid wastes (i.e., EP tests conducted on
wastes that contain less than one-half of one percent solids content are actually total constituent analyses).
In addition, to present mineral commodity profiles that were as complete as possible, EPA used a step-wise
mediodology for estimating bodi annual waste generation rates and waste characteristics for individual waste streams
when documented waste generation rates and/or analytical data were not available. EPA's application of this
metiiodology to estimate waste generation rates resulted in the development of low, medium, and high annual waste
generation rates for non-wastewaters and wastewaters that were bounded by zero and 45,000 metric tons/yr/facility
and by zero and 1,000,000 metric tons/yr/facility, respectively (the thresholds for determining whether a waste
stream was a high volume, Bevill-exempt waste). Due to die paucity of waste characterization data (particularly,
TCLP data), EPA used total constituent data (if available) or best engineering judgment to determine whether a
particular waste exhibited one of the characteristics of a RCRA hazardous waste (i.e., toxicity, corrosivity,
ignitability, and reactivity).
To determine whetiier a waste might exhibit the characteristic of toxicity, EPA first compared 1/20* of the
total constituent concentration of each TC metal to its respective TC level4. In cases where total constituent data
were not available, EPA men used best engineering judgment to evaluate whether the waste stream could potentially
exhibit me toxicity characteristic for any of die TC metals. For example, if a particular waste stream resulted
through die leaching of a desired metal from an incoming concentrated feed, we assumed that die precipitated leach
stream contained high total constituent (and therefore, high leachable) concentrations of non-desirable metals, such
as arsenic. Continuing through die step-wise methodology, we relied on EPA's best engineering judgment to
determine, based on our understanding of the nature of a particular processing step diat generated die waste in
question, whether the waste could possibly exhibit one (or more) of the characteristics of ignitability, corrosivity, or
reactivity. The Agency acknowledges die inherent limitations of mis conservative, step-wise mediodology and notes
that it is possible dial EPA may have incorrectly assumed diat a particular waste does (or does not) exhibit one or
more of the RCRA hazardous waste characteristics.
4 Based on the assumption of a theoretical worst-case leaching of 100 percent and the design of the TCLP extraction test,
where 100 grams of sample is diluted with two liters of extractant, the maximum possible TCLP concentration of any TC metal
would be l/20th of the total constituent concentration.
-------
B. MINERAL OPERATIONS THAT MAY GENERATE HAZARDOUS WASTE
1. Introduction
EPA collected, evaluated for relevance (both applicability and age), and compiled publicly available
information to prepare 49 analyses covering 62 commodity groups. Each commodity analysis consists of a
commodity summary describing the uses of and salient statistics pertaining to the particular commodity, a process
description section with detailed, current process information and process flow diagram(s), and a process waste
stream section that identifies — to the maximum extent practicable — individual wastes, sorted by the nature of the
operation (i.e., extraction/beneficiation or mineral processing).
Through this process, EPA identified a total of 553 waste streams from a review of all mineral sectors.
After careful analysis, EPA determined that 40 commodity sectors generated a total of 358 waste streams that could
be classified as mineral processing wastes, 133 of which are believed to exhibit one or more of the characteristics of
a hazardous waste. At this time, EPA has insufficient information to determine whether the following commodity
sectors also generate wastes that could be classified as mineral processing wastes: Bromine, Gemstones, Iodine,
Lithium, Lithium Carbonate, Soda Ash, Sodium Sulfate, and Strontium.
EPA strongly cautions that the process information and identified waste streams presented in the commodity
reports should not be construed as an authoritative list of processes and waste streams. - These reports represent a
best effort, and clearly do not include every potential process and waste stream affected by today's final rule.
Furthermore, the omission of an actual waste stream (and thus it's not being classified as either an
extraction/beneficiation or mineral processing waste in this report) does not relieve the generator from its
responsibility of correctly determining whether the particular waste is covered by the Mining Waste Exclusion.
2. Alphabetical Listing of Mineral Commodities and Waste Streams
A listing of the mineral commodity sectors that are likely to generate newly identified hazardous wastes is
presented in Exhibit 1-2. Exhibit 1-2 also presents a brief description of the production operations used to generate
the mineral processing wastes, estimated/reported annual waste generation rates, and the specific RCRA
characteristics causing individual wastes to be hazardous. This table lists only those mineral processing wastes
which EPA believes are or may be hazardous. The Agency's assumptions concerning the characteristics of the
wastes are indicated in Exhibit 1-2 as follows:
Y = known to be hazardous
Y? = suspected to be hazardous
N? = suspected to be not hazardous
N = believed to be not hazardous
-------
EXHIBIT 1-2
LISTING OF HAZARDOUS MINERAL PROCESSING WASTES BY COMMODITY SECTOR
Commodity
Alumina and Aluminum
Metallurgical grade alumina is extracted from bauxite
by the Bayer process and aluminum is obtained from
this purified ore by electrolysis via the Hall-Heroult
process. The Bayer process consists of the following
five steps; (1) ore preparation, (2) bauxite digestion,
(3) clarification, (4) aluminum hydroxide precipitation,
and (5) calcination to anhydrous alumina. In the
Hall-Heroult process, aluminum is produced through
the electrolysis of alumina dissolved in a molten
cryolite-based bath, with molten aluminum being
deposited on a carbon cathode.
Antimony
Primary antimony is usually produced as a by-
product or co-product of mining, smelting, and
refining of other antimony-containing ores such as
tetrahedrite or lead ore. Antimony can be produced
using either pyrometallurgicai processes or a
hydrometallurgical process. For the
pyrometallurgicai processes, the method of recovery
depends on the antimony content of the sulfide ore,
and will consist of either volatilization, smelting in a
blast furnace, liquation, or iron precipitation,
Antimony also can be recovered hydrometallurgically
by leachinq and electrowinninq.
Beryllium
Bertrandite and beryl ores are treated using two
separate processes to produce beryllium sulfate,
BeSO4: a counter-current extraction process and the
Kjeligren-Sawyer process. The intermediates from
the two ore extraction processes are combined and
fed to another extraction process. This extraction
process removes impurities solubilized during the
processing of the bertrandite and beryl ores and
converts the beryllium sulphate to beryllium
hydroxide, Be(OH)2. The beryllium hydroxide is
further converted to beryllium fluoride, BeF2, which is
then catalytieally reduced to form metallic beryllium.
Waste Stream
Cast house dust
Electrolysis waste
Autoclave filtrate
Stripped anolyte solids
Slag and furnace residue
Chip treatment
wastewater
Spent barren filtrate
Filtration discard
Reported
Generation
JIOOOmtM
19
58
NA
0.19
21
NA
55
NA
Est ./Reported
Generation
(1000mt/yr)
Min
19
58
0.32
0.19
21
0,2
55
0.2
Avg,
19
58
27
0.19
21
100
55
45
Max
19
58
54
0.19
21
2000
55
90
Number
of
with
Process
23
23
6
2
6
2
1
2
TC Metals
As
Y?
Y?
Ba
Cd
Y
Y?
Cr
Y?
Pb
Y?
Y?
Y?
Y?
Hfl
Y
Y?
Se
Y
Af?
Other Hazardous
Characteristics
Corr
N?
N?
Y?
N?
N?
N?
N?
N?
Ignit
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Bismuth
Bismuth is recovered mainly during the smelting of
copper and lead ores. Bismuth-containing dust from
copper smelting operations is transferred to lead
smelting operations for recovery. At lead smelting
operations bismuth is recovered either by the
Betterton-Kroll process or the Belts Electrolytic
process. In the Betterton-Kroll process, magnesium
and calcium are mixed with molten lead to form a
dross that contains bismuth. The dross is treated
with chlorine or lead chloride and oxidized by using
air or caustic soda to remove impurities. In the Belts
Electrolytic process, lead bullion is electrolyzed. The
resulting impurities, including bismuth, are smelted,
reduced and refined.
CadmiumCadmium is obtained as a byproduct of
zinc metal production. Cadmium metai is obtained
from zinc fumes or precipitates via a
lydrometallurgical or a pyrometallurgical process.
The hydrometailurgical process consists of Ihe
following steps: (1) precipitates leached with sulfuric
acid, (2) cadmium precipitated with a zinc dust
addition, (3) precipitate filtered and pressed into filter
cake, (4) impurities removed from filter cake to
produce sponge, (5) sponge dissolved with sulfuric
acid, (6) electrolysis of solution, and (7) cadmium
metal melted and cast. The pyrometallurgical
process consists of the following steps: (1) cadmium
fumes converted to water- or acid-soluble form, (2)
leached solution purified, (3) galvanic precipitation or
electrolysis, and (4) metal briquetted or cast.
Calcium
Calcium metal is produced by the Aluminothermic
method. In the Aluminothermic method, calcium
oxide, obtained by quarrying and calcining calcium
limestone, is blended with finely divided aluminum
and reduced under a high temperature vacuum. The
process produces 99% pure calcium metal which
can be further purified through distillation.
Waste Stream
Alloy residues
Spent caustic soda
Electrolytic slimes
Lead and zinc chlorides
Metal chloride residues
Slag
Spent electrolyte
Spent soda solution
Waste acid solutions
Waste acids
Caustic washwater
Copper and lead sulfate
filter cakes
Copper removal filter
cake
Iron containing impurities
Spent leach solution
Lead sulfate waste
Post-leach filter cake
Spent purification solution
Scrubber wastewater
Spent electrolyte
Zinc precipitates
Dust with quicklime
Reported
Generation
(1000mt/yr)
NA
NA
NA
NA
3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.04
EsUReported
Generation
(1000mtfyr)
Mfn
0.1
0.1
0
0.1
3
0.1
0.1
0.1
0.1
0
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.04
Avg.
3
6.1
0.02
3
3
1
6.1
6.1
6.1
0.1
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
0.04
Max
6
12
0.2
6
3
10
12
12
12
0.2
19
19
19
19
19
19
19
19
19
19
19
0.04
Number
of
Facilities
with
Process
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
1
TC Metals
As
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Cr
Pb
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Htj
Se
ACJ
Other Hazardous
Characteristics
Corr
N?
N?
N?
N?
N?
N?
N?
Y?
Y?
Y?
Y?
N?
N?
N?
Y?
N?
N?
Y?
Y?
Y?
N?
Y?
Ignft
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Chromium and Ferrochromium
Chromite ore is prepared for processing using
several methods, depending on the ore source and
the end use requirements, although many of these
beneficiation operations may not be conducted in the
United States. Either ferrochromium or sodium
chromate is initially produced, and may be sold or
further processed to manufacture other chromium
compounds, as well as chromium metal,
Ferrochromium is made by smelting chromite ore in
an electric arc furnace with flux materials and
carbonaceous redcutant.
Coat Gas
Coal is crushed and gasified in the presence of
steam and oxygen, producing carbon dioxide and
carbon monoxide, which further react to produce
carbon oxides, methane and hydrogen. The product
gas is separated from the flue gas, and is processed
and purified to saleable methane.
Copper
Copper is recovered from ores using either
pyrometallurgical or hydrometallurgical processes.
In both cases, the copper-bearing ore is crushed,
ground, and concentrated (except in dump leaching).
Pyrometallurgical processing can take as many as
five steps: roasting, smelting, converting, fire
refining, and electrorefining. Hydrometallurgical
processing involves leaching, followed by either
precipitation or solvent extraction and electrowinning.
Elemental Phosphorus
Phosphate rock or sintered/agglomerated fines are
charged Into an electric arc furnace with coke and
silica. This yields calcium silicate slag and
ferrophosphorus, which are tapped. Dusts are
removed from the furnace offgases and phosphorus
is removed from the dusts by condensation.
Waste Stream
ESP dust
GOT sludge
Multiple effects
evaporator concentrate
Acid plant blowdown
APC dusts/sludges
Waste contact cooling
water
Tankhouse slimes
Spent bleed electrolyte
Spent furnace brick
Process wastewaters
WWTP sludge
Andersen Filter Media
Precipitator slurry
NOSAP slurry
Phossy Water
Furnace scrubber
blowdown
Furnace Building
Washdown
Reported
Generation
(1000mt/yr)
3
NA
NA
5300
NA
13
4
310
3
4900
6
0.46
160
160
670
410
700
Est^Re ported
Generation
(1000mt/yr)
Win
3
0.03
0
5300
1
13
4
310
3
4900
6
0.46
160
160
670
410
700
Avg.
3
0.3
0
5300
220
13
4
310
3
4900
6
0.46
160
160
670
410
700
Max
3
3
65
5300
450
13
4
310
3
4900
6
0.46
160
160
670
410
700
Number
of
Facilities
with
Process
1
1
1
10
10
10
10
10
10
10
10
2
2
2
2
2
2
TC Metals
As
Y
Y
Y?
Y?
Y?
Y
Y
Ba
Cd
Y
Y
Y
Y?
Y
Y?
Y?
Y
Y
Cr
Y
Y?
Y
Y
Y?
Pb
Y
Y?
Y
Y
Y?
HH
Y
Y
Se
Y
Y
Y
Y?
Y
Y?
Aq
Y
Y?
Y
Other Hazardous
Characteristics
Corr
N?
N?
N?
Y
N?
N?
N?
Y
N?
Y
N?
N?
N?
N?
N?
Y
N?
Igntt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Y
N?
Y
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Y
Y
Y
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Fluorspar and Hydrofluoric Acid
Raw fluorspar ore is crushed, ground, and
concentrated. Acid grade fluorspar (a pure form of
concentrate) is mixed with sulfuric acid in a heated
retort kiln, reacting to produce hydrogen fluoride gas
and fluorogypsum. The gas is cooled, scrubbed, and
condensed, and sold as either hydrofluoric acid
solution or anhydrous hydrogen fluoride.
Germanium
Germanium is recovered as a by-product of other
metals, mostly copper, zinc, and lead. Germanium-
bearing residues from zinc-ore processing facilities,
a main source of germanium metal, are roasted and
sintered. The sintering fumes, containing oxidized
germanium, are leached with suffuric acid to form a
solution. Germanium is precipitated from the
solution by adding zinc dust. Following precipitation,
the germanium concentrates are refined by adding
hydrochloric acid or chlorine gas to produce
germanium tetrachloride, which is hydrolyzed to
produce solid germanium dioxide. The final step
involves reducing germanium dioxide with hydrogen
to produce qermanium metal.
Waste Stream
Off-spec fluosilicic acid
Waste acid wash and
rinse water
Chlorinator wet air
pollution control sludge
Hydrolysis filtrate
Leach residues
Spent acid/leachate
Waste still liquor
Reported
Generation
(KiOOnWyr)
NA
NA
NA
NA
0.01
NA
NA
Est./Reported
Generation
(1000mt/yr)
Win
0
0.4
0.01
0.01
0.01
0.4
0.01
Avg.
15
2.2
0.21
0.21
0.01
2.2
0,21
Max
44
4
0.4
0.4
0.01
4
0.4
Number
of
Facilities
with
Process
3
4
4
4
3
4
4
TC Metals
As
Y?
Y?
Y?
Y?
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y?
H1
Se
Y?
Y?
Y?
Y?
A1
Y?
Y?
Y?
Y?
Other Hazardous
Characteristics
Corr
Y?
Y?
N?
N?
N?
Y?
N?
tgnit
N?
N?
N?
N?
N?
N?
Y?
Rctv
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Gold and Silver
Gold and Silver may be recovered from either ore or
the refining of base metals. Extracted ore Is crushed
or ground and then subjected to oxidation by
roasting, autociaving, bio-oxidation, or chlorination,
and then cyanide leaching (heap, vat, or agitation).
The metals are recovered by activated carbon
loading or the Merrill Crowe process. Activated
carbon loading involves bringing precious metal
leach solutions into contact with activated carbon by
the carbon-in-column, carbon-in-pulp, orcarbon-in-
leach process. Gold and silver are then separated
by acid leaching or electrolysis. The Merrill Crowe
process consistes of filtering and deaerating the
leach solution and then precipitating the precious
metals with zinc powder. The solids are filtered out,
melted and cast into bars. The recovery of precious
metals from lead refinery slimes is a normal part of
the operation called "desilverizing." Lead from
previous stages of refining is brought into contact
with a zinc bath which absorbs the precious metals.
Base metals are removed and the dore is sent to
refininq.
Lead
Lead ores are crushed, ground, and concentrated.
Pelletized concentrates are then fed to a sinter unit
with other materials (e.g., smelter byproducts, coke).
The sintered material is then introduced into a blast
furnace along with coke and fluxes. The resulting
bullion is drossed to remove lead and other metal
oxides. The lead bullion may also be decopperized
before being sent to the refining stages. Refining
operations generally consist of several steps,
including (in sequence) softening, desilverizing,
dezincing, bismuth removal and final refining.
During final refining, lead bullion is mixed with
various fluxes and reagents to remove remaining
impurities.
Waste Stream
Slag
Spent furnace dust
Acid plant sludge
Baghouse incinerator ash
Slurried ARC Dust
Solid residues
Spent furnace brick
Stockpiled miscellaneous
plant waste
WWTP solids/sludges
WWTP liquid effluent
Reported
Generation
(1000mt/yr)
NA
NA
14
NA
7
0.4
1
NA
380
2600
Est/Reported
Generation
(1000mt/yr)
Win
0,1
0.1
14
0.3
7
0.4
1
0.3
380
2600
Avg.
360
360
14
3
7
0.4
1
67
380
2600
Max
720
720
14
30
7
0.4
1
130
380
2600
Number
of
with
Process
16
16
3
3
3
3
3
3
3
3
TC Metals
As
Ba
Cd
Y
Y
Y
Y?
Cr
Pb
Y
Y
Y?
Y
Y
Y?
Y?
Hq
Se
Aft
Y?
Y?
Other Hazardous
Characteristics
Corr
N?
Y?
Y?
N?
N?
N?
N?
N?
Y
Y?
ignit
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Magnesium and Magnesia from Brines
Magnesium is recovered through two processes:
(1) electrolytic and (2) thermal. In electrolytic
aroduction with hydrous feed, magnesium hydroxide
s precipitated from seawater and settled out. The
underflow Is dewatered, washed, reslurried with
wash water, and neutralized with HCL and H,SO4.
The brine Is tittered, purified, dried, and fed into the
electrolytic cells. Alternatively, surface brine is
pumped to solar evaporation ponds, where it is dried,
concentrated, and purified. The resulting powder is
melted, fed into the electrolytic cells, and then
casted. The two thermal production processes for
magnesium are the carbothermic process and the
silicotherrnic process. In the carbothermic process,
magnesium oxide is reduced with carbon to produce
magnesium in the vapor phase, which is recovered
by shock cooling. In the silicothermic process, silica
is reacted with carbon to give silicon metal which is
subsequently used to produce magnesium.
Magnesia is produced by calcining magnesite or
magnesium hydroxide or by the thermal
decomposition of magnesium chloride, magnesium
sulfate, magnesium sulfite, nesquehonite, or the
basic carbonate.
Mercury
Mercury currently is recovered only from gold ores.
Sulfide-bearing gold ore is roasted, and the mercury
is recovered from the exhaust gas. Oxide-based
oolct or© is crustiGd snot mixscf with wstsr einti sent
to a classifier, followed by a concentrator. The
concentrate is sent to an agitator, where it is leached
with cyanide. The slurry is filtered and the filtrate is
sent to electrowinning, where the gold and mercury
are deposited onto stainless steel wool cathodes,
The cathodes are sent to a retort, where the mercury
vaporizes with other impurities. The vapor is
condensed to recover the mercury which is then
purified.
Waste Stream
Cast house dust
Smut
Dust
Quench water
Furnace residue
Report GO
Generation
(1000mt/yr)
NA
26
0.007
NA
0.077
EstTHeported
Generation
(1000mt/yr)
Min
0.076
26
0.007
63
0,077
Avg.
0.76
26
0.007
77
0.077
Max
7.6
26
0.007
420
0.077
Number
of
B2«i*III*I»«»
raciiiues
with
Process
1
2
7
7
7
TC Metals
As
Ba
Y?
Y
Cd
Cr
Pb
Y?
Hci
Y?
Y?
Y?
Se
Aa
Other Hazardous
Characteristics
Corr
N?
N?
N?
N?
N?
Ignit
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Molybdenum, Ferromolybdenum, and Ammonium
Molybdate
Production of molybdenum and molybdenum
products, including ammonium molybdate, begins
with roasting. Technical grade molybdic oxide is
made by roasting concentrated ore. Pure molybdic
oxide is produced from technical grade molybdic
oxide either by sublimation and condensing, or by
leaching. Ammonium molybdate is formed by
reacting technical grade oxide with ammonium
hydroxide and crystallizing out the pure molybdate.
Molybdenum powder is formed using hydrogen to
reduce ammonium molybdate or pure molybdic
oxide. Ferromolybdenum is typically produced by
reaction of technical grade molybdic oxide and iron
oxide with a conventional metallothermic process
using silicon and/or aluminum as the reductant.
Platinum Group Metals
Platinum-group metals can be recovered from a
variety of different sources, including electrolytic
slimes from copper refineries and metal ores. The
production of platinum-group metals from ore
involves mining, concentrating, smelting, and
refining. In the concentrating step, platinum ore is
crushed and treated by froth flotation. The
concentrates are dried, roasted, and fused in a
smelter furnace, which results in the formation of
platinum-containing sulfide matte. Solvent extraction
is used to separate and purify the six platinum-group
metals in the sulfide matte.
Rare Earths
Rare earth elements are produced from monazite
and bastnasite ores by sulfuric and hydrochloric acid
digestion. Processing of rare earths involves
fractional crystallization and precipitation followed by
solvent extraction to separate individual rare earth
elements from one another. Ion exchange or
calcium reduction produces highly pure rare earths in
small quantities. Electrolytic reduction of rare earth
chlorides followed by crushing produces a complex
alloy of rare earth metals commonly known as
mischmetal.
Waste Stream
Flue dust/gases
Liquid residues
Slag
Spent acids
Spent solvents
Spent ammonium nitrate
processing solution
Electrolytic cell caustic
wet APC sludge
Process wastewater
Spent scrubber liquor
Solvent extraction crud
Spent lead filter cake
Waste solvent
Wastewater from caustic
wet APC
Reported
Generation
(1000mt/yr)
NA
1
NA
NA
NA
14
NA
7
NA
NA
NA
NA
NA
EstTReported
Generation
(lOOOmtfyr)
Min
1.1
1
0.0046
0.3
0.3
14
0.07
7
0.1
0.1
0.17
0.1
0.1
Avg.
250
1
0.046
1.7
1.7
14
0.7
7
500
2.3
0.21
50
500
Max
500
1
0.46
3
3
14
7
7
1000
4.5
0.25
100
1000
Number
of
Facilities
with
Process
11
2
3
3
3
1
1
1
1
1
1
1
1
TC Metals
As
Y?
Ba
Cd
Y?
Cr
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y?
H1
Se
Y?
Y?
ACJ
Y?
Y?
Other Hazardous
Characteristics
Corr
N?
N?
N?
Y?
N?
Y
Y?
Y?
Y?
N?
N?
N?
Y?
Ignlt
N?
N?
N?
N?
Y?
N?
N?
N?
N?
Y?
N?
Y?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
»
Commodity
Rhenium
In general, rhenium is recovered from the off-gases
produced when molybdenite, a byproduct of the
arocessing of porphyry copper ores for molybdenum,
is roasted. During the roasting process, molybdenite
concentrates are converted to molybdic oxide and
rhenium oxides are sublimed and carried off with the
roaster flue gas. Rhenium is then recovered from
the off-gases by the following five steps: (1)
scrubbing; (2) solvent extraction or ion exchange; (3)
precipitation (addition of H?S and HCI) and filtration;
(4) oxidation and evaporation; and (5) reduction.
Scandium
Scandium is generally produced by small bench-
scale batch processes. The principal domestic
scandium resource is fluorite tailings containing
thortveitite and associated scandium-enriched
minerals. Scandium can be recovered from
thortveitite using several methods. Each method
involves a distinct initial step (i.e., acid digestion,
grinding, or chlorination) followed by a set of
common recovery steps, including leaching,
precipitation, filtration, washing, and ignition at
900 C to form scandium oxide.
Selenium
The two principle processes for selenium recovery
are smelting with soda ash and roasting with soda
ash. Other methods include roasting with fluxes,
during which the selenium is either volatilized as an
oxide and recovered from the flue gas, or is
incorporated in a soluble calcine that is subsequently
leached for selenium. In some processes, the
from the calcine. To purify the crude selenium, it is
dissolved in sodium sulfite and filtered to remove
with sulfuric acid to precipitate selenium. The
selenium precipitate is distilled to drive off impurities.
Waste Stream
Spent barren scrubber
liquor
Spent rhenium raffinate
Spent acids
Spent solvents from
solvent extraction
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste solids
Generation
{1000mt/yr)
NA
88
NA
NA
NA
66
NA
NA
NA
EstJReported
Generation
(lOOOmtfyr)
Mfn
0
88
0.7
0.7
0.05
66
0.05
0.05
0.05
Avg.
0.1
88
3.9
3.9
0.5
66
0.5
0.5
0.5
Max
0.2
88
7
7
5
66
5
5
5
Number
of
with
Process
2
2
7
7
3
2
3
3
3
TC Metals
As
Ba
Cd
Cr
Pb
Y?
Y
Ha
Se
Y?
Y?
Y?
Y?
Y1?
An
Other Hazardous
Characteristics
Corr
N?
N?
Y?
N?
N?
Y
N?
N
N?
Ignlt
N
N?
N?
Y?
N?
N?
N?
N?
N1?
Rctv
N
N?
N?
N?
N?
N?
N?
N?
N'
-------
EXHIBIT 1-2 (Continued)
Commodity
Synthetic Rutile
Synthetic rutile is manufactured through the
upgrading of ilmenite ore to remove impurities
(mostly iron) and yield a feedstock for production of
titanium tetrachloride through the chloride process.
The various processes developed can be organized
in three categories: (1) processes in which the iron
in the ilmenite ore is completely reduced to metal
and separated either chemically or physically;
(2) processes in which iron is reduced to the ferrous
state and chemically leached from the ore; and
(3) processes in which selective chlorination is used
to remove the iron. In addition, a process called the
Benelite Cyclic process uses hydrochloric acid to
leach iron from reduced ilmenite.
Tantalum, Columbium, and Ferrocolumbium
Tantalum and columbium ores are processed by
physically and chemically breaking down the ore to
form columbium and tantalum salts or oxides, and
separating the columbium and tantalum salts or
oxides from one another. These salts or oxides may
be sold, or further processed to reduce the salts to
the respective metals. Ferrocolumbium is made by
smelting the ore with iron, and can be sold as a
product or further processed to produce tantalum
and columbium products.
Tellurium
The process flow for the production of tellurium can
be separated into two stages. The first stage
involves the removal of copper from the copper
slimes. The second stage involves the recovery of
tellurium metal and purification of the recovered
tellurium. Copper is generally removed from slimes
by aeration in dilute sulfuric acid, oxidative pressure-
leaching with sulfuric acid, or digestion with strong
acid. Tellurous acid (in the form of precipitates) is
then recovered by cementing, leaching the cement
mud, and neutralizing with sulfuric acid. Tellurium is
recovered from the precipitated tellurous acid by the
following three methods: (1) direct reduction; (2) acid
precipitation; and (3) electrolytic purification.
Waste Stream
Spent iron oxide slurry
APC dust/sludges
Spent acid solution
Digester sludge
Process wastewater
Spent raffinate solids
Slag
Solid waste residues
Waste electrolyte
Wastewater
Reported
Generation
(lOOumtfYr)
45
30
30
1
150
2
NA
NA
NA
NA
EstJReported
Generation
(1000mt/yr)
Mfn
45
30
30
1
150
2
0.2
0.2
0.2
0,2
Avfl.
45
30
30
1
150
2
2
2
2
20
Max
45
30
30
1
150
2
9
9
20
40
Number
of
Facilities
with
Process
1
1
1
2
2
2
2
2
2
2
TC Metals
As
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Pb
Y?
Y?
H<^
Se
Y?
Y?
Y?
Y?
Y?
An
Other Hazardous
Characteristics
Corr
N?
N?
Y?
Y?
Y
Y?
N?
N?
N?
Y?
Igntt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Hctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Titanium and Titanium Dioxide
Titanium ores are utilized in the production of four
major titanium-based products: titanium dioxide
TiO2) pigment, titanium tetrachloride (TiCIJ, titanium
sponge, and titanium ingot/metal. The primary
titanium ores for manufacture of these products are
ilmenite and rutile, TiO2 pigment is manufactured
through either the sulfate, chloride, or chloride-
ilmenite process. The sulfate process employs
digestion of ilmenite ore or TiO2-rich slag with sulfurie
acid to produce a cake, which is purified and
calcined to produce TiO2 pigment. In the chloride
srocess, rutile, synthetic rutiie, or high-purity ilmenite
s chlorinated to form TiCl,, which is purified to form
ow-purity ilmenite is converted to TiCI4 in a two-stage
chlorination process. Titanium sponge is produced
ay purifying TiCl4 generated by the chloride or
chloride-ilmenite process. Titanium sponge is cast
into ingots for further processing into titanium metal.
Tungsten
Tungsten production consists of four distinct stages:
(1) ore preparation, (2) leaching, (3) purification to
APT, and (4) reducing APT to metal. Ore
preparation involves gravity and flotation methods.
Concentration is usually accomplished by froth
flotation, supplemented by leaching, roasting, or
magnetic or high tension separation. The
concentrate is then processed to APT via either
sodium tungstate or tungstic acid (which was
digested with aqueous ammonia) to solubilize the
tungsten as ammonia tungstate. Further purification
and processing yields APT. APT is converted to
tungsten oxide by calcining in a rotary furnace.
Tungsten oxides are reduced to metal powder in
high temperature furnaces. Tungsten carbide is
formed by reducing APT or tungsten oxides in the
presence of carbon.
Waste Stream
Pickle liquor and wash
water
Scrap milling scrubber
water
Smut from Mg recovery
Leach liquor and sponge
wash water
Spent surface
impoundment liquids
Spent surface
impoundments solids
Waste acids (Sulfate
process)
Waste acids (Chloride
process)
WWTP sludge/solids
Spent acid and rinse
water
Process wastewater
Reported
Generation
(1000mt/yr)
NA
NA
NA
NA
NA
36
NA
49
420
NA
NA
EsUReported
Generation
(WOQmtlyr)
Win
2.2
4
0.1
380
0.63
36
0.2
49
420
0
2.2
Avg.
2.7
5
22
480
3.4
36
39
49
420
0
4.4
Max
3,2
6
45
580
6.7
36
77
49
420
21
9
Number
of
Facilities
with
Process
3
1
2
2
7
7
2
7
7
6
6
TC Metals
As
Y
Ba
Cd
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y?
HC(
Se
Y?
Y
Y?
A1
Y
Other Hazardous
Characteristics
Corr
Y?
N?
N?
Y
N?
N?
Y
Y
N
Y?
Y?
Ignit
N?
N?
N?
N?
N?
N?
N
N
N
N?
N?
ectv
N?
N?
Y
N?
N?
N?
N
N
N
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Uranium
Uranium ore is recovered using either conventional
milling or solution mining (;'n situ leaching).
Beneficiation of conventionally mined ores involves
crushing and grinding the extracted ores followed by
a leaching circuit. In situ operations use a leach
solution to dissolve desirable uraniferous minerals
from deposits in-place. Uranium in either case is
removed from pregnant leach liquor and
concentrated using solvent extraction or ion
exchange and precipitated to form yellowcake.
Yellowcake is then processed to produce uranium
fluoride (UF6), which is then enriched and further
refined to produce the fuel rods used in nuclear
reactors.
Zinc
Zinc-bearing ores are crushed and undergo flotation
to produce concentrates of 50 to 60% zinc. Zinc is
then processed through either of two primary
processing methods: electrolytic or
pyrometallurgical. Electrolytic processing involves
digestion with sulfuric acid and electrolytic refining.
In pyrometallurgical processing, calcine is sintered
and smelted in batch horizontal retorts, externally-
heated continuous vertical retorts, or electrothermic
furnaces. In addition, zinc is smelted in blast
furnaces through the Imperial Smelting Furnace
process, which is capable of recovering both zinc
and lead from mixed zinc-lead concentrates.
Waste Stream
Waste nitric acid from
UO2 production
Vaporizer condensate
Superheater condensate
Slag
Uranium chips from ingot
production
Acid plant blowdown
Waste ferrosilicon
Process wastewater
Discarded refractory brick
Spent cloths, bags, and
filters
Spent goethite and leach
cake residues
Spent surface
impoundment liquids
WWTP Solids
Spent synthetic gypsum
TCA tower blowdown
Wastewater treatment
plant liquid effluent
Reported
Generation
(1000mt/yr)
NA
NA
NA
NA
NA
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
EsUReported
Generation
(1000mt/yr)
Min
1.7
1.7
1.7
0
1.7
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
Avg.
2.5
9.3
9.3
8.5
2.5
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
Max
3.4
17
17
17
3.4
130
17
5000
1
0.15
15.
1900
0.75
16
0.25
2600
Number
of
Facilities
with
Process
17
17
17
17
17
1
1
3
1
3
3
3
3
3
1
3
TC Metals
As
Y
Y
Y?
Y
Y?
Y?
Ba
Cd
Y
Y
Y?
Y?
Y
Y?
Y?
Y
Y?
Y?
Cr
Y
Y
Y?
Y
Pb
Y?
Y?
Y
Y?
Y?
Y?
Y?
Y?
Y?
HCJ
Y?
Y?
Y?
Y?
Y?
Se
Y
Y
Y?
Y
Y?
Y?
Aa
Y
Y
Y?
Y
Y?
Other Hazardous
Characteristics
Corr
Y?
Y?
Y?
N?
N?
Y
N?
Y
N?
N?
N?
Y
N?
N?
Y?
N?
Ignlt
N?
N?
N?
Y?
Y?
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 1-2 (Continued)
Commodity
Zirconium and Hafnium
The production processes used at primary zirconium
and hafnium manufacturing plants depend largely on
the raw material used. Six basic operations may be
performed: (1) sand chlorination, (2) separation, (3)
purification. Plants that produce zirconium and
hafnium from zircon sand use all six of these process
steps. Plants which produce zirconium from
zirconium dioxide employ reduction and purification
steps only.
Waste Stream
Spent acid leachate from
Zr alloy prod.
Spent acid leachate from
Zr metal prod.
Leaching rinse water from
Zr alloy prod.
Leaching rinse water from
Zr metal prod.
Generation
(1000mt/yr)
NA
NA
NA
NA
EsUReported
Generation
(1000mt/yr)
Min
0
0
34
0.2
Avg.
0
0
42
1000
Max
850
1600
51
2000
Number
of
with
Process
2
2
2
2
TC Metals
As
Ba
Cd
Cr
Pb
H1
Se
A1
Other Hazardous
Characteristics
Corr
Y?
Y?
Y'
Y?
Ignit
N?
N?
fv|9
N?
Rctv
N?
N?
N?
N?
I/ Corr., Ignit., and Rctv. refer to the RCRA hazardous characteristics of corrosivity, ignitability, and reactivity.
-------
c.
SUMMARY OF FINDINGS
EPA has determined that 48 commodity sectors generate a total of 553 waste streams that could be-
classified as either extraetion/beneficiation or mineral processing wastes. After careful review, EPA determined that
40 commodity sectors generate a total of 358 waste streams that could be classified as mineral processing wastes.
Of the 358 mineral processing waste streams identified by the Agency, EPA has sufficient information
(based on either analytical test data or engineering judgment) to determine that 133 waste streams (from 30
commodity sectors) are possibly RCRA hazardous wastes because they exhibit one or more of the RCRA hazardous
waste characteristics. Exhibit 1-3 identifies the mineral processing-commodity sectors that are likely to generate
RCRA, hazardous mineral processing wastes and therefore are likely to be subject to the Land Disposal Restrictions.
Exhibit 1-3 also summarizes the total number of hazardous waste streams by sector and the estimated total volume of
hazardous wastes generated annually. At this time, however, EPA has insufficient information to determine whether
the following sectors also generate wastes that could be classified as hazardous mineral processing wastes: Bromine,
Gemstones, Iodine, Lithium, Lithium Carbonate, Soda Ash, Sodium Sulfate, and Strontium.
EXHIBIT 1-3
IDENTIFICATION OF HAZARDOUS MINERAL PROCESSING WASTE STREAMS
LIKELY SUBJECT TO THE LDRs
Mineral Processing Commodity Sectors
Alumina and Aluminum
Antimony
Beryllium
Bismuth
Cadmium
Calcium Metal
Chromium and Ferrochromium
Coal Gas
Copper
Elemental Phosphorus
Fluorspar and Hydrofluoric Acid
Germanium
Gold and Silver
Lead
Magnesium and Magnesia from Brines
Mercurv
Molybdenum, Ferromolybdenum. and
Ammonium Molybdate
Platinum Group Metals
Rare Earths
Number of
Waste
Streams I/
2
3
3
10
11
1
2
1
8
6
1
6
2
8
2
3
"?
3
8
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
77
22
55
3,7
2.1
0.040
3.0
0
10,500
2,100
0
0.84
0.2
3,000
26
63
2.1
0.45
21
77
48
200
35
21
0.040
3.3
0
10,800
2,100
15
5.0
720
3,080
27
77
250
3.5
1.050
77
75
2.100
73
210
0.040
6.0
65
11.000
2,100
45
9.2
1400
3.200
34
420
500
6.5
2,100
22
-------
EXHIBIT 1-3 (Continued)
Mineral Processing Commodity Sectors
Rhenium
Scandium
Selenium
Synthetic Rutile
Tantalum, Columbium, and Ferroeolumbium
Tellurium
Titanium and Titanium Dioxide
Tungsten
Uranium
Zinc
Zirconium and Hafnium
TOTAL:
Number of
Waste
Streams 11
2
2
5
3
3
4
9
2
5
11
4
133
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
88
1.4
66
100
150
0,80
890
2.2
6.8
9,800
34
27,016
88
7.8
68
100
150
26
1,050
4.4
32
9,800
1,000
30,838
88
14
86
100
150
78
1,250
30
58
9,800
4,500
39,575
II In calculating the total number of waste streams per mineral sector. EPA included both non-wastewaters and wastewater mineral
processing wastes and assumed that each of the hazardous mineral processing waste streams were generated in all three waste generation
scenarios (low, medium, and high).
Exhibit 1-4 identifies those solid wastes from the processing of ores and minerals that are exempt from
RCRA Subtitle C regulation (as defined in 40 CFR Part 261.4(b)(7).
EXHIBIT 1-4
1
2
3
4
5
6
7
Slag from primary copper processing
Slag from primary lead processing
Red and brown muds from bauxite refining
Phosphorgympsum from phosphoric acid production
Slag from elemental phosphorus production
Gasifier ash from coal gasification
Process wastewater from coal gasification
-------
EXHIBIT 1-4 (continued)
8
9
10
11
12
13
14
15
16
17
18
19
20
Calcium sulfate wastewater treatment plant sludge from primary copper processing
Slag tailings from primary copper processing
Fluorogypsum from hydrofluoric acid production
Process wastewater from hydrofluoric acid production
Air pollution control dust/sludge from iron blast furnaces
Iron blast furnace slag
Treated residue from roasting/leaching of chrome ore
Process vvastwater from primary' magnesium processing by the anhydrous process
Process wastewater fromphosphoric acid productions
Basic oxigen furnace and open hearth furnace air pollution' control dust/sludge from carbon steel
production
Basic oxygen furnace and open hear furnace slag from carbon steel production
Chloride proces waste solids from titanium tetrachloride production
Slag from primary zinc processing
D.
Structure of the Document
The remainder of this document is organized into three additional sections. Section II discusses the data
sources and methodology used to develop the mineral commodity reports and to identify waste streams potentially
subject to RCRA Subtitle C. Section III presents the individual commodity summaries describing the uses of and
salient statistics pertaining to the particular commodity, a process description section with detailed, current process
information and process flow diagram(s), and waste streams generated by each process. Section IV summarizes the
findings of this study.
E.
Disclaimer
This document is intended solely to provide information to the public and the regulated
community regarding the wastes that are potentially subject to the requirements of this rule. This information was
also utilized by the Agency to assist in evaluating the potential impacts on the industry associated with complying
with the rule. While the guidance contained in this document may assist the industry, public and federal and state
regulators in applying statutory and regulatory requirements of RCRA, the guidance is not a substitute for those
legal requirements; nor is it a regulation itself. Thus, it does not impose legally-binding requirements on any party,
including EPA, States or the regulated community. Based on the circumstances, the conclusions in this document
may not apply to a particular situation, and EPA and State decision makers retain the discretion to adopt approaches
on a case-by-case basis that differ from this guidance where determined to be appropriate based on the facts of the
case and applicable statutes and regulations.
-------
II.
METHODS AND DATA SOURCES
This chapter details EPA's step-wise methodology for both defining the universe of mineral processing
sectors, facilities, and waste streams potentially affected by the proposed Phase IV Land Disposal Restrictions and
estimating the corresponding waste volumes.
The Agency developed a step-wise methodology that began with the broadest possible scope of inquiry to
ensure that EPA captured all of the potentially affected mineral commodity sectors and waste streams. The Agency
then narrowed the focus of its data gathering and analysis at each subsequent step. The specific steps and sources of
data employed throughout this analysis are described below, and are summarized in Exhibit 2-1.
EXHIBIT 2-1
Overview of the Agency's Methodology for Defining the Universe of Potentially
Affected Mineral Processing Waste Streams
STEP1
Identify Mineral
Commodity
Sectors of Interest
STEP 2
Conduct Exhaustive
Information Search on Mineral
Commodity Sectors of Interest
STEP 3
STEP 4
Prepare Mineral Commodity
Analysis Reports on
Each Sector
Define Universe of Mineral
Processing Waste Streams
Potentially Affected by
The Phase IV LDRs
STEPS
Define Universe of Mineral
Processing Facilities Potentially
Affected by the Phase IV LDRs
25
-------
A. Identify Mineral Commodity Sectors of Interest
Step One EPA reviewed the 36 industrial sectors (commodities) and 97
•I different general categories of wastes previously developed and published in
y
y
y
Identify Mineral Commodity I _ ,
sectors of interest the October 21, 1991 Advanced Notice of Public Rule Making (ANPRM).
EPA also reviewed the U.S. Bureau of Mines' 1991 Minerals Yearbook. 1995
Mineral Commodities Summary, and the 1985 Mineral Facts and Problems.
uct Exhausnvc intoruuuon search The Agency reviewed this comprehensive listing of all of the mineral
icra! Commodity Sectors of Interest j • < j r ri • i • 11
_ __ commodity sectors and removed from further consideration all non-
domestically produced mineral commodities; all inactive mineral
— — - commodities, such as nickel; and all mineral commodities generated from
operations known not to employ operations that meet the Agency's definition
— - - of mineral processing.1 As a result of this process, EPA identified a total of
62 mineral commodities that potentially generate "mineral processing" waste
streams of interest. These mineral commodity sectors are listed in Exhibit 2-
2.
The Agency notes that Exhibit 2-2 represents EPA's best efforts at
identifying mineral commodities that may generate mineral processing
_ _ _ — wastes. Omission or inclusion on this list does not relieve the generator of
the responsibility of appropriately managing wastes that would be subject to
RCRA Subtitle C requirements.
B. Conduct Exhaustive Information Search
EPA researched and obtained information characterizing the mineral processing operations and wastes
associated with the mineral commodities listed in Exhibit 2-2. This information was used by EPA both to update
existing data characterizing mineral processing wastes obtained through past Agency efforts and to obtain
characterization information on newly identified waste streams not previously researched.
To provide the necessary foundation to develop a fully comprehensive inventory of mineral commodity
sectors, facilities, and waste streams that might be affected by the Phase IV LDRs program, EPA embarked on an
ambitious information collection program. Specifically, to capitalize on information collected through past efforts,
as well as to collect more recent data, the Agency conducted the following activities:
• Reviewed mineral processing survey instruments (NSSWMPF) and public comments (submitted in
response to the 1991 ANPRM) for process-related information (e.g., process flow diagrams, waste
characterization data, and waste management information) contained in our in-house files.
• Reviewed numerous documents (e.g., Bureau of Mines publications, the Randol Mining Directory
and other Industrial Directories, and various Agency contractor reports) for process-related
information.
• Reviewed trip reports prepared both by EPA and its contractors from sampling visits and/or
inspections conducted at approximately 50 mineral processing sites located throughout the United
States.
1 Sectors that employ operations that mill (e.g., grind, sort, wash), physically separate (e.g., magnetic, gravity, or electrostatic
separation, froth flotation), concentrate using liquid separation (e.g., leaching followed by ion exchange), and/or calcine (i.e.,
heat to drive off water or carbon dioxide), and use no techniques that the Agency considers to be mineral processing operations
(e.g., smelting or acid digestion) are unaffected by the Phase IV LDRs.
26
-------
EXHIBIT 2-2
MINERAL COMMODITIES OF POTENTIAL INTEREST
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
20)
21)
22)
23)
24)
25)
26)
27)
28)
29)
30)
31)
Alumina
Aluminum
Ammonium Molybdate
Antimony
Arsenic Acid
Asphalt (natural)
Beryllium
Bismuth
Boron
Bromine (from brines)
Cadmium
Calcium Metal
Cerium, Lanthanides, and Rare Earths
Cesium/Rubidium
Chromium
Coal Gas
Copper
Elemental Phosphorus
Ferrochrome
Ferroehrome-Silicon
Ferrocolumbium
Ferromanganese
Ferromolybdenum
Ferrosilicon
Gemstones
Germanium
Gold and Silver
Hydrofluoric Acid
Iodine (from brines)
Iron and Steel
Lead
32)
33)
34)
35)
36)
37)
38)
39)
40)
41)
42)
43)
44)
45)
46)
47)
48)
49)
50)
51)
52)
53)
54)
55)
56)
57)
58)
59)
60)
61)
62)
Lightweight Aggregate
Lithium (from ores)
Lithium Carbonate
Magnesia (from brines)
Magnesium
Manganese and MnO2
Mercury
Mineral Waxes
Molybdenum
Phosphoric Acid
Platinum Group Metals
Pyrobitumens
Rhenium
Scandium
Selenium
Silicomanganese
Silicon
Soda Ash
Sodium Sulfate
Strontium
Sulfur
Synthetic Rutile
Tantalum/Columbium
Tellurium
Tin
Titanium/TiO,
Tungsten
Uranium
Vanadium
Zinc
Zirconium/Hafnium
27
-------
Step Two
• Reviewed sampling data collected by EPA's Office of Research and
Development (ORD), EPA's Office of Water (OW), and Agency
" .dennfy M,^^™^ ~ ~ survey data collected to support the preparation of the 1990 Repon
Sectors of Interest £
Reviewed the 1993, 1994, and 1995 "Mineral Commodity
ral Ci
Exhaustive information search | Summaries" prepared by the U.S. Bureau of Mines (BOM) for
salient statistics on commodity production.
— - — . Partially reviewed and summarized damage case information
Prepare Mineral Commodity Analysis . . , . rr^r
Repons on Each secior ' presented in the Mining Sites on the National Priorities List, NPL
~~ ~~ Site Summary Reports" to support work on assessing the
appropriateness of the Toxicity Characteristic Leaching Procedure
(TCLP) for mineral processing wastes.
y
y
• Contacted the BOM Commodity Specialists associated with the
commodity sectors of interest to (1) obtain current information on
mining companies, processes, and waste streams, and (2) identify
___________ other potential sources of information.
• Retrieved applicable and relevant documents from the BOM's FAXBACK document retrieval
system. Documents retrieved included monthly updates to salient statistics, bulletins, and
technology review papers.
• Conducted an electronic query of the 1991 Biennial Reporting System (BRS) for waste generation
and management information on 34 mineral processing-related Standard Industrial Classification
(SIC) numbers.
• Conducted an electronic literature search for information related to mineral processing and waste
treatment technologies contained in numerous technical on-line databases, including: NTIS,
Compendex Plus, METADEX, Aluminum Industry Abstracts, ENVIROLINE, Pollution Abstracts,
Environmental Bibliography, and GEOREF.
B.I Review of Hard Copy Reports, Comments, and Survey Instruments
Using the information obtained from our in-house files and the various BOM and contractor documents,
EPA was able to find process flow diagrams for the following 21 commodities:
• Alumina • Lightweight Aggregate
• Aluminum • Magnesium
• Antimony • Mercury
• Bismuth • Molybdenum
• Cerium/Lanthanides/Rare Earth Metals • Phosphoric Acid
• Cesium/Rubidium • Rhenium
• Coal Gas • Scandium
• Copper • Soda Ash
• Elemental Phosphorus • Synthetic Rutile
• Germanium • Titanium/TiO2
• Gold and Silver • • Tungsten
• Hydrofluoric Acid • Uranium
• Iron and Steel • Zinc
• Lead
28
-------
EPA also found either less detailed or fewer (in number) process flow diagrams for all of the remaining mineral
commodities except:
• Ammonium Molybdate « Gemstones
* Asphalt (natural) • Mineral Waxes
• Ferrocolumbium • Pyrobitumens
* Ferromolybdenum • Silicomanganese
« Ferrosilicon
EPA has been unable to locate any process information for the above nine commodities. All of the process-
related information that we retrieved was then photocopied and filed by commodity,
B.2 Electronic Literature Search
EPA devised a search strategy and performed an electronic literature search for journal articles, conference
reports, technical reports and bulletins, books, doctoral dissertations, patents, and news articles containing
information related to the production of mineral commodities, and the characterization and treatment of mineral
processing wastes. We searched the on-line databases summarized below in Exhibit 2-3.
Using the on-line databases summarized in Exhibit 2-3, we searched for relevant information (published
since 1990) on the mineral commodities listed in Exhibit 2-2 using the keywords presented in Exhibit 2-4. We chose
1990 as the cutoff year so as not to duplicate past information collection activities conducted by EPA and EPA
contractors, and to obtain information on mineral processes "retooled" since clarification of the Bevill Exclusion to
address truly "high volume, low hazard" mineral processing wastes.
Accordingly, using the strategy outlined in Exhibit 2-4, an article would have been selected if anywhere in
either the title, record descriptors, or full text, one of the mineral commodities listed in Exhibit 2-2 and the keywords
(waste, residue, wastewater, sludge, slag, dust, or blowdown) with one or more modifiers was found. For example, if
a particular record had the industrial sector - "alumina" or "aluminum" and the keyword - "waste" and the modifier -
"characteristics", the database record would have been selected. Unfortunately, this search strategy proved to be too
expansive; the first search for information on alumina and aluminum turned up over 3,000 citations. We therefore
elected to modify the search strategy by requiring the commodity, keyword, and modifier to be present in either the
title or record descriptor (and not in die full text). This modification allowed for a more manageable number of
citations - 1,242 titles,
To conserve resources, we first reviewed the results of the literature search output which contained the full
title of the selected record to see if the article seemed promising. If, based on our review of the title the record
appeared promising, we then requested the full abstract. We then reviewed the full abstract to further screen the
appropriateness of the record. If the abstract appeared relevant, we then ordered the document. Using the
alumina/aluminum example, we reviewed the 1,242 title citations and determined that it was necessary to request full
abstracts for 333 of the title citations. Using this protocol, we identified a total of 10,298 citations relating to one or
more of the commodities listed in Exhibit 2-2. We then reviewed the title citations and requested a total of 1,776 full
abstracts. Lastly, based on our review of the abstracts, we requested a total of 863 documents (using a tracking
system to ensure that a selected reference material was not requested more than once). The top five industrial sectors
that appear to be the most studied (based on number of citations meeting our search strategy specifications) are the
following:
Iron and Steel (1,460 titles);
• Alumina/Aluminum (1,242 titles);
Copper (1,081 titles);
« Chromium (833 titles); and
• Lead (800 titles).
29
-------
LO
o
EXHIBIT 2-3
SUMMARY OF ON-LINE DATABASES SEARCHED
Databases
Description
Subjects Covered
Sources
NTIS
Dales Covered
1964 to the present.
File Size
1,639,906 records as of 1/93.
Update Frequency
Biweekly.
The NTIS database consists of government-sponsored research,
development, and engineering plus analyses prepared by federal
agencies, their contractors, or grantees. It is the means through which
unclassified, publicly available, unlimited distribution reports are made
available for sale from agencies such as NASA, DDC, DOE, EPA,
HUD, DOT, Department of Commerce, and some 240 other agencies.
In addition, some state and local government agencies now contribute
iheir reports to the database. Truly multi-disciplinary, this database
covers a wide spectrum of subjects including: administration and
management, agriculture and food, behavior and society, building,
business and economics, chemistry, civil engineering, energy, health
planning, library and information science, materials science, medicine
and biology, military science, transportation, and much more,
Administration and Management — Aeronautics and
Aerodynamics — Agriculture and Food ~- Astronomy
and Astrophysics — Atmospheric Sciences — Behavior
and Society — Biomedieal Technology and Engineering
— Building Industry Technology — Business and
Economics — Chemistry — Civil Engineering —
Communication — Computers, Control, and Information
Theory — Electrotechnology — Energy — Environmental
Pollution and Control — Health Planning — Industrial
and Mechanical Engineering -- Library and Information
Sciences — Materials Sciences — Mathematical Sciences
~ Medicine and Biology — Military Sciences — Missile
Technology — Natural Resources and Earth Sciences —
Navigation, Guidance, and Control — Nuclear Science
and Technology — Ocean Technology and Engineering
— Photography and Recording Devices — Physics —
Propulsion and Fuels — Space Technology —
Transportation — Urban and Regional Technology.
The NTIS database represents the reports of
four major U.S. federal government
agencies: U.S. Department of Energy
(DOli), U.S. Department of Defense (DoD),
U.S. Environmental Protection Agency
(EPA), National Aeronautics and Space
Administration (NASA), plus many other
agencies.
COMPENDEX PLUS
Dates Covered
1970 to the present.
3,015,116 records as of 1/93.
Update Frequency
Weekly.
The COMPENDEX PLUS database is the machine-readable version of
the Engineering Index (monthly/annual), which provides abstracted
information from the world's significant engineering and technological
literature. The COMPENDEX database provides worldwide coverage
of approximately 4,500 journals and selected government reports and
books. Subjects covered include: civil, energy, environmental,
geological, and biological engineering; electrical, electronics, and
control engineering; chemical, mining, metals, and fuel engineering;
mechanical, automotive, nuclear, and aerospace engineering; and
computers, robotics, and industrial robots. In addition to journal
literature, over 480,000 records of significant published proceedings of
engineering and technical conferences formerly indexed in Ei
ENGINEERING MEETINGS are included.
Aeronautical and Aerospace Engineering — Applied
Physics (High Energy, Plasma, Nuclear and Solid Slate)
— Bioengineering and Medical Equipment — Chemical
Engineering, Ceramics, Plastics and Polymers, Food
Technology — Civil and Structural Engineering.
Environmental Technology — Electrical,
Instrumentation, Control Engineering, Power
Engineering -- Electronics, Computers,
Communications — Energy Technology and Petroleum
Engineering — Engineering Management and Industrial
Engineering — Light and Optical Technology -- Marine
Engineering, Naval Architecture, Ocean and
Underwater Technology - Mechanical Engineering,
Automotive Engineering and Transportation — Mining
and Metallurgical Engineering, and Materials Science.
Publications from around the world are
indexed, including approximately 4,500
journals, publications of engineering
societies and organizations, approximately
2,000 conferences per year, technical
reports, and monographs.
-------
EXHIBIT 2-3 (Continued)
SUMMARY OF ON-LINE DATABASES SEARCHED
Databases
Description
Subjects Covered
Sources
METADEX
Dates Covered
1966 to the present.
File Size
911,907 records as of 1/93.
Update Frequency
Monthly^
The METADEX (Metals Abstracts/Alloys Index) database, produced
by Materials Information of ASM International and the Institute of
Metals, provides comprehensive coverage of international metals
literature. The database corresponds to the printed publications:
Review of Metal Literature (1966-1967), Metals Abstracts (1968 to the
present), Alloys Index (1974 to the present), Steels Supplement
(1983-1984), and Steels Alert (January - June 1985). The Metals
Abstracts portion of the file includes references to about 1,200 primary
journal sources. Alloys Index supplements Metals Abstracts by
providing access to the records through commercial, numerical, and
compositional alloy designations; specific metallic systems; and
intermetallic compounds found within these systems.
Materials — Processes — Properties — Products — Forms
— Influencing Factors.
Each month over 3,(XX) new documents
from a variety of international sources are
scanned and abstracted for the ASM
database, with intensive coverage of
appropriate journals, conference papers,
reviews, technical reports, and books.
Dissertations, U.S. patents, and government
reports have been included since 1979,
British (GB) patents since 1982, and
European (EP) patents since 1986.
ALUMINUM INDUSTRY
ABSTRACTS
Dates Covered
1968 to the present.
File Size
172,000 records as of 7/93.
Update Frequency
Monthly.
ALUMINUM INDUSTRY ABSTRACTS (AIA), formerly World
Aluminum Abstracts (WAA), provides coverage of the world's
technical literature on aluminum, ranging from ore processing through
applications. The AIA database includes information abstracted from
approximately 2,300 scientific and technical journals, government
reports, conference proceedings, dissertations, books, and patents. All
aspects of the aluminum industry, aside from mining, are covered.
Aluminum Industry - General — Ores, Extraction of
Alumina and Aluminum -- Melting, Casting, and
Foundry — Physical and Mechanical Metallurgy —
Business Information — Extractive Metallurgy —
Metalworking, Fabrication, and Finishing —
Engineering Properties and Tests — Quality Control and
Tests — End Uses of Aluminum -- Aluminum
Intermetallics — Patents.
The AIA database includes information
abstracted from approximately 2,300
scientific and technical journals, patents,
government reports, conference
proceedings, dissertations, books, and other
publications.
ENVIROLINE
Dates Covered
January 1, 1971 to the present.
File Size
165,000 records as of 10/93.
Update Frequency
Monthly.
ENVIROLINE covers the world's environmental related information. It
provides indexing and abstracting coverage of more than 1,000
international primary and secondary publications reporting on all
aspects of the environment. These publications highlight such fields as
management, technology, planning, law, political science, economics,
geology, biology, and chemistry as they relate to environmental issues.
Air Pollution -- Environmental Design & Urban
Ecology — Energy — Environmental Education — Food
and Drugs — General Environmental Topics --
International Environmental Topics — Land Use &
Pollution -- Noise Pollution — Non-Renewable
Resources — Oceans and Estuaries — Population
Planning & Control — Radiological Contamination —
Renewable Resources - Terrestrial - Water -
Toxicology & Environmental Safety — Transportation -
Waste Management — Water Pollution — Weather
Modification & Geophysical Change -- Wildlife.
ENVIROLINE draws material from over
1,000 scientific, technical, trade,
professional, and general periodicals;
conference papers and proceedings;
government documents; industry reports;
newspapers; and project reports.
-------
EXHIBIT 2-3 (Continued)
SUMMARY OF ON-LINE DATABASES SEARCHED
Databases
Description
Subjects Covered
Sources
POLLUTION ABSTRACTS
Dates Covered
1970 to the present.
File Size
185,55! records as of 1/93,
Update Frequency
Bimonthly.
POLLUTION ABSTRACTS is a leading resource for references to
environmentally related literature on pollution, its sources, and its
control.
Air Pollution — Environmental Action — Freshwater
Pollution — Land Pollution — Marine Pollution — Noise
— Radiation — Sewage and Wastewater Treatment --
Toxicology and Health -- Waste Management.
References in POLLUTION ABSTRACTS
are drawn from approximately 2,500
primary sources from around the world,
including hooks, conference
papers/proceedings, periodicals, research
papers, and technical reports.
ENVIRONMENTAL
BIBLIOGRAPHY
Dates Covered
1973 to the present.
File Size
451,702 records as of 1/93.
Update Frequency
Bimonthly (4,000 records per
update).
ENVIRONMENTAL BIBLIOGRAPHY provides access to the
contents of periodicals dealing with the environment. Coverage
includes periodicals on water, air, soil, and noise pollution, solid waste
management, health hazards, urban planning, global warming, and
many other specialized subjects of environmental consequence.
Air — Energy — Human and Animal Ecology — Land
Resources — Nutrition and Health — Water Resources.
More than 400 of the world's journals
concerning the environment are scanned to
create ENVIRONMENTAL
BIBLIOGRAPHY.
-------
EXHIBIT 2-3 (Continued)
SUMMARY OF ON-LINE DATABASES SEARCHED
Databases
Description
Subjects Covered
Sources
GEOREF
Dales Covered
1785 to the present (North American
material).
1933 to the present (worldwide
material).
File Size
1,818,777 records as of 1/93.
Update Frequency
Monthly (approximately 6,700
records per update).
GEOREF, the database of the American Geological Institute (AGI),
covers worldwide technical literature on geology and geophysics.
GEOREF corresponds to the print publications Bibliography and Index
of North American Geology, Bibliography of Theses in Geology,
Geophysical Abstracts, Bibliography and Index of Geology Exclusive
of North America, and the Bibliography and Index of Geology.
GEOREF organizes and indexes papers from over 3,500 serials and
other publications representative of the interests of the twenty
professional geological and earth science societies that are members of
the AGI.
Areal Geology — Economic Geology — Energy Sources
— Engineering Geology — Environmental Geology —
Extraterrestrial Geology — Geochemistry —
Geochronology — Geomorphology — Geophysics —
Hydrology — Marine Geology — Mathematical Geology
-- Mineralogy -- Mining Geology — Paleontology —
Petrology -- Seismology -- Stratigraphy -- Structural
Geology - Surficial Geology.
GEOREF is international in coverage with
about 40 percent of the indexed publications
originating in the United States and the
remainder from outside the U.S.
Publications of international organizations
represent about 7 percent of the file. The
database includes coverage of over 3,500
journals as well as books and book chapters,
conference papers, government publications,
theses, dissertations, reports, maps, and
meeting papers.
MATERIALS BUSINESS FILE
Dates Covered
1985 to the present.
File Size
83,228 records as of 1/93.
Update Frequency
Monthly.
MATERIALS BUSINESS FILE covers technical and commercial
developments in iron and steel, nonferrous metals, composites,
plastics, etc. Over 1,300 publications including magazines, trade
publications, financial reports, dissertations, and conference
proceedings are reviewed for inclusion. Subjects covered are grouped
into nine categories: 1) Fuel, Energy Usage, Raw Materials,
Recycling; 2) Plant Developments and Descriptions; 3) Engineering,
Control and Testing, Machinery; 4) Environmental Issues, Waste
Treatment, Health and Safety; 5) Product and Process Development; 6)
Applications, Competitive Materials, Substitution; 7) Management,
Training, Regulations, Marketing; 8) Economics, Statistics, Resources,
and Reserves; and 9) World Industry News, Company Information, and
General Issues.
Fuel, Energy Usage, Raw Materials, Recycling -- Plant
Developments and Descriptions — Environmental
Issues, Waste Treatment, Health and Safety -- Product
and Process Development — Applications, Competitive
Materials, Substitution -- Management, Training,
Regulations, Marketing — Economics, Statistics,
Resources, and Reserves — World Industry News,
Company Information, and General Issues.
Each month over 1,300 magazines, trade
publications, journals, financial reports,
dissertations, and conference proceedings
are reviewed and abstracted from worldwide
sources.
UJ
UJ
-------
EXHIBIT 2-4
KEYWORDS AND SEARCH STRATEGY
Keywords
Industrial Sector with Waste
-- or --
Residue
— or —
Wastewater
-- or --
Sludge
-- or --
Slag
— or —
Dust
-- or --
Blowdown
Modifiers
with Characteristics
— or —
Composition
-- or -
Properties
-- or --
Recovery
— or —
Recycling
— or —
Reduction
-- or --
Generation
- or -
Management
- or --
Treatment
Finally, as part of the electronic literature search, we queried the Chemical Economics Handbook (CEH)
database prepared by SRI International and last updated in February 1994. Due to the high cost of using the
database (i.e., $85 per record — each chemical is divided into numerous records — and $3 per minute of on-line
time), we only attempted to retrieve information on the following ten commodities for which published information
is extremely limited or absent:
Arsenic Acid
Asphalt (natural)
Ferroalloys (all of them)
Manganese
Pyrobitumens
Rare Earths
Rubidium
Tantalum/Columbium
Waxes (mineral)
Zirconium/Hafnium
Limited process information was available only for ferroalloys, manganese, rare earths, waxes (natural), and
zirconium/hafnium.
B.3
Contacts with Bureau of Mines
EPA contacted commodity experts at the U.S. Bureau of Mines in an attempt to collect up-to-date
information on the names and locations of the facilities within each mineral sector. We also attempted to obtain
process and waste characterization information; however, only a limited number of commodity specialists were able
to provide such technical information. We present below in Exhibit 2-5, a listing of the Bureau of Mines personnel
contacted by EPA.
34
-------
EXHIBIT 2-5
LIST OF PERSONAL COMMUNICATIONS
Contacts
John Blossom
Larry Cunningham
Joseph Gambogi
James Hedrick
Henry Hillard
Steve Jasinski
Thomas Jones
Deborah Kramer
Peter Kuck
Roger Loebenstein
John Lucas
Phyllis Lyday
McCaulin
Dave Morris
Joyce Ober
John Papp
Robert Reese
Erol Sehnke
Gerald Smith
Telephone Nos.
202-501-9435
202-501-9443
202-501-9390
202-501-9412
202-501-9429
202-501-9418
202-501-9428
202-501-9394
202-501-9436
202-501-9416
202-501-9417
202-501-9405
202-501-9426
202-501-9402
202-501-9406
202-501-9438
202-501-9413
202-501-9421
202-501-9431
Commodity Sectors
Molybdenum
Rhenium
Columbium (niobium)
Tantalum
Zirconium/Hafnium
Cerium
Lanthanides
Rare Earths
Scandium
Vanadium
Mercury
Selenium
Tellurium
Manganese
Beryllium
Cadmium
Arsenic Acid
Platinum Group Metals
Gold
Bromine
Iodine
Antimony
Elemental Phosphorus
Phosphoric Acid
Lithium
Chromium
Ferrochrome
Ferroehrome-silicon
Cesium
Rubidium
Silver
Alumina
Aluminum
Germanium
Tungsten
35
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B.4 Review of Outside Data/Reports
In light of both the significant changes in the regulatory status of many of these wastes and the passing of
several years since the 1991 ANPRM was published, EPA also reviewed several additional information sources:
« Sampling Data from EPA's Office of Research and Development
• Data from the Effluent Guidelines from the Office of Water
• Survey Data contained in the 1990 Report to Congress
* Publications from the Bureau of Mines, Randol Mining Directory, and other Industrial
Directories and Sources
« Files available form the Waste Treatment Branch and the Special Wastes Branch in OSW
* Industry Profiles
• Comments and Information received through the 1991 ANPRM
to (1) determine which industrial commodities and waste streams are still generated today and (2) identify new
commodities and/or waste streams that should be added to the existing universe.
EPA also queried the 1991 Biennial Reporting System (BRS) for waste generation and management
information on 34 mineral processing-related Standard Industrial Classification (SIC) numbers. Specific information
requested included:
- RCRA Facility Identification No. - Facility Name
- Location (City & State) - Origin Code
- Source Code - Form Code
- Waste Volume - On-site/Off-site Management
- EPA Hazardous Waste ID No.(s)
As shown in Exhibit 2-6, the 1991 BRS contained data for 24 of the 34 mineral processing-related SIC
numbers (71 percent). We note that several of these SICs encompass a wide variety of mineral/inorganic chemical
products. For example, SIC 2819 represents "Industrial Inorganic Chemicals, Not Elsewhere Classified," which
includes more than 170 products ranging from activated carbon, alkali metals, and alumina to tin salts, water glass,
and zinc chloride. Although some of these materials are outside the scope of primary mineral processing, there was
no effective way to screen these products from the BRS search.
Also shown in Exhibit 2-6 is the relative ranking of the quantity of available information contained in the
BRS (1 being the greatest and 24 being the smallest). The top five SIC number categories are:
« SIC 2819 - Industrial Inorganic Chemicals, Not Elsewhere Classified;
* SIC 3312 - Blast Furnaces (including Coke Ovens), Steel Works, and Rolling Mills;
* SIC 3334 - Primary Smelting and Refining of Aluminum;
SIC 2812 - Alkalies and Chlorine; and
» SIC 3339 - Primary Smelting and Refining of Nonferrous Metals, Not Elsewhere
Classified.
36
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EXHIBIT 2-6
SUMMARY OF SIC CODES SEARCHED IN THE 1991BRS
SIC Code
1011
1021
1031
1041
1044
1051
1061
1092
1094
1099
1446
1452
1453
1455
1459
1472
1473
1474
1475
1477
1479
1499
2812
2819
2874
3274
3295
3312
INDUSTRIAL COMMODITY SECTOR
Iron Ores
Copper Ores
Lead and Zinc Ores
Gold Ores
Silver Ores
Bauxite and Other Aluminum Ores
Ferroalloy Ores, Except Vanadium
Mercury Ores
Uranium-Radium-Vanadium Ores
Metal Ores Not Elsewhere Classified
Industrial Sand
Bentonite
Fire Clay
Kaolin and Ball Clay
Clay, Ceramic, and Refractory Minerals, Not Elsewhere
Classified
Barite
Fluorspar
Potash, Soda, and Borate Minerals
Phosphate Rock
Sulfur
Chemical and Fertilizer Mineral Mining, Not Elsewhere
Classified
Miscellaneous Nonmetallic Minerals, Not Elsewhere
Classified
Alkalies and Chlorine
Industrial Inorganic Chemicals, Not Elsewhere'Classified
Phosphatic Fertilizers
Lime
Minerals and Earths, Ground or Otherwise Treated
Blast Furnaces (Including Coke Ovens), Steel Works, and
Rolling Mills
REPORTED
IN 1991 BRS
Yes
Yes
Yes
Yes
Yes
No
Yes
No
Yes
Yes
Yes
No
No
No
No
Yes
No
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
RANK IN
BRS
8
7
19
9
17
-
22
-
21
16
20
-
-
-
-
15
-
23
14
-
24
10
4
1
12
18
13
2
37
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EXHIBIT 2-6 (Continued)
SUMMARY OF SIC CODES SEARCHED IN THE 1991BRS
SIC Code
3313
3331
3332
3333
3334
3339
INDUSTRIAL COMMODITY SECTOR
Electrometallurgical Products
Primary Smelting and Refining of Copper
Primary Smelting and Refining of Lead
Primary Smelting and Refining of Zinc
Primary Smelting and Refining of Aluminum
Primary Smelting and Refining of Nonferrous Metals, Not
Elsewhere Classified
REPORTED
IN 1991 BRS
Yes
Yes
No
No
Yes
Yes
RANK IN
BRS
6
11
.
-
3
5
It is not surprising that the above SIC number categories comprise the top five because these industries are (1)
known to generate listed hazardous wastes such as K061, K062, K064, K065, K066, K071, K088, K090, K09L and
K106, and (2) are SICs that encompass a wide variety of mineral/inorganic chemical products. The lack of
information for the other mineral processing related wastes may be explained by the age of the data evaluated.
Specifically, the most recent data available at the time of the original analysis were from the 1991 Biennial Reports.
Thus, at that time many of the respondents (and potential respondents) might not yet have been required to manage
their mineral processing-derived wastes as if they were no longer considered "high volume, low toxicity wastes."
Although EPA did not perform an exhaustive review and analysis of the BRS reports, it appears as though
the bulk of the records contained in the BRS appear to be related to non-mineral processing activities (e.g., painting
wastes, laboratory wastes, used oil, discarded chemicals, and cleaning/degreasing wastes). The BRS does, however,
contain limited information on production-derived wastes, product filtering wastes, spent process liquids, routine
cleaning wastes, and wastes from rinsing operations (flushing, dipping, and spraying). The typical types of wastes
include:
Halogenated and non-halogenated solvents;
Thinners and petroleum distillates;
Other halogenated and non-halogenated organic
solids;
Asbestos solids and debris;
Caustics with inorganics and cyanide;
Caustics with inorganics;
Reactive sulfide and salts;
Other inorganic sludges;
Air pollution control wastes;
Solvent extraction wastes; and
Spent acids.
Much of the information reported is for listed hazardous wastes. For example, within the SIC 3312
classification, the following EPA Hazardous Waste Identification Numbers were used at least once (but not at every
facility):
D001
D002
D003
D004
D005
D006
D007
D008
D028
D029
D030
D032
D034
D035
D036
D038
F008
F012
K060
K061
K062
K087
P010
POO
P119
U002
U012
U019
U044
U080
U144
U154
38
-------
D009 D039 P022 U159
D010 D040 P029 U161
DO 11 F001 P030 U196
D018 F002 P039 U201
DO 19 F003 P048 U210
D021 F004 P098 U211
D022 F005 PI 04 U218
D026 F006 PI 05 U220
D027 F007 PI 06 U239
Lastly, although we did not perform a rigorous analysis, it seems that most of the reported wastes were
managed off-site. Treatment/disposal options for wastes that were reportedly managed on-site included wastewater
treatment, discharge to a publicly owned treatment works (POTW), incineration, deep-well injection, stabilization
and land disposal, and materials (e.g., metals) recovery.
After an exhaustive search through both the publicly available and Agency-held information sources, EPA
assembled and organized all of the collected information by mineral commodity sector.
C. Prepare Mineral Commodity Analysis Reports
Step Three
f
As discussed above, EPA embarked on its information collection
program to collect current information on relevant mineral processes, salient
statistics, waste characteristics, waste generation rates, and waste management
information. All of the publicly available information was collected,
evaluated for relevance (both applicability and age), and compiled to prepare
conduct Eshausnve information search 49 analyses covering 62 mineral commodities. Each mineral commodity
on Mineral Commodity Sectors of Interest
— — -• analysis report consists of three major sections:
V
• A commodity summary describing the uses and salient statistics
Prepare Mineral Commodity Analysis I . .
on Each sector I of the particular mineral commodity or commodities.
7
• A process description section with detailed, current process
Define Universe of Mineral Processing Waste information and pTOCCSS flOW diagTaiTl(s).
Streams Potentially Affected by
_ _ The Phase IV LDRs _ _
• A process waste stream section that identifies — to the
_ ~ _ — maximum extent practicable — individual waste streams, sorted
by the nature of the operation (i.e., extraction/beneficiation or
— — — - mineral processing).2 Within this section, EPA also identified:
waste stream sources and form (i.e., wastewater (<1 percent solids and total organic content), 1-
10 percent solids, and >10% solids);
Bevill Exclusion status of the waste stream (i.e., extraction/beneficiation waste stream, mineral
processing waste stream, or non-uniquely associated waste stream);
waste stream characteristics (total constituent concentration data, and statements on whether the
waste stream does or is likely to exhibit one of the RCRA hazardous waste characteristics of
toxicity, ignitability, corrosivity, or reactivity);
annual generation rates (reported or estimated);
2 EPA strongly cautions that the process information and identified waste streams presented in the commodity sector reports
should not be construed to be an authoritative list of processes and waste streams. These reports represent a best effort, and may
not include every potential process and waste stream. Furthermore, the omission of an actual waste stream (and thus its not being
classified as either an extraction/beneficiation or mineral processing waste in this report) does not relieve the generator from its
responsibility of correctly determining whether the particular waste is covered by the Mining Waste Exclusion.
39
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management practices (e.g., tank treatment and subsequent NPDES discharge, land disposal, or
in-process recycling); and
whether the waste stream was being (or could potentially be) recycled, and thus be classified as
either as a sludge, by-product, or spent material.
The collection and documentation of the commodity summary and process description sections of the
mineral commodity analysis reports was relatively straightforward and involved little interpretation on the pan of
EPA. However, the preparation of the process waste stream sections of the mineral commodity analysis reports
required extensive analysis and substantive interpretation of the publicly available information by the Agency, The
process used by EPA to develop descriptions of waste stream sources, form, characteristics, management, and
recyclability is described below.
C.I Bevill-Exclusion Status
Determining the Special Waste Status of Mineral Industry Wastes
EPA used the Agency's established definitions and techniques for determining which operations and waste
streams might be subject to LDR standards. EPA decisions concerning whether individual wastes are within the
scope of the RCRA Mining Waste Exclusion are based upon a number of different factors. The Agency examines
these factors in sequence, in such a way as to yield unambiguous and consistent decisions from site to site and across
all regions of the country. The basic thought process is illustrated conceptually in the flow diagram presented on the
next page (Exhibit 2-7).
By resolving the basic questions posed in this diagram in step-wise fashion, persons should be able to
generally understand the special waste status of any individual mineral production waste. The steps in this process
are outlined below. The sequence of these steps is very important, as the need for proceeding to the next step is
determined by the answer to the question posed in the current step. Of particular importance is determining the point
at which mineral processing first occurs; all wastes generated after that initial processing step are considered
processing wastes or downstream manufacturing wastes.
EPA's evaluation sequence proceeds as follows:
* Ascertain whether the material is considered a solid waste under RCRA,
* Determine whether the waste is generated by a primary mineral production step, and, more generally,
whether or not primary production occurs in the sector/within a process type.
• Establish whether the waste and the operation that generates it are uniquely associated with mineral
production.
* Determine whether the waste is generated by a mineral extraction, beneficiation, or processing step.
• Check to see whether the waste, if it is a processing waste, is one of the 20 special wastes from
mineral processing. This analytical sequence results in one of three outcomes:
(1) the material is not a solid waste and hence, not subject to RCRA;
40
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EXHIBIT 2-7
Process Summary for Mining Waste Exclusion Determinations
Material
in Question
Not Subject
to RCRA
Generated by
Primary Mineral
Production?
Uniquely
Associated
with Mineral
Production?
Not Covered
by the Mining
Waste Exclusion
(See Exhibit 3-9)
(e.g., spent solvents,
used oil. lab wastes)
(e.g., alloying wastes,
chemical manufacturing
wastes)
Generated
Downstream of
Initial Processing
Operation?
Reclaimed
With No Land
Storage?
Generate
by Extraction or
Beneficiation
Operation1;
Generated
by Processing
Operation?
One of the
20 Special Mineral
Processing
Wastes?
Exempt from
RCRA Subtitle C
41
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(2) the material is a solid waste but is exempt from RCRA Subtitle C because of the Mining Waste
Exclusion; or
(3) the material is a solid waste that is not exempt from RCRA Subtitle C and is subject to regulation as a
hazardous waste if it is listed as a hazardous waste or it exhibits any of the characteristics of
hazardous waste.3
General Considerations
The first step in evaluating whether or not wastes produced by a facility are excluded from RCRA Subtitle
C regulation is to establish whether primary mineral production takes place at the facility. The Mining Waste
Exclusion does not apply to secondary production of mineral commodities; wastes from scrap recycling, metals
recovery from flue dust, and similar activities have always been subject to Subtitle C regulation if these wastes
exhibit hazardous characteristics or are listed hazardous wastes (as some are).
Primary mineral production operations are defined as those using at least 50 percent ores,
minerals, or beneficiated ores or minerals as the feedstock(s) providing the mineral value. In addition, the Exclusion
is limited in scope to wastes from the extraction, beneficiation, and processing of ores and minerals; it does not
extend to alloying or to downstream chemical manufacturing, metal casting or fabrication, or other activities that use
a saleable commodity (e.g., carbon steel, cathode copper, titanium tetraehloride, merchant grade phosphoric acid) as
the primary raw material.
It may, therefore, be possible to establish easily and quickly that a particular facility and its wastes are not
eligible for special waste status. If primary mineral production does not occur at the facility, then, by definition, the
Mining Waste Exclusion does not apply to any of the wastes that the facility generates. The key questions that arise
here are, "What does this facility produce?" and "From what?" If the facility does not produce intermediate or final
mineral commodities from a raw material mix containing at least 50 percent ores, minerals, or beneficiated ores or
minerals, then no wastes generated at the site are eligible for the Exclusion, and the facility (and its wastes) has the
same RCRA status as that of any other industrial plant.
If (and only if) it has been determined by EPA that primary mineral production occurs at a particular
facility, then the analytical focus can shift to specific operations, materials, and waste streams.4 In that instance, the
next logical question is whether or not the material in question is a solid waste. If the material is not a solid waste,
then the question of whether the Mining Waste Exclusion applies will be irrelevant, because RCRA requirements
will not apply to that material. In general, EPA's position has always been that materials that are discarded or are
managed in a waste-like manner (e.g., placed on the ground) are solid wastes and subject to RCRA. This policy is
amplified and tailored to the particular circumstances found in the minerals industry in today's final rule. EPA is
today establishing a conditional exclusion from the definition of solid waste for secondary materials from mineral
processing that are recycled; the conditions for the exclusion are no land placement of the materials5, legitimate
recovery of metals, water, acid, and/or cyanide values, and no speculative accumulation of secondary materials. A
one-time notification also is required. EPA recognizes that establishing whether a material is a solid waste may be
difficult, but believes that this determination needs to be made so that the regulatory status of the material in question
can be ascertained.
3 RCRA Subtitle C regulations define toxicity as one of the four characteristics of a hazardous waste. EPA uses the Toxicity
Characteristic Leaching Procedure (TCLP) to assess whether a solid waste is a hazardous waste due to toxicity. In today's final
rule, EPA is reinstating the application of the TCLP to mineral processing wastes in response to a Court remand. For further
discussion, see the preamble to today's final rale.
4 Because of the confusion regarding the scope of the Mining Waste Exclusion that has occurred in the past, EPA believes
that it is important to clarify its long-standing position that the Exclusion applies to wastes, not to facilities. Therefore, it must be
understood that claims that a particular facility is "exempt" from regulation under Subtitle C because of the Bevill Amendment
are inaccurate; the applicability of the Exclusion is judged "one waste at a time."
* Site-specific waivers of the land placement prohibition may be obtained from delegated state agencies for storage of solid
(i.e., no free liquids) materials on concrete or asphalt pads, provided that run-on/run-off controls are installed, fugitive dust is
controlled, and all of these constituent release controls are maintained properly.
42
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Once it has been determined that a material is a solid waste generated by a facility engaged in primary
mineral production, the more difficult questions concerning whether the waste is excluded from Subtitle C
requirements may be tackled. In evaluating whether a particular solid waste is or is not covered by the Mining Waste
Exclusion. EPA starts at the beginning of the production sequence, i.e., where the ores or minerals are in their most
impure form, and focuses on the operations in the production sequence that are directly involved in producing the
mineral commodity. It is very important to follow the sequence of production operations carefully. The same
activities, occurring at different points in the production sequence, may generate wastes that are classified very
differently under the Mining Waste Exclusion.
It is worth emphasizing that only wastes that are "uniquely associated" with primary mineral production
operations are eligible for special waste status. All other types of wastes are not eligible for special waste status.
even if they are generated and/or managed at a mineral production site, and even if that site generates some wastes
that are defined as special wastes. This "uniquely associated" concept is discussed in greater detail in the next
section.
It is also worthy of note that spills of certain materials require prescribed actions on the part of the facility
operator. If the spilled substance has a Reportable Quantity (RQ) limit and that limit is exceeded, then the facility
operator must report the incident to the appropriate regulatory authority.6 This requirement has been established by
EPA pursuant to the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA);
accordingly, it is not affected by the Mining Waste Exclusion to RCRA. That is, exempt status (or even the question
of whether a material is a solid waste) has no bearing on whether or not the spill reporting requirements must be met.
The Uniquely Associated Concept - "Indigenous" to Mineral Production or Not?
As mentioned earlier, in order for a waste generated at a mineral production site to be eligible for special
waste status, it must be "uniquely associated" with the extraction or beneficiation of ores and minerals and with
certain processing wastes. The Agency believes that the following summary of the uniquely associated concept can
enable persons to understand the required site-specific decisions unambiguously:
(1) Uniquely associated mineral production wastes originate from, and obtain all or substantially
all of their chemical composition through direct contact with, ores, minerals, or beneficiated
ores or minerals;
(2) Operations that generate uniquely associated wastes are restricted to those that serve to remove
mineral values from the ground, concentrate or otherwise enhance their characteristics, remove
impurities, or are part of a sequence leading to the production of a saleable mineral product; and
(3) Wastes from all ancillary operations (e.g., vehical maintenance shop) taking place at mineral
extraction, beneficiation, and processing sites are not uniquely associated.
This concept has been a central part of EPA's interpretation of the Bevill Amendment since the Agency's
first response to Congressional directives was published in 1980 and is illustrated in the example provided in
Highlight 1. In this notice, EPA stated that
Reportable quantity substances, limits, and requirements may be found at 40 CFR Part 301.
43
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[T]his exclusion does not, however,
apply to solid wastes, such as spent
solvents, pesticide wastes, and discarded
commercial chemical products, that are
not uniquely associated with these
mining and allied processing operations,
or cement kiln operations. Therefore,
should either industry generate any of
these non-indigenous wastes and the
waste is identified or listed as hazardous
under Part 261 of the regulations, the
waste is hazardous and must be
managed in conformance with the
Subtitle C regulations. (45 FR 76619,
November 19, 1980)
The Agency further stated at 54 FR 36616 (September 1,
1998) that:
Highlight 1.
Lubrication Wastes
Chemical Spills
and
EPA reviewed the claims of a company in
the minerals industry in 1992, regarding the regulatory
status of several wastes generated at its lanthanide
production facility. Among the wastes discussed were
pinion gear grease and residues from cleanup of spills
of clean solvents that are used in solvent extraction
operations. EPA concluded that these wastes were not
uniquely associated with mineral extraction,
beneficiation, or processing operations, and thus, were
not excluded wastes. EPA based this conclusion on
the fact that these wastes do not originate from, and do
not obtain their chemical composition primarily
through direct contact with, ores, minerals, or
beneficiated ores or minerals.
"Congress intended to put within the regulatory exclusion only wastes generated as a consequence of
exploiting a natural resource, not wastes from other industrial activities, even if both occur at the same
facility".
EPA reiterated the "non uniquely associated" standard in the 1989 Final Bevill Rule:
[T]he Agency finds no compelling reason to provide exemptions for particular small volume wastes that
may be associated with mineral processing operations, such as cleaning wastes. Many other industrial
operations also generate such wastes, and EPA does not believe that the fact that current management
involving co-management justifies continued regulatory exclusion...
The Agency has repeatedly applied the uniquely associated concept to delineate the boundaries of the Mining Waste
Exclusion since that time, and it remains a key determinant of whether or not a particular waste should be afforded
exclusion from RCRA Subtitle C. In fact, EPA addressed this issue at length in the preambles to its final rules
establishing the boundaries of the Mining Waste Exclusion for mineral processing wastes.
Mineral extraction, beneficiation, and processing facilities usually generate some wastes that are not unique
to mineral production, some of which may exhibit characteristics of hazardous waste. It is critical to understand that
such wastes are not and have never been exempt from regulation as hazardous wastes under RCRA Subtitle C. To the
extent that any such materials are solid wastes and are listed or exhibit characteristics of hazardous wastes, they must
be managed as hazardous wastes, i.e., in accordance with the standards found at 40 CFR Parts 261-264 or analogous
state requirements.
The Agency believes that it is appropriate to evaluate whether a particular waste is uniquely associated with
mining and mineral processing as follows:
(1) Any waste from ancillary operations are not "uniquely associated" because they are not properly
viewed as being "from" mining or mineral processing;
(2) In evaluating wastes from non-ancillary operations, one must consider the extent to which the waste
originates or derives from processes that serve to remove mineral values from the ground,
concentrated or otherwise enhance their characteristics or remove impurities; and
(3) The extent to which the mineral recovery process imparts its chemical characteristics to the waste.
Under this test, the greater the extent to which the waste results from the mineral recovery process
itself, and the more the process imparts to the waste its chemical characteristics, the more likely the
waste is "uniquely associated."
44
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The Agency believes that this approach provides a reasonable basis to determine whether a waste is
"uniquely associated."
The Agency believes that these factors touch on the full range of facts that are likely to be relevant in any
particular case. As is evident from the criteria summarized above, judgment must be exercised where the question is
whether a waste from a non-ancillary operation is uniquely associated. EPA believes that this is appropriate because
of the fact-specific nature of this determination and the myriad circumstances that can arise. However, as noted
above, the Agency believes that wastes generated from ancillary operations (such as truck maintenance shops at a
mine and not from the mining or mineral recovery process itself), are not uniquely associated. Such circumstances
would likely present the most readily identifiable cases of non-uniquely associated wastes.
The approach noted above reflects the longstanding principle, based on the clear language in Section 3001
of RCRA, that uniquely associated wastes must result from mining and mineral processes themselves. This approach
also is generally consistent with industry's underlying contention that the uniquely associated concept should exempt
wastes that are "indigenous" to mining. EPA disagrees, however, with industry's contention that uniquely associated
wastes are any wastes that are unavoidably generated by mining operations.
Examples of non-exempt wastes that may be found at mineral extraction, beneficiation, and/or processing
sites, and that may be subject to regulation if they are listed as hazardous wastes or exhibit characteristics of
hazardous waste, include (but are not limited to) the following:
• Cleaning wastes (e.g., spent solvents);
• Used oil and antifreeze from motor vehicles and equipment;
« Wastes from automotive and equipment maintenance shops;
• Pesticide, painting, and other chemical product wastes;
• Off-specification products;
• Spills (including contaminated soil) of any material outside of the primary mineral commodity
production process, including unused beneficiation or processing reagents (e.g., sodium
cyanide);
» Laboratory wastes (e.g., cupels, spent or contaminated reagents);
* Certain types of wastewater treatment sludges.7
Evaluating whether or not a particular waste is uniquely associated with primary mineral production
operations should be straightforward in most cases. The key concept to bear in mind is that the composition and
chemical characteristics of uniquely associated wastes are determined, or at least heavily influenced, by whether they
are generated from resources that serve to remove or concentrate mineral values. Accordingly, wastes generated by
generic industrial activities (e.g., vehicle or machinery operation, maintenance, or cleaning), laboratory operations,
painting, pesticide application, and plant trash incineration, among others, are not uniquely associated and therefore,
are not eligible for the Mining Waste Exclusion. In addition, discarded, spilled, or off-specification chemicals are
ineligible for the same reason. (See Highlight 2.)
Finally, as a practical matter, the uniquely associated question is critical only in determining the exempt
status of wastes from extraction and beneficiation operations. All mineral processing wastes except for the 20
specific wastes listed at 40 CFR Part 261.4(b)(7) have been removed from the scope of the Exclusion through formal
rulemaking procedures. Therefore, all solid wastes produced by mineral processing operations (except the 20
7 Only sludges resulting from mineral extraction and beneficiation operations plus the 20 exempt mineral processing wastes
are covered by the exclusion: all other treatment sludges are not exempt under the Mining Waste Exclusion.
45
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specific wastes) are either not uniquely associated or were removed from the Exclusion through rulemaking. In
either case, such wastes are not covered by the Mining Waste Exclusion.
Highlight 2.
Off-Specification Products
In response to an inquiry related to the special waste status of
several materials generated at a facility that produces boron and related
products from brines, in 1992 EPA stated, "The Bevill Exclusion does not
apply to solid wastes such as discarded commercial chemicals; they are
not uniquely associated with mineral extraction, beneficiation, or
processing. Discarded commercial chemicals include finished mineral-
derived products that are generated at these plants but found to be off-
specification and, thus, are discarded. Other wastes not uniquely
associated with mineral extraction, beneficiation, or processing include
many cleaning wastes (such as spent commercial solvent that was used in
cleaning production vessels) and used lubricating oils."
Consequently, the need to
determine whether a waste is or is not
uniquely associated is limited to
operations in the upstream end of the
production sequence, which is generally
simpler and easier to understand from a
conceptual standpoint than downstream
processing and/or manufacturing
operations. The issue of where the "line"
between beneficiation and
processing lies and how this line is
applied to individual mineral production
facilities is discussed below.
Definitions of Beneficiation and Processing - Finding the Line
Once it has been established that extraction, beneficiation, and/or processing occurs at a particular facility
and that the facility generates wastes that are uniquely associated with minerals production, the next question is
whether mineral processing activities (as distinct from extraction or beneficiation) occur on site, and if so, whether
these activities generate solid wastes that are subject to RCRA Subtitle C. The distinction between extraction/
beneficiation and processing is critical because all wastes that are uniquely associated with extraction and
beneficiation operations are excluded from Subtitle C, while only 20 specific mineral processing wastes are exempt
from Subtitle C requirements under the Mining Waste Exclusion.
In response to a 1988 Federal
Appeals Court decision, EPA has
developed explicit regulatory definitions
of mineral beneficiation and processing,
which are articulated in two final rules
published in 1989 and 1990. As a
consequence, when considering the
regulatory status of wastes generated by a
particular facility, EPA no longer relies
upon pre-September. 1989 EPA notices.
correspondence, or other guidance. (See
Highlight 3) As delineated in the final
rule published on January 23, 1990 (55
FR 2322),8 beneficiation of ores and
minerals includes and is restricted to a set
of discrete activities that are generally
performed in a predictable sequence,
while processing of ores, minerals, and
beneficiated ores and minerals is defined
by a set of attributes rather than by
Highlight?, Decisions on Regulatory Status Made Prior to
September 1, 19S9 Must be Reevaluated and
Should not be Relied Upon
In 1985, EPA was asked to clarify the special waste status of
leachate derived from certain smelter wastes. Because at that time smelter
wastes were considered to be special wastes (and thus, excluded from
Subtitle C regulation under the Mining Waste Exclusion) and because
wastes derived from special wastes were also deemed special wastes, EPA
concluded that leachate from smelter slag and pyritic cinders (the smelter
wastes in question) were covered by the Mining Waste Exclusion and,
accordingly, were exempt from regulation' under RCRA Subtitle C.
Subsequently, however, the scope of the Exclusion for mineral processing
wastes (such as those from smelting) was narrowed considerably, to a list
of 20 specific high volume, low hazard solid wastes. Wastes derived
from these 20 wastes (or any other processing wastes, for that matter)
were explicitly removed from the scope of the Exclusion in 1989 and
1990 (54 FR 36623). That is, EPA's earlier findings notwithstanding.
leachates and other wastes derived from any mineral processing wastes
are not excluded from RCRA Subtitle C regulation under the Mining
Waste Exclusion, unless they are one of the 20 wastes listed in Figure 1 -
1, above.
8 The final rule establishing the definition of beneficiation was first published on September 1, 1989 (54 FR 36592). The
January 23, 1990 publication includes a technical correction to the definition originally promulgated in September.
46
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specific activities.9 Moreover, processing wastes were evaluated using specific quantitative criteria to determine
whether they were of high volume and low hazard, and thus, eligible for special waste status.
Residues arising from treatment of extraction or beneficiation wastes (e.g., sludge from treatment of acid
mine drainage) are also excluded from regulation. In contrast, treatment residues of mineral processing wastes are
not eligible for the Exclusion unless they are one of the 20 wastes identified during the rulemaking process, because
no such additional treatment residues were found to meet the special waste criteria (high volume and low hazard)
during the rulemaking process. One important additional point concerns the mixing of excluded and-hazardous, non-
excluded wastes; this practice is generally subject to Subtitle C regulation and is addressed below.
EPA has emphasized that operations following the initial "processing" step in the production sequence are
also considered processing operations, irrespective of whether they involve only techniques otherwise defined as
beneficiation. Therefore, solid wastes arising from such operations are considered mineral processing wastes, rather
than beneficiation wastes. For that reason, a clear understanding of the mineral production sequence is vital to sound
decision-making; the sequence considered extends to the operations preceding entry of the mineral value into a
particular facility or portion thereof. (See Highlight 4).
Highlight 4. When "Beneficiation" Follows Processing
The primary copper industry provides an interesting illustration of the distinctions that exist between mineral
beneficiation and processing. At a number of active primary copper facilities, copper is recovered from ores in two
different ways: dump leaching is used to solubilize copper values in mined and stockpiled low grade ores, and
conventional raining, milling, flotation, smelting, and refining are used to process higher grade ores. Metal-bearing
solution from the dump leaching operation is, in many cases, sent to electrowinning (a type of beneficiation operation),
which yields purified metallic copper. In contrast, after smelting, conventional copper production yields partially purified
copper, in the form of "anodes," which is then further purified in an electrolytic refining process that is functionally very
similar to that used to recover copper values from the dump leaching solution. Because, however, the anode copper is
produced by operations that are defined as mineral processing, wastes generated by this electrolytic refining operation
are mineral processing wastes, while wastes generated by the electrowinning of copper from the dump leach solution are
defined as beneficiation wastes and are excluded from Subtitle C regulation. Because wastes from refining of anode
copper are not among the 20 special mineral processing wastes, they are not exempt from Subtitle C regulation. Thus,
in this case and in others, waste streams from similar operations may be subject to different regulatory requirements, even
if they are generated at the same facility, depending upon the points in the production sequence from which they arise.
Defining which operations are beneficiation and which (if any) are processing can be a complex
undertaking, and is best approached in a step-wise fashion, beginning with relatively straightforward questions and
proceeding into more detailed examination of unit operations, as necessary. To perform this type of analysis, the
level and depth of information needed on facility operations increases dramatically over that required to resolve the
issues discussed above. A detailed process flow diagram, as well as information on ore type(s), the functional
importance of each step in the production sequence, waste generation points and quantities, and waste
management practices are the minimum data needs for locating the beneficiation/processing "line" at a given
facility. Typically, EPA must obtain this information directly from the facility operator. Because mineral production
operations are almost always non-linear (i.e., include internal cycling of materials), at least to some degree, the
process flow diagram is probably the single piece of information that is most critical to establishing which activities
are defined as beneficiation operations.
The meaning of some mineral production terms may not be readily apparent. Furthermore, minerals
industry terminology is not highly standardized. Therefore, it is important to focus on the nature of individual
operations in a mineral production sequence, rather than simply relying on the names or descriptions that may be
applied to portions of the facility by the owner or operator.
9 It is worthy of note that, as stated in the September 1, 1989 (54 FR 36592) rulemaking notice, no new special mineral
processing wastes will be recognized by EPA in the future, even if particular newly generated wastes should happen to comply
with the established criteria. That is, the list of 20 excluded processing wastes will not be expanded under any circumstances.
47
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Once the necessary information has been obtained from the facility operator, the Agency can begin an
analysis to determine at what point beneficiation activities end and processing begins. As a first step, the Agency
applies it's definitions of beneficiation activities. Using these definitions as a reference point, the decision-maker
may then evaluate information that he/she has gathered concerning specific operations to determine whether those
operations comport with Agency definitions. In EPA's experience, the following activities are generally easy to
identify as beneficiation using this simple analytical process:
crushing
sorting
sintering
calcining
washing
grinding
sizing
pelletizing
drying
filtration
briquetting
flotation
gravity concentration
magnetic separation
electrostatic separation
roasting, autoclaving, and/or chlorination
10
It is useful to note that these operations share certain qualities that make them easily identifiable as
beneficiation activities. Many of these operations do not generate any waste streams or effluents under typical
operating conditions. To the extent that others on the list do generate wastes (e.g., flotation), such wastes generally
share certain common attributes. First, the wastes typically fall into one of three general categories: 1) waste rock: 2)
mill tailings; or 3) mine water. Second, the volumes of waste generated by beneficiation activities tend to be very
large. Where there is doubt concerning whether a particular waste is generated by beneficiation or processing
operations, the Agency finds it useful to consider whether or not the waste shares these identifying attributes.
Other mineral industry activities are more difficult to classify unambiguously as beneficiation operations.
Certain beneficiation activities may bear a close resemblance to certain mineral processing operations. The lack of
standard industry terminology means that beneficiation activities may be described using a mineral processing term
and vice versa. Beneficiation activities that may easily be confused with processing activities are listed below. The
mineral processing operations which these beneficiation operations resemble are included in parentheses.
• Amalgamation (similar to smelting)
• Crystallization (similar to chemical conversion)
• Dissolution (similar to digestion)
• Leaching (similar to digestion)
• Ion Exchange (similar to chemical conversion)
• Solvent Extraction (similar to chemical conversion)
• Electrowinning (similar to electrolytic refining)
• Precipitation (similar to chemical conversion)
As a result of the similarity of these activities to certain mineral processing operations, it is critical that the
decision-maker have complete and detailed information concerning the unit operations in question in order to
adequately evaluate whether they qualify as beneficiation activities. In most cases, the amount of information and
the level of detail required will exceed that required for evaluating the simpler activities discussed above. In
addition, the potentially complex nature of some of these operations means that more in-depth study of unit
operations may be necessary before a determination can be made. Once the decision-maker has all of the relevant
information needed and fully understands the unit operations involved, analysis can proceed. The decision-maker
first consults Agency definitions, and then evaluates unit operations using the definitions as a reference point.
It is likely that, when evaluating facility information that includes references to these more
complex operations, the state or regional decision-maker will be required to make judgment calls as to the nature of
the operation. This may be particularly true in cases in which a production sequence involves the use of heat or acid
10 Only in preparation for a leaching operation that does not produce a final or intermediate product that does not undergo
further beneficiation or processing.
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(see discussion at 54 FR 36618). For example, there may be disagreement regarding whether a particular operation
is "leaching" or "dissolution" (beneficiation) or is "acid attack" or "digestion" (processing). When faced with
operations that cannot be classified unambiguously as beneficiation or processing activities, EPA decision-makers
sometimes find that considering the following information can help them in making these difficult determinations.
• Beneficiation operations typically serve to separate the mineral value(s) from waste material.
i.e., remove impurities, or otherwise improve the characteristics of the material for further
refinement. Beneficiation activities do not change the mineral values themselves and typically
include reducing (e.g., by crushing or grinding) or enlarging (e.g., pelletizing or briquetting)
particle size to facilitate processing. Where heat or chemicals, such as acid, are applied in a
beneficiation operation, it is generally to drive off impurities (e.g., water), dissolve mineral
values in a solution as a means of separation (leaching), or to retrieve dissolved values from a
solution (e.g., crystallization or solvent extraction). A chemical change in the mineral value
does not typically occur.
« Processing operations, in contrast, generally follow beneficiation and serve to change the
value(s) into a more useful chemical form, often by use of vigorous, even destructive, thermal
or chemical reactions of the value(s) and/or waste material with fluxes or reagents. In contrast
to beneficiation operations, processing activities often destroy the physical structure of the
incoming ore or mineral feedstock(s), such that the materials leaving the operations do not
closely resemble those that entered the operation. Examples of the differences between
beneficiation and processing operations are provided in Highlights 5 and 6.
Highlight 5. "Acid Treatment" of Clay is Beneficiation
A facility produces desiccant and adsorbent products from calcium roontmorillonite clay using a sequence of
steps that includes crushing, drying, acid treatment, washing and filtration, drying, and sizing. In response to an inquiry
from the relevant state agency in 1989, EPA reviewed the available information regarding the acid treatment operation
and concluded that it is a beneficiation operation, for the following reasons: (1) it uses a beneficiated ore as the primary
feedstock; and (2) the acid treatment process (which substitutes protons for some aluminum, magnesium, and iron ions
in the clay) does not "appear to destroy or substantially change the physical structure of the clay particles entering the
operation." Consequently, the aqueous waste that results from the acid treatment operation (as well as the wastes
generated by the other operations listed above) is a beneficiation waste that is exempt from hazardous waste regulation
under the Mining Waste Exclusion.
Highlight 6. Bauxite Refining is Mineral Processing
Bauxite refining in the U.S. is accomplished through the use of the Bayer process, in which bauxite ore
(impure hydrated aluminum oxide) is digested with a concentrated caustic (sodium hydroxide) solution under elevated
temperature and pressure conditions. This yields soluble sodium aluminate, which is cooled, diluted, and hydrolyzed to
form insoluble aluminum hydroxide, which can then be filtered out and calcined to produce alumina (aluminum oxide).
Because in the Bayer process the bauxite ore is vigorously attacked by a strong chemical agent, thereby destroying the
physical structure of the mineral, and because a large percentage of the solid material entering the process is chemically
altered, EPA concluded in its rulernaking activities in 1989 that this operation constitutes mineral processing, rather than
beneficiation. Even though strong acids and extreme temperatures are not employed in the Bayer process, the
combination of the strongly alkaline (rather than acidic) reagent and the high pressures (several times atmospheric)
applied to the ore slurry are sufficient to change die chemical form of the mineral value and die physical form of the feed
material stream.
Typically, beneficiation wastes are earthen in character and comprise a relatively high
proportion of the material entering the operation. Processing wastes, on the other hand, are
often very different in character from the material(s) entering the operation (i.e., are typically
not earthen in character), and comprise a comparatively small proportion of the feedstock. This
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distinction is illustrated in Highlight 6. Waste streams that differ substantially in character or
volume from the input materials are in most cases either processing wastes or wastes from
downstream operations (e.g., chemical manufacturing) that are completely outside the scope of
the Mining Waste Exclusion. Indeed, the generation rates and accumulated quantities of
extraction and beneficiation wastes typically dwarf those of downstream, on-site processing and
manufacturing operations.
If it is determined that a material is a processing waste, the EPA decision-maker checks to determine if the
waste is on the list of 20 excluded wastes. If the processing waste is on that list, it is unambiguously exempt from
RCRA Subtitle C hazardous waste regulations under the Mining Waste Exclusion. Any processing wastes that are
not listed under the 20 excluded wastes are not covered by the Exclusion, and therefore are subject to regulations
under Subtitle C, if the wastes are listed hazardous wastes or exhibit a characteristic of hazardous waste.
Active Management - Disturbing Old Wastes Can Influence Regulatory Status
EPA believes that among the positive effects of this proposal would be to encourage the "re-mining" of
previously generated mineral processing wastes—that is, the excavation of such wastes from disposal sites (including
remediation sites) for purposes of mineral recovery. Many of the 60 or more mine and mineral processing sites on
the National Priorities List could reduce costs of remediation by remining. Such recovery would promote the
statutory goals of less land disposal, increased material recovery, and also proper waste treatment, (since the
treatment standards for most mineral processing wastes are based on performance of High Temperature Metal
Recovery processes such as smelting). The reason re-mining could be encouraged is that the previously disposed
mineral processing materials would not be solid wastes once they are excavated for purposes of legitimate recovery
by mineral processing or beneficiation processes, provided they satisfy the same conditions that a newly-generated
secondary material from mineral processing would satisfy. See also 261.1(c)(8) (stating that a material that is
speculatively accumulated need not be considered a solid waste any longer "once they are removed from
accumulation for recycling").
EPA notes further that excavation of wastes would not render the historic disposal unit subject to RCRA
requirements. See 53 FR at 51444 (Dec. 21, 1988) (movement of waste from one unit to another does not subject the
initial unit to land disposal restriction requirements); 55 FR at 8758 (same); Letter from Lisa K. Friedman, Associate
General Counsel Solid Waste and Emergency Response Division to Richard Stoll (Sept. 5,1990) (indicating that
under the same reasoning movement of waste from one unit to another, by itself, does not trigger RCRA permitting
requirements for the initial unit). EPA notes that some questions have been raised about the scope of EPA's
discussion of "active management" in the preamble to the Sept. 1, 1989 rule. In that discussion, EPA described some
activities that could subject existing waste management units containing non-Bevill wastes to Subtitle C. 55 FR at
8755; 54 FR at 36597. The 1989 preamble did not specifically address the question of whether removal of some
waste from an existing unit subjects the waste remaining in the unit to Subtitle C regulation. EPA is clarifying that
the Agency's position, as discussed above, is that removal of waste from such a unit does not constitute "disposal"
for purposes of triggering Subtitle C regulation, and the language of the 1989 preamble, although somewhat unclear,
should be read to be consistent with EPA's statements in the NCP preamble on this point.
Mixture Rule
Under today's rale, the Agency has decided that if subtitle C hazardous waste exhibiting a characteristic is
mixed with Bevill-exempt waste exhibiting the same characteristic and the mixture continues to exhibit that common
characteristic, then the entire mixture should be considered to be non-exempt hazardous waste. This result is
consistent with normal rules on when wastes are hazardous, which state that if a waste exhibits a hazardous waste
characteristic, it remains a hazardous waste unless and until it no longer exhibits a characteristic, 261.3(d)(l). In
addition, such a principle will make this rule easier to administer (should this situation actually occur), since
enforcement officials will not have to parse out which portion of the waste mixture is imparting the characteristic
property. Finally, the result is consistent with the overall object of today's rule: not to let Bevill wastes be used as a
means of allowing unregulated management of normal subtitle C hazardous wastes.
The Agency reiterates that the rule does not alter in any way the current Agency mixture rule. The purpose
of this rulemaking is to eliminate the current Bevill mixture rule and place the mixing of hazardous wastes that may
occur at mineral processing plants on the same status as all other hazardous waste management.
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Illustrations of how today's rule operates
Although the regulatory parlance for today's rule has always been the 'Bevill mixture rule', the greatest
practical consequence of the rule is probably on the units where mixing occurs. This is because units (i.e. tanks,
impoundments, piles, landfills, etc.) where hazardous wastes are placed will (absent some exemption or exclusion
other than that provided by the Bevill amendment) be regulated units, i.e. units subject to subtitle C standards for
treatment, storage, and/or disposal, This point is illustrated by the following examples, which also illustrate the
effect of the rule on the resulting mixtures;
Example 1. Facility A generates F 001 listed spent solvents which it mixes with a solid waste that has
Bevill exempt-status. The mixing occurs in a landfill. The landfill is a regulated unit because hazardous
waste --F 001 —is being disposed in it. (Among other things, this means that the F 001 wastes could not be
placed in the landfill until the LDR treatment standard is satisfied.) In addition, all of the wastes with which
the F 001 wastes are mixed are hazardous wastes carrying the F 001 waste code by application of the
mixture rule.
Example ia. Same facts as in example 1, except that the waste being mixed is F 003 spent solvent, a waste
listed only because it exhibits a characteristic of hazardous waste. The landfill becomes a regulated unit for
the same reason as in example 1. (See Chemical Waste Management v. EPA. 976 F.2d at 20 n.4 and 24 n.
10 (placement of waste which is hazardous for any amount of time in a unit subject that unit to subtitle C
regulation); 61 FR at 2352 (same). However, the status of the resulting waste mixture is determined by the
principles for characteristic hazardous wastes, illustrated below.
Example 2. Facility B generates a characteristic ignitable solvent which it adds to a surface impoundment
containing a Bevill-exernpt waste that would exhibit the TC for lead. The resulting mixture exhibits TC for
lead but is no longer ignitable. The surface impoundment is a regulated unit, since it is engaged in
treatment (elimination of the ignitability characteristic) and disposal (the placement of the ignitable waste).
The remaining wastes in the unit retain their Bevill-exempt status because they do not exhibit the
characteristic property of the non-Bevill hazardous waste. Thus, if the waste were to be removed from the
impoundment and disposed elsewhere, disposal need not occur in a regulated unit.
Example 3. Facility C generates a characteristic hazardous waste exhibiting TC for lead which it mixes in a
tank with Bevill-exempt wastes which also would exhibit the TC for lead. The resulting mixture continues
to be TC for lead. The tank is engaged at least in storage of hazardous waste, and possibly treatment
(depending on how the D008 hazardous waste is affected by the mixing). If waste is removed from the
tank, it remains subject to subtitle C because it continues to exhibit the characteristic of the non-exempt
hazardous waste.
C.2 Waste Stream Sources and Form
EPA reviewed process descriptions and process flow diagrams obtained from numerous sources including,
Kirk-Othmer. EPA's Effluent Guideline Documents. EPA survey instruments, and the literature. As one would
expect, the available process descriptions and process flow diagrams varied considerably in both quality and detail,
both by commodity and source of information. Therefore, EPA often needed to interpret the information to identify
specific waste streams. For example, process descriptions and process flow charts found through the Agency's
electronic literature search process often focused on the production process of the mineral product and omitted any
description or identification of waste streams (including their point of generation). In such cases, the Agency used
professional judgment to determine how and where wastes were generated.
C.3 Waste Stream Characteristics
EPA used waste stream characterization data obtained from numerous sources to document whether a
particular waste stream exhibited one (or more) of the characteristics of a RCRA hazardous waste (i.e., toxicity,
corrosivity, ignitability, and reactivity). In cases in which actual data indicated that a waste did exhibit one of the
characteristics of a hazardous waste, the specific characteristic was designated with a Y. Despite, however, more
than ten years of Agency research on mineral processing operations, EPA was unable to find waste characterization
data for many waste streams. To present mineral commodity profiles that were as complete as possible, EPA used a
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step-wise methodology for estimating waste characteristics for individual waste streams when documented waste
generation rates and analytical data were not available. Specifically, due to the paucity of waste characterization
data (particularly, TCLP data), EPA used total constituent data (if available) or professional judgment to determine
whether a particular waste exhibits one of the characteristics of a RCRA hazardous waste (i.e., toxicity, corrosivity,
ignitability, or reactivity).
To determine whether a waste might exhibit the characteristic of toxicity, EPA first compared 1/20^ of the
total constituent concentration of each TC metal to its respective TC level." In cases in which total constituent data
were not available. EPA then used professional judgment to evaluate whether the waste stream could potentially
exhibit the toxicity characteristic for any of the TC metals. For example, if a particular waste stream resulted
through the leaching of a desired metal from an incoming concentrated feed, the Agency assumed that the
precipitated leach stream contained high total constituent (and therefore, high leachable) concentrations of non-
desirable metals, such as arsenic. Continuing through the step-wise methodology, EPA relied on professional
judgment to determine, based on its understanding of the nature of a particular processing step that generated the
waste in question, whether the waste could possibly exhibit one (or more) of the characteristics of ignitability,
corrosivity, or reactivity. Waste streams that EPA determined could potentially exhibit one or more of the
characteristics of a RCRA hazardous waste were designated by Y?. The Agency acknowledges the inherent
limitations of this conservative, step-wise methodology and notes that it is possible that EPA may have incorrectly
assumed that a particular waste does (or does not) exhibit one or more of the RCRA hazardous waste characteristics.
The Agency stresses that the results and information presented in the individual commodity analysis reports
are based on the review of publicly available information. The accuracy and representativeness of the collected
information are only as good as the source documents. As a result of this limited data quality review, EPA notes that
in some instances, Extraction Procedure (EP) leachate data reported by various sources are greater than 1/20* of the
total constituent concentration. Generally one would expect, based on the design of the EP testing procedure, the
total constituent concentrations to be at least 20-times the EP concentrations. This apparent discrepancy, however,
can potentially be explained if the EP results were obtained from total constituent analyses of liquid wastes (i.e., EP
tests conducted on wastes that contain less than one-half of one percent solids content are actually total constituent
analyses).
C.4 Waste Stream Generation Rates
As data were available, EPA used actual waste generation rates reported by facilities in various Agency
survey instruments and background documents. Due, however, to the general lack of data for many of the mineral
commodity sectors and waste streams, the Agency needed to develop a step-wise method for estimating mineral
processing waste stream generation rates when actual data were unavailable.
Specifically, EPA developed an "expected value" estimate for each waste generation rate using draft
industry profiles, supporting information, process flow diagrams, and professional judgment. From the "expected
value" estimate, EPA developed upper and lower bound estimates/which reflect the degree of uncertainty in our data
and understanding of a particular sector, process, and/or waste in question. For example, EPA obtained average or
typical commodity production rates from published sources (e.g., BOM Mineral Commodity Summaries) and
determined input material quantities or concentration ratios from published market specifications. In parallel with
this activity, EPA reviewed process flow diagrams for information on flow rates, waste-to-product ratios, or material
quantities. The Agency then calculated any additional waste generation rates and subtracted out known material
flows, leaving a defined material flow, which was allocated among waste streams using professional judgment.
Finally, EPA assigned a maximum, expected, and minimum volume estimate to each waste stream.
A key element in developing waste generation rates was the fact that by definition, average facility level
generation rates of solids and sludges are less that 45,000 metric tons/year, and generation rates of wastewaters are
less than 1,000,000 metric tons/year. Using this fact, in the absence of any supporting information, maximum values
1' Based on the assumption of a theoretical worst-case leaching of 100 percent and the design of the TCLP extraction test,
where 100 grams of sample is diluted with two liters of extractant, the maximum possible TCLP concentration of any TC metal
would be l/20th of the total constituent concentration.
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for solids and sludges were set at the highest waste generation rate found in the sector in question or 45,000 metric
tons/year/ facility, whichever is lower.
The precise methodology for determining waste generation rates varied depending on the quantity and
quality of available information. The waste streams for which EPA had no published annual generation rate were
divided into five groups and a methodology for each group was assigned as follows.
1. Actual generation rates for the waste in question from one or more facilities were available.
EPA extrapolated from the available data to the sector on the basis of waste-to-product ratios to
develop the expected value, and used a value of +/- 20% of the expected value to define the upper -and
lower bounds.
2. A typical waste-to-product ratio for the waste in question was available. EPA multiplied the
waste-to-product ratio by sector production (actual or estimated) to yield a sector wide waste
generation expected value, and used one-half and twice this value for the lower and upper bounds,
respectively.
3. No data on the waste in question were available, but generation rates for other generally
comparable wastes in the sector were available. EPA used the maximum and minimum waste
generation rates as the upper and lower bounds, respectively, and defined the expected value as the
midpoint between the two ends of the range. Adjustments were made using professional judgment if
unreasonable estimates resulted from this approach.
4. No data were available for any analogous waste streams in the sector, or information for the
sector generally was very limited. EPA drew from information on other sectors using analogous
waste types and adjusting for differences in production rates/material throughput. The Agency used
upper and lower bound estimates of one order of magnitude above and below the expected value
derived using this approach. Results were modified using professional judgment if the results seemed
unreasonable.
5. All EPA knew (or suspected) was the name of the waste. The Agency used the high value
threshold (45,000 metric tons/year/facility or 1,000,000 metric tons/year/facility) as the maximum
value, 0 or 100 metric tons per year as the minimum, and the midpoint as the expected value.
Appendix A provides detailed descriptions of the methodology used to estimate waste generation rates for
individual waste streams.
C.S Waste Stream Management Practices
EPA reviewed process descriptions and process flow diagrams obtained from numerous sources including,
Kirk-Othmer. EPA's Effluent Guideline Documents, EPA survey instruments, and the literature. As noted earlier, the
available process descriptions and process flow diagrams varied considerably in both quality and detail, both by
commodity and source of information. Therefore, EPA often needed to interpret the information to determine how
specific waste streams were managed. For example, process descriptions and process flow charts found through the
Agency's electronic literature search process often focused on the production process of the mineral product and
omitted any description or identification of how or where waste streams were managed. In such cases, the Agency
used professional judgment to determine how and where specific waste streams were managed. For example, EPA
considered (1) how similar waste streams were managed at mineral processing facilities for which the Agency had
management information, (2) the waste form and whether it was amenable to tank treatment, (3) generation rates, and
(4) proximity of the point of waste generation to the incoming raw materials, intermediates, and finished products to
predict the most likely waste management practice.
C.6 Waste Stream Recyclability and Classification
As was the case for the other types of waste stream-specific information discussed above, EPA was unable
to locate published information showing that many of the identified mineral processing waste streams were being
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recycled. In cases in which the Agency found information showing that a particular waste stream was being either
fully or partially recycled, the recyclability of the waste stream is designated by Y and YS, respectively.
However, due to the paucity of data for many of the mineral commodity sectors and waste streams, the
Agency needed to develop a method for determining whether a particular mineral processing waste stream was
expected to be either fully or partially recycled, designated by Y? and YS?, respectively. The Agency developed a
work sheet to assist EPA staff in making consistent determinations of whether the mineral processing waste streams
could potentially be recycled, reused, or recovered. This work sheet, shown in Appendix B, was designed to capture
the various types of information that could allow one, when using professional judgment, to determine whether a
particular waste stream could be recycled or if it contained material of value.
If EPA determined that the waste stream was or could be fully/partially recycled, it used the definitions
provided in 40 CFR §§ 260.10 and 261.1 to categorize the waste streams as either by-products, sludges, or spent
materials. Appendix C presents the RCRA definitions and examples of by-products, sludges, and spent materials.
Work sheets developed for individual waste streams are presented in Appendix D.
EPA, through the process of researching and preparing mineral commodity analysis reports for the mineral
commodities listed in Exhibit 2-2, identified a total of 553 waste streams that are believed to be generated at
facilities involved in mineral production operations. These extraction/beneficiation and mineral processing waste
streams are listed in Appendix E.
D. Identify Mineral Processing Waste Streams Potentially Affected by the Phase IV LDRs
Step Four The Agency then evaluated each of the waste streams listed in
Appendix E using the process outlined in Exhibit 2-9, to remove waste
streams that would not be affected by the Phase IV LDRs. Specifically, EPA
removed:
y
y
All of the extraction and beneficiation waste streams:
The "Special 20" Bevill-Exempt mineral processing waste
streams;
re Mineral commodity Analysis . • Waste streams that were known to be fully recycled in process:
Reports on Each Sector ,
and
The Phase IV LDRs
y
All of the mineral processing waste streams that did not
exhibit one or more of the RCRA characteristics of a
hazardous waste (based on either actual analytical data or
professional judgment).
c of Mineral
ies Potentially
As a. result of this evaluation process, EPA narrowed the potential
universe of waste streams that could potentially be affected by the proposed
Phase IV LDRs to the 120 hazardous mineral processing waste streams
presented below in Exhibit 2-10.
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EXHIBIT 2-9
Waste Streams Potentially Affected by the Phase IV LDRs
Waste Stream Not
Covered by the
Mining Waste Exclusion
(see Exhibit 3-7)?
Does
Material Exhibit
Hazardous
Characteristics?*
Not a Hazardous
Waste
Is
Material
Recycled?
Does Material
Meet Conditional
Exclusion?**
Subject to
LDRs
Not A Solid
Waste
* Listed hazardous waste are excluded from further analysis because they are already subject to all relevant Subtitle C
requirements.
** To meet the conditional exclusion, materials must be stored in tanks, containers, of buildings for less than one year,
or have a site specific determination that sold material may be stored on a concrete or asphalt pad. (Other requirements
can be found in 261.4(a)(15))
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EXHIBIT 2-10
POTENTIALLY HAZARDOUS MINERAL PROCESSING WASTE STREAMS BY COMMODITY SECTOR
Alumina and Aluminum
Cast house dust
Electrolysis waste
Antimony
Autoclave filtrate
Slag and furnace residue
Stripped anolyte Solids
Beryllium
Chip treatment wastewater
Filtration discard
Spent Barren Filtrate
Bismuth
Alloy residues
Spent caustic soda
Electrolytic slimes
Lead and zinc chlorides
Metal chloride residues
Slag
Spent electrolyte
Spent soda solution
Waste acid solutions
Waste acids
Cadmium
Caustic washwater
Copper and lead sulfate filter cakes
Copper removal filter cake
Iron containing impurities
Spent leach solution
Lead sulfate waste
Post-leach filter cake
Spent purification solution
Scrubber wastewater
Spent electrolyte
Zinc precipitates
Calcium
Dust with quick lime
Chromium and Ferrochromium
ESP Dust
Coal Gas
GCT Sludge
s
Multiple effects evaporator concentrate
Copper
Acid plant blowdown
APC dust/sludge
Process wastewaters
Spent bleed electrolyte
Tankhouse slimes
Waste contact cooling water
Spent furnace brick
WWTP sludge
Elemental Phosphorus
Andersen Filter Media
Precipitator slurry
NOSAP slurry
Phossy Water
Furnace building washdown
Furnace scrubber blowdown
Fluorspar and Hydrofluoric Acid
Off-spec fluosilicic acid
Germanium
Waste acid wash and rinse water
Chlorinator wet air pollution control
sludge
Hydrolysis filtrate
Leach residues
Spent acid/leachate
Waste still liquor
Gold and Silver
Slag
Spent furnace dust
Lead
Acid plant sludge
Baghouse incinerator ash
Slurried APC dust
Solid residues
Spent furnace brick
Stockpiled miscellaneous plant waste
Wastewater treatment plant solids/sludges
Wastewater treatment plant liquid effluent
Magnesium and Magnesia front Brines
Cast house dust
Smut
Mercury
Dust
Furnace residue
Quench water
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EXHIBIT 2-10 (Continued)
Molybdenum, Ferromolybdenum, and
Ammonium Molybdate
Flue dust/gases
Liquid residues
Platinum Group Metals
Slag
Spent acids
Spent solvents
Rare Earths
Spent ammonium nitrate processing
solution
Electrolytic cell caustic wet APC
sludge
Process wastewater
Spent scrubber liquor
Solvent extraction erud
Spent lead filter cake
Waste solvent
Wastewater from caustic wet APC
Rhenium
Spent barren scrubber liquor
Spent rhenium raffinate
Scandium
Spent acids
Spent solvents from solvent extraction
Selenium
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste solids
Synthetic Rutile
Spent iron oxide slurry
APC dust/sludges
Spent acid solution
Tantalum, Columbium. and Ferrocolumbium
Digester sludge
Process wastewater
Spent raffinate solids
Tellurium
Slag
Solid waste residues
Waste electrolyte
Wastewater
Titanium and Titanium Dioxide
Pickle liquor and wash water
Scrap milling scrubber water
Smut from Mg recovery
Leach liquor and sponge wash water
Spent surface impoundment liquids
Spent surface impoundments solids
Waste acids (Sulfate process)
Waste acids (Chloride process)
WWTP sludge/solids
Tungsten
Spent acid and rinse water
Process wastewater
Uranium
Waste nitric acid from UO2 production
Vaporizer condensate
Superheater condensate
Slag
Uranium chips from ingot production
Zinc
Acid plant blowdown
Waste ferrosilicon
Process wastewater
Spent refractory brick
Spent cloths, bags, and filters
Spent goethite and leach cake residues
Spent surface impoundment liquids
Spent synthetic gypsum
TCA tower blowdown
Wastewater treatment plant liquid effluent
WWTP solids
Zirconium and Hafnium
Spent acid leachate from zirconium
alloy production
Spent acid leachate from zirconium
metal production
Leaching rinse water from zirconium
alloy production
Leaching rinse water from zirconium
metal production
Note; EPA was unable to collect sufficient information to determine whether the production of Bromine,
Gemstones, Iodine, Lithium and Lithium Carbonate, Soda Ash, Sodium Sulfate, and Strontium produce
mineral processing wastes.
Note: This is not necessarily a complete list of hazardous mineral processing waste. This is only a list of
wastestream the Agency believes could be hazardous based on best available information.
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E. Identify Mineral Processing Facilities Potentially Affected by the Phase IV LDRs
Step Five EPA then used the information contained in the individual sector
~ " — — - - — — - — analysis reports to identify the number of facilities, by commodity, that
potentially generate the hazardous mineral processing wastes listed in Exhibit 2-
10. As discussed earlier, the individual sector analysis reports listed the
facilities involved in the production of a particular mineral commodity. In
addition, as the available information allowed, the Agency also (1) identified
which facilities used which processes and (2) which processes generated which
waste streams. In cases in which the Agency had insufficient information to
determine which of the individual facilities generated a particular waste stream.
EPA assumed that the waste stream was generated at all of the reported facilities
known to be using the same process.
The Agency then used the individual sector analysis reports, various
U.S. Bureau of Mines documents, the Randol Mining Directory, and the Mine
Safety and Health Administration (MSHA) address/employment database to
determine which of the mineral processing facilities were collocated with mining
(extraction) and/or extraction/beneficiation facilities.
y
*
Affected bv the Phase FV LDRs
Lastly, the Agency used the 1990 Report to Congress and the
individual commodity sector analysis reports to identify the mineral processing
facilities that also generate one (or more) of the special 20 Bevill-Exempt mineral processing wastes.
Exhibit 2-11 presents the final mineral processing database developed using our methodology as
discussed above. Appendix F presents a summary of the mineral processing facilities by mineral commodity
sector that EPA believes generate hazardous mineral processing wastes. Appendix F also indicates whether the
mineral processing facilities are collocated and/or generate one (or more) of the "Special 20" waste streams.
Appendix G, presents the same information (as shown in Appendix F) for the mineral processing sectors that do
not generate hazardous mineral processing wastes.
F. Caveats and Limitations
The results and information presented in this report are based on extensive review of publicly available
information, supplemented by information provided in public comment. The accuracy and representativeness of
the collected information are only as good as the source documents. As a result of this limited data quality review,
EPA notes that in some instances, Extraction Procedure (EP) leachate data reported by various sources are greater
than 1/20^ of the total constituent concentration. Generally, one would expect, based on the design of the EP
testing procedure, the total constituent concentrations to be at least 20-times the EP concentrations. This apparent
discrepancy, however, can potentially be explained if the EP results were obtained from total constituent analyses
of liquid wastes (i.e., EP tests conducted on wastes that contain less than one-half of one percent solids content are
actually total constituent analyses).
In addition, to present mineral commodity profiles that are as complete as possible, EPA used a step-wise
methodology for estimating both annual waste generation rates and waste characteristics for individual waste
streams when documented waste generation rates and analytical data were not available. EPA's application of this
methodology to estimate waste generation rates resulted in the development of low, medium, and high annual
waste generation rates for non-wastewaters and wastewaters that were bounded by zero and 45,000 metric
tons/yr/facility and by zero and 1,000,000 metric tons/yr/facility, respectively (the thresholds for determining
whether a waste stream is a high volume, Bevill-exempt waste). Due to the paucity of waste characterization data
(particularly, TCLP data), EPA used total constituent data (if available) or best engineering judgment to determine
whether a particular waste exhibited one of the characteristics of a RCRA hazardous waste (i.e., toxicity,
corrosivity, ignitability, and reactivity).
58
-------
To determine whether a waste might exhibit the characteristic of toxicity, EPA first compared 1/20^ of
the total constituent concentration of each TC metal to its respective TC level12. In cases in which total constituent
data were not available, EPA then used best engineering judgment to evaluate whether the waste stream could
potentially exhibit the toxicity characteristic for any of the TC metals. For example, if a particular waste stream
resulted through the leaching of a desired metal from an incoming concentrated feed, we assumed that the
precipitated leach stream contained high total constituent (and therefore, high leachable) concentrations of,non-
desirable metals, such as arsenic. Continuing through the step-wise methodology, we relied on EPA's best
engineering judgment to determine, based on our understanding of the nature of a particular processing step that
generated the waste in question, whether the waste could possibly exhibit one (or more) of the characteristics of
ignitability, corrosivity, or reactivity. The Agency acknowledges the inherent limitations of this conservative,
step-wise methodology and notes that it is possible that EPA may have incorrectly assumed that a particular waste
does (or does not) exhibit one or more of the RCRA hazardous waste characteristics.
'" Based on the assumption of a theoretical worst-case leaching of 100 percent and the design of the TCLP extraction test,
where 100 grams of sample is diluted with two liters of extractant, the maximum possible TCLP concentration of any TC metal
would be l/20th of the total constituent concentration.
59
-------
en
o
EXHIBIT 2-11
Final Mineral Processing Waste Stream Database
Commodity
Alumina and Aluminum
Antimony
Beryllium
Bismuth
Cadmium
Calcium
Chromium and Ferrochromium
Coal Gas
Waste Stream
Cast house dust
Electrolysis waste
Autoclave filtrate
Stripped anolyte solids
Slag and furnace residue
Chip treatment wasfewater
Spent barren filtrate
Filtration discard
Alloy residues
Spent caustic soda
Electrolytic slimes
Lead and zinc chlorides
Metal chloride residues
Slaq
Spent electrolyte
Spent soda solution
Waste acid solutions
Waste acids
Caustic washwater
Copper and lead sulfate filter cakes
Copper removal filter cake
Iron eontainina. impurities
Spent leach solution
Lead sulfate waste
Post-leach filter cake
Spent purification solution
Scrubber wastewaier
Spent electrolyte
Zinc precipitates
Dust with quicklime
ESP dust
GCT sludge
Multiple effects evaporator concentrate
Reported
Generation
(1000mt/yr)
19
58
NA
0.19
21
NA
55
NA
NA
NA
NA
NA
3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.04
3
NA
NA
EsUReported
Generation (1000mt/yr)
Mln
19
58
0.32
0.19
21
0.2
55
0.2
0.1
0.1
0
0.1
3
0.1
0.1
0.1
0.1
0
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.19
0.04
3,
0.03
0
Avg.
19
58
27
0.19
21
100
55
45
3
6.1
0.02
3
3
1
6.1
6.1
6.1
0.1
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
0.04
3
0.3
0
Max
19
58
54
0.19
21
2000
55
90
6
12
0.2
6
3
10
12
12
12
0.2
19
19
19
19
19
19
19
19'
19
19
19
0.04
3
3
65
Number
of Facilities
with Process
23
23
6
2
6
2
1
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
Average Facility Generation (mt/yr)
Minimum
830
2,500
53
95
3,500
100
55,000
100
100
100
0
100
3,000
100
100
100
100
0
95
95
95
95
95
95
95
95
95
95
95
40
3,000
30
0
Expected
830
2,500
4,500
95
3,500
50,000
55,000
23,000
3,000
6,100
20
3,000
3,000
1,000
6,100
6,100
6,100
100
950
950
950
950
950
950
950
950
950
950
950
40
3,000
300
0
Maximum
83C
2,500
9,OOC
95
3.50C
1 ,oootooc
55.00C
45,000
6,000
12,OOC
20C
6.00C
3fOOC
10.00C
12.00C
12.00C
12,000
200
9,500
9.50C
9,500
9.50C
9.50C
9.50C
9.50C
9.50C
9.SOC
9,500
9,500
40
3,000
3,000
65,000
-------
EXHIBIT 2-11 (Continued)
Commodity
Copper
Elemental Phosphorus
Fluorspar and Hydrofluoric Acid
Germanium
Lead
Magnesium and Magnesia from
Brines
Mercury
Molybdenum, Ferromolybdenum,
and Ammonium Molybdate
Platinum Group Metals
Waste Stream
Acid plant blowdown
Spent furnace brick
WWTP sludge
Andersen Filter Media
Precipitator slurry
NOSAP slurry
Phossy Water
Furnace scrubber blowdown
Furnace Building Washdown
Off-spec fluosilicic acid
Waste acid wash and rinse water
Chlorinator wet air pollution control
sludge
Hydrolysis filtrate
Leach residues
Spent acid/leachate
Waste still liquor
Acid plant sludqe
Baqhouse incinerator ash
Slurried APC Dust
Solid residues
Spent furnace brick
Stockpiled miscellaneous plant waste
WWTP liquid effluent
Cast house dust
Smut
Dust
Quench water
Furnace residue
Flue dust/gases
Liquid residues
Slao
Spent acids
Spent solvents
Reported
Generation
(lOMmtfyr)
5300
3
6
0.46
160
160
670
410
700
NA
NA
NA
NA
0.01
NA
NA
14
NA
7
0.4
1
NA
2600
NA
26
0.007
NA
0.077
NA
1
NA
NA
NA
Est7R8ported
Generation (lOOOmt/yr)
Mtn
5300
3
6
0.46
160
160
670
410
700
0
0.4
0.01
0.01
0.01
0.4
0.01
14
0,3
7
0,4
1
0.3
2600
0.076
26
0.007
63
0.077
.1.1
1
0.0046
0.3
0.3
Avg.
5300
3
6
0,46
160
160
670
410
700
15
2.2
0.21
0.21
0.01
2.2
0.21
14
3
7
0,4
1
67
2600
0.76
26
0.007
77
0.077
250
1
0.046
1.7
1.7
Max
5300
3
6
0.46
160
160
670
410
700
44
4
0.4
0.4
0.01
4
0.4
14
30
7
0,4
1
130
2600
7.6
26
0.007
420
0.077
500
1
0.46
3
3
Number
of Facilities
with Process
10
10
10
2
2
2
2
2
2
2
4
4
4
3
4
4
£
£
z
2
3
£
£
1
o
£_
7
7
7
11
2
'
(
3
Average Facility Generation Cmt/yr)
Minimum
530,000
300
600
230
80,000
80,000
340,000
210,000
350,000
0
100
3
g
3
100
q
4,700
100
2,300
130
330
100
870,000
76
13,000
1
9,000
11
100
500
f.
100
100
Expected
530,000
300
600
230
80,000
80,000
340,000
210,000
350,000
5,000
550
53
53
3
550
53
4,700
1,000
2,300
130
330
22,000
870,000
760
13,000
1
1 1 ,000
11
23,000
500
15
570
570
Maximum
530, OOC
30C
600
23C
80.00C
80.00C
340.00C
210.00C
350,000
15,000
1,000
100
10C
j
1.00C
100
4.70C
10.00C
2.30C
13C
33C
43,000
870,000
7.60C
13, OOC
!
60,000
11
45.00C
5QC
150
1,000
1,000
-------
EXHIBIT 2-11 (Continued)
en
Commodity
Rare Earths
Rhenium
Scandium
Selenium
Synthetic Rutiie
Tantalum, Columbium, and
Ferroeolumbium
Tellurium
Titanium and Titanium Dioxide
Tungsten
Wast* Stream
Spent ammonium nitrate processing
solution
Electrolytic cell caustic wet ARC sludge
Process wastewater
Spent scrubber liquor
Solvent extraction crud
Wastewater from caustic wet ARC
Spent barren scrubber liquor
Spent rhenium raffinate
Spent acids
Spent solvents from solvent extraction
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste solids
Spent iron oxide slurry
APC dust/sludges
Spent acid solution
Digester sludge
Process wastewater
Spent raffinate solids
Slag
Solid waste residues
Waste electrolyte
Wastewater
Pickle liquor and wash water
Scrap milling scrubber water
Smut from Mg recovery
Leach liquor and sponge wash water
Spent surface impoundment liquids
Spent surface impoundments solids
Waste acids (Sulfate process)
WWTP sludge/solids
Spent acid and rinse water
Reported
Generation
(IQQQmtfyrJ
14
NA
7
NA
NA
NA
NA
88
NA
•NA
NA
66
NA
NA
NA
45
30
30
1
150
2
NA
NA
NA
NA
NA
NA
NA
NA
NA
36
NA
420
NA
EsURoported
Generation (lOOOmt/yrj
Min
14
0.07
7
0.1
0.1
0.1
0
88
0.7
0.7
0.05
66
0.05
0.05
0.05
45
30
30
1
150
2
0.2
0.2
0.2
0.2
2.2
4
0.1
380
0.63
36
0.2
420
0
Avg.
14
0.7
7
500
2.3
500
0.1
88
3.9
3,9
0.5
66
0.5
0.5
0.5
45
30
30
1
150
2
2
2
2
20
2.7
5
22
480
3.4
36
39
420
0
Max
14
7
7
1000
4.5
1000
0.2
88
7
7
5
66
5
5
5
45
30
30
1
150
2
9
9
20
40
3.2
6
45
580
6.7
36
77
420
21
Number
of Facilities
with Process
1
1
1
1
1
1
2
2
7
7
3
2
3
3
3
1
1
1
2
2
2
2
2
2
2
3
1
2
2
7
7
2
7
6
Average Facility Generation (mt/yr)
Minimum
14,000
70
7,000
100
100
100
0
44,000
100
100
17
33,000
17
17
17
45,000
30,000
30,000
500
75,000
1,000
100
100
100
100
730
4,000
50
190,000
90
5,100
100
60,000
0
Expected
1 4,000
700
7,000
500,000
2,300
500,000
50
44,000
560
560
170
33,000
170
170
170
45,000
30,000
30,000
500
75,000
1,000
1,000
1,000
1,000
10,000
900
5,000
11,000
240,000
490
5,100
20,000
60,000
0
Maximum
14.00C
7,000
7,000
1 ,000,000
4,500
1,000,000
10C
44,000
1,000
1.00C
1.70C
33,000
1.700
1,700
1,700
45.00C
30.00C
30,000
50C
75.00C
1,000
4,500
4,500
10.00C
20,000
1,100
6.00C
23.00C
290.00C
960
5,1 OC
39.00C
60.00C
3,500
-------
EXHIBIT 2-11 (Continued)
Commodity
Uranium
Zinc
Zirconium and Hafnium
Waste Stream
Process wastewater
Waste nitric acid from UO2 production
Vaporizer condensate
Superheater condensate
Slag
Uranium chips from ingot production
Acid plant blowdown
Waste ferrosilicon
Process wastewater
Discarded refractory brick
Spent cloths, bags, and filters
Spent (joethite and leach cake residues
Spent surface impoundment liquids
WWTP Solids
Spent synthetic gypsum
TCA tower blowdown
Wastewatar treatment plant liquid
effluent
Spent acid leachate from Zr alloy prod.
Spent acid leachate from Zr metal prod.
Leachinq rinse water from Zr alloy prod.
Leaching rinse water from Zr metal
prod.
Repotted
Generation
(1000mt/yr)
NA
NA
NA
NA
NA
NA
130
17
5000
1
0,15
15
1900
0.75
16
0.25
2600
NA
NA
NA
NA
EsUReported
Generation flOQOmt/yr)
Min
2.2
1.7
1.7
1.7
0
1.7
130
17
5000
1
0.15
15
1900
0.75
16
0,25
2600
0
0
34
0.2
Avg.
4.4
2.5
9.3
9.3
8.5
2.5
130
17
SOOO
1
0.15
15
1900
0.75
16
0.25
2600
0
0
42
1000
Max
9
3.4
17
17
17
3.4
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
850
1600
51
2000
Number
of Facilities
with Process
6
17
17
17
17
17
1
1
3
1
3
3
3
3
3
1
3
2
2
2
2
Averaqe Facility Generation (mt/yr)
Minimum
370
100
100
100
0
100
1 30,000
17,000
1 ,700,000
1,000
SO
5,000
630,000
250
5,300
250
870,000
0
0
17,000
100
Expected
730
150
550
550
500
150
130,000
1 7,000
1 17001000
1,000
50
5,000
630,000
250
5,300
250
870,000
0
0
21,000
500,000
Maximum
1,500
20C
1.00C
1,000
1.00C
20C
130.00C
17.00C
1 ,700,000
1.00C
50
5.00C
630,000
250
5,300
250
870,000
430.00C
800.00C
26.00C
1 ,000,000
cn
ou
-------
EXHIBIT 2-11 (Continued)
Commodity
Alumina and Aluminum
Antimony
Ben/Ilium
Bismuth
Cadmium
Calcium
Chromium and
Ferrochromium
Waste Stream
Cast house dust
Electrolysis waste
Autoclave filtrate
Stripped anolyte solids
Slag and furnace residue
Chip treatment wastewater
Spent barren filtrate
Filtration discard
Alloy residues
Spent caustic soda
Electrolytic slimes
Lead and zinc chlorides
Metal chloride residues
Slaq
Spent electrolyte
Spent soda solution
Waste acid solutions
Waste acids
Caustic washwater
Copper and lead sulfate filter
cakes
Copper removal filter cake
Iron containing impurities
Spent leach solution
Lead sulfate waste
Post-leach filter cake
Spent purification solution
Scrubber wastewater
Spent electrolyte
Zinc precipitates
Dust with quicklime
ESP dust
GCT sludge
TC Metals
As
Y?
Y?
Y?
Ba
Cd
Y
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Cr
Y?
Y
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Hg
Y
Y?
Se
Y
Y
Ag
Corr
N?
N?
Y?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Y?
Y?
Y?
Y?
N?
N?
N?
Y?
N?
N?
Y?
Y?
Y?
N?
Y?
N?
N?
Ignlt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Haz
?
1
0.5
0.5
0.5
0.5
0.5
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
0.5
Cur-
rent
Re-
cycle
Y?
Y?
YS?
Y
N
YS?
YS
N
N
Y?
Y?
N
N
N
N
Y?
N
YS?
Y?
Y?
Y?
N
Y?
Y?
N
N
Y?
N
Y?
Y
YS
Y
RCRA Waste Type
By-
Prod
1
1
1
1
1
1
Spent
Mat'l
1
1
1
1
1
1
1
1
Sludge
1
1
1
1
1
1
Treatment Type
Waste
Water
0
0
1
0
0
1
1
0
0
0
0
0
0
0
0
1
1
1
1
0
0
0
0
0
0
1
1
0
0
0
0
0
1-10%
Solids
0
0
0
0
0
0
0
0
0
1
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
1
0
0
0
0
Solid
1
1
0
1
1
0
0
1
1
0
1
1
1
1
0
0
0
0
0
1
1
1
0
1
1
0
0
0
1
1
1
1
-------
EXHIBIT 2-11 (Continued)
Commodity
Coal Gas
Copper
Elemental Phosphorus
Fluorspar and
Hydrofluoric Acid
Germanium
Lead
Magnesium and
Maqnesta from Brines
Mercury
Waste Stream
Multiple effects evaporator
concentrate
Acid plant blowdown
Spent furnace brick
WWTP sludge
Andersen Filter Media
Precipitator slurry
NOSAP slurry
Phossy Water
Furnace scrubber blowdown
Furnace Building Washdown
Off-spec fluosilicic acid
Waste acid wash and rinse water
Chlorinator wet air pollution control
sludge
Hydrolysis filtrate
Leach residues
Spent acid/leachate
Waste still liquor
Acid plant sludqe
Baqhouse incinerator ash
Slurried ARC Dust
Solid residues
Spent furnace brick
Stockpiled miscellaneous plant
waste
WWTP liquid effluent
Cast house dust
Srnut
Dust
Quench water
Furnace residue
TC Metals
As
Y
Y
Y?
Y?
Y?
Y?
Y?
Ba
Y?
Y
Cd
Y
Y?
Y
Y?
Y?
Y
Y
Y?
Y?
Y?
Y?
Y?
Y
Y
Y
Cr
Y
Y?
Y?
Y?
Y?
Y?
Pb
Y
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y
Y
Y?
Y
Y
Y?
Y?
Hg
Y
Y?
Y?
Y?
Se
Y
Y
Y?
Y'
Y?
Y?
Ag
Y
Y?
Y?
Y?
Y?
Corr
N?
Y
N?
N?
N?
N?
N?
N?
Y
N?
Y?
Y?
N?
N?
N?
Y?
N?
Y?
N?
N?
N?
N?
N?
Y?
N?
N?
N?
N?
N?
Ignlt
N?
N?
N?
N?
N?
Y
N?
Y
N?
N?
N?
N?
N?
N?
N?
N?
Y?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
Y
Y
Y
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Haz
?
1
1
0.5
0.5
1
1
1
1
1
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
1
0.5
1
1
0.5
0.5
1
0.5
0.5
0.5
Cur-
rent
Re-
cycle
YS
YS
Y?
YS
N
YS
N
YS
Y
Y
YS
YS?
YS?
N
N
YS?
N
Y?
N
Y
Y?
Y
YS?
Y
Y?
N
N
Y?
N
RCRA Waste Type
By-
Prod
1
1
1
Spent
Mali
1
1
1
1
1
1
1
1
1
Sludge
1
1
1
1
1
1
1
1
Treatment Type
Waste
Water
0
0
0
0
0
0
0
0
1
1
1
1
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
1
0
1-10%
Solids
1
1
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Solid
0
0
1
1
1
0
0
0
0
0
0
0
1
1
1
0
1
1
1
1
1
1
1
0
1
1
1
0
1
-------
EXHIBIT 2-11 (Continued)
1
\
Commodity
Molybdenum,
Ferromolybdenum, and
Ammonium Molybdate
Platinum Group Metats
Rare Earths
Rhenium
Scandium
Selenium
Synthetic Rutile
Tantalum, Columbium,
and Ferrocolumbium
Tellurium
Waste Stream
Flue dust/gases
Liquid residues
Slag
Spent acids
Spent solvents
Spent ammonium nitrate
processing solution
Electrolytic cell caustic wet ARC
sludge
Process wastewater
Spent scrubber liquor
Solvent extraction crud
Wastewater from caustic wet APC
Spent barren scrubber liquor
Spent rhenium raffinate
Spent acids
Spent solvents from solvent
extraction
Spent filter cake
Plant process wastewater
Slaq
Tellurium slime wastes
Waste solids
Spent iron oxide slurry
APC dust/sludges
Spent acid solution
Digester sludge
Process wastewater
Spent raffinate solids
Slag
Solid waste residues
Waste electrolyte
TC Metals
As
Y?
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y?
Y
Y?
Y?
Hg
So
Y?
Y?
y.
Y7
Y1
Y?
Y?
Y?
Y'
Y?
Y?
Ag
Y?
Y?
Corr
N?
N?
N?
Y?
N?
Y
Y?
Y?
Y?
N?
Y?
N?
N?
Y?
N?
N?
Y
N?
N
N?
N?
N?
Y?
Y?
' Y
Y?
N?
N?
N?
Ignlt
N?
N?
N?
N?
Y?
N?
N?
N?
N?
Y?
N?
N
N?
N?
Y?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Haz
7
0.5
0.5
0.5
0.5
0.5
1
0.5
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0,5
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
0.5
0.5
0.5
0.5
Cur-
rent
Re-
cycle
N
N
Y?
N
N
0
Y
YS?
YS?
N
YS?
Y?
N
N
Y?
Y?
YS?
YS?
Y?
N
YS?
Y
Y
N
Y?
N
YS?
N
N
RCRA Waste Typo
By-
Prod
1
1
1
1
1
1
Spent
Mat't
1
1
1
1
1
Sludge
1
1
1
1
1
Treatment Type
Waste
Water
0
1
0
1
1
1
0
1
1
0
1
1
0
1
1
0
1
0
0
0
0
0
1
0
0
0
0
0
1
1-10%
Solids
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
Solid
1
0
1
0
0
0
1
0
0
1
0
0
1
0
0
1
0
1
1
1
1
1
0
1
0
1
1
1
0
-------
EXHIBIT 2-11 (Continued)
Commodity
Titanium and Titanium
Dioxide
Tungsten
Uranium
Zinc
Waste Stream
Wastewater
Pickle liquor and wash water
Scrap milling scrubber water
Smut from Mg recovery
Leach liquor and sponge wash
water
Spent surface impoundment
liquids
Spent surface impoundments
solids
Waste acids (Sulfate process)
WWTP sludge/solids
Spent acid and rinse water
Process wastewater
Waste nitric acid from UO2
production
Vaporizer condensate
Superheater condensate
Slag
Uranium chips from ingot
production
Acid plant blowdown
Waste ferrosilicon
Process wastewater
Discarded refractory brick
Spent cloths, bags, and filters
Spent goethite and leach cake
residues
Spent surface impoundment
liquids
WWTP Solids
Spent synthetic gypsum
TCA tower blowdown
Wastewater treatment plant liquid
effluent
TC Metals
As
Y
Y
Y
Y?
Y
Y?
Y?
Ba
Cd
Y?
Y?
Y
Y
Y?
Y?
Y
Y?
Y?
Y
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y
Y
Y?
Y
Pb
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y?
Y?
Y?
Y?
Y?
Hg
Y?
Y?
Y?
Y?
Y?
Se
Y?
Y?
Y
Y
Y
Y?
Y
Y?
Y?
ftg
Y
Y
Y
Y?
Y
Y?
Corr
Y?
Y?
N?
N?
Y
N?
N?
Y
N
Y?
Y?
Y?
Y?
Y?
N?
N?
Y
N?
Y
N?
N?
N?
Y
N?
N?
Y?
N?
lgn«
N?
N?
N?
N?
N?
N?
N?
N
N
N?
N?
N?
N?
N?
Y?
Y?
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
Y
N?
N?
N?
N
N
N?
N?
N?
N?
N?
N?
N?
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Haz
?
0.5
0.5
0.5
1
1
0.5
0.5
1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
0.5
1
0.5
0.5
1
1
0.5
1
0.5
0.5
Cur-
rent
Re-
cycle
Y
YS?
YS?
Y?
YS?
Y?
N
N
N
YS?
YS?
YS?
N
N
Y
Y?
Y
Y?
Y?
N
Y
Y
YS?
YS
N
YS
YS?
RCRA Waste Type
By-
Prod
1
1
1
1
Spent
Mat!
1
1
1
1
1
1
1
1
1
1
1
1
Sludge
1
1
1
Treatment Type
Waste
Water
1
1
1
0
1
1
0
1
0
1
1
1
1
1
0
0
1
0
1
0
0
0
1
0
0
1
1
1-10%
Solids
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Solid
0
. 0
0
1
0
0
1
0
1
0
0
0
0
0
1
1
0
1
0
1
1
1
0
1
1
0
0
-------
EXHIBIT 2-11 (Continued)
Commodity
Zirconium and Hafnium
Waste Stream
Spent acid leachate from Zr alloy
prod.
Spent acid teachate from Zr metal
prod.
Leaching rinse water from Zr alloy
prod.
Leaching rinse water from Zr metal
prod.
TC Metals
As
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
Y?
Y?
Y?
Y?
Igntt
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
Haz
?
0.5
O.S
0.5
0,5
Cur-
rent
He-
cycle
N
N
YS?
YS?
RCH A Waste Type
By-
Prod
Spent
Mat'l
1
1
Sludge
Treatment Type
Waste
Water
1
1
1
1
1-10%
Solids
0
0
0
0
Solid
0
0
0
0
-------
III. MINERAL COMMODITIES
A. INDIVIDUAL MINERAL COMMODITY REVIEWS
69
-------
70
-------
ALUMINA & ALUMINUM
A.
Commodity Summary
Aluminum, the third most abundant element in the earth's crust, is usually combined with silicon and oxygen
in rock. Rock that contains high concentrations of aluminum hydroxide minerals is called bauxite. Although
bauxite, with rare exceptions, is the starting material for the production of aluminum, the industry generally refers to
metallurgical grade alumina extracted from bauxite by the Bayer Process, as the ore. Aluminum is obtained by
electrolysis of this purified ore.'
The United States is entirely dependent on foreign sources for metallurgical grade bauxite. Bauxite
imports are shipped to domestic alumina plants, which produce smelter grade alumina for the primary metal industry.
These alumina refineries are in Louisiana, Texas, and the U.S. Virgin Islands.2 The United States must also import
alumina to supplement this domestic production. Approximately 95 percent of the total bauxite consumed in the
United States during 1994 was for the production of alumina. Primary aluminum smelters received 88 percent of the
alumina supply. Fifteen companies operate 23 primary aluminum reduction plants. In 1994, Montana, Oregon, and
Washington accounted for 35 percent of the production; Kentucky, North Carolina, South Carolina, and Tennessee
combined to account for 20 percent; other states accounted for the remaining 45 percent. The United States is the
world's leading producer and the leading consumer of primary aluminum metal. Domestic consumption in 1994 was
as follows: packaging, 30 percent; transportation, 26 percent; building, 17 percent: electrical, 9 percent; consumer
durables, 8 percent; and other miscellaneous uses, 10 percent. The 1994 production of aluminum was 3,300,000
metric tons while the production capacity was 4,163,000 metric tons per year.3 Exhibits 1 and 2 list the names and
locations of the domestic alumina and aluminum production plants. In addition, 1992 production capacities have
been provided in Exhibit 2 for some of the aluminum producers.
EXHIBIT 1
SUMMAHY OF ALUMINA PROCESSING FACILITIES
Facility Name
ALCOA
Kaiser (1992 alumina prod, was 1.06 mt4)
Martin
Ormet
Reynolds
Location
Point Comfort, TX
Gramercy, LA
St. Croix, VI
Burnside, LA
Corpus Christi, TX
Process Methods
Bayer
Bayer
Bayer
Bayer
Bayer
1 "Aluminum and Alloys," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. II, 1991, pp. 190-
212.
2 Patricia A. Plunkert and Errol D. Sehnke, "Aluminum, Bauxite, and Alumina," from Minerals Yearbook
Volume 1. Metals and Minerals. U.S. Bureau of Mines, 1992, pp. 183-203.
3 Patricia Plunkert, "Aluminum," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995,
pp. 16-17.
4 Patricia Plunkert, 1992. Op. Cit.. pp. 183-203.
71
-------
EXHIBIT 2
SUMMARY OF ALUMINUM PROCESSING FACILITIES
Facility Name
ALCOA
ALUMAX
Alcan Aluminum Corp.
1 Columbia Aluminum Corp.
Eastico
Intalco
Kaiser Aluminum Corp.
Columbia Falls Aluminum Corp.
National South Wire
Noranda
Northwest
Ormet
Ravenswood
Reynolds
Venalco
Location
Warrick, IN
Massena, NY
Badin, NC
Alcoa, TN
Rockdale, TX
Wenatchee, WA
Mt. Holly, SC
Henderson, KY
Goldendale, WA
Frederick, MD
Ferndale, WA
Spokane, WA
Tocoma, WA
Columbia Falls, MT
Hawesville, KY
New Madrid, MO
The Dalles, OR
Hannibal, OR
Ravenswood, WV
Massena, NY
Troutdale, OR
Longview, WA
Vancouver, WA
Type of
Operations
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
1992 Production
Capacity5
(1000 metric tons)
Unknown
Unknown
Unknown
Unknown
Unknown
Unknown
275
Unknown
Unknown
Unknown
Unknown
Unknown
Unknown
Unknown
Unknown
215
82
Unknown
Unknown
123
121
204
Unknown
Ibid.
72
-------
B. Generalized Process Description
1. Discussion of Typical Production Processes
Free moisture in crude bauxite, as mined, may range from five to 30 percent. To produce dry bauxite, most
of the free moisture is removed by heating crude bauxite in rotary drying kilns. Calcined bauxite is produced by
heating bauxite to reduce total volatile matter, including chemically combined water, to less than one percent.
Approximately two tons of crude ore is required to produce one ton of calcined bauxite.
Alumina tri-hydrate is used for the production of the pure aluminum chemicals, high quality refractories.
and otiier high aluminum products, while aluminum is used for the preparation of the purest aluminum chemicals.
Alumina and bauxite are the principal raw materials for the production of aluminum chemicals such as aluminum
sulfate, aluminum chloride, aluminum fluoride, sodium aluminate, and aluminum acetate.6
Metallurgical grade alumina (i.e., 30 to 60 percent aluminum oxide)7 is extracted from bauxite by the Bayer
process and aluminum is obtained from this purified ore by electrolysis via the Hall-Heroult process. These
processes are described below. Exhibits 3 and 4 present process flow diagrams for the Bayer process and the Hall-
Heroult process.
2. Generalized Process Flow Diagram
Bayer Process
A process flow diagram of the Bayer process is shown in Exhibit 3. The primary purpose of a Bayer plant
is to process bauxite to provide pure alumina for the production of aluminum. All bauxite refineries share five
common process steps: (1) ore preparation; (2) bauxite digestion; (3) clarification; (4) aluminum hydroxide
precipitation; and (5) calcination to anhydrous alumina. Additional operations include steam and power generation,
heat recovery to minimize energy consumption, process liquor evaporation to maintain a water balance, impurity
removal from process liquor streams, classification and washing of trihydrate, lime causticization of sodium
carbonate to sodium hydroxide, repair and maintenance of equipment, rehabilitation of residue disposal sites, and
quality and process control. Each step in die process can be carried out in a variety of ways depending upon bauxite
properties and optimum economic tradeoffs. Each of these steps is discussed in further detail below.8
Ore Preparation
Bauxite mining processes depend largely on the nature of the ore body. If the ore is not uniform, contains
an excessive amount of kaolin, or is difficult to handle due to the moisture content, blending operations, physical
beneficiation, and bauxite drying are used. Grinding is designed to produce feed material small enough to ensure
easy alumina extraction, yet coarse enough to avoid clarification problems with bauxite residue. Uniform,
consistent, easily digested bauxite slurry is formed by blending properly ground bauxite slurry in slurry storage
"surge" tanks prior to digestion.9
* VJ. Hill, "Bauxite," from Industrial Minerals and Rocks. 6th ed., Society for Mining, Metallurgy, and
Exploration, 1994, pp. 135-147.
7 Aluminum Company of America. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
8 "Aluminum Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. II, 1991, pp. 254-
261.
4
9 Ibid.
73
-------
Bauxite Digestion
Digestion extracts and solubilizes the available aluminum mineral from the bauxite. In digestion, which is
performed in steel vessels, autoclaves, or tubular reactors, hot spent liquor reacts with the aluminum minerals in the
bauxite to form soluble sodium aluminate (NaAlO3)10. Virtually all other constituents are rejected as undissolved
solids. Other important reactions that occur in digestion are desilication, causticization of liquor, and precipitation of
impurities. The reactive silica in bauxite, such as that in kaolin, reacts with the caustic solution to form soluble
sodium silicate, which then reacts at digester temperature to form an insoluble sodium aluminum silicate known as
"desilication product." Causticization, the reaction of hydrated lime with sodium carbonate to regenerate sodium
hydroxide and precipitate calcium carbonate, is an important part of the Bayer process chemistry. Na2CO, is formed
in Bayer liquors by caustic degradation of the organics in bauxite and by absorption of carbon dioxide during
exposure of process liquors to the atmosphere. Although poor lime efficiency and alumina losses during digestion as
calcium aluminates have led to the practice of "outside" causticization of dilute pregnant liquors in the residue
washing area of the plant, digestion lime additions are still made to control impurities such as phosphorus
pentoxide."
Clarification
Clarification is necessary to separate bauxite residue solids from the supersaturated pregnant liquor near its
boiling point. Coarse particles, called sand because of their high silica content, are usually removed by cycloning
followed by washing on sand classifiers prior to disposal. Iron oxide, silica, and other undigested portions of the ore
are also removed in settling, thickening, and filtration units, and sent to treatment and disposal units. These wastes
are commonly called red and brown muds; these two wastes are RCRA special wastes and therefore are not subject
to LDR regulations.12 In most plants, the fine fraction of residue is settled in raking thickeners with the addition of
flocculants to improve the clarity of thickener overflow. The concentrated thickener underflow is washed before
disposal in countercurrent decantation washers, on vacuum drum-type filters, or a combination of both. Thickener
overflow is filtered to remove the final traces of solids and ensure product purity. Kelly-type pressure filters are
most widely used, but some plants use sand filters in which the liquor is filtered by gravity through a bed of properly
sized sand. Filtered solids are removed from filter press cloth by hosing and are elutriated from the sand by
backwashing.13
Aluminum Hydroxide Precipitation
Precipitation is the heart of the Bayer process where recovery of the A1(OH)3 from process liquors occurs in
high yield and product quality is controlled. In 1988, practically all of the hydroxide was obtained by Bayer
processing and 90 percent of it was calcined to metallurgical grade alumina (A12O3). The liquor is usually seeded
with fine gibbsite seed from previous cycles to initiate precipitation. Precipitation can be continuous or batch.
Modern plants use the continuous system. Slurry leaving precipitation is classified into a coarse fraction and one or
more fine fractions, usually by elutriation in hydroclassifiers. In smelting grade alumina plants, the coarse fraction,
called primary product, is sent to calcination; the fine fractions, called secondary and tertiary seed, are recycled to be
grown to product size.14
10 Aluminum Company of America. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
11 Ibid.
12 U.S. Environmental Protection Agency, "Aluminum Production," from Report to Congress on Special Wastes
from Mineral Processing. Vol. II, Office of Solid Waste, July 1990, pp. 3-1 - 3-15.
13 "Aluminum Compounds," Op.Cit.. pp. 254-261.
14 Ibid.
74
-------
Calcination to Anhydrous Alumina
Calcination, the final operation in the Bayer process for production of metallurgical grade alumina, is
performed either in rotary kilns or fluid bed stationary calciners. Prior to calcination, the process liquor is washed
from the A1(OH)3 using storage tanks and horizontal vacuum filters. During heating, the trihydroxide undergoes a
series of changes in composition and crystal structure but essentially no change in particle shape. The product is a
white powder and consists of aggregates of differing sizes.1S
Evaporation and Impurity Removal
Evaporation over and above that obtained in the cooling areas from flashed steam is usually required to
maintain a water balance by accounting for the dilution arising from residue and A1(OH)3 washing, free moisture in
the ore, injected steam, purge water, and uncontrolled dilutions. Evaporation also serves to concentrate impurities
in the liquor stream such as sodium oxalate (a product of organics degradation), facilitating the removal of these
impurities.16
Hall-Heroult Process
Reduction
Since the development of the Hall-Heroult process, nearly all aluminum has been produced by electrolysis
of alumina dissolved in a molten cryolite based bath. Molten aluminum is deposited on a carbon cathode, which
serves also as the melt container. Simultaneously, oxygen is deposited on and consumes the cell's carbon anodes.
The overall all reaction is17;
2A12O3 + 3C - 4A1 + 3 CO2
Cryolite is the primary constituent of the Hall-Heroult cell electrolyte. Because of its rarity and cost,
synthetic cryolite is substituted. Synthetic cryolite is manufactured by reacting hydrofluoric acid,with sodium
aluminate from the Bayer process. Once the smelting process is in operation, no cryolite is needed because cryolite
is produced in the reduction cells by neutralizing the Na,O brought into the cell as an impurity in the alumina using
aluminum fluoride. Thus, the operating cells require inputs of aluminum fluoride. Aluminum fluoride is produced in
a fluidized bed by the reaction of hydrofluoric acid gas and activated alumina made by partially calcining the
alumina hydrate from the Bayer process. Alumina fluoride is also made by the reaction of fluosilicic acid, a by-
product of phosphoric acid production, and aluminum hydroxide from the Bayer process. The aluminum fluoride
solution is filtered, and A1F3 is precipitated by heating, then is flash dried and calcined.
The equivalent of 3-4 kg of fluoride per metric ton of aluminum produced is absorbed from the bath into the
cell lining over the lining's 3 to 10 year life. The most common method of recovery treats the crushed lining using
dilute NaOH to dissolve the cryolite and other fluorides. The solution is filtered and Na3AlF6 is precipitated by
neutralizing the NaOH using carbon dioxide. The aluminum industry in the United States uses about 15 kg of
fluoride ion per metric ton aluminum, 10-25 percent of which is lost. The remainder, consisting of cryolite generated
in reduction cells and of bath in scrap cell linings, is stored for future use. New fluoride for the aluminum industry
comes largely from fluorspar and phosphate rock.
15 Ibid.
16 Ibid.
17 Ibid.
75
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•vl
en
EXHIBIT 3
THE BAYER PROCESS
(Adapted from: Development Document for Effluent Limitations, 1989.)
Atmosphere
H,O
t
Limestone
Cortdcnsatc
to Boilers or
Hydrate
FiHralion
Lime Filter
Aid
H?O
Bauxite
-------
EXHIBIT 3 (Continued)
THE BAYER PROCESS
Spent Caustic
-J
-J
©
— >-
t~^ —
"
Heat
Exchange !
|
1
H2O
1
„ ^_ Barometric
Evaporators ^- i
Condensers
1
1 Barometric
Condenser
Effluent
Scale By-Product for
Activated Alumina
Production
Hydrate
^^ PicLipilatiuii ^^ CldssiliLdtioii ^^ Washing 01
Filtration
A Seed Solid Seed X Solid Seed X
.CO,
f
T
T
Calcining
Hydrate Product
^ Hydrate
Drying
Calcined Alumina
Product
Carbonation Plant
^ Eftluenl
j Soluble T
^^" Salts to Recovered Sodium Aluminale
Disposal Returned to Digestion
-------
EXHIBIT 4
THE HALL-HEROULT PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989.)
Coke
Solids lo
Recycle
t
1
r
quette n .
_ Briquette
oling -^B — ., , ,
Manufacture
aler
Cryolite, (CaF2, A1F2
Disposal
* l
H2O — )»~
Soderberg
Anodes
Anode and Cathode
Paste Blending
^ Crushing
Classifying
1 I Emissions
Prebaked Anode
Pressing and
Baking
^^
- - "• • «^-
Spent Cathodes
Caustic and Poliinc
F W Scrubber Litjuor
Cathode
Reprocessing
olids
agoon
Blowdown
or Disc
Cl2or
Mixed Gases
H;
10 Potline
large
Cooling ^
Water
Emissions ^ a..^~..^
w^.
— ^^- Anode Cooling Water
Emissions
Liquor
Direct i
W IF w Current T
Electrolytic
Cell
1 Molten
I Aluminur
Degassing
°l 1
Casting
Cooling
r- . • Potline and
emissions
Pollution Control
n
_ Activated
Fumes
Alumina
Adsorption
1
Alumina to Electrolytic Cell
^^
^^~ Aluminum
(Pig, Billet, Ingot
and Roti)
,
Paste Plant
Control
f Liquor
^ Bake Plant
Air Pollution
H20 ..'
Liquor
H2O
1
Scrubber — |^- Liquor
-------
Fluxing, and Degassing
The molten aluminum collected in the bottom of the electrolytic pots is tapped and conveyed to holding
furnaces for subsequent refining and alloying. Refining consists of fluxing to remove impurities and degassing to
reduce entrapped hydrogen gas in the molten aluminum. These two operations are often performed prior to casting.
Degassing is performed by injecting chlorine, nitrogen, argon, helium, and mixtures of chlorine and inert gases into
the molten aluminum. Hydrogen desorbs into the chlorine bubble due to the partial pressure difference between the
elements. The addition of a gas to the melt also mixes the aluminum to assure that all materials added concurrently
for alloying are distributed evenly in the molten aluminum. Chlorine gas reacts with trace element impurities to form
insoluble salt particles. These salt particles and the metal oxide impurities rise to the surface of the molten bath
through specific gravity differences and flotation, respectively. The impurities collect at the surface of the molten
metal and are skimmed and removed from the furnace.18
Casting
Casting is generally the final step at most aluminum reduction plants. The most common methods for
casting include: pig and sow casting, direct chill casting, continuous rod casting, and shot casting.
Stationary casting is used to cast pigs and sows (ingots). In this method of casting, the molds are stationary
and the contact cooling water (if used) generally evaporates.19
There are two methods of direct chill casting, vertical and horizontal. Vertical direct chill casting is
characterized by continuous solidification of the metal while it is being poured. The length of the ingot or billet cast
using this method is determined by the vertical distance it is allowed to drop rather than by mold dimensions.
Molten aluminum is tapped from the smelting furnace and flows through a distributor channel into a shallow mold.
Noncontact cooling water circulates within this mold, causing solidification of the aluminum. As the solidified
aluminum leaves the mold, it is sprayed with contact cooling water to reduce the temperature of the forming ingot or
billet. The cylinder descends into a tank of water, causing further cooling of aluminum as it is immersed. When the
cylinder reaches its lowest position, pouring stops, the ingot is removed, and the process is repeated to create another
ingot. Horizontal chill casting is performed in much the same manner as vertical chill casting. The main difference
is that the cast aluminum is conveyed from the mold in the horizontal direction rather than vertically.20
In continuous rod casting, a ring mold is fitted into the edge of a rotating casting wheel. Molten aluminum
is then poured into the mold and cools as the mold assembly rotates. After the wheel has rotated about 160 degrees,
the pliable aluminum bar is released. Immediately following release from casting, the rod is transported on
conveyers to a rolling mill where the diameter of the rod is reduced.21
In shot casting, aluminum shot is used as a deoxidant. Molten metal is poured into a vibrating feeder,
where droplets of molten metal are formed through perforated openings. The droplets are cooled in a quench tank,2!
16 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category, Vol II, Office of Water Regulations
Standards, May 1989.
19 IMd.
20 Ibjd.
21 Ibid.
22 Ibid.
79
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Anode Paste Plant
Fabrication of anodes takes place in the anode paste plant where coal tar pitch and ground petroleum coke
are blended together to form paste. During electrolysis, the prebaked anode is gradually consumed and becomes too
short to be effective. The resulting anode "butts" are recycled for use in the paste plant. Operations in the paste
plant include crushing, screening, calcining, grinding, and mixing. The paste is then formed into briquettes or into
green prebaked anodes. In this stage, briquettes and green anodes are essentially the same, differing only in size.
Briquettes are formed through an extrusion process in which the paste is forced through a die and then chopped into
small pieces using a dicer. Green anodes, which are much larger than briquettes, are formed by pressing paste into a
mold. Vibration may also be used. After forming, cooling water is used to quench the briquette or anodes to
facilitate handling.
Anode Bake Plant
Anodes used in prebaked potline cells are baked prior to their use in the potline. Two basic furnace types
are used to bake anodes, ring furnaces and tunnel kilns. In the ring furnace, green anodes are packed into pits with a
blanket of coke or anthracite filling the space between the anode blocks and the walls of the pits. A blanket of
calcined petroleum coke also fills the top of each pit above the top layer of anodes to help prevent oxidation of the
carbon anodes.
Each pit is baked for a period of about 40-48 hours. The flue system of the furnace is arranged so that hot
gas from the pits being baked is drawn through the next section of pits to gradually preheat the next batch of anodes
before they are baked. Air for combustion is drawn through the sections previously baked, cooling them. The baked
anodes are then stripped from the furnace pits.
In the tunnel kiln, a controlled atmosphere is maintained to prevent oxidation of the carbon anodes. Green
anode blocks are loaded on transporter units that enter the kiln through an air lock, pass successively through a
preheating zone, a baking zone, and a cooling zone, and leave the kiln through a second air lock. The refractory
beds of the cars are sealed mechanically to the kiln walls to form the muffle chamber and permit movement of the
units through the kiln. The muffle chamber is externally heated by combustion gases and the products of combustion
are discharged through an independent stack system. Effluent gases from the baking anodes may be introduced into
the fire box so as to recover the fuel value of hydrocarbons and reduce the quantity of unburaed hydrocarbons.
Baked anodes are delivered to air blast cleaning machines using fine coke as blasting grit. Fins, scrafs, and adherent
packing are removed by this treatment, and the baked anodes are then transferred to the rod shop where the
electrodes are attached.23
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Several diverse research initiatives have been carried out to reduce the quantity and/or toxicity of the
numerous production wastes generated in the alumina/aluminum industry. Spent potliner wastes (SPL) from
aluminum reduction (Hazardous Waste Number K088) have become one of the aluminum industry's biggest
environmental concerns. Reynolds Metals Company (Reynolds) developed a process for detoxifying SPL in which
the SPL was blended with limestone and an antiaggiomeration agent and thermally treated in a rotary kiln. The
process is successful in destroying cyanides and reducing the concentration of soluble fluorides in the kiln residue.
The cyanides are destroyed by oxidation and the majority of soluble fluoride salts are converted to stable, insoluble
calcium fluoride by reaction with limestone. The process was developed and utilized for more than 2 years on an
industrial scale at Reynolds' idled Hurricane Creek Alumina Plant in Bauxite, AR. More than 300,000 tons of SPL
reportedly were treated successfully during this period.24 In fact, Reynolds received a RCRA delisting variance for
this waste stream.
23 Ibid.
24 Patricia Plunkert, 1992. Op. Cit. pp. 183-203.
80
-------
On April 8, 1996, EPA finalized land disposal restrictions for K088 and established treatment standards
based on the Reynolds process described above. While the Agency determined at that time that adequate treatment
capacity was available, for several logistical and other reasons, the Agency decided to grant a nine-month capacity
variance for K088, until January 8, 1997. Some of the logistical barriers to complying with the LDRs included
pretreament requirements, such as grinding or crushing, that generators of waste would need to meet prior to sending
the wastes to the treatment facility. Also, some facilities generating K088 needed time to work out such logistical
issues as transportation, pretreatment capacity, and contracting for treatment capacity. Shortly following the
Agency's decision to grant the extension, several aluminum producers petitioned for a full two-year capacity
variance and modification of the treatment standards. The petition cited problems that had been identified with the
Reynolds process. In response to the petition, the Agency extended the capacity variance for an additional six
months, to July 8, 1997. A further extension was granted to October 8, 1997. No further action was taken by the
Agency when that variance expired; LDRs and the the treatment standards promulgated in April 1996 therefore
became effective on October 8, 1997,
An alternative treatment known as the COMTOR process was developed at Cornalco's Research Center in
Melbourne, Australia. The process has three stages—feed preparation, calcination, and fluoride recovery. Crushing
the SPL before treatment reportedly improved the rate and quality of the detoxification process. The COMTOR
process utilized a new type of calciner, known as a Torbed. Calcination reportedly was the most effective method
for reducing the leachable cyanide content of the SPL. Ash treatment recovered the fluoride values for recycling
directly to the electrolytic cell. Once the cyanide was destroyed and die fluorides either recovered or stabilized, the
residue reportedly passed the standard leach tests and was no longer considered toxic.25
The Florida Institute of Phosphate Research (FIPR) reportedly has developed a dewatering process that may
achieve promising results on red mud waste streams from the Bayer process operations. The FIPR process consists
of adding pulp fibers with a polyacrylamide flocculant. The fibers assist in the formation of large floes that have the
physical stability to withstand normal industrial dewatering techniques.26
Biological methods of converting sodium oxalate, generated from the Bayer process production of alumina,
have been tested. The use of micro-organisms to dispose of sodium oxalate was said to be far simpler and cheaper
than the currently employed burning and landfilling methods of disposal.27
Manganese dioxide treatment has been found to cause a beneficial decrease in the soda content of the
alumina and that a small reduction in the total organic carbon levels with this treatment also may be significant in
improving the viscosity of the liquor.28
4. Beneficiation/Proccssing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crashing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
25 Ibid.
26 Ibid.
27 Ibid.
28 Ibid.
81
-------
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between bauxite ore preparation and bauxite digestion because the bauxite ore is vigorously attacked (digested) by a
strong chemical agent, thereby destroying the physical structure of the mineral, to produce sodium aluminate.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated downstream of the beneficiation/processing line, along with associated
information on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Water softener sludge. The 1991 total waste volume generation rate for this waste stream was 2,000
metric tons per year.29 Because this waste is not a mineral processing waste, the Agency did not evaluate it further.
2. Mineral Processing Wastes
Alumina Production
Existing data and engineering judgment suggest that the materials listed below from alumina production do
not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
Evaporator Salt Waste. The 1991 total waste volume generation rate for this waste stream was 2,000
metric tons per year.30
Bauxite Residue. The 1991 total waste volume generation rate for this waste stream was 137,000 metric
tons per year.31 Placement in impoundments behind retaining dikes built around clay-lined ground is commonly used
for disposal of bauxite residue. Leaks into aquifers have motivated the installation of underdrains between the
residue and a clay-sealed, plastic-lined lake bottom. Another method of disposal is called semidry disposal, dry-
stacking, or the drying field method. This method takes advantage of the thixotropic nature of the residue. The
29 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Wastes Characterization Data
Set, Vol. I, Office of Solid Waste, August 1992, pp. 1-2 -1-8.
30 Ibid.
31 Ibid.
82
-------
residue is concentrated by vacuum filtration or other means to 35-50 percent solids. Using agitation and/or
additives, the viscosity of the concentrated slurry is reduced so it can be pumped to the disposal area where it flows
like lava. The slurry is called nonsegregating because neither water nor sand separate from it. As viscosity
increases, the flow stops. There is no free water on the surface of the impoundment, so the deposited residue dries
and cracks whenever it is not raining. When the percent solids approaches 70-75 percent, bulldozers can work on
the deposit.'12
Waste Alumina. The 1991 total waste volume generation rate for this waste stream was 7,000 metric tons
per year.3j
Spent Cleaning Residue. The 1991 total waste volume generation rate for this waste stream was 3,000
metric tons per year.34
Pisolites. Kaiser, in Gramercy, LA reported generating 72,920 metric tons of this waste in 1988.
Reportedly, this waste was either sold for construction of farm roads or sent to a pisolite storage pile which is lined
with an in-siru clay barrier.35
Wastewater. There are four sources of wastewater from bauxite production—(1) digester condensate, (2)
barometric condenser effluent, (3) carbonation plant effluent, and (4) mud impoundment effluent. Digester
condensate may be recycled to product wash or boiler water. Barometric condensate is a good quality, somewhat
alkaline water. Mud impoundment effluent is recycled or discharged. These wastewaters are not expected to be
hazardous. Waste characterization data are presented in Attachment 1.
Red and brown muds result from the clarification step of the Bayer process and are RCRA exempt special
wastes. The 1991 total waste generation rate for this waste stream was 2,800,000 metric tons per year,36 The red
and brown muds are routed to large on-site surface impoundments known as red and brown mud lakes. In these
lakes, the red and brown muds settle to the bottom and the water is removed, treated, and either discharged or reused.
The muds are not removed, but are accumulated and disposed in place. The muds dry to a solid with a very fine
particle size. The impoundments that receive the muds typically have a surface area of between 44.6 and 105.3
hectares. The depth of the impoundments ranges from 1 to 16 meters and averages 7 meters. As of 1988, the
quantity of muds accumulated on-site ranged from 500,000 to 22 million metric tons per facility, with an average of
9.7 million metric tons per facility.37
Red and brown muds contain significant amounts of iron, aluminum, silicon, calcium, and sodium. Red
muds may also contain trace amounts of elements such as barium, boron, cadmium, chromium, cobalt, gallium,
vanadium, scandium, and lead, as well as radionuclides. The types and concentrations of minerals present in the
muds depend on the composition of the ore and the operating conditions in the digesters.
32 "Aluminum Compounds," Op. Cit.. pp. 254-261.
33 U.S. Environmental Protection Agency, 1992, Op. Cit.. pp. 1-2 -1-8.
34 U.S. Environmental Protection Agency, Op. Cit., 1992, pp. 1-2 -1-8.
35 RTI Survey, Kaiser, Gramercy, LA, 1988, ID# 100339.
36 Ibid.
37 U.S. Environmental Protection Agency, Op. Cit. 1990, 3-1 - 3-15.
83
-------
Aluminum Production
APC dust/sludge is a possible waste stream from aluminum production operations, including electrolysis.
fluxing, degassing, and anode production. Emissions may consist of unreacted chlorine and aluminum chloride gas.
aluminum oxide, sulfur, fluoride, hydrocarbons, and organics.38 Existing data and engineering judgment suggest that
this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Flue Dust. The 1991 waste generation rate was 39,000 metric tons per year.39 Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further.
Sweepings. The 1991 waste generation rate was 23,000 metric tons per year."0 Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further.
Electrolysis Waste. Electrolysis wastes include fluoride emissions and hydrocarbon fumes. Both sodium
tetrafluoroaluminate gas and entrained liquid solidify to form fluoride particulates. Treatment consists of dry
scrubbers that catch particulates and sorb HF on alumina that is subsequently fed to the cells. Nearly all the fluoride
evolved is fed back into the cell.41 Hydrocarbon fumes are generally disposed of by burning. This waste is
generated at a rate of 58,000 metric tons per year (adjusted from a 1991 reported value to reflect recent changes in
the sector) and may be toxic for lead.42 This waste was formerly classified as a sludge.
Baghouse Bags and Spent Plant Filters. The 1991 waste generation rate was 19,000 metric tons per
year.43 Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Skims and Discarded Drosses.44 The Aluminum Association has provided the Agency with information
about skims and drosses. They stated these materials are byproducts, generated as part of the aluminum melting
process. Specifically, when exposed to the atmosphere, a thin layer of aluminum oxide forms on the molten
aluminum's surface (i.e., scrap aluminum being melted is coated with aluminum oxide). This oxide material is the
starting point for byproducts derived from melting aluminum. The oxide layer increases during stirring, transferring,
fluxing, and pouring operations, and floats to the surface of the molten aluminum. It builds up in troughs, furnaces,
and crucibles during the casting process, and free aluminum becomes mixed and entrapped with the oxide. Dross is
the solidified material, generally consisting of oxides of aluminum and other alloying materials, formed when molten
aluminum reacts with the atmosphere or moisture. Skim are accumulations of oxide with entrapped metal, formed on
the metal surface after melting from oxide films introduced as surface oxides on all charge components. Skims and
drosses were formerly categorized by EPA as characteristic byproducts.
38 U.S. Environmental Protection Agency, 1989. Qp, Cit, Vol. II.
39 Ibid.
40 Ibid.
41 "Aluminum Alloys," 1992. Op. Cit.. pp. 190-212.
42 U.S. Environmental Protection Agency, 1992, Op. Cit., pp. 1-2 -1-8.
43 Ibid.
"4 The Aluminum Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
84
-------
In 1994, the U.S. aluminum industry generated approximately 439,000 metric tons of skims and drosses.
Approximately 80,000 metric tons were reclaimed on-site, while an estimated 350,000 metric tons went off-site for
reclamation. On a facility-specific basis, one company processed 76,900 metric tons of aluminum byproducts which
it generated, sending other volumes off-site for further processing to companies which specialize in aluminum
byproduct recovery. Recycling of aluminum skims and drosses is very common, and economically feasible with
metal contents as low as eight percent. Depending on the material and processes employed, recovery rates may
exceed 60 percent. For example, in 1994, one recovery facility processed 90,500 metric tons of byproducts at an
average recovery rate of 60 percent. The facility then returned the recovered metal to its customers. The U.S.
exports approximately 4,700 metric tons of aluminum byproducts annually, while aluminum companies import
13,600 metric tons of aluminum byproducts per year.
Anode Prep Waste. The 1991 waste generation rate was 20,000 metric tons per year.45 Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further.
Scrap Furnace Brick. The 1991 waste generation rate was 77,000 metric tons per year.46 Existing data
and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Cryolite Recovery Residue. The 1991 waste generation rate was 30,000 metric tons per year.47 Historical
management of this waste has included disposal in an unlined surface impoundment.48 This waste may contain high
levels of lead. Existing data and engineering judgment suggest, however, that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Cast House Dust. This waste is generated at a rate of 19,000 metric tons per year (adjusted from a 1991
reported value to reflect recent changes in the sector) and may contain toxic levels of cadmium and mercury.49 This
waste may be recycled and was formerly classified as a sludge. Attachment 1 presents waste characterization data
for casthouse dust.
Spent Potliners. This waste is a listed hazardous waste (K088). The 1991 waste generation rate was
118,000 metric tons per year.30 This waste stream may contain toxic levels of arsenic, cyanide, and selenium as well
as detectable levels of cadmium, chromium, barium, lead, mercury, silver, and sulfates. This waste is generally
managed through landfilling, indefinite "storage," or cathode reprocessing. Cathode reprocessing serves a hazardous
waste treatment function by reducing waste volume, and incidentally recovering cryolite. Cathode reprocessing
consists of grinding the spent potliners in a ball mill and then leaching with caustic to solubilize fluoride.
Undigested cathode material is separated from the leachate using sedimentation and then sent to lagoons. Sodium
aluminate is then added to the leachate to initiate the precipitation of cryolite and a second solid-liquid separation is
performed to recover cryolite, which can be reused in the electrolytic cell. Lime is added to the supernatant to
precipitate calcium fluoride and a third solid-liquid separation is performed. The resulting supernatant is then routed
45 Ibid.
46 Ibid.
47 Ibid.
48 U.S. Environmental Protection Agency, Technical Background Document. Development of Cost. Economic,
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, pp. 3-4-3-6.
49 U.S. Environmental Protection Agency, 1992, Op.Cit.. pp. 1-2 -1-8.
30 Ibid.
85
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back to the front of the process and used for leaching. Slowdown from the system varies from plant to plant but it is
universally used as potline scrubber liquor make-up when wet potline scrubbers are used. It is also common to route
potline scrubber liquor through the cathode reprocessing circuit. In this way, fluoride concentrations of the scrubber
liquor are controlled and recycling is possible. Spent potliners are listed wastes, KO88.
Sludge. This waste is generated at a rate of 80,000 metric tons per year (adjusted from a 1991 reported
value to reflect recent changes in the sector). Management of this waste includes disposal in an unlined surface
impoundment.51 Attachment 1 presents waste characterization data for this waste stream. Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore.
the Agency did not evaluate this material further.
Treatment plant Effluent. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further. Waste
characterization data are presented in Attachment 1.
Miscellaneous Wastewater. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further. Waste
characterization data are presented in Attachment 1.
D. Non-uniquely Associated Hazardous Wastes
Cooling tower blowdown was generated at a rate of 8,000 metric tons per year in 1991.52 Because this
waste stream is non-uniquely associated, the Agency did not evaluate it further. Ancillary hazardous wastes may be
generated at on-site laboratories, and may include used chemicals and liquid samples. Other hazardous wastes may
include spent solvents (e.g., petroleum naptha), and acidic tank cleaning wastes. Non-hazardous wastes may include
tires from trucks and large machinery, sanitary sewage, waste oil (which may or may not be hazardous), and other
lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Two commenters provided new information on the processes used in the alumina/aluminum sector
(COMM65, COMM77). This new information has been incorporated into the Agency's sector report, as
appropriate.
Sector-specific Issues
None.
51 U.S. Environmental Protection Agency, Technical Background Document. Development of Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, pp. 3-4-3-6.
52 Patricia Plunkert, 1992, Op. Cit.
86
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BIBLIOGRAPHY
"Aluminum and Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. II. 1991. pp. 190-212
"Aluminum Compounds." Kirk-Othmer Encyclopedia, of Chemical Technology. 4th ed. Vol.11. 1991. pp. 254-
261.
Hill, VJ. "Bauxite." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. pp. 135-147.
McCawley, Frank and Luke H. Baumgardner. "Aluminum." From Mineral Facts and Problems. U.S. Bureau of
Mines. 1985. pp. 9-30.
Plunkert, Patricia. "Aluminum." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 16-17.
Plunkert, Patricia A. and Errol D, Sehnke. "Aluminum, Bauxite, and Alumina." From Minerals Yearbook Volume
1. Metals and Minerals. U.S. Bureau of Mines. 1992. pp. 183-203.
RTI Survey, Kaiser, Gramercy, LA, 1988, ID# 100339.
Sehnke, Errol. "Bauxite." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.26-
27.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol.1. August 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol. III. August 1992. pp. 1-2-1-45.
U.S. Environmental Protection Agency. "Alumina Production." From Report to Congress on Special Wastes
from Mineral Processing. Vol.11. Office of Solid Waste. July 1990, pp. 3-1-3-15.
U.S. Environmental Protection Agency. Developement Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Vol. II. Office of Water Regulations
Standards. May 1989.
U.S. Environmental Protection Agency, Technical Background Document. Development of Cost, Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989. pp. 3-4-3-6.
87
-------
ATTACHMENT 1
88
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER - ALUMUMINA/ALUMINUM
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Vtagnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
0.0005
0.001
-
0.0001
0.001
0.004
-
0.01
0.008
0.0001
0.004
0.0005
0.0005
0.0005
-
0.01
0.002
-
-
-
-
-
_
-
0.298
0.333
-
0.033
0.057
0.074
-
0.285
0.491
0.001
0.682
2.488
0.075
0.191
-
0.168
39.44
-
-
-
-
-
_
-
1.5
1.5
-
0.4
0.2
0.6
-
1.6
5
0.0062
4
44
0.36
0.69
-
1
180
-
-
-
-
-
-
Detects
0/0
20/20
20/20
0/0
20/20
0/0
20/20
20/20
0/0
20/20
0/0
20/20
0/0
0/0
19/19
0/0
20/20
20/20
20/20
20/20
0/0
20/20
22/22
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
5.0 0
0.2 0
1.0 0
5.0 0
-
-
-
-
.
-
-
_
-
212 0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented
-------
10
o
SUMMARY OF EPA/ORD, 3007, AND RTi SAMPLING DATA - CASTHOUSE DUST - ALUMINA/ALUMINUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickef
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
7.5
32
10
-
-
7.2
110
-
510
93000
17
-
1100
0.0001
-
260
0.92
1.9
-
-
120
-
-
-
-
-
-
-
-
-
-
-
7.5
32
10
-
-
7,2
110
-
510
93000
17
-
1100
0.0001
-
260
0.92
1.9
-
-
120
-
-
-
-
-
-
-
-
-
-
-
7.5
32
10
-
-
7.2
110
-
510
93000
17
-
1100
0.0001
-
260
0.92
1.9
-
-
120
-
-
-
-
-
-
-
-
-
-
Detects
0/0
1/1
1/1
1/1
0/0
0/0
1/1
1/1
0/0
1/1
1/1
1/1
0/0
1/1
0/1
0/0
1/1
1/1
1/1
0/0
0/0
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis -
Minimum Average
-
0.42
0.001
0.28
-
-
3.5
0.086
-
0.25
0.47
0.024
-
19
0.84
-
0.74
0.001
0.15
-
-
0.58
-
-
18
61
-
-
27000
-
0.42
0.001
0.28
3.5
0.086
0.25
0.47
0.024
19
0.84
0.74
0.001
0.15
0.58
18
61
27000
PPM
Maximum
-
0.42
0.001
0.28
-
-
3.5
0.086
.
0.25
0.47
0.024
-
19
0.84
-
0.74
0.001
0.15
. .
.
0.58
-
-
18
61
-
-
27000
.
# Detects
0/0
1/1
0/1
1/1
0/0
0/0
1/1
1/1
0/0
1/1
1/1
1/1
0/0
1/1
1/1
0/0
1/1
0/0
1/1
0/0
0/0
1/1
0/0
0/0
1/1
1/1
0/0
0/0
1/1
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 1
5.0 0
-
-
-
5.0 0
-
-
0.2 1
-
-
1.0 0
5,0 0
.
-
-
-
-
-
-
-
-
-
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - TREATMENT PLANT EFFLUENT - ALUMINA/ALUMINUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
vlinimum Average Maximum
-
0.0005
0.002
-
0.001
-
0.002
0.004
-
0.006
-
0.02
-
-
0.0001
-
0.005
0.001
0.002
0.001
-
0.056
0.004
-
-
-
-
-
-
-
-
-
-
0.3438
0.3326
-
0.0191
-
0.0690
0.0434
-
0.0975
-
0.2222
-
-
0.0019
-
0.1985
0.3743
0.1416
0.2288
-
0.2561
37.0253
-
-
-
-
-
-
-
-
-
-
1.1
1.9
-
0.06
-
0.2
0.24
-
0.744
-
0.6
-
-
0.0213
-
0.56
3
0.7
0.69
-
2
200
-
-
-
-
-
-
-
-
-
# Detects
0/0
15/15
15/15
0/0
15/15
0/0
15/15
15/15
0/0
• 15/15
0/0
15/15
0/0
0/0
14/14
0/0
15/15
15/15
15/15
15/15
0/0
15/15
17/17
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
.
-
-
-
.
-
212 0
-
Non-deteets were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - MISCELLANEOUS WASTEWATERS - ALUMINA/ALUMINUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0.0005
0.01
-
0.0005
-
0.001
0.004
-
0.008
-
0.01
-
-
0.0001
-
0.005
0.001
0.002
0.0005
-
0.02
0.004
-
-
-
-
-
-
-
-
-
-
0.377
0.512
-
0.019
-
0.037
0.029
-
0.299
-
0.438
-
-
0.001
-
0.326
3.964
0.129
0.189
-
0.108
95.24
-
-
-
-
-
-
-
-
-
-
2
2.3
-
0.08
-
0.1
0.2
-
1.3
-
3
-
-
0.003
-
1
40
0.5
0.73
-
0.6
180
-
-
-
-
-
-
-
-
-
# Detects
0/0
11/11
11/11
0/0
11/11
0/0
11/11
11/11
0/0
. 11/11
0/0
11/11
0/0
0/0
11/11
0/0
11/11
11/11
11/11
11/11
0/0
11/11
11/11
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
• - o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
.
-
-
.
-
-
.
-
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SLUDGE - ALUMINA/ALUMINUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
0.64
0.72
4
-
-
0.0465
1.3
-
0.38
730
5
-
0.41
0.0001
-
15
0.05
0.04
-
-
1.4
-
-
-
-
-
-
-
-
-
-
-
1.68
7.18
31.2
-
-
1.04
13.7
-
95.40
2386
30.98
-
24.96
0.06
-
224
0.32
1.02
-
-
82.48
-
-
-
-
-
-
-
-
-
-
-
3
16
78
-
-
2
33
-
380
5300
63
-
60
0.32
-
520
0.78
2
-
-
320
-
-
-
-
-
-
-
-
-
-
Detects
0/0
3/5
5/5
5/5
0/0
0/0
3/5
5/5
0/0
5/5
5/5
5/5
0/0
5/5
3/5
0/0
5/5
4/5
3/5
0/0
0/0
5/5
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
tP Toxicity Analysis - PPM
Minimum Average Maximum #
-
0.032
0.001
0.01
-
-
0.001
0.002
-
0.001
0.27
0.001
-
0.12
0.0001
-
0.045
0.001
0.001
-
-
0.011
-
-
2
0.48
-
-
2.2
-
-
0.032
0.014
0.024
-
-
0.013
0.005
-
0.011
0.300
0.002
-
0.235
0.0002
-
0.045
0.004
0.002
-
-
0.056
-
-
436
48.74
-
-
12.60
-
-
0.032
0.026
0.037
-
-
0.025
0.008
-
0.021
0.33
0.003
-
0.35
0.0002
-
0.045
0.006
0.002
-
-
0.1
-
-
870
97
-
-
23
-
Detects
0/0
1/1
1/2
2/2
0/0
0/0
1/2
2/2
0/0
2/2
2/2
1/2
0/0
2/2
1/2
0/0
1/1
1/2
1/2
0/0
0/0
2/2
0/0
0/0
2/2
2/2
0/0
0/0
2/2
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
94
-------
ANTIMONY
A.
Commodity Summary
According to the U.S. Bureau of Mines, antimony metal and oxide are produced by seven companies
domestically. Additionally, a small amount of antimony is recovered domestically as a byproduct of smelting lead
and silver-copper ores. Exhibit 1 presents the names, locations, and type of processes used by the facilities involved
in the primary production of antimony metals and oxides. Estimated apparent domestic consumption was 45.000
metric tons during 1994. Antimony is used mainly in flame retardants, transportation (including batteries),
chemicals, ceramics, and glass.
Antimony is generally found in association with other elements in complex ores as the sulfide mineral
stibnite. Antimony is made available commercially as antimony trioxide. Most of the antimony trioxide produced is
derived from imported original sources.
EXHIBIT 1
SUMMABY OF ANTIMONY FACILITIES
Facility Name
Amspec Chemical Corp
Ant. Process (inactive)
Anzon, Inc.
ASARCO Incorporated
ASARCO (inactive)
Chemet (inactive)
Laurel Ind.
M&T Chemical (inactive)
McGean Chemical
Sunshine Mining Company
US Antimony Corp.
Location
Gloucester, NJ
Moscow, TN
Laredo, TX
Omaha, NE
El Paso, TX
Moscow, TN
LaPorte, TX
Baltimore, MD
Cleveland OH
Kellogg, ED
Thompson Falls, MT
Type of Operations
Pyrometallurgical
Pyrometallurgical
Pyrometallurgical
Pyrometallurgical
Electro winning
Pyrometallurgical
Pyrometallurgical
Pyrometallurgical
Pyrometallurgical
Electrowinning
Pyrometallurgical
Antimony Specialist, "Antimony," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995, p. 18.
95
-------
B. Generalized Process Description
1. Discussion of Typical Production Processes
Primary antimony production usually arises as a byproduct or coproduct of mining, smelting, and refining
other antimony-containing ores such as tetrahedrite (a complex silver-copper-antimony-sulfide ore) or lead ore.2
2, Generalized Process Flow Diagram
Antimony can be produced using either pyrometallurgical processes or a hydro metallurgical process. As
shown in Exhibits 2 through 7, for the pyrometallurgical processes, the method of recovery depends on the antimony
content of the sulfide ore. For example, the lowest grades of sulfide ores, containing 5-25% antimony, are
volatilized as oxides; ores containing 25-40% antimony are smelted in a blast furnace; and 40-60% antimony ores
are either liquated or treated by iron precipitation. As shown in Exhibit 6, the rich oxide ores that result from either
volatilization, smelting, or liquation can be reduced directly in a reverberatory furnace. Exhibit 7 outlines the
process used to refine the antimony metal resulting from pyrometallurgical process.
Alternatively, antimony can be recovered hydrometallurgically by leaching and electrowinning as shown in
Exhibit 8.3 Currently, the Sunshine Mining Company in Kellogg, Idaho is the only domestic mine that employs the
hydrometallurgical process.
Pyrometallurgical Recovery
Oxide Volatilization. As indicated in Exhibit 2, low grade ore is recovered through oxide volatilization.
The ore is roasted with coke or charcoal in a rotary kiln or shaft furnace. As a result of the roasting step, sulfur is
burned away and removed in the waste gases and antimony trioxide, which condenses, can be recovered in flues,
condensing pipes, or a Cotrell precipitator. The resultant oxide is briquetted and reduced to metal.4 The largest
producer of antimony metal from roasting is Anzon in Laredo, Texas.
Blast Furnace Smelting, As shown in Exhibit 3, the blast furnace smelting process used to recover
antimony from intermediate (25-40%) grades of oxide and sulfide ores, flue dust, liquation residues, mattes,
briquetted fines, and rich slags is similar to the blast furnace method used to process lead. A low pressure, high
smelting column, water-jacketed blast furnace is used. The slag is separated from the antimony metal and sent to
waste or reprocessing.5
Sulfur Liquation. As indicated in Exhibit 4, liquation is used to recover antimony from high grade ores.
The ores can be heated either in batch mode in a perforated pot, or in continuous mode using a reverberatory
furnace. This process separates the antimony sulfide from the gangue. The liquated product is known as crude or
needle antimony, which can either be distributed as antimony sulfide or converted to recover antimony metal. Either
iron precipitation or oxide reduction can be used to recover metallic antimony from the sulfide.6
2 Thomas O. Llewelyn, "Antimony," from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines, 1992, p. 225.
3 "Antimony," Kirk-Othmer Encyclopedia of Chemical Technology, 1992, 4th ed., Vol. Ill, p. 370.
4 Ibid.
5 Ibid., p. 371.
6 Ibid.
96
-------
EXHIBIT 2
ANTIMONY OXIDE VOLATILIZATION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45)
Low Grade Ore (5 - 20% Sb)
SO,
Wastewater
Gangue
Sb2O3 (gas)J
Sb2O3 (partieulate
Sb2O3 (particulate)
Briquetting
I
Antimony Metal
97
-------
EXHIBITS
ANTIMONY SMELTING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Fuel
Medium Grade Antimony Ore
Slag
Waste or
Reprocessing
Antimony Metal
EXHIBIT 4
ANTIMONY LIQUATION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Antimony Ore
1(40 - 60% Sb)
Perforated Pot or
Reverberatory Furnace
(550 - 600 °C)
Gangue
(12-30%Sb)
Needle Antimony
Product
To Oxide Volatilization
98
-------
EXHIBITS
ANTIMONY IRON PRECIPITATION REDUCTION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
p High Grade Antimony Ore
(40 - 60%) or
Needle Antimony
Iron Scrap ^-
Carbon + Na^SC^ ^~
Fusion
Iron Sulfide Matte »
Waste or
Smelting
A
Antimony Metal
Needle Antimony
Salt
Iron Sulfide Matte
Purified Antimony Metal
EXHIBIT 6
ANTIMONY OXIDE REDUCTION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Antimony Oxide
iO-^ (particulate)
Charcoal
Soda, Potash, or
Sodium Sulfate
Slag
Antimony Metal
99
-------
Iron Precipitation. Iron precipitation is used to convert crude antimony sulfide to metallic antimony. As
Exhibit 5 illustrates, the molten antimony sulfide is heated in combination with iron scrap, carbon, and Na2SO4. The
process uses iron as the reductant to replace antimony in the molten antimony sulfide. Sodium sulfate and carbon are
added to produce sodium sulfide. Alternatively, salt is added to form a fusible light matte with iron sulfide and
facilitate the separation of the metal. Because the resultant metal contains high concentrations of iron and sulfur, a
second fusion with liquate antimony and salt is used to produce a purified antimony metal.7
Oxide Reduction. Antimony trioxide or other antimony oxides are reduced with charcoal in reverberatory
furnaces as shown in Exhibit 6. The addition of an alkaline flux of soda, potash, and sodium sulfate dissolves
residual sulfides and gangue and also minimizes volatilization. During this process, the loss of antimony due to
volatilization necessitates the use of Cotrell precipitators or baghouses to recover the antimony trioxide for
reprocessing. During this process, a slag is produced and separated from the antimony metal.8
Refining. Metal resulting from pyrometallurgical reduction requires refining to remove arsenic, sulfur,
iron, and copper impurities. Exhibit 7 presents a typical flow process diagram for the refining process. The iron and
copper concentrations can be reduced by adding stibnite or a mixture of sodium sulfate and charcoal to form an iron-
bearing matte. The matte is skimmed from the surface of the molten metal, after which the metal is treated with an
oxidizing flux of caustic soda or sodium carbonate and niter (sodium nitrate) to remove arsenic and sulfur. Although
lead is not readily removed from antimony, material containing lead may be used for lead based alloy applications.9
Hvdrometallurgical Recovery
Antimony can also be recovered using the hydrotnetallurgical process outlined in Exhibit 8, which involves
leaching followed by electrowinning and autoclaving. The hydrometallurgical process is based on the knowledge
that: (i) an alkaline sodium sulfide solution acts as an effective solvent for most antimony compounds and (2) most
other metals are insoluble in such a solution (excluding arsenic, tin, and mercury).1010 The Sunshine Mining
Company is the only domestic antimony facility that uses this hydrometallurgical technique. The Sunshine facilities
are a complete mine-to market operation. In addition to their antimony plant, their operations include a mill, a silver-
copper refinery, and a functional mint. Their antinomy facility produces both antimony metal and sodium
antimonate. The process at this facility involves: (1) leaching and filtration, (2) electrowinning, and (3) autoclaving
and tails treatment.
Leaching and Filtration. The ore concentrates from the mill are leached in a batch process in a heated,
pressurized vat. Some of the concentrates are blended, prior to leaching, with coke, sodium sulfate, and sodium
carbonate and then melted in a furnace. The resultant material is then leached with a sodium hydroxide solution.
Other concentrates are combined with sodium sulfide and sulfur and leached with a sodium hydroxide solution
without prior melting. This leach solution is created by combining the barren catholyte (depleted electrolyte from
downstream electrowinning), elemental sulfur, sodium sulfide, and sodium hydroxide. The solution matrix then
solubolizes the antimony and any arsenic present that is not in the form of arsenopyrite, producing soluble thio
compounds including NaSbS2, Na3SbS3, Na3SbS4, and Na3AsS3. The solids can then be separated from the leaching
7 Ibid.
8 Ibid.
9 Ibid., pp. 372-373.
10 Corby G. Anderson, Suzzann M. Nordwick, and L. Ernest Kyrs, "Processing of Antimony at the Sunshine
Mine," from Residues and Effluents - Processing and Environmental Considerations. The Minerals, Metals, &
Materials Society, 1991, p. 349-366.
100
-------
Efflmrr?
ANTIMONY REFINING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Antimony Metal From
Pyrometallurgie Process
Charcoal +
or
Stibnite
NaOH
Na^COj
NaNO3
Iron Matte
Waste or
Further Processing
Waste Containing
As andS
Antimony Metal
(85 - 90% Sb)
101
-------
EXHIBIT 8
HYDROMETALLURGICAL ANTIMONY PRODUCTION PROCESS
{Adapted from: Residues and Effluents - Processing and Environmental Considerations, 1991, pp. 349 - 366.)
Mil) Concentrate
Sodium Sulfidc
and/or Sulfur
Diaphragmed
Antimony
Electrowinning
Cells
Silver Concentrate
to Refinery
To Market
Tails Pond
102
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solution by thickening and filtration. The leached residue is either disposed of or processed further to recover other
metals."
As shown in Exhibit 7, when the leaching is complete, the resultant slurry is diluted to enhance solid
separation from the alkaline solution. Dilution involves the use of water recovered from downstream repulping.
After dilution the slurry consists of an antimony bearing pregnant catholyte solution and a high grade silver-copper
residue. The solid-liquid separation takes place by conventional settling and thickening. Both primary and
secondary thickeners are used with a repulp stage occurring in between. Including this first repulping step, there
three total repulping steps involved in the Sunshine Mine recovery process. Residue from the secondary thickener is
repulped a second time and then recovered with a disc filter. The mixture is then sent through a third and final
repulping stage during which fresh water enters the process. The final filtration step involves a drum filter. The
wash water flows from the drum filter back through to the second repulping stage. From the second repulping step,
the wash water flows through the disc filter and back to the first repulp step and from there the water is sent back to
the leach stage for use in the dilution step. The three repulping steps allow for maximum recovery of the leached
antimony and provide a copper-silver residue that is free from alkaline sulfur compounds that might interfere with
acid pressure leaches downstream when the resultant solid filter cake is sent to the Sunshine silver refinery.12
Electrowinning. As shown in Exhibit 8, the pregnant solution from the leaching process is used as feed for
the electrowinning circuit. Antimony metal is deposited on the cathode as a brittle, non-adherent layer which is
periodically stripped and washed. The resultant product is either sold or sent for further processed to antimony
trioxide.
Because the products of oxidation at the anode interfere with the deposition of antimony at the cathode, two
different and physically separated solutions are used. The catholyte, in this case the pregnant solution from the
leachin:: process, surrounds the cathode and the anolyte, a combination of barren catholyte and sodium hydroxide
solution, surrounds the anode. Mixing of the two solutions is minimized by the use of a canvas barrier or diaphragm.
The canvas barrier has small pores that allow the solutions to come into contact, maintaining the integrity of the
electrical circuit.
The recovered metal is washed by blowing steam into a tank containing hot water and the metallic
antimony. This step removes any solutions or soluble solids that have adhered to the metal during the plating
process. This wash water is sent to tails treatment and can be autoclaved to recover sodium antimonate. After
drying, the antimony metal product is packaged and sold to secondary smelters for use as a lead hardener or for
antimony oxide production.13
After the antimony has been removed, the barren catholyte can be recycled to the process through one of
two methods. In the process where the ore is melted prior to leaching, the spent electrolyte is spray dried and the
dried salts are captured in a baghouse for reuse during the blending step. In the other process where the concentrates
are leached without melting them first, the barren catholyte solution is recycled directly into the leaching process.
Site-specific information indicates that the fouled anolyte is removed and treated by autoclaving to recover sodium
antimonate, which is then recycled to the leaching process. The resultant antimony metal can be converted to
antimony trioxide in a fuming furnace.14
11 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. IV, Office of Water Regulations
Standards, 1989, p. 2062.
12 Corby G. Anderson, 1991, Op. Cit. p. 355.
13 Corby G. Anderson, 1991, Op. Cit.. p. 360.
14 U.S. Environmental Protection Agency, 1989. Op. Cit.. p. 2063.
103
-------
Autoclaving. Sodium antimonate (NaSbO,) is produced by autoclaving the antimony-bearing fouled
anolyte solution from the electrowinning process. Residual caustic sodas are also present in the fouled anolyte and
can be recovered. Oxygen autoclaving, heating the solution under pressure in the presence of oxygen, is used to
produce the sodium antimonate. The elevated temperature and pressure drive the oxidation reaction and result in the
formation of insoluble sodium antimonate which is separated from the remaining liquid by sedimentation and
decanting. The resultant sodium antimonate either recycled back to the leaching step or sold depending on market
conditions.15
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
, 4. Beneficiation/Processing Boundary
Since antimony is generally recovered as a co-product or a by-product of other metals, all of the wastes
generated during antimony recovery are mineral processing wastes. For a description of where the
beneficiation/processing boundary occurs for this mineral commodity, please see the report for lead presented
elsewhere in this background document.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Because antimony is recovered as a co-product or a by-product of other metals, mining wastes are
addressed in the descriptions of the initial ore/mineral. For a further description of these wastes see the report for
lead presented elsewhere in this background document.
2. Mineral Processing Wastes
The following wastes have been identified as generated during the oxide volatilization process.
Gangue. Gangue generated from roasting during the oxide volatilization process may contain traces of
antimony and other heavy metals. Gangue generated from either smelting or other higher grade recovery processes
may be sent to oxide volatilization for further antimony recovery, since that process is designed for lower grade ores.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
Wastewater. The wastewater generated from the wet scrubber process following oxide volatilization may
contain sulfur and some heavy metals. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
The following wastes have been identified as generated during the smelting and refining portions of the
antimony recovery process. Although no published information regarding waste generation rate or characteristics
was found, we used the methodology outlined in Appendix A of this report to estimate low, medium, and high waste
generation rates.
APC Dust/Sludge. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Sludge from Treating Process Waste Water. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
' Corby G. Anderson, 1991. Op. Cit. p. 361.
104
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Refining Dross. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Slag and Furnace Residue. The slag generated during the oxide reduction process may contain residual
soda, potash, or sodium sulfate. The waste generation rate for this waste stream is reported to be 32,000 mt/yr. We
used best engineering judgment to determine that this waste may exhibit the characteristic of toxicity for lead.
Waste Solids. Wastes produced from fluxing during the refining process contain arsenic (As) and sulfur
(S). Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Hydrometallurgical Recovery
Leach Residue. The leach residue contains antimony, sulfur, sodium, pyrite, silica, and stibnite.16 In the
antimony plant in Kellogg, Idaho, a hot alkaline sulfide solution is used to dissolve antimony and most arsenic
species from the ore concentrate, leaving a leach residue containing less than one percent antimony.'7 Existing data
and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Gangue (Filter Cake). At the Kellogg plant, slurry from the leach tanks is diluted and then thickened and
filtered in a series of repulp-filtration steps. The resulting filter cake, containing 18-20 percent moisture, becomes
feed material at the silver refinery. Filtered leach solution containing antimony (primarily as sodium thioantimonate)
is fed to the antimony electrowinning circuit.18 Existing data and engineering judgment suggest that this material
does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Stripped Anolyte Solids. Electrowinning "tails" consist of fouled anolyte and cathode wash water. The
fouled anolyte is heated and pressurized with oxygen in a 1,500 gallon autoclave to recover sodium antimonate
before being sent to the tailings pond.19 The waste generation rate for this waste stream is reported to be 190 metric
tons/yr. This waste stream is fully recycled and is classified as a by-product. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity for arsenic.
Spent Barren Solution. Barren catholyte solution is recycled back to the leach step and to the anolyte
make up water added prior to the electrowinning step. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Autoclave Filtrate. The liquid phase from the autoclave, which contains sodium arsenate and residual
antimony is treated with solid ferrous sulfate to precipitate arsenic as Fe3(AsO4) and antimony as Sb2S3 at a pH of 8
to 8.5. Quicklime is then added to precipitate residual iron in the solution. The resulting anolyte slurry is then
commingled with mill tailings and pumped to an unlined on-site surface impoundment. Natural sedimentation
removes solids under the liquid outflow which is discharged under an NPDES permit.20 The low, medium, and high
annual waste generation rates were estimated as 380 metric tons/yr, 32,000 metric tons/yr, and 64,000 metric tons/yr,
16 U.S. Environmental Protection Agency, 1989, Op. Cit, p. 2062.
17 Gary Light, ICF, Incorporated, "Report on July 1993 Mineral Processing and Incinerator Site Visits," Draft
memorandum to Bengie Carroll, August 10, 1993, p. 2-1.
18 Ibid., p. 2-2.
19 Ibid.
20
bid.
105
-------
respectively. We used best engineering judgment to determine that this waste stream may be partially recycled and
may exhibit the characteristics of toxicity (arsenic, cadmium, lead, and mercury) and corrosivity. This waste stream
is classified as a spent material. Waste characterization sampling data for this waste stream is included as
Attachment 1.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
106
-------
BIBLIOGRAPHY
Anderson, Corby G., Nordwick, Suzzann M,, and Kyrs, L. Ernest. "Processing of Antimony at the Sunshine Mine,"
From Residues and Effluents - Processing and Environmental Considerations. The Minerals, Metals, &
Materials Society. 1991. p. 349-366.
"Antimony." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. III. 1992. pp. 367-382.
Antimony Specialist. "Antimony." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 18-19.
Llewellyn, Thomas O. "Antimony." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines. 1992. pp. 223-226.
Light, Gary. ICF Incorporated. "Report on July 1993 Mineral Processing and Incinerator Site Visits." August 10,
1993.Draft memorandum to Bengie Carroll.
U.S. Environmental Protection Agency. Development Document for Effluent Limitation Guidelines and Standards
for Nonferrous Metals Manufacturing Point Source Category. Vol V. Office of Water Regulations
Standards. May 1989. p. 2079
U.S. Environmental Protection Agency. "Antimony." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste, p. 3-31-3-45.
107
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ATTACHMENT 1
108
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - AUTOCLAVE FILTRATE - ANTIMONY
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
_ead
Magnesium
Manganese
vlercury
VIolybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH'
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
3.7 40.59 120 8/8
260 1977,75 3700 8/8
0/0
0/0
- 0/0
0.002 0.069 0.3 8/8
0/0
0/0
0.2 0.391 0.8 . 8/8
0/0
0.01 0.458 3.05 8/8
070
0/0
0.015 5.30 12.6 7/7
0/0
0/0
0/0
0/0
0/0
0/0
0.01 0.110 0.27 8/8
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
5.0 0
0.2 0
1.0 0
5.0 0
-
-
-
-
.
-
.
.
-
212 0
o
UD
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
110
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ARSENIC
A. Commodity Summary
The most common source of arsenic is as a byproduct from the smelting of copper and lead concentrates as
arsenic trioxide (As:O3). Arsenic trioxide is commonly convened to arsenic acid for use in producing arsenical
wood preservatives, which accounted for 75% of the U.S. demand for arsenic in 1992.' Other uses include
agricultural chemicals (16% of demand), glass manufacturing (4%), and other uses (2%). In addition, arsenic metal
is produced by the reduction of arsenic trioxide and is used in nonferrous alloys and electronics, which accounted for
emand in 1992.
China and Chile are the world's largest producers of arsenic trioxide, followed by Mexico and the
Philippines. The United States imported over 13,000 metric tons of arsenic trioxide and over 500 metric tons of
arsenic metal from China in 1992.2 U.S. production of arsenic ceased in 1985 when ASARCO closed indefinitely its
copper smelter and associated arsenic recovery plant in Tacoma, Washington, largely due to the increasing costs of
complying with air quality standards.3 Arsenic is no longer produced in the U.S., but three facilities, Hickson Corp.
of Conley, GA, CSI of Harrisburg, NC, and Osmose Corp. of Memphis, TN, convert arsenic trioxide to arsenic acid
for use in producing wood preservatives.4
B. Generalized Process Description
1. Discussion of Typical Production Processes
Arsenic trioxide (As2O3) is volatilized during smelting, concentrated in flue dusts, and extracted through
distillation or roasting of the flue dusts to produce crude arsenic trioxide of minimum 95% purity.5 This product can
be refined through resublimation in a reverberatory furnace or through hydrometallurgical leaching methods to
produce commercial-grade arsenic trioxide, known as white arsenic.6
2. Generalized Process Flow Diagram
Exhibit 1 presents a typical process flow diagram for the production and/or recovery of arsenic trioxide. As
shown in the exhibit, vapor and gases laden with dust containing arsenic trioxide are liberated during smelting of
copper (and lead) concentrates. Flue dust containing up to 30% arsenic trioxide is then roasted after a small amount
of pyrite or galena is added to prevent the formation of arsenites and to promote formation of low-arsenic residue
that can be recycled. The resulting high-arsenic fumes are passed through a series of brick chambers called kitchens
(not shown in the diagram) that operate at progressively decreasing temperatures, from 220 °C to 1QO°C or less, to
condense the arsenic trioxide vapor to concentrations of 90-95%. This crude trioxide is either pyrometallurgically
1 U.S. Bureau of Mines, Mineral Industry Surveys: Arsenic in 1992, Branch of Metals and the Branch of Data
Collection and Coordination, June 1993, p. 4.
2 Ibid.
3 Loebenstein, J., The Materials Flow of Arsenic in the United States, U.S. Bureau of Mines Information Circular
9382, 1994, p. 2.
4 U.S. Bureau of Mines, 1993, Op. Cit.. p. 1.
5 "Arsenic and Arsenic Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. Ill, 1992, pp.
626-628.
6 U.S. Bureau of Mines, Mineral Facts and Problems. Bulletin 675, 1985, p. 45.
111
-------
EXHIBITl
ARSENIC TMOXTOE PRODUCTION PROCESS
(Adapted from: "Arsenic and Arsenic Alloys," 1992, Op. Cit. p. 627.)
y
Roaster keverberatory
I
I 1 1
Dust Laden Vapor and Gases
I
Expansion Chamber
1
Waste Heat Fumes
Boiler an^
Baghouse — '
He
i
1
Cottrell
ftBcipitators
To SC>2 Recovery
White/
y Mai
Converter
Low Arsenic
& Valuable
Residue
^ Roaster
I
High Arsenic
Fumes
_^
* *
verberatory Leach
Valuable
i
^K 1
T
Crystallize
Arsenic f
yr White Arsenic
tet For
Market
Residue
Cleaned Gases to Stack
112
-------
refined through resublimation in a reverberatory furnace or hydrometallurgically refined through leaching. In the
former method, the trioxide vapors pass through a settling chamber and then through about 40 additional kitchens to
promote additional condensation, yielding white arsenic of 99-99.9% purity. Dust from the kitchens having 90%
arsenic trioxide collects in baghouses and is reprocessed. In the latter method, arsenic trioxide fumes are pressure-
leached in an autoclave using water or mother liquor. Arsenic trioxide dissolves and the resulting residue is
reprocessed. The arsenic trioxide is recovered through vacuum-cooling to promote crystallization; arsenic trioxide is
removed through centrifuging to yield white arsenic of 99% purity.7
3, Identification/Discussion of Novel (or otherwise distinct) Processes
The Bureau of Mines has investigated the recovery of arsenic from flue dusts from copper processing using
an alternative method to distillation or roasting. Flue dusts were first leached with sulfuric acid and refinery-bleed
solution to solubilize arsenic and copper. Arsenic was recovered as arsenic trioxide from the resulting leach liquor
through reduction and precipitation using sulfur dioxide.8 In 1981, Equity Silver Mines Limited in Houston, British
Columbia began operating a leach plant to reduce arsenic levels in silver-gold-copper flotation concentrate. The
concentrate was leached with caustic sulfide, producing a leach liquor containing most of the arsenic in the
concentrate. The leached arsenic was originally recovered as calcium arsenate through oxidation and lime
precipitation but was found to be not marketable. Full-scale plant tests were conducted in 1983 to produce a heavy
metal arsenate thought to be marketable; however, the circuit was shut down in 1984 due to economic factors.9
4, Beneficiation/Processing Boundary
Since arsenic trioxide is recovered as a by-product of copper and lead smelting, please see the reports for
lead and copper presented elsewhere in this background document for a description of where the
beneficiation/processing boundary occurs for this mineral commodity.
C. Process Waste Streams
The recovery of arsenic trioxide as a byproduct from copper and lead smelting constitutes primary mineral
processing in the context of the Mining Waste Exclusion. In contrast, the manufacture of arsenic acid and arsenic
metal from arsenic trioxide is considered to be chemical manufacturing and clearly has always been outside the
scope of the Mining Waste Exclusion. Therefore, as there currently is no primary production of arsenic in the United
States, there are no newly identified "mineral processing" wastes subject to the RCRA LDR program.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
7 "Arsenic and Arsenic Alloys," 1992, Qp.Cit.. pp. 626-628.
8 Gritton, K., D. Steele, and J. Gebhardt, "Metal Recovery from Copper Processing Wastes," presented at the
Second Internationa] Symposium, Recycling of Metals and Engineered Materials, Williamsburg, Virginia, October
28-31, 1990, sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
9 Edwards, C., "The Recovery of Metal Values from Process Residues," Journal of Mines. June J991, p. 32.
113
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BIBLIOGRAPHY
"Arsenic and Arsenic Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. III. 1992. pp.
626-628.
Edwards, C. "The Recovery of Metal Values from Process Residues." Journal of Mines. June 1991. p. 32.
Gritton, K., D. Steele, and J. Gebhardt. "Metal Recovery from Copper Processing Wastes." Presented at the Second
International Symposium, Recycling of Metals and Engineered Materials, Williamsburg, Virginia, October
28-31, 1990. Sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
Loebenstein, J. The Materials Flow of Arsenic in the United States. U.S. Bureau of Mines Information Circular
9382. 1994. p. 2.
U.S. Bureau of Mines. Mineral Facts and Problems. Bulletin 675. 1985. p. 45.
U.S. Bureau of Mines. Mineral Industry Surveys: Arsenic in 1992. Branch of Metals and the Branch of Data
Collection and Coordination. June 1993. p. 4.
114
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BERYLLIUM
A. Commodity Summary
Beryllium (Be) is used as an alloy, oxide, or metal in electronic components, electrical components,
aerospace applications, defense applications, and other applications.1 Beryllium is processed into three forms --
beryllium alloys (principally beryllium-copper); beryllium oxide or beryllia ceramic; and metallic beryllium.2
Beryllium-copper alloys account for about 75 percent of the United States annual consumption of beryllium on a
metal equivalent basis. These alloys, most of which contain about two percent beryllium, are used because of their
high electrical and thermal conductivity, high strength and hardness, good fatigue and corrosion resistance, and non-
magnetic properties.3 Beryllia ceramic is specified for its electrical insulating properties and its unusual ability to
conduct heat. Metallic beryllium offers light weight, strength, stiffness, specialized nuclear properties, and the
ability to dissipate heat rapidly,4
Beryllium is a recognized constituent in some 40 minerals. However, only two minerals — beryl, an
aluminosilicate (3BeOAl3O3»6SiO2) containing 5 to 13 percent beryllium oxide (BeO), and bertrandite
(Be4Si,O7(OH)2), which occurs as tiny silicate granules containing less than one percent BeO — are commercially
available as beryllium ores.5 A BeO content of 10 percent is considered necessary for the economic extraction of
beryllium from beryl and bertrandite ores. Bertrandite ores are considered a commercially viable source of
beryllium because of the large reserves present, the ability to mine it in an open pit, and the fact that beryllium may
be extracted by leaching with sulfuric acid. In fact, the majority of beryllium produced is now obtained from
bertrandite.6
The major deposits of beryllium in the United States are bertrandite deposits in the Spor Mountains of Utah.
Brush Wellman, Inc. bought the mineral rights to these deposits and began mining in the 1960's.7 Its plant near
Delta, Utah, is the only commercial beryllium extraction and production plant operating in the Western world.8 The
Delta plant uses both beryl and bertrandite ores as inputs for the production of beryllium hydroxide. Although
bertrandite ore is mined on-site using open-pit methods, the beryl ore is imported primarily from Brazil. However,
beryl deposits also occur in China, Argentina, India, Russia, and some African countries. Beryl is usually obtained
as a by-product from mining zoned pegmatite deposits to recover feldspar, spodumene, or mica.9 Two other
facilities process the beryllium hydroxide to produce beryllium metal, alloy or oxide. Exhibit 1 presents the name.
1 Deborah A. Kramer, "Beryllium," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995,
p. 28.
2 Brush Wellman, Inc. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
3 U.S. Bureau of Mines, "Beryllium in 1992," Mineral Industry Surveys. April 1993, p. 3.
4 Brush Wellman, Inc. Op. Cit.
5 Brush Wellman, Comments of Brush Wellman Inc. on EPA's Proposed Remteipretarion of the Mining Waste
Exclusion. December 30, 1985, p. 1.
6 "Beryllium and Beryllium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. IV, 1992,
p. 126.
7 "From Mining to Recycling," Metal Bulletin Monthly — MBM Copper Supplement. 270, 1993, p. 27.
8 Deborah A. Kramer, January 1995, Op, Cit,. p. 28.
9 "Beryllium and Beryllium Alloys," 1992, Op. Cit., p. 126,
115
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location, the type of processing, input material and product for each of the beryllium processing facilities. Exhibit 2
presents general site information on the Delta, UT facility.
EXHIBIT 1
SUMMARY OF PRIMARY AND SECONDARY BERYLLIUM ORE PROCESSORS"
Facility Name
Brush Wellman
Brush Wellman
NGK Metals
Location
Delta, UT
Elmore, OH
Revere, PA
Type of Process
Primary
Secondary
Secondary
Input Material
Ores
Be(OH)2
Be(OH)2
Products
Be(OH)2
Be Metal and Alloys
Be Metal
' - Personal Communication between ICF Incorporated and Deborah Kramer, U.S. Bureau of Mines, October 1994.
EXHIBIT 2
SITE INFORMATION
Facility Name
Facility Location
Potential Factors Related to Sensitive Environment
Brush Wellman, Inc.
Delta, Utah
Brush Wellman mill located 10 miles north of Delta,
Utah; mine located 50 miles west of the mill.
Nearest resident lives 5 miles from Brush Wellman
facility
Brush Wellman facility is not located in: a 100-year
floodplain, an area designated as wetland, Karst
terrain, fault area, or an endangered species habitat
No public drinking water wells are located within 5
miles of the Brush Wellman facility
Private drinking water wells are located within 1 mile
of the Brush Wellman facility
B. Generalized Process Description
1. Discussion of Typical Production Processes
Brush Wellman extracts bertrandite ore at a mine site located approximately 50 miles northwest of Delta.
Utah. The ore is transported to a mill located 10 miles north of Delta and is treated using a counter-current
extraction process to produce beryllium sulfate, BeSO4. A second route, using the Kjellgren-Sawyer process, treats
the beryl ore and provides the same beryllium sulfate intermediate. The intermediates from the two ore extraction
processes are combined and fed to another extraction process. This extraction process removes impurities
solubilized during the processing of the bertrandite and beryl ores and converts the beryllium sulfate to beryllium
hydroxide, Be(OH)2. The beryllium hydroxide is either sold, or sent off-site to either be converted to beryllium
fluoride, BeF2, which is then catalytically reduced to form metallic beryllium, converted to beryllium oxide, or
converted to beryllium alloys.
116
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2. Generalized Process Flow Diagram
Exhibit 3 (Parts 1-3) presents a generalized process flow diagram for the production of metallic beryllium.
Each part of the process is described in greater detail below,
Part 1: Extraction of Beryllium as Beryllium Sulfate
Processing of bertrandite and imported beryl ores takes place at the Brush Wellman plant in Delta, Utah,
Even though beryllium is extracted from both ores as beryllium sulfate, there are significant differences in the two
extraction procedures. For example, the beryl extraction procedure requires five 15-foot diameter thickeners, while
the bertrandite process uses eight 90-foot diameter thickeners.10
Bertrandite Ore. The bertrandite ore is crushed, sized, and wet milled to provide a pumpable slurry of
particles below 840 urn." The slurry is leached with sulfuric acid, H2SO4, at moderate temperatures (about 95 °C) to
solubilize the beryllium. The resulting beryllium sulfate solution is separated from unreacted solids using thickeners
and counter-current decantation (CCD). The solids from the thickener underflow are discarded to a tailings pond.12
Beryl Ore. In contrast to bertrandite, beryl ore contains beryllium in a tightly bound crystalline structure.
Therefore, in order to effectively leach the beryllium with sulfuric acid, it is first necessary to destroy the crystalline
structure. The Kjellgren-Sawyer process is used commercially to extract beryllium from beryl. In this process, the
ore is crushed, melted at 1650SC, and quenched by pouring the molten ore into water. The resulting noncrystalline
glass (frit) is heat treated at 900-950°C to further increase the reactivity of the beryllium component. After grinding
to <74 urn, a slurry of the frit powder is reacted with concentrated sulfuric acid at 250-300°C to produce soluble
beryllium sulfate and aluminum sulfate, A12(SO4)3.U The spent solid fraction is separated from the beryllium sulfate
solution using thickeners and CCD and discarded to a tailings pond.
Beryllium sulfate leach solutions from the bertrandite and beryl CCD thickeners are combined in a surge
tank and pumped to another tank where sulfuric acid is added. The solution is then pumped to a filter which is pre-
coated with diatomaceous earth. The clarified filtrate solution from the filter (called extraction feed) is pumped to
another surge tank before being introduced into the next step of the process, the production of beryllium hydroxide.
The filter cake from the filter is continuously scraped off, repulped with fresh water, and pumped to the leach output
where it is recycled to the CCD thickeners for beryllium recovery.14
In the past, the beryllium sulfate solution produced from the extraction of beryl ore was neutralized with
ammonia in order to separate the bulk of the aluminum as ammonium alum. The ammonium alum crystals were then
removed by centrifugation. Organic chelating agents, such as the sodium salt of ethylenediaminetetraacetic acid
(EDT A) and triethanolamine, were added to the alum-free solution in the presence of sodium hydroxide to form a
10 U.S. Environmental Protection Agency, "Beryllium," 1988 Final Draft Summary Report of Mineral Industrial
Processing Wastes. 1988, p. 3-47.
1' Crushing, sizing, and wet milling are shown as physical processing in Exhibit 1.
12 Brush Wellman, Comments of Brush Wellman Inc. on EPA's Proposed Reinterpretation of the Mining Waste
Exclusion. Revised November 21, 1988, p. 8.
13
Crushing, melting, quenching, heat treating, and grinding are shown as physical treatment in Exhibit 1.
14 Brush Wellman, Inc. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
117
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solution of sodium beryllate. Heating the solution to just below its boiling point precipitated a granular beryllium
hydroxide that was recovered by continuous centrifugation.15
Part 2: Production of Beryllium Hydroxide from Beryllium Sulfate
During the extraction processes performed on the bertrandite and beryl ores, elements other than beryllium
(e.g., aluminum, iron, and magnesium) are solubilized and must be removed in order to prevent product
contamination. Therefore, extraction feed solution is pumped from the surge tank to the solvent extraction circuit.
Solvent extraction is a closed-loop circuit consisting of three steps: loading, stripping, and acid conversion. The
loading step consists of ten pairs of mixer and settler tanks. To liberate the beryllium from the extraction feed, the
extraction feed is mixed with kerosene containing di(2-ethyUiexyl)phosphate in each mixer tank and allowed to
separate by gravity in each settler tank, where beryllium-laden organic liquid floats to the top. This is done
sequentially through all ten mixer/settler pairs with aqueous liquid moving downcurrent from the first extraction
mixer tank to the last settling tank, while the organic liquid moves upcurrent from the last mixer tank to the first
settling tank. The aqueous liquid that leaves the end of the loading step of the solvent extraction circuit is known as
raffinate, and it contains all of the magnesium (Mg) and most of the aluminum (Al) found in the beryllium sulfate
extraction feed solution. The raffmate is pumped to a surge tank where any residual organic liquid is allowed to
separate. The raffmate is then pumped to a water collection tank where it is combined with other wastewater streams
and pumped to the tailings disposal tank, and then to the tailings pond. None of the raffinate is recycled.
The beryllium-laden organic liquid that comes out of the loading step of the solvent extraction circuit is
called loaded organic. It is pumped to a surge tank and then to two pairs of mixer/settler tanks which comprise the
stripping step of the solvent extraction circuit. The loaded organic is contacted with a small volume of aqueous
ammonium carbonate in the mixer tanks, and allowed to separate in the settler tanks. The ammonium carbonate
solution strips the beryllium, any remaining aluminum, iron, and uranium from the loaded organic, and results in an
ammonium-beryllium carbonate solution with a ten-fold higher beryllium concentration than the loaded organic. The
ammonium-beryllium carbonate solution is pumped to a surge tank before being introduced into the iron hydrolysis
step. The remaining organic liquid from the stripping step is termed stripped organic.
The stripped organic has a basic pH from the stripping step and is converted to an acid pH for reuse in the
loading step of the solvent extraction circuit. This is done in the acid conversion step of the solvent extraction
circuit. In this step, the stripped organic is treated in two pairs of mixer/settler tanks by contacting it with aqueous
sulfuric acid solution. The acidified, or converted, organic is pumped to two surge tanks prior to being recycled to
the loading step of the solvent extraction circuit. The aqueous liquid from the acid conversion step is a wastewater
called converted aqueous feed (CAP) and is pumped to the raffinate surge tank for discard. None of the CAP is
recycled.l6
Heating the ammonium beryllium carbonate solution to 95 °C liberates part of the ammonia (NH4) and
carbon dioxide (CO2) and causes the precipitation of beryllium carbonate, BeC03. The beryllium carbonate is
separated on a rotary drum filter and may be drummed as an intermediate product. However, the beryllium
carbonate may also be reslurried in deionized water and processed to beryllium hydroxide. Heating the beryllium
carbonate slurry to 165°C in a pressure vessel liberates the remaining carbon dioxide and the resulting beryllium
hydroxide is recovered by filtration.17
15 "Beryllium and Beryllium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed^, Vol. IV,
1978, p. 808.
16 Brash Wellman, Inc. January, 26, 1996. Qg. Cit.
"Ibid.
118
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EXHIBIT 3
Process Flow Diagram for Production of Metallic Beryllium (Part 1 of 3)
Raw Water
BeS04, AI2(S04)3
Sluice Water
(£>
Tailings Pond
-------
NJ
o
EXHIBITS
Process Flow Diagram for Production of M etallic Beryllium (Part 2 of 3)
Sump Water [
I T
S04, AI2(S04>3 BeSO
^ Solvent 4 ^ Stripped ^ A^id
^_ Extraction fe fe Conversion
^ W H W
Kerosene , .
Ma.Al
\ Spent /j ^
/ Ratfinate V" ^
Tailings Pond ^
ir
Sll
H SO
2 ' Lea
1
}\
^ ' i
' Amrnonium Carbonate H SO
(
^ T b . ,
k BeSO^ |ron ^ - P- C
BeSO
4
. F«,AI iaCO ,
dge 3
^ Steam
chlng ^ f
\ Barrar, / FMra^n
/ Rltrato \" BeCO.,
Fe. Al
f CAP
H.
02
ir
^ Cake
Repulp
Steam
^r v
Hydrolysis
^ C02
R.(nH) T
ir
T
\ Barren /
V B82 ) Filtrate <
/ \
Product
k-
pr Drumming
r
rry (
^^ To Bertrandite ^
^
^" CCD Thickener "^
f
Tailings Pond
ABC = Ammonium Beryllium Carbonate
CAP = Converted Aqueous Feed
-------
EXHIBIT 3
Process Flow Diagram for Production of Metallic Beryllium (Part 3 of 3)
Ammonium
Fluoroberyllate
Ammonium
Fluoroberyllate
Ammonium
Fluoroberyllate
Ammonium
Fluoroberyllate
Be(OH)
\ Heavy-Metal
/ Impurities, Pb
Be Metal
Mg Metal
-------
Beryllium hydroxide production is the starting point for all further beryllium processing. Following
hydroxide extraction, separate production processes are involved in producing the three basic beryllium lines (i.e..
metallic beryllium, beryllium alloys, and beryllia).
Part 3: Production of Beryllium Metal. Oxide, and Alloys
Production of Metallic Beryllium. Brush Wellman uses the Schwenzfeier process to prepare a purified.
anhydrous beryllium fluoride for reduction to beryllium metal. The first step of this process involves dissolving
beryllium hydroxide in ammonium bifluoride to yield a solution of ammonium fluoroberyllate at pH 5.5. The
solution is neutralized by adding aquaammonia. Then, solid calcium carbonate, CaCO3, is added and the solution is
heated to 60°C to remove aluminum before filtering. After filtration, ammonium sulfide is added to the filtrate to
remove any heavy-metal impurities. Following the filtration step, ammonium fluoroberyllate is crystallized by co-
current evaporation under vacuum. The crystals are continuously removed by centrifugation and washed lightly,
while the mother liquor and washings are returned to the evaporator.18 The ammonium fluoroberyllate is charged
into inductively heated, graphite-lined furnaces where it is thermally decomposed to beryllium fluoride and
ammonium fluoride. The ammonium fluoride is vaporized into fume collectors for recycle to the dissolution
operation, whereas the molten beryllium fluoride is removed from the bottom of the furnace and solidified as a
glassy product on water-cooled casting wheels.19
The beryllium fluoride is then reduced by magnesium metal (Mg) at a stoichiometric ratio of 1 BeF, : 0.7
Mg. In this process, magnesium metal and beryllium fluoride are charged into a graphite crucible at a temperature of
about 900°C. The excess beryllium fluoride produces a slag of magnesium and beryllium fluorides having a melting
point substantially below that of beryllium metal. The excess BeF2 prevents the formation of an oxide film on the
beryllium particles and assists in the coalescence of the metal.20
When the exothermic reaction is completed, the reaction products are heated to about 1300°C to allow
molten beryllium to separate and float on top of the slag. The molten beryllium and slag are then poured into a
graphite receiving pot where both solidify. The reaction product is then crushed and water-leached in a ball mill.
The excess beryllium fluoride quickly dissolves, causing disintegration of the reaction mass and liberation of the
beryllium metal as spherical pebbles. The leach liquor in this step is continuously passed through the ball mill in
order to remove the fine, insoluble magnesium fluoride (MgF2) particles formed during the reduction reaction. The
magnesium fluoride is ultimately separated from the leach liquor and discarded. The leach liquor, which includes the
excess beryllium fluoride, is then recycled as part of the input for making ammonium fluoroberyllate. The beryllium
metal pebbles contain 98 percent beryllium along with entrapped reduction slag and unreacted magnesium. To
remove these impurities, the metal is melted in induction furnaces under a vacuum. The excess magnesium and
beryllium fluoride from the slag vaporize and are collected in suitable filters. Nonvolatiles, such as beryllium
carbide (Be2C), beryllium oxide, and magnesium fluoride, separate from the molten metal as a dross that adheres to
the bottom of the crucibles. The purified beryllium metal is poured and cast into ingots of 150-200 kilograms.21
Production of Beryllium Oxide. Exhibit 4 illustrates the production of beryllium oxide. Beryllium
hydroxide is dissolved in water and sulfuric acid. The resulting beryllium sulfate solution is filtered to remove
impurities. The solution flows to one of two evaporators followed by two crystallizers in parallel where beryllium
sulfate crystals are formed. The crystals are separated from the mother liquor in a centrifuge, and the mother liquor
is recycled to the beryllium hydroxide dissolver.
18 Evaporation, centrifugation, and washing are shown as processing in Exhibit 1.
19 "Beryllium and Beryllium Alloys", 1992, Op. Cit.. pp. 129-130.
20 Ibid., p. 130.
4 - l
21 "Beryllium and Beryllium Alloys," 1978, Op. Cit.. p. 810.
122
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EXHIBIT 4
PROCESS FLOW DIAGRAM FOR PRODUCTION OF BERYLLIUM OXIDE
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 3647.)
H,O
Be(OH),
Mother Liquor to
Beryllium
Hydroxide Production
Periodic Bleed
Centrate
Dissolver
Filter
Waste Solids
Evaporator
Condensates
Crystallizer
Centrifuge
Vent to
Main Stack
Beryllium
Sulfate Crystals
Calcining
Furnace
Caustic
Scrubber
Water
Beryllium
Oxide
Wastewater
123
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The beryllium sulfate is calcined in gas fired furnaces at about 1100° C to beryllium oxide. The exhaust gas from the
calcining furnace is scrubbed in caustic scrubbers to remove sulfur dioxide. The scrubber water is sent to
it.21
Production of Beryllium-copper Alloys. Beryllium hydroxide, electrolytic copper, and carbon are
combined in an electric arc furnace to make beryllium-copper master alloy. The resultant melt, containing about four
percent beryllium is cast into ingots. Remelting master alloy ingots with additional copper and other alloying
elements yields the desired beryllium-copper alloy, which is then cast into slabs or billets. Slabs of beryllium copper
alloys are processed further into strip or plate, and billets are extruded into tube, rod, bar, and wire products,23
3. Identification/Discussion of Novel (or otherwise distinct) Processes
The Fluoride process, an alternative to the Kjellgren-Sawyer process, converts the beryllium oxide found in
beryl ore to a water-soluble form by roasting with fluxes. In this process, pulverized beryl ore is roasted with sodium
fluorosilicate at approximately 750°C to form slightly soluble sodium fluoroberyllate. The reaction products are
extruded as wet briquettes and ground in a wet pebble mill. The sodium fluoroberyllate is then leached with water at
room temperature. The filtered solution is treated with sodium hydroxide to form sodium beryllate, from which a
filterable beryllium hydroxide is precipitated by boiling. The beryllium hydroxide can then be processed to metallic
beryllium using the process discussed in Part 3.24
4. Beneflciation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
22 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. VII, Office of Water Regulation
Standards, May 1989, p. 3643.
23 Deborah A. Kramer, "Beryllium Minerals," from Industrial Rocks and Minerals. 6th Ed.. Society for Mining,
Metallurgy, and Exploration, 1994, p. 152.
24 "Beryllium and Beryllium Alloys," 1978, Op.Cit.. pp. 808-809.
124
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Bertrandite and Beryl Ore Processes
EPA determined that for the production of beryllium via the bertrandite and beryl ore processes, mineral
processing occurs between solvent extraction and iron hydrolysis, due to the change in chemical composition that
occurs during hydrolysis.25 Therefore, because EPA has determined that all operations following the initial
"processing" step in the production sequence are also considered processing operations, irrespective of whether they
involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after
the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes,
EPA presents below the mineral processing waste streams generated after the beneficiation/processing line, along
with associated information on waste generation rates, characteristics, and management practices for each of these
waste streams.
Other Beryllium Processing
Because other beryllium products are produced after either bertrandite ore processing or beryl ore
processing, all of the wastes generated during these operations are mineral processing wastes. For a description of
where the beneficiation/processing boundary occurs for this mineral commodity, please see the bertrandite ore and
beryl ore process sections above.
C. Process Waste Streams
During the production of metallic beryllium from beryl and bertrandite ores, several waste streams are
generated. Each waste stream is identified below, along with the portion of the process in which it is created. For
each waste stream, any specific information regarding its physical and chemical characteristics is provided, as well as
generation rates and management practices.
1. Extraction/Beneficiation Wastes
Part 1: Extraction of Beryllium as Beryllium Sulfate
Physical Processing/Treatment wastes. These wastes are generated by the physical processing or
treatment of ore, and may include tailings, gangue, and wastewater. No other information on waste characteristics.
waste generation, or waste management was available in the sources listed in the bibliography.
Bertrandite thickener slurry. Approximately 370,000 metric tons of bertrandite thickener slurry were
discarded to a tailings pond in 1992.26 The pH of the bertrandite thickener slurry has been reported between 2,5 and
3,5.T! The attached data in Attachment 1 indicate that the pH of bertrandite thickener slurry ranges from 2 to 3.
Therefore, this waste may sometimes exhibit the hazardous characteristic of corrosivity. We used best engineering
judgment to determine that this waste stream may be recycled to extraction/beneficiation units. Bertrandite thickener
slurry was formerly classified as a by-product. This waste stream is combined with approximately 250,000 metric
tons of miscellaneous water streams prior to disposal.28 The miscellaneous water streams are generated during the
bertrandite ore extraction process, but the origin of these streams is unknown. See Attachment 1 for waste
characterization data.
25 U.S. Environmental Protection Agency, Letter from Mr. Robert Tonetti. Acting Deputy Director. Waste
Management Division. Office of Solid Waste to Mr. Richard Davis, Brush Wellman, Inc.. March 15, 1990.
26 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, Volume I, August, 1992, p. 1-2.
27
Brush Wellman, 1988, Op. Cit.. p. 8.
28 RTI Survey 101006, National Survey of Solid Wastes From Mineral Processing Facilities. Brush Wellman Co..
Delta, UT, 1989, p. 2-4.
125
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Beryl thickener slurry. In 1992, beryl thickener slurry was discarded to a tailings pond at a rate of 3,000
metric tons/yr.29 The beryl thickener slurry has a pH of 2.30 Therefore, this waste exhibits the hazardous
characteristic of corrosivity. We used best engineering judgment to determine that this waste stream may be recycled
to extraction beneficiation units. Beryl thickener slurry was formerly classified as a by-product. This waste stream
is combined with about 21,000 metric tons of sluice water prior to disposal,31 The sluice water is used to transport
the beryl ore to the start of the ore extraction processes. See Attachment 1 for waste characterization data.
Part 2: Production of Beryllium Hydroxide from Beryllium Sulfate
Spent raffinate. Approximately 380,000 metric tons of spent raffinate were discarded to a tailings pond in
1992. This waste exhibits the hazardous characteristics of toxicity (for selenium) and corrosivity.32 The raffinate has
a pH of 1.4.33 This aqueous waste stream also contains magnesium and aluminum,34 and may contain treatable
concentrations of metal impurities, total suspended solids, and low levels of organics.3* This waste stream is
discarded to a tailings pond.36 Spent raffinate was formerly classified as a spent material. This waste stream is
combined with approximately roughly 33,000 metric tons of an acid conversion stream prior to disposal.3' See
Attachment 1 for waste characterization data.
Sump water. This waste is generated during the solvent extraction process that removes metal impurities
from the beryllium sulfate solution. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Acid conversion stream. This waste is the resultant aqueous liquid of the stripping step of the solvent
extraction process and is referred to as converted aqueous feed. This waste stream is combined with spent raffinate
and discarded to a tailings pond.38 Existing data and engineering judgment suggest that this material does not exhibit
any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
29 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-2.
30 Ibid., p. 6-61.
31 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
32 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
33 Brush Wellman, 1988, Op. Cit.. p. 11.
34 "Beryllium and Beryllium Alloys", 1992, Op. Cit.. p. 129.
35 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 3569.
36 Brush Wellman, Inc. January 25, 1996. Op. Cit.
37 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
38 Brush Wellman, Inc. January 25, 1996. Op. Cit.
126
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2. Mineral Processing Wastes
Part 2: Production of Beryllium Hydroxide from Beryllium Sulfate
Separation slurry. In 1992, the separation slurry was discarded to a tailings pond at a rate of 2,000 metric
tons/yr.39 The separation slurry has a pH of 3.40 The slurry contains iron and aluminum which have been
precipitated as hydroxides and carbonates from the aqueous ammonium beryllium carbonate stream.41 This waste
stream is combined with about 39,000 metric tons of scrubber water prior to disposal.42 The scrubber water is
probably basic because it is used to scrub the ammonia and carbon dioxide stream released during the heating of the
ammonium beryllium carbonate. See Attachment 1 for waste characterization data.
Spent barren filtrate streams. The barren filtrate streams are produced during the filtration of beryllium
carbonate and beryllium hydroxide. Approximately 88,000 metric tons of barren filtrate were discarded to a tailings
pond in 1992. This waste exhibits the hazardous characteristic of toxicity for selenium.43 The barren filtrate streams
have a pH of 9.8.44 EPA received conflicting data about whether this waste stream is recycled to the bertrandite
CCD thickeners or is disposed, so we used best engineering judgment to determine that this waste stream is partially
recycled. The streams were formerly classified as spent material. The barren filtrate stream from the filtration of
beryllium carbonate operation contains uranium that was solubilized in the ore extraction processes. See Attachment
1 for waste characterization data.
Beryllium hydroxide supernatant. When beryllium is recovered from recycled customer material,
internally generated residues, scrap, and recycled mother liquor from the beryllium oxide crystallization operations,
the raw material is dissolved in sulfuric acid and beryllium and then precipitated with caustic as beryllium hydroxide.
After gravity separation, the supernatant is discharged as a wastewater stream.45 Existing data and engineering
judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further. See Attachment 1 for waste characterization data.
Part 3: Production of Beryllium Metal, Oxide, and Alloys
Production of Metallic Beryllium
The following waste streams are generated during the conversion of beryllium hydroxide to beryllium
metal.
Neutralization discard. This waste stream contains precipitated aluminum. Existing data and engineering
judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
39 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
40 Brush Wellman, 1988, Op. Cit. p. 9.
41 "Beryllium and Beryllium Alloys," 1978, Op. Cit.. p. 807.
42 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
43 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
44 Brush Wellman, 1988, OP. Cit. p. 10.
45
U.S. Environmental Protection Agency, 1989, Op. Cit. p. 3660.
127
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Precipitation discard. This waste stream contains precipitated manganese dioxide and lead chromate.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
Filtration discard. This waste stream contains lead and other heavy-metal impurities. Although ho
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 100 metric
tons/yr, 23,000 metric tons/yr, and 45,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristics of toxicity for lead. This waste stream is not recycled.
Leaching discard. This waste stream contains insoluble magnesium fluoride. Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further.
Dross discard. This waste stream contains nonvolatiles, such as beryllium oxide, magnesium fluoride, and
beryllium carbide which separate from die molten beryllium metal during the final melting process. Existing data
and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Melting emissions. This gaseous waste stream contains magnesium and beryllium fluoride which
vaporized during the final melting process and collected on suitable filters. Existing data and engineering judgment
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,- the Agency did not
evaluate this material further.
Process wastewater. Process condensates are generated from the ammonium beryllium fluoride
crystallizer and the ammonium fluoride sludge filtrate evaporator. The condensed water is used as makeup for the
fluoride furnace scrubbing system, for the beryllium pebble plant scrubbing system, for sludge washing, and general
plant water usage such as floor washing. Periodic discharge from the process water pit is necessary to prevent
dissolved solids build-up. The process wastewater has a neutral pH, and treatable concentrations of beryllium and
fluoride. Ammonia and cyanide are also reported as present above treatable concentrations.46
Pebble plant area vent scrubber water. The beryllium pebble plant contains a ventilation system for air
circulation. A wet scrubber is employed to clean the used air prior to venting to the atmosphere. Although the
scrubber is recycled extensively, a blowdown stream is periodically discharged to the process water pit. Makeup
water for the scrubber is obtained from the process water pit. This scrubber water has a slightly acidic pH, and
treatable concentrations of beryllium and fluoride.47 Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further. See Attachment 1 for waste characterization data.
Chip treatment wastewater. Pure beryllium metal scrap in the form of chips is treated with nitric acid and
rinsed prior to being vacuum cast along with beryllium pebbles into a beryllium metal billet. The spent acid and
rinse water are discharged. This operation combines refining beryllium from secondary as well as primary sources.48
Although no published information regarding waste generation rate or characteristics was found, we used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
of 100 metric tons/yr, 50,000 metric tons/yr, and 1,000,000 metric tons/yr, respectively. We used best engineering
judgment to determine that this waste may exhibit the characteristics of toxicity for chromium. See Attachment 1 for
46 U.S. Environmental Protection Agency, 1989, Op. Cit. p. 3661.
47 Ibid., p. 3662.
48 Ibid., p. 3661.
128
-------
waste characterization data. We also used best engineering judgment to determine that this waste stream may be
partially recycled. This waste stream was formerly classified as a spent material.
Production of Beryllium Oxide
Scrubber liquor. This waste contains the sulfur dioxide removed from the furnace exhaust gas and sent to
treatment. While over 90 percent of this stream is recycled, the rest is discharged as a wastewater stream. Scrubber
liquor has a neutral pH, very high concentrations of dissolved solids (primarily sodium sulfate), and treatable
concentrations of beryllium, fluoride and suspended solids.49 Existing data and engineering judgment suggest that
this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Waste solids. This waste stream contains the impurities filtered from beryllium sulfate solution. Existing
data and engineering judgment suggest that this material does hot exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Production of Beryllium-copper alloys
No other information on waste characteristics, waste generation, or waste management of wastes generated
during production of beryllium-copper alloys was available in the sources listed in the bibliography.
D. Non-uniquely Associated Wastes
Non-uniquely associated hazardous wastes may be generated at on-site laboratories, and may include used
chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank cleaning wastes.
Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and waste oil and other
lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Four commenters provided new factual information on beryllium sector processes and waste streams.
(COMM58, COMM59, COMM60, COMM64). This information has been incorporated into the commodity
summary, process description, and waste stream description sections of this sector report.
Sector-Specific Issues
Three commenters indicated that the Agency had incorrectly placed the beneficiation/processing line in the
beryllium sector. (COMM58, COMM60, COMM64) The commenters indicated that the Agency's placement of the
beneficiation/processing line was inconsistent with prior Agency determinations. The Agency agrees that the
beneficiation/processing line was incorrectly located in the initial-draft of the sector report, and has revised the
discussion of the beneficiation/processing boundary to reflect the decision made in the March 15, 1990 letter from
Robert Tonetti, Acting Deputy Director, Waste Management Division, to Richard Davis of Brush Wellman, Inc.50
49 Ibid., p. 3660.
50 In the process of incorporating this change into two supporting documents of this Rulemaking (Regulatory
Impact Analysis and Characterization of Mineral Processing Wastes and Materials), EPA inadvertently removed
spent barren filtrate from cost and risk modeling analyses as a beneficiation waste. This waste is a processing waste
because it is generated downstream of the initial mineral processing step of beryllium production, iron hydrolysis.
EPA has corrected this error in the supporting documents.
129
-------
EPA received conflicting information about the disposition of spent barren filtrate. One commenter
indicated that spent barren filtrate is recycled to the bertrandite CCD thickeners (COMM59). However, in comments
on the Regulatory Impact Analysis, the same commenter indicated that spent barren filtrate is not recycled
(COMM60). In the May 12. 1997 Second Supplemental Proposed Rule Applying Phase IV Land Disposal
Restrictions to Newly Identified Mineral Processing Wastes, this same commenter indicated that a waste stream
known as "fine barren filtrate" is recycled (Brush Wellman, Inc., 2P4P-00052). It is unclear whether "fine barren
filtrate" and spent barren filtrate are the same waste stream because the commenter provided differing generation
quantities for "fine barren filtrate" and "barren filtrate." Furthermore, a process flowsheet provided in the comment
did not indicate direct recycling of barren filtrate to the CCD thickeners. In light of this conflicting information,
EPA is assuming that this material is partially recycled as described in the spent barren filtrate waste stream
description.
130
-------
BIBLIOGRAPHY
"Beryllium and Beryllium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. Srded. Vol. IV. 1978.
"Beryllium and Beryllium Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992.
Brash Wellman. Comments of Brush Wellman Inc. on EPA's Proposed Reinterpretation of the Mining Waste
Exclusion. December 30, 1985.
Brush Wellman. Comments of Brush Wellman Inc. on EPA's Proposed Reinterpretation of the Mining Waste
Exclusion. Revised November 21, 1988.
Brush Wellman, Inc. Comments submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictionsjo Newly Identified Mineral Processing Wastes. January 25, 1996.
"From Mining to Recycling." Metal Bulletin Monthly — MBM Copper Supplement. 270. 1993. p. 27.
ICF Incorporated. Brush Wellman: Mineral Processing Waste Sampling Visit — Trip Report. August 1989.
ICF Incorporated. "Notes from November 30, 1989 Meeting with Brush Wellman." Memorandum to Bob Hall from
David Bauer. December 11, 1989.
Kramer, Deborah, A. "Beryllium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 28-29.
Kramer, Deborah, A. "Beryllium Minerals." From Industrial Rocks and Minerals. 6th Ed. Society for Mining,
Metallurgy, and Exploration. 1994. pp. 149-156.
Personal Communication between ICF Incorporated and Deborah Kramer, U.S. Bureau of Mines. October 20, 1994.
RTI Survey 101006. National Survey of Solid Wastes From Mineral Processing Facilities. Brush Wellman Co.,
Delta, UT. 1989.
U.S. Bureau of Mines. "Beryllium in 1992." Mineral Industry Surveys. April 1993.
U.S. Environmental Protection Agency. "Beryllium." 1988 Final Draft Summary Report of Mineral Industrial
Processing Wastes. 1988. pp. 3-46 - 3-52.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Vol. VII. Office of Water Regulation
Standards. May 1989.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
131
-------
ATTACHMENT 1
132
-------
3007, ^NDRTl SWUNSmTA- BEWWJETHO
-------
wSUMVIWCF ffMH} 3007, WD RT1 SWFUN3 CftTA- BBFM_PL/M"aJUR^DSO-WR3E-BB:MJJUM
QjbliliJEnts
^inrfim
Atimry
Aseric
BBriim
BerylliLrn
Bonn
Cadrrium
Oroniim
Ob*
CCpper
lien
LeaJ
N/fegresiLrn
IVbngaresB
IVbtxiy
IVtiybcfenm
Nckd
Seteriun
3h«r
Thaltiun
\tenadun
Znc
SJfate
RLofcte
Qtakte
PH*
QgaricsfTOQ
Tctel ttretituat Aialya's- FFM
Mrirrun Astags IVWmm # Detected
0.62
Q05
Q30
Q06
QC5
-
QOCB
(ME
Q06
Q05
Q05
Q03
529
Q05
QODD8
Q05
Q05
0,05
0.06
0.25
0.06
Q05
$740.00
-
1S5.00
200
579.00
062
005
030
005
4,660.02
-
0.005
Q05
005
005
005
003
529
005
0.0003
0.05
0.05
Q05
005
0.25
005
005
3740.00
-
15500
200
579.00
062
005
030
005
9,330.00
-
Q.COS
005
005
005
005
003
529
005
00003
005
0.05
Q05
Q05
025
005
0.05
$740.00
-
15500
200
579.00
1/1
01
1/1
01
22
00
01
0/1
m
0/1
01
m
1/1
01
m
0*1
01
01
01
01
01
01
1/1
00
1/1
1/1 .
1/1
ffTcsieity Aralysis - PFM
Mrirrun Asrap
022
005
013
005
0.19
-
QOCB
005
005
015
005
003
4.13
005
0.0001
0.05
0.05
005
005
025
0.05
232
022
0.05
013
005
019
-
0005
005
0.05
015
0.05
0.03
4.13
005
0.0001
Q05
005
005
0.05
025
005
232
IVWrnm
022
0.05
013
005
019
-
0.005
005
005
015
005
003
4.13
005
00001
0.05
0.05
Q05
005
025
0.05
232
#Daected
1/1
01
1/1
01
1/1
00
01
01
01
1/1
01
01
1/1
01
01
01
01
01
01
01
01
1/1
1C
Lad
-
-
50
1000
-
-
1.0
50
-
-
-
50
-
-
02
-
-
1.0
50
-
-
-
-
-
-
2
-------
SLMWFtfCF BWCFD, 3007, ^D RT SWFUNS DATA- SPBJT FWFRNME- BffMULM
jtrEtituerts
Air-inm
Atmry
Aseric
Baiim
BayHiun
ibtcn
Qchiirn
Qiuiiun
Gttelt
Ctpper
Ircn
Leal
IVbgieaun
Msrtpress
Nfetuiy
N/bytxfenjn
Nckd
Seleriim
Slver
TlTalliLm
Vfenadun
Zrc
aifde
Ricride
CHoride
PH*
agarics (TOQ
Total CCnstituert Analysis - PPW
Mrirrun Average
1570
Q10
aos
Q10
262
-
0.01
0.81
0.10
010
288
0.05
1690
6070
0.0001
0.10
0.46
041
0.10
050
010
141.00
55900
7000
29800
090
-
1610
0.10
aos
0.10
552
-
001
081
0.10
010
288
005
1690
6070
00301
0.10
046
041
010
050
010
141.00
55900
7000
298.00
0.95
-
IVfeMrrun
1650
010
aos
010
aoo
-
001
081
0.10
0.10
283
005
1690
6070
00001
0.10
046
041
0.10
050
010
141.00
55900
7000
29800
1.00
-
#Caects
22
0/1
1/1
01
55
00
0/1
1/1
0/1
0/1
1/1
0/1
1/1
1/1
0/1
0/1
1/1
1/1
0/1
0/1
0/1
1/1
1/1
1/1
1/1
22
0
EPTodtity Analysis - PFM
Mrimm Averarp
3050
1.00
1.19
1.00
283
-
010
1.00
1.00
1.00
aie
069
1640
61.10
0.0002
1.00
1.00
1.00
1.00
500
1.00
125
3050
1.00
1.19
1.00
283
-
010
1.00
1.00
1.00
aie
069
1640
61.10
00002
1.00
1.00
1.00
1.00
5.00
1.00
125
IVtodmm #Caects
3050
1.00
1.19
1.00
283
-
0.10
1.00
1.00
1.00
aie
0.69
1640
61.10
00002
1.00
1.00
1.00
1.00
500
1.00
125
1/1
1/1
1/1
1/1
1/1
00
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
TC
Level
-
-
5.0
100.0
-
-
1.0
50
-
-
-
5.0
-
-
0.2
-
-
1.0
50
-
-
-
-
-
-
212
-
#\£ues
InBcess
-
-
0
0
-
-
0
0
-
-
-
0
-
-
0
-
-
1
0
-
-
-
-
-
-
2
-
-------
wSLJMVWVCF EWCFOi 3007, /VORT1 SAWRINaEKTA- SBWraiCNSLLJFFft'- BffMJJUM
cr>
GbnsBhJsrts
Mirnnsn
A-timcry
Aseric
Eanim
Berytun
Bcttn
CsMum
Orcrrlum
QtHlt
Offer
Iron
Lead
MagTsum
fi/bngarese
Nfercuy
(VHybcfenun
Nckel
Ssterium
Slver
TrBiliun
\fenadun
Znc
SJfete
RLCride
Qtakte
pH*
agarics (TOQ
Total (insfituert Aralya's- PFM
Mrinun A/erap h/Wrrun iDeteds
1110
64.60
500
500
18000
-
0.50
500
500
500
28000
2650
1580
500
0.1300
10.70
500
1280
500
2500
500
2830
8030
7.00
-
300
475.00
1110
64.60
500
500
262.80
-
0.50
500
500
500
47300
2650
1580
500
01300
1070
500
1280
500
2500
500
28.30
8030
7.00
-
303
47500
1110
64.60
500
500
330.00
-
0.50
500
500
500
66800
2650
1580
500
01300
10.70
500
1280
500
2500
500
2R30
8030
7.00
-
315
47500
1/1
1/1
0/1
01
SiS
GO
01
01
01
01
2/2
1/1
1/1
01
1/1
1/1
01
1/1
01
01
01
1/1
1/1
1/1
00
2/2
1/1
Broadly Analysis- PPM
Mrimm Aeags Ivbx
54.10
Q12
Q05
010
34.80
-
0.02
0.05
005
0.11
321
003
321
0.13
0,0001
005
0.05
005
0.05
025
005
1.60
54.10
0.12
005
0.10
34.80
-
0.02
005
0.05
011
321
003
321
0.13
00001
005
0.05
005
0.05
0.25
005
1.60
imm #Detecfe
54.10
0.12
0.05
010
34.80
-
0.02
0.05
0.05
011
321
003
321
Q13
0.0001
0.05
005
0.05
0.05
Q25
Q05
1.60
1/1
1/1
01
1/1
1/1
00
1/1
01
01
1/1
1/1
1/2
22
1/1
01
0/1
01
01
0/1
01
01
1/1
TC
Lasi
-
-
50
1000
-
1.0
5.0
-
-
-
50
-
-
0.2
-
-
1.0
50
-
-
-
-
-
-
312
-
InBcess
.
-
0
0
-
0
0
-
-
-
0
-
-
0
-
-
0
0
0
0
-
-
-
-
0
-
hta-KMectsvHBassunedtobepresert A 1/2thedetectkrHimt. TCLPcfetaareeurertlyira/ailafcle; therefor crty ffcfetaarepneserted
-------
SUVMflR/CFBWCFD, 3007, ^NDRTl SfllVPUNSDMA- BAFPBMRLTTWE- BBMI1LM
GbnsBtuerts
AirrinLm
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3dcn
ZfetfrriLm
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ten
Lead
Magregim
N/bngarese
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M^xterun
Nckel
Seleriim
Slver
"mslliLiTi
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Zrc
SLtfate
Ruiicte
Qiaride
pH*
QgaricsfTCq
Total QTBtitLErtA^as- PPM
Mrimm Aeage Maxirrum tfCfeteds
0.30
1.35
Q05
Q05
7.90
-
Q03
0.05
0.05
Q10
0.20
0.03
272
Q05
0.0001
0.05
Q05
0.05
0.05
0.25
Q05
0.76
710.00
81.00
175.00
9.00
370.00
579.83
318
253
253
4804
-
Q26
253
253
255
22213
7.56
51636
101.08
Q0251
253
253
253
253
1263
253
57.33
14,705.00
121.00
17550
9.33
1,405.00
2290.00
5.00
5.00
500
76.30
-
0.50
5.00
5.00
500
833.00
1510
1,030.00
20200
00500
500
500
5.00
500
2500
5.00
114.00
28,700.00
161.00
182.00
9.60
2440.00
4/4
1/2
02
02
56
00
1/2
02
02
1/2
4/4
1/2
2/2
1/1
0/2
02
02
02
02
02
02
2/2
2/2
212
2/2
4/4
212
EPTodcity A-elysis- PPM
Mrirrun A«age
14.73
0.79
Q05
0.15
265
-
0.02
Q05
005
005
0.34
0.03
248
005
00001
005
005
Q05
005
0.25
005
0.78
293.85
090
0.53
058
1503
-
005
0.53
053
053
103.67
027
147.74
663
0.0002
053
0.53
0.53
053
263
0.53
1329
Maxirrun #C6tects
573.00
1.00
1.00
1.00
27.40
-
0.10
1.00
1.00
1.00
217.00
0.52
293.00
1320
0.0002
1.00
1.00
1.00
1.00
5.00
1.00
2580
212
212
1/2
2/2
2/2
00
212
1/2
1/2
1/2
212
1/2
212
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
2/2
1C
La/el
-
-
50
100.0
-
-
1.0
50
-
-
-
5.0
-
-
0.2
-
-
1.0
50
-
-
-
-
-
-
212
-
#\£ues
InBcess
-
-
0
0
-
-
0
0
-
-
-
0
-
-
0
-
-
1
0
-
-
-
-
-
-
0
-
-------
C3SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - BERYLLIUM HYDROXIDE SUPERNATANT RAW WASTEWATER
oo
BERYLLIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0.003
0.003
-
12
-
0.004
0.11
.
1.4
-
0.168
-
-
0.0002
-
0.12
0,003
0.32
0.002
-
0,19
-
-
-
-
-
.
-
-
-
-
-
0.003
0.003
-
12
-
0.004
0.11
-
1.4
-
0.168
-
-
0.0002
-
0.12
0.003
0.32
0.002
-
0.19
-
-
-
-
-
-
-
-
-
-
-
0.003
0.003
-
12
-
0.004
0.11
-
1.4
-
0.168
-
-
0.0002
-
0.12
0.003
0.32
0.002
-
0.19
-
-
-
-
-
-
-
-
-
-
# Detects
0/0
1/1
1/1
0/0
1/1
0/0
1/1
1/1
0/0
1/1
0/0
1/1
0/0
0/0
0/0
0/0
1/1
1/1
1/1
1/1
0/0
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
.
5.0 0
100.0 0
-
.
1.0 0
5.0 0
.
-
-
5.0 0
.
.
0.2 0
-
-
1,0 0
5.0 0
-
-
-
.
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SJVMWCFffWCFQ 3007, PtOm Saft/FUNBCKTA- PRDCSSV\^STBAATm- BBMIIUM
!ln3titU£rtS
/Nuririm
ACmcry
Aseric
Baiun
Beryllium
3dron
CMriun
D lUTiim
GCbeft
Qflper
ran
Lead
Magiesium
\taxprese
Wbrcuy
Mdyfccterim
Nctel
Seleriun
Slver
TlTalliLm
Vanadun
Znc
atfsie
Rmride
Oloricfe
pH*
QgEriGsflOQ
Total Gnstitusrt flcetyas- PFM
Mrimm Aaage IVfewmrn #Detects
Q30
1.35
QCB
QCB
7.90
-
O.OB
QCB
QCB
Q10
0,20
QCB
272
O.CE
Q0001
QC5
QCB
QCB
QCB
Q25
QCB
Q76
71QOO
81.CD
175CD
9.00
s/aoo
579.88
318
2S3
233
4RM
-
Q26
253
253
255
222.13
7.56
5ia36
101.CO
QCE51
253
253
253
253
12©
253
57.38
14,705.00
121.00
17850
9.33
1,40600
229QOD
503
500
5.00
7630
-
Q50
500
500
500
eaaoo
1510
1,03QOO
2D200
QCBOO
5.00
5.00
5.00
500
2500
500
114.00
aaToaoo
161.00
182.00
9.60
2440.00
4/4
1/2
02
02
m
00
1/2
02
02
1/2
4/4
1/2
22
1/1
02
02
02
02
02
02
02
22
22
22
2/2
4/4
22
EPTdKicity Analysis - PFM
Vlrirrim A«rag3
14.70
Q79
0.05
0.15
266
-
Q02
0.05
0.05
0.05
Q34
QCB
248
QCB
Q0001
0.05
QCB
QCB
QCB
Q25
QCB
Q7B
23185
Q90
0.53
0.53
1503
-
0.03
Q53
0.53
Q53
108.67
Q27
147.74
B63
0.0002
Q53
Q53
Q53
Q53
263
0.53
1329
Nfeorrum # Detects
573.00
1.00
1.00
1.00
27.40
-
Q10
1.00
1.00
1.00
217.00
0.52
29300
1320
0.0002
1.CO
1.00
1.00
1.00
5.00
1.00
2580
22
22
1/2
22
22
00
22
1/2
1/2
1/2
22
1/2
212
1/2
1/2
V2
1/2
1/2
M2
1/2
1/2
2/2
1C
Lewsl
-
-
50
100.0
-
-
1.0
50
-
-
-
50
-
-
Q2
-
-
1.0
5.0
-
-
-
-
-
-
212
-
#V*JE3
InBcess
-
-
0
0
-
-
0
0
-
-
-
0
-
-
0
-
-
1
0
-
-
-
-
.
-
0
-
-------
£SUMMARYQFEPA/ORD, 3007, ANDRT1 SAMPLING DATA- PLANT AREA VENT SCRUBBER WATER -BERYLLIUM
o
Constituents
Aluminum
Antirrony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chrom'um
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sufflde
Sulfate
Fluoride
Phosphate
Slica
Chloride
TSS
pH*
Organics (TCC)
Total Constituent Analysis - PPM
Mnimum Average Maximum # Detects
-
0.003
0.042
-
210
-
0.033
0.093
-
0.5
-
0.168
-
-
0.0003
-
0.064
0.003
0,0005
0.002
-
0.096
-
-
-
-
-
-
-
-
-
-
-
0.0030
0.0510
-
210
•
0.0335
0.1165
-
0.5400
-
0.1680
-
-
0.0004
-
0.0640
0.0030
0.0043
0.0020
-
0.1130
-
-
-
-
-
-
-
-
-
-
.
0.003
0.06
-
210
-
0.034
0.14
-
0.58
-
0.168
-
-
0.0004
-
0.064
0.003
0.008
0.002
-
0.13
-
-
-
-
-
-
-
-
-
-
0/0
212
212
0/0
212
0/0
212
212
0/0
2/2
0/0
2J2
Q/0
0/0
2/2
0/0
212
212
212
212
0/0
2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxioity Analysis - PPM
Mrirrun Average Maxtrrun # Detects
0/0
0/0
0/0
0/0
0/0
O/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
00
0*0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
00
Q/0
0/0
0/0
Q/0
m
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
.
-
-
-
.
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection lirrit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPUNG DATA - CHIP TREATMEhfT WASTEWATER - BERYUJUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
vtercury
Molybdenum
Nickel
Selenium
Slver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Slica
Chloride
TSS
pH*
Organics(TOC)
Total Constituent Analysis - PPM
t/irimum Average Maximum
-
0,003
0.003
-
3300
-
0.063
7.4
-
1.4
-
0.2
-
-
0.0002
-
0.78
0,003
0.04
0.002
-
7.2
-
-
-
'
-
-
-
-
-
-
-
0.003
0.003
-
3300
-
0.063
7.4
-
1.4
-
0.2
-
-
0.0002
-
0.78
O.OOQ
0.04
0.002
-
7.2
-
-
-
-
-
-
-
-
-
-
# Delects
-
0.003
0.003
-
3300
-
0.063
7.4
-
1.4
-
0.2
-
-
0.0002
-
0.78
0.003
0.04
0.002
-
7.2
-
-
-
-
-
-
-
-
-
-
0/0
1/1
1/1
0/0
1/1
0/0
1/1
1/1
0/0
1/1
0/0
1/1
070
0/0
1/1
0/0
1/1
1/1
1/1
1/1
0/0
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxictty Analysis - PPM
Mrirrum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
OX)
0/0
o/o
0(0
wo
no
0/0
0/0
0/0
0/0
0/0
0/0
O/O
0/0
0/0
0/0
0/0
0/0
o/o
0/0
0/0
0/0
0/0
070
0/0
TC # Values
Level In Excess
,
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
.
-
.
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
f^Non-detects were assumed to be present at 1/2 the detection limit. TOP data are currently unavailable; therefore, only EP data are presented.
-------
^SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SCRUBBER LIQUOR - BERYLLIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH«
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0.003
0.003
-
0.49
0,004
0.042
-
0.12
0.16
0.0002
0.019
0.003
0.024
0.002
-
0,039
-
-
-
-
-
-
„
-
0.0067
0.0030
-
1 .0733
0.0073
0.0675
-
0.4100
0.1667
0.0002
0.0297
0.0030
0.0655
0.0020
-
0.0553
-
-
-
-
-
-
„
-
0.015
0.003
-
2
0.015
0.13
-
1.5
0.168
0.0002
0.043
0.003
0.1
0.002
-
0.087
-
-
-
-
-
-
„
f Detects
0/0
6/6
6/6
0/0
6/6
0/0
6/6
6/6
0/0
6/6
0/0
6/6
0/0
0/0
6/6
0/0
6/6
6/6
6/6
6/6
0/0
6/6
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum f Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
0
5.0 0
100.0 0
-
1.0 0
5,0 0
.
-
5.0 0
0.2 0
1.0 0
5.0 0
.
.
-
-
-
-
-
-
-
212 0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
BISMUTH
A. Commodity Summary
According to the Bureau of Mines, bismuth is produced, as a byproduct of lead refining, at only one facility
(ASARCO - Omaha, NE). Reported consumption of bismuth was estimated at 1,500 metric tons during 1994 and 40
companies in the East were responsible for 98 percent of the total bismuth consumption. Bismuth is used primarily
in the following industries: Pharmaceuticals and chemicals (including cosmetics), metallurgical additives, and
fusible alloys and solder.'
B. Generalized Process Description
1. Discussion of Typical Production Processes
Bismuth is recovered mainly during the smelting of copper and lead ores. Exhibit 1 shows the extraction of
bismuth-containing dust from copper-based sources. Bismuth-containing dust from copper smelting operations is
transferred to lead smelting operations for recovery. At lead smelting operations, bismuth is recovered by one of two
processes: the Betterton-Kroll Process (shown in Exhibit 2) and the Belts Electrolytic Process (shown in Exhibit 3).2
Bismuth can also be recovered from other bisrmuh -bearing materials by the process shown in Exhibit 4. Exhibit 5
presents the flow diagram for the process used to refine the bismuth-lead alloy produced during either the Betterton-
Kroll or the Belts Electrolytic Process.
2. Generalized Process Flow Diagram
Betierton-Kroll Process
As shown in Exhibit 2, the Betterton-Kroll process is based on the formation of high-melting compounds
such as Ca^Bi, and Mg3Bi2 that separate from the molten lead bullion badi and can be skimmed off as dross. During
this process, magnesium and calcium are mixed with the molten lead to form ternary compounds (e.g.. CaMg,BU).
The ternary compounds rise to the surface when the lead is cooled to just above its melting point, forming a dross
containing bismuth, calcium, magnesium, and lead, which is skimmed. Bismuth is recovered by melting the dross in
a furnace, treating the dross with chlorine or lead chloride to remove the calcium, magnesium, and lead,3 The
resulting chlorides are skimmed off the molten bismuth as a slag. The addition of air and caustic soda to oxidize any
remaining impurities forms additional slag which can be disposed in conjunction with the slag from the blast
furnace.4
1 Stephen M. Jasinski, "Bismuth," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p.
30.
2 "Bismuth," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.. Vol. IV, 1992, p. 238.
3 Laurence G. Stevens and C.E.T. White, "Indium and Bismuth." from Metals Handbook Volume 2. Properties
and Selection: Nonferrous Alloys and Special-Purpose Materials. Tenth ed., 1990, p. 753-754.
4 U.S. Environmental Protection Agency, Industrial Process Profiles for Environmental Use: Chapter 27. Primary
Lead Industry. Office of Research and Development, July 1980.
143
-------
EXHIBIT 1
BISMUTH COPPER SOURCES
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-70 - 2-76.)
Copper Matte
Blister
Copper
1
Fire
Refining
I
Electrolytic
Refining
I
Pure Copper
1
Slimes
Processing
1
Lead Bullion
I
Bismuth
Extraction
1^ Flue Dusts
(Containing Bismuth)
I
Lead
Smelting
^ Baghouse
Dust
144
-------
EXHIBIT 2
BISMUTH BETTERTON-KROLL PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-7- - 2-76.
Metallic Calcium and
Magnesium
Molten Lead Bullion
Mixing
Molten Compound
Cooling Process
Lead Bullion
Dross Containing Intermetallic Bismuth, Calcium, Magnesium, and Lead
Heat
Residual Lead
Chlorine
Lead-Free Dross
\
Chlorination
Magnesium and Calcium
Chlorides
Bismuth-Lead Alloy
Refining
Bismuth Metal
145
-------
Betts Electrolytic Process
As shown in Exhibit 3, in the Betts Electrolytic Process the lead bullion with impurities is electrolyzed in a
solution of fluosilicate and free fluosilicic acid with pure lead cathodes. The impurities, including bismuth, are
retained in the form of a black anode slime. This slime is then scraped from the anode, washed, and partially dried
prior to processing for bismuth. The recovery of bismuth is only one of several process end-product objectives in the
treatment of the process residue. The primary objective is the fusion of the dried residues to produce a slag
containing lead, arsenic, and antimony.5 The slimes are smelted and the resulting metal is cupelled, yielding a slag
containing bismuth. The cupel slag is reduced and refined.6 One important difference between the Betts process and
the Betterton-Kroll process is that in the Betterton-Kroll process, the lead bullion is purified prior to mixing with
calcium and magnesium, while in the Betts process, the impurities are left in the lead bullion.7
Extraction From Bismuth Bearing Materials
As shown in Exhibit 4, bismuth also can be extracted from roasted tin concentrates and other bismuth-
bearing materials by leaching with hydrochloric acid. After dilution of the acid leach, bismudi is precipitated as
bismuth oxychloride. Further purification is achieved by redissolving the bismuth oxychloride in hydrochloric acid.
The bismuth oxychloride is reprecipitated, dried, and reduced with carbon using soda ash flux to produce crude
bismuth bullion.8
Exhibit 5 presents one method of bismuth refining in which the bismuth-lead alloy is mixed with caustic
soda to form a purified metal mix. Zinc is added to the metal mix, which then undergoes Parkes Desilverization, a
process used to recover gold and silver from softened lead bullion. The zinc combines with the molten bullion to
form a skim with the gold and copper, which is then removed. More zinc is then added to form a silver skim layer
which also is removed. Once the silver and gold are separated, they are sent for further processing and the recovered
zinc can be recycled. More detailed description of Parkes Desilvering can be found in the description of lead
processing found elsewhere in this report.
Following the desilverization process, chlorine is added to the resultant bismuth-bearing material which is
then heated to 500° C. After heating, the impure bismuth is oxidized with air and caustic soda, producing 99.999
percent pure bismuth metal.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
The bismuth recovery process starts with materials obtained from the smelting of lead which is a minerals
processing operation. Therefore, all of the wastes generated in the recovery process are categorized as mineral
processing wastes. For example, even though leaching is typically considered to be a beneficiation operation, in this
particular situation where it follows a minerals processing operation, waste from this step is categorized as mineral
5 Funsho K. Ojebuoboh, "Bismuth-production, properties, and applications," JOM, 44, No. 4, April 1992, p. 47.
6 Laurence G. Stevens and C.E.T. White, 1990, Op. Cit.. pp. 753-754.
7 Funsho K. Ojebuoboh, 1992, Op. Cit.. p. 47.
8 Ibid.
146
-------
EXHIBITS
BETTS ELECTROLYTIC EXTRACTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-70 - 2-76.)
90% Lead Bullion
Lead Product
Arsenic, Antimony
Lead to Refining
Gold and Silver
to Refining
Bismuth to Refining
Anode Casting
Electrolytic Refining
Anode Slimes
Slimes Melting
Selective Oxidation
Cupelation
Crashing
1
Sulfur Mixing
1
Carbon Reduction
Copper Matte to
Cu Processing
Spent Electrolyte
Slag
147
-------
EXHIBIT 4
RECOVERY FROM BISMUTH BEARING MATERIALS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-70 - 2-76.)
Hydrochloric Acid
Spent Material
Bismuth-bearing ^
Materials
Leaching
Process
1.
Leach Liquid
Clarifier
\
Dilution
**
Wastewater
Bismuth Oxychloride (ppt)
Hydrochloric Acid
Soda Ash
Carbon
Bismuth Oxychloride (wet)
T
Reduction With
-^- Waste Acid Solution
Fe, Zn, and HC1
Oxychloride Process
i
More
Refining
Waste Acid Solution
Bismuth Metal
148
-------
EXHIBIT 5
BISMUTH REFINING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-70 - 2-76.)
Caustic Soda
Bismuth-Lead Alloy
Spent Soda Solution
Zinc
Silver, Zinc, and Gold
to Processing
Chlorine Gas
Lead and Zinc Chlorides
- Excess Chlorine
Air Caustic Soda
Alloy Residue Spent
Caustic Soda Solution
Bismuth Metal
99.999% Pure
149
-------
processing waste. For a description of where the beneficiation/processing boundary occurs for this mineral
comodity, please see the report for lead presented elsewhere in this background document.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Because bismuth is recovered as a byproduct of lead and copper ore production, mining wastes are
addressed in the descriptions of the initial ore/mineral. For a further description of these wastes see the reports for
copper and lead presented elsewhere in this background document.
2. Mineral Processing Wastes
The extraction methods used to recover bismuth (e.g., leaching, electrolysis) generate wastes including
waste caustic sodas, electrolytic slimes, and waste acids. In addition, the following wastes are also generated during
the processes described above. Although no published information regarding waste generation rate or characteristics
was found, we used the methodology outlined in Appendix A of this report to estimate low, medium, and high annual
waste generation rates.
Extraction
Spent Caustic Soda. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/yr, 6,100 metric tons/yr, and 12,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste stream may be recycled and may exhibit the characteristic of toxicity for lead. This waste
is classified as a spent material.
Electrolytic Slimes. The slimes generated during this process are likely to be reprocessed. Low, medium.
and high annual waste generation rates were estimated as 0 metric tons/yr, 20 metric tons/yr, and 200 metric tons/yr.
respectively. We used best engineering judgment to determine that this waste stream may be recycled and may
exhibit the characteristic of toxicity for lead. This waste is classified as a by-product.
Waste Acids. The waste acids generated are likely to be neutralized and discharged with waste water from
the process. Low, medium, and high annual waste generation rates were estimated as 0 metric tons/yr, 100 metric
tons/yr, and 200 metric tons/yr, respectively. We used best engineering judgment to determine that this waste stream
may be partially recycled and may exhibit the characteristic of corrosivity. This waste is classified as a spent
material.
Betterton-Kroll Process
Metal Chloride Residues. Chlorination generates magnesium and calcium chlorides. This waste stream
has a reported annual waste generation rate of 3,000 metric tons/yr. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity for lead.
Slag. The slag produced during this process contains magnesium, lead, and calcium. It is disposed with the
blast furnace slag. Low, medium, and high annual waste generation rates were estimated as 100 metric tons/yr, 1,000
metric tons/yr, and 10,000 metric tons/yr, respectively. We used best engineering judgment to determine that this
waste may exhibit the characteristic of toxicity for lead.
Betts Electrolytic Process
Spent Electrolyte. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/yr, 6,100 metric tons/yr, and 12,000 metric tons/yr, respectively. We used best engineering judgment to
detei'mine that this waste may exhibit the characteristic of toxicity for lead.
Slag. Slag is generated from carbon reduction as shown in Exhibit 3.
150
-------
Extraction From Bismuth-Bearing Materials
Spent Material. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Wastewater. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further,
Waste acid solutions. As shown in Exhibit 4, these wastes are generated when the bismuth oxychloride is
dissolved in hydrochloric acid. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/yr, 6,100 metric tons/yr, and 12,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristic of corrosivity,
Bismuth Refining
As shown in Exhibit 5, the following wastes are associated with the bismuth refining process,
Spent soda solution. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/yr, 6,100 metric tons/yr, and 12,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste stream may be recycled and may exhibit the characteristics of toxicity (lead) and
corrosivity. This waste is classified as a spent material.
Excess chlorine. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/; r, 150 metric tons/yr, and 200 metric tons/yr, respectively. We used best engineering judgment to determine
that this waste may exhibit the characteristics of toxicity (lead) and reactivity.
Alloy residues. Low, medium, and high annual waste generation rates were estimated as 100 metric
tons/yr, 3000 metric tons/yr, and 6000 metric tons/yr, respectively. We used best engineering judgment to determine
that this waste may exhibit the characteristic of toxicity for lead.
Lead and Zinc chlorides. Low, medium, and high annual waste generation rates were estimated as 100
metric tons/yr, 3000 metric tons/yr, and 6000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity for lead.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
151
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BIBLIOGRAPHY
"Bismuth." Kirk-Qthrner Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992. pp. 237-243.
Jasinski, Stephen M. "Bismuth." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
30-31.
Ojebuoboh, Funsho K. "Bismuth-production, properties, and applications." JOM, 44, No. 4. April 1992. pp. 46-
49.
Stevens, Laurence G. and White, C.E.T. "Indium and Bismuth." Metals Handbook Volume 2. Properties and
Selection: Nonferrous Alloys and Special-Purpose Materials. Tenth ed. 1990. pp. 750- 757.
U.S. Environmental Protection Agency. "Bismuth." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste, pp. 2-70 - 2-76.
U.S. Environmental Protection Agency. Industrial Process Profiles for Environmental Use: Chapter 27, Primary
Lead Industry. Office of Research and Development, July 1980.
152
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BORON
A. Commodity Summary
Borates are defined by industry as any compound that contains or supplies boric oxide. A large number of
materials contain boric oxide, but the three most common boron containing minerals are borax, ulexite. and
cole.manite.' Kernite is a metamorphic phase of borax and is an important borax mineral. Borate production in the
United States in centered mainly in the Mojave Desert in southern California. Borax and kernite are mined by U.S.
Borax (located in Boron, California) and borate is also recovered from brines pumped from Searles Lake.2 Kernite
comprises more than one-third of the boron deposit in Boron, California.
Borax is the most important boron mineral for the borate industry. It crushes freely, and dissolves readily in
water, and its solubility and rate of solution increase with water temperature. Kernite has a higher B203 content than
borax, but its excellent cleavage causes it to form fibers that mat and clog handling equipment. Being slowly soluble
in water, kernite requires autoclaving or pre-refinery hydration for efficient conversion into refined products. It is
currently used primarily as feed for the boric acid plant located in Boron, California.3 Colemanite is the preferred
calcium-bearing borate used by the non-sodium fiberglass industry. Although it has low solubility in water, it readily
dissolves in acid,4
The major uses of borates include: fiberglass insulation, textile or continuous-filament glass fibers, glass,
detergents and bleaches, enamels and frits, fertilizers, and fire retardants.5 According to the U.S. Bureau of Mines,
apparent domestic consumption of boric oxide in 1994 was estimated at 362 thousand metric tons.6
B. Generalized Process Description
1. Discussion of Typical Production Processes
There are two companies that operate borate recovery plants domestically, each using a distinctly different
borate-containing source. The first plant near Searles Lake recovers borax from natural mineral-rich lake brines.
The process at Searles Lake involves fractional distillation followed by evaporation. Borax is only one of the
products recovered there; other products include sodium sulfate, lithium compounds, potash, and other salts. The
second company, U.S. Borax, mines and processes crude and refined sodium borates, their anhydrous derivatives,
and anhydrous boric acid at a plant in Boron, California.7
2. Generalized Process Flow Diagram
Exhibits 1 through 4 present the process flow diagrams for borate brine extraction and boric acid recovery.
Exhibit 1 illustrates the processes used to prepare boric acid from ore in Boron, California. Exhibits 2, 3 and 4
1 Robert B. Kistler and Cahit Helvaci, "Boron and Borates," from Industrial Minerals And Rocks. 1994, p. 171.
2 Ibid.
3 Ibid.
4 Ibid.
5 IMd., p. 183.
6 Phyllis A. Lyday, "Boron," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995, pp. 32-33.
7 Phyllis A. Lyday, "Boron," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, p. 249.
153
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present the methods used at two of the plants involved in the Searles Lake operations to recover borates from the
brines deposits in California.
Borate Ore Processing
At the U.S. Borax facility in Boron, California, the ores are selectively mined, crushed, and stockpiled for
production at two distinct facilities producing sodium borate and boric acid, respectively.
Sodium Borate Production, The principal ore used in the process, tincal, is soluble in water. After the
ore is crushed, the tincal is dissolved in water. The resulting insolubles are then separated from the solution and the
clarified liquor is fed to the crystallizers. Next, the crystals of sodium borate are separated from the weak solution
which then can be recycled back to the dissolution step. The crystals are dried and can either be sold as borax or
treated further to produce other borate materials.8 One of the products prepared when the crystals are cooled is
sodium borate decahydrate. If sodium borate pentahydrate is the desired product, the sodium borate decahydrate can
be sent to further recrystallization. Anhydrous sodium borate can be produced by thermally dehydrating either the
sodium borate decahydrate or sodium borate pentahydrate.9 U.S. Borax also produces boric acid from ores,
discussed below.
Boric Acid Production. Some of the solid sodium borate ore from the stockpile at the U.S. Borax facility
is reacted with sulfuric acid and used as feed in the production of boric" acid.10 Exhibit 1 presents the process used to
produce boric acid from the ore stockpile. Clays, sands and other impurities are also present in the ore. After the ore
is crushed and ground, it is acid digested using sulfuric acid to produce two new compounds, sodium sulfate and
boric acid. The clay and other insolubles are then removed from the aqueous stream. Rake classifiers separate out
the larger material, while settling tanks and thickeners are used to remove the finer materials. The stream is then
filtered further to remove any remaining insoluble materials. After filtration, the solution is pumped to crystallizers.
In the crystallizers, the solution is cooled, forming a slurry containing solid boric acid crystals and a boric acid
solution. Further filtration and centrifugation separate the solid boric acid, which can be dried and packaged for
sale." The remaining liquor can be further evaporated to recover a sodium sulfate co-product.
Brine Extraction
Operations at Searles Dry Lake in California involve the recovery of boron from brine deposits at three
separate facilities: Trona, Argus, and Westend. Not all of these facilities are directly involved with the extraction of
boron from brines. The Argus facility, for example, only produces soda ash, however, the carbonated liquid from
this plant is used at the Westend plant. Borates can be recovered from concentrated brines prepared by either of two
methods: carbonation or evaporation. Exhibit 2 presents the process flow diagrams for the method used at the
Westend plant. Exhibit 3 presents the liquid-liquid extraction steps used at the Trona plant to process brine prepared
by evaporation.
8 U.S. Environmental Protection Agency, "Boron," from 1988 Final Draft Summary Report of Mineral Industry
Processing jV_astes. 1988, pp. 2-77-2-84.
9 Vefsar, Inc., "Boron Derivatives," Multi-media Assessment of the Inorganic Chemicals Industry. Prepared for
U.S. Environmental Protection Agency, August 1980, p. 2-5.
10 Ibid.
" "Comments Regarding Classification of the Boric Acid Production Line at Boron Operation of United States
Borax & Chemical Corporation," Memorandum and Enclosures from W.W. Cooper, Ph.D., Senior Environmental
Scientist, U.S. Borax to Mr. Lynn E. Johnson, R.E.H.S., Toxic Substances Control Program, October 3 and 11,
1991.
154
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EXHIBIT 1
BORIC ACID PRODUCTION AT BORON, CALIFORNIA
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-77 - 2-84.)
Sodium Sulfate
Solid Boric Acid
155
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Westend Plant (Carbonated Liquor). Carbonation is used at the Argus facility to supersaturate the brine
solution with sodium bicarbonate. As shown in Exhibit 2, the carbonated liquor from this facility is used in
combination with the brine solution at the Westend facility. The Westend facility produces anhydrous sodium
borate. sodium borate pentahydrate, sodium borate decahydrate, boric acid, sodium sulfate, and sodium bicarbonate.
At the Westend plant, after the sodium bicarbonate has precipitated out, the brine and carbonated liquor mixture is
cooled to crystallize sodium borate decahydrate. The crude sodium decahydrate is filtered out from the liquor, which
can be sent for further processing to the sulfate plant. The crude sodium borate decahydrate is then either heated to
its melting point to remove hydrated water, thus producing anhydrous sodium borate, which can either be packaged
and sold or sent to further processing or, acid digested using sulfuric acid to produce boric acid. Although not shown
in the Exhibit 2, the sodium borate decahydrate can be redissolved and hydrated and then cooled to form either
sodium borate decahydrate or sodium borate pentahydrate. If the anhydrous sodium borate is reacted with sulfuric
acid instead, the resulting product is boric acid.12
Trona Plant (Evaporated Brine). Evaporation processes are used in the Searles Lake operations to
remove sodium chloride from the brine and to concentrate other desired constituents of the brine prior to further
processing. The brine is pumped initially to solar evaporation ponds and concentrated. As the brine is evaporated,
the sodium chloride concentration increases until the NaCl crystallizes out of solution. In addition, during the
evaporation process, a rapid, controlled cooling selectively crystallizes various other salts including sodium
bicarbonate and sodium sulfate. The concentrated brine from the evaporation ponds is then sent to the Trona plant
for use as brine feedstock.13
Liquid-Liquid Extraction. The Trona facility uses a proprietary liquid-liquid extraction process to remove
borate compounds from the brine (Exhibit 3). Specifically, during the process the brine is mixed with a chelating
agent in a kerosene solution to remove the borates from the brine. Brine is pumped to the plant and emulsified. The
emulsion is sent to a settling tank and through an API separator to break the emulsion and the extractant from the
brine. The spent brine is returned to Searles Lake. The extractant is then combined with dilute sulfuric acid to
convert the sodium borate to boric acid. This step produces a strip liquor containing boric acid, sodium sulfate,
potassium sulfate, and sodium chloride. The strip liquor is then sent to a carbon filtration column to remove any
remaining organic fractions. The filtered liquor is vacuum cooled in a boric acid crystallizer. The resulting boric
acid crystals are centrifuged to separate them from the liquor, washed, dried, and packaged for sale. The resulting
"mother liquor" is vacuum cooled further to crystallize the mixed sulfates, which are centrifuged to form a sulfate
cake and sent to a potash production line.14
Potash/Borax Line. The potash/borax line is part of the Trona plant that produces pentahydrate borax,
anhydrous borax, potassium chloride (potash), and potassium sulfates. As shown in Exhibit 4, brine is pumped to the
plant from the evaporation ponds and sent to further evaporation. Following the evaporation, some of the
concentrated brine is fed to tanks and vacuum cooled. Following this, the resultant halite is slurried, filtered,
washed, and sent back to Searles Lake with the spent liquor. After the drying step, the solution is cooled and the
potassium chloride that precipitates out can be sold as a product. The remaining brine is mixed with the sulfate cake
from the liquid-liquid extraction process and potassium sulfate is precipitated. Following the precipitation of
potassium chloride, the residual solution can be cooled to allow sodium borate pentahydrate to precipitate out ;rom
the remaining solution. This is then redissolved, hydrated, and filtered, producing dehydrated borax products (i.e..
sodium borate decahydrate or sodium borate pentahydrate). The decahydrate borax can be further processed by
heating to remove hydrated water, thus producing anhydrous sodium borate.15 At Searles Lake the same processes
12 California Department of Toxic Substances Control, "Searles Lake Mining Operation," Memorandum from
William Soo Hoo, Chief Counsel to Van Housman, Office of Solid Waste, U.S. Environmental Protection Agency,
August 1, 1991.
13 Ibid.
14 Ibid.
15 Ibid.
156
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EXHIBIT 2
BORATE BRINE PROCESSING AT SEARLES LAKE, CALIFORNIA
WESTEND PLANT (CARBONATED LIQUOR FEEDSTOCK)
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-77 - 2-84.)
CO, Brine
Sodium Bicarbonate
Borax
Sodium borate decahydrate
and
Sodium borate pentahydrate
Boric Acid
H,SO.
157
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EXHIBIT 3
BORATE BRINE PROCESSING AT SEARLES LAKE, CALIFORNIA
TRONA PLANT (LIQUID-LIQUID EXTRACTION)
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-77 - 2-84.)
Brine To Further Processing
Evaporated Brine
Boric Acid
Dilute H,SOi
Liquor
Mixed Sulfate Cake (sent to potash/borax line)
158
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EXHIBIT 4
PRODUCTION OF POTASH AND BORAX AT SEARLES LAKE,
CALIFORNIA TRONA PLANT
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-77 - 2-84.)
Evaporated Brine
Potash (KC1)
Borax Product
159
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are also used to produce chemicals including sodium chloride, soda ash, and potassium chloride. These solids are
precipitated from the brine solution as the solution evaporates.16
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA reviewed the processes used to produce sodium borate and boric acid from borate ores (at U.S. Borax)
and from brines (at Searles Lake) and determined that the beneficiation/mineral processing line is crossed when
sodium borate is digested using sulfuric acid to produce boric acid and sodium sulfate. Specifically, at the U.S.
Borax facility, the beneficiation/mineral processing line occurs between the crushing and grinding of the solid
sodium borate ore and acid digestion with sulfuric acid. At the Searles Lake, Westend Plant, the
beneficiation/mineral processing line occurs when borax is removed from the crystallizer and reacted with sulfuric
acid to produce boric acid. At the Searles Lake, Trona Plant, the beneficiation/mineral processing line occurs
between the liquid/liquid extraction and acidification step. EPA identified these points in the processes as where
beneficiation ends and mineral processing begins because it is here where a significant chemical change to the
sodium borate occurs (sodium borate reacts with the sulfuric acid to produce two new chemicals - boric acid and
sodium sulfate). Therefore, because EPA has determined that all operations following the initial "mineral
processing" step in the production sequences are also considered mineral processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents the mineral processing waste streams generated after the beneficiation/
processing line in section C.2, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
With regard to the production of potash and borax at the Searles Lake, Trona Plant, EPA determined that all
of the processes may be classified as extraction or beneficiation activities. As a result, all of the wastes associated
16 Versar Inc., 1980,;
160
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with the production of borates are considered to be extraction or beneficiation wastes and, thus, eligible for the
Bevill Mining Waste Exclusion.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Borate Ore Processing
Gangue. Gangue solids are generated from the initial dissolution step during the production of sodium
borate decahydrate. In 1980, these waste were reported as generally inert insolubles, although they contained 0.08
percent natural arsenic mineral realgar. The solid wastes from ore residues and evaporation wastes were sent to on-
site lined evaporation ponds."
Wastewater. Process wastewater from washing contains dissolved borax and other salts may be sent to
lined evaporation ponds.18
From Brines
Spent Solvents, Crud, and Waste Brine. The brine extraction process generates waste brine and spent
solvents. The plant extract or crud generated during the recovery of boron from brines at the Trona plant contains
arsenic and halogens and is ignitable,"
Particulate Emissions. Particulates generated from drying operations are collected in dry bags and
recycled. In 1980, the wastes were generated at approximately 14 kg per kkg of product.20
Boric Acid Production
Spent Sodium Sulfate. Crystallization produces sodium sulfate. Existing data and engineering judgment
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
2. Mineral Processing Wastes
Boric Acid Production
Spent Clay and Other Insolubles. No information is available.
Waste Liquor and Underflow Mud. Some of the liquor remaining after the boric acid is filtered off
contains arsenic. In 1980, one site reported that the arsenic was present as a natural impurity in the ore used to make
die sodium pentahydrate. Another site reported returning the arsenic-containing wastes to the original subterranean
brine source. One cornmenter reported a combined generation rate for waste liquor and mud of 150,000 tons/yr and
17 Ibid.
18 Versar, Inc., 1980, Op. Cit.. p. 2-7.
19 California Department of Toxic Substances Control, Memorandum from William Soo Hoo, Director, to Sylvia
K, Lowrance, Office of Solid Waste, U.S. Environmental Protection Agency, May 8, 1992.
20
Versar, Inc., 1980, p. 2-5.
161
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indicated that the TCLP analysis performed for arsenic is consistently well below 5 ppm.2lLow, medium, and high
annual waste generation rates were estimated as 300 metric tons/yr, 150,000 metric tons/yr, and 300,000 metric
tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit the characteristic
of toxicity for arsenic. This waste is recycled and formerly was classified as a spent material. Existing data and
engineering judgment suggest that waste liquor and underflow mud material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent Sodium Sulfate. Crystallization following acid digestion produces sodium sulfate. Existing data
and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
D, Non-uniquely Associated Wastes
There are no non-uniquely associated wastes in this specific sector. However, standard ancillary hazardous
wastes may be generated at on-site laboratories, and may include used chemicals and liquid samples. Other
hazardous wastes may include spent solvents, and acidic tank cleaning wastes. Non-hazardous wastes may include
tires from trucks and large machinery, sanitary sewage, and waste oil and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
One commenter addressed the boron sector report (COMM 86). The commenter provided some technical
corrections and some specific line edits for the report. These comments have been included, as appropriate, in the
revised boron sector report.
Sector-specific Issues
None.
21 U.S. Borax. Comments submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
162
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BIBLIOGRAPHY
"Boron." Kirk-Othmer Encyclopedia of Chemical Technology 4th ed. Vol. 4. 1992 pp. 360-364.
"Boron." From 1988 Final Draft Summary Report of Mineral Industry Processing Wastes. Office of Solid Waste,
U.S. Environmental Protection Agency, p. 2-77-2-84.
California Department of Toxic Substances Control. Memorandum from William Soo Hoo, Director, to Sylvia K.
Lowrance, Office of Solid Waste, U.S. Environmental Protection Agency. May 8, 1992.
California Department of Toxic Substances Control. "Searles Lake Mining Operation," Memorandum from William
Soo Hoo, Chief Counsel to Van Housman. Office of Solid Waste. U.S. Environmental Protection Agency.
August 1, 1991.
"Chemicals From Brine." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992.
p. 823.
"Comments Regarding Classification of the Boric Acid Production Line at Boron Operation of United States Borax
& Chemical Corporation," Memorandum and Enclosures from W.W. Cooper, Ph.D., Senior Environmental
Scientist, U.S. Borax to Mr. Lynn E. Johnson, R.E.H.S., Toxic Substances Control Program. October 3 and
11, 1991.
Kistler, Robert B. and Helvaci, Cahit. "Boron and Borates." From Industrial Minerals and Rocks. 1994. 6th ed. p.
171-186.
Lyday, Phyllis A. "Boron." From Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995. pp. 32-
33.
Lyday, Phyllis A. "Boron." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. pp. 247-252.
163
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Page Intentionally Blank
164
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BROMINE (from brines)
A. Commodity Summary
Bromine is a member of the halogen family of elements. Elemental bromine is highly reactive and occurs in
nature only as bromide compounds. Sources of bromide include sea water, subterranean brines, saline lakes, oil and
gas well brines, and evaporate chloride minerals including halite (NaCl), sylvite (KC1), and carnallite.1 Bromide
compounds are used in fire retardants, agriculture, petroleum additives (ethylene dibromide is an antiknock additive
in leaded gasoline), and well drilling fluids. Domestic consumption of bromide was estimated to be 287 million
kilograms in 1994.2
According to the U.S. Bureau of Mines, companies in Arkansas and Michigan were responsible for all
elemental bromine production in 1993. Exhibit 1 presents the names, locations, and types of operations employed by
the facilities involved in the production of bromine. The Dow Chemical Company (Dow) in Ludington, Michigan is
not directly involved in the purification of bromine; however, Dow removes bromine from its magnesium brines
because it is an impurity in their magnesium operation. Dow ships the recovered bromine to the Ethyl Corporation
in Arkansas to be purified and prepared for sale.
EXHIBIT 1
SUMMARY OF BROMINE FACILITIES
Facility Name
Dow Chemical Company
Ethyl Corp.
Great Lakes Chemical Corp.
Locations
Ludington, MI
Magnolia, AR
El Dorado, AR (3 plants)
Type of Operations
Brine extraction prior to production of
magnesium chloride. Sent to Ethyl
Corporation for purification.3
Brine Extraction
Brine Extraction
a Personal communication between Jocelyn Spielman, ICF Incorporated and Phyllis Lyday, U.S. Bureau of Mines. October 5. 1994.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Commercial bromine production processes involve the oxidation of bromide to bromine, using chlorine as
the oxidant. Most of the liberated bromine remains dissolved in the brine. The brine is then stripped of bromine and
the bromine is then recovered from the stripping agent. Further purification by distillation is often a final step in the
process.3 Exhibits 2 and 3 present the generalized process flow diagrams for the production of bromine and each of
the steps is described in further detail below.
1 M.J. Wilhelm and K.C. Williams, "Bromine Resources," from Industrial Minerals and Rocks. 1994, 6th ed. p.
187.
2 Phyllis Lyday, "Bromine," Mineral Commodity Summaries, 1995, U.S. Bureau of Mines, p. 34.
3 "Chemicals from Brines," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. IV, 1992, p. 823.
165
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2. Generalized Process Flow Diagram
As shown in Exhibits 2 and 3, there are three principal steps involved in the production of bromine from
brines: (1) skimming and acid stripping; (2) bromine extraction from the aqueous solution; and (3) condensation and
purification of the bromine. Variations on this production process generally differ in the extraction step.4
Skimming and Acid Stripping
Skimming and Hydrocarbon Removal. The first step in bromine recovery is skimming the oil from the
well brines and removing hydrocarbons. Following the skimming process, the brine solution undergoes acidification
and stripping with the addition of sulfuric acid. Spent hydrogen sulfate (H2S) is stripped from the solution and sent
to sodium sulfate (Na2S) recovery.
Acidification and Chlorination. Although bromine occurs in the form of bromide in sea water and in
natural brine deposits containing chloride, additional chlorine may be added to oxidize bromide to bromine.
Chlorine is used because it has a higher reduction potential than bromine.5 As shown in Exhibit 3, acidification with
H2SO4 can be part of the recovery process.
Extraction of Bromine
Bromine is extracted or stripped from the chlorinated solution using either steam (steaming out) or air
(blowing out process). Steam is used when the concentration of bromine in die brine is greater than 1,000 ppm. The
advantage of this memod is that bromine can be condensed directly from the steam. Air is used when the bromine
source is sea water because large volumes of stripping gas would be required, thereby making the use of steam too
expensive. However, when air is used, bromine must be trapped in an alkaline or reducing solution to concentrate
it.6
Steaming Out. As shown in Exhibit 3, brine is pumped to the top of a granite absorption tower filled with
ceramic packing material. Steam and chlorine are pumped in from the bottom of the tower. The bromine is oxidized
by the chlorine as it falls through the ceramic material. The chlorine replaces the bromine in the brine and the
gaseous bromine rises to the top of the tower with the steam, where it is condensed to a liquid.7
Blowing Out. Generally, sea water contains bromine as either magnesium bromide or sodium bromide.
When the source of the bromine is sea water, the blowing out method is used to strip the bromine from the brine. In
the blowing out method, prior to reaching the tower, raw sea water is acidified with sulfuric acid followed by the
addition of chlorine. Air is drawn into the base of the tower and rises as the bromine descends. Air containing
bromine passes to the absorption tower, where the bromine reacts with sulfur dioxide to form hydrogen bromide.8
4 "Bromine," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. IV, 1992, p. 548.
5 Ibid., pp. 548-549.
6 Ibid.
7 Phyllis Lyday, "Bromine," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, p. 259.
8 Ibid., pp. 259-260.
166
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EXHIBIT 2
BROMINE EXTRACTION FROM WELLS
(Adapted from: Kirk-Qthmer Encyclopedia of Chemical Technology, 1992, pp. 547 - 550.)
Brine from Wells
Skimming
hydrocarbon Removal
H,S
Acidification and
Stripping
H2S to Na->S Recovery
Chlorination
NH4OH (Neutralize)
Bromine Vapor
Extraction
\
Condensation
(Br,)
Cooling
Spent Brines
(to disposal wells)
H2SO4 (98%)
Drying
Spent H2SO4 (70%)
Dry Bromine
(to sale or use)
167
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EXHIBIT 3
STEAMING OUT PROCESS FOR RECOVERY OF BROMINE FROM HIGH
BROMIDE BRINES
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1992, pp. 547 - 550.)
Raw Brine
\
Settling ^»
|
Heat Exchange
. ^
1
H2SO4 ^- Acidification/
C12 ^~ Chlorination
1^
r
^tcam fe> Steaming-out
Tower
u
Hot Brine S
•a
Slime
^
^w"tUl"w
^
1
T
^ Gravity
Separator
|
Distillation
Bromine
168
-------
Condensation and Purification of Bromine
Following either method of extraction, the brine stream can be separated from the emerging gas stream
containing free bromine. The gas is then cooled to condense water and bromine. The spent brine from the vapor
extraction process can be neutralized with the addition of NH4OH and cooled. After removing the ammonia, spent
brine can either be used in other processes, sent to disposal wells, or returned to the source.
Condensation. The condensation process varies depending on the extraction process used. After the
steaming out method, the bromine is condensed directly from the steam. Following the blowing out method, the
bromine can be separated by adding acid to the extracted solution and distilling with steam. The gaseous stream
containing bromine can be condensed and purified.9 The liquid resulting from the condensation step is separated and
the recovered water is recycled back to the absorption tower.
Purification. Typically, following condensation the bromine is dried with sulfuric acid and then purified
by distillation. As shown in Exhibit 2, a 98 percent H2SO4 can be added, resulting in the generation of a spent
solution containing 70 percent H,SO4. The resultant dry bromine is sent to sale or use.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Recent patents describe a single-stage vacuum and a double-stage vacuum process for bromine recovery
which modify existing recovery procedures. The single-stage vacuum is similar to the steaming out process, except
that it is carried out under subatmospheric pressure. The double-stage vacuum re-strips the tail brines from the first
stripping under greater vacuum. The use of a vacuum in these modified process eliminates the need to heat the brine
with steam by matching the vapor pressure of the brines. Additional benefits of the vacuum modification include
increased tower capacity, reduction in chlorine use, and reduction in the amount of lime needed to treat the spent
brine.10
4. Beneflciation/Processing Boundary
EPA does not have enough information on this mineral commodity sector to determine where in the
production sequence mineral processing begins.
C. Process Waste Streams
1. Kxtraction/Beneficiation Wastes
Waste Brine. Waste liquids are generated during the vapor extraction and once these are neutralized and
cooled they can either be sent to disposal wells or returned to the brine deposit. These spent brines may contain
ammonia from the neutralizing step. Alternatively, waste brine can also be generated during the steaming out
process in the form of a hot bromine-free liquor that emerges from the bottom of the tower. This liquor is
neutralized with lime and discharged to a waste pond.l!
Slimes. Slimes are generated from the settling step in the steaming out process.
Water Vapor. Some chlorine and water vapor are captured at the top of the tower during steaming out.
9 Ibid., p. 260.
1° "Bromine," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. IV, 1992, p. 550.
" Phyllis Lyday, 1992, Op. Cit. p. 260.
169
-------
2. Mineral Processing Wastes
Bromine is used to make several organic chemical compounds in operations in close proximity to the brine
extraction process. EPA does not have enough information to determine where in the production sequence mineral
processing begins.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
170
-------
BIBLIOGRAPHY
"Bromine." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992. pp. 547-550
"Chemicals From Brine." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992. p.. 823.
Lyday, Phyllis. "Bromine." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. pp. 259-270
Lyday, Phyllis. "Bromine." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 34-35
Personal Communication with Phyllis Lyday, Bromine Specialist, U.S. Bureau of Mines. October 5, 1994.
U.S. Environmental Protection Agency. "Bromine." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988.' Office of Solid Waste, pp. 2-85 - 2-88.
Wilhelm, M.J. and Williams, K.C. "Bromine Resources." From Industrial Minerals and Rocks. 6th ed. 1994. pp.
187-189.
171
-------
Page Intentionally Blank
177
-------
CADMIUM
A. Commodity Summary
Four companies are responsible for producing all of the domestic primary cadmium. According to the U.S.
Bureau of Mines, cadmium is used in batteries, 71%; pigments, 10%; coating and plating, 8%; stabilizers for
engineering plastics and similar synthetic products, 5%; and alloys and other miscellaneous uses. 6%.'
Cadmium is produced mainly as a byproduct of refining zinc metal from sulfide ore concentrates. It is also
produced as a byproduct of beneficiating and refining lead ores or complex copper-zinc ores. Cadmium minerals are
not found alone in commercially viable deposits. Greenockite (CdS) is the only cadmium mineral of importance. It
is not found in any isolated deposits, but is nearly always associated with sphalerite (ZnS).2
Exhibit 1 shows the names and locations of the four primary cadmium producers. Three of the four
companies (Big River Zinc Corporation, ZCA, and Jersey Miniere Zinc Company) recover cadmium as a byproduct
of smelting domestic and imported zinc concentrates. The fourth company (ASARCO) recovered cadmium from
other sources such as lead smelter baghouse dust.3
EXHIBIT 1
SUMMARY Or CADMIUM PRODUCING FACILITIES
Facility Name
ASARCO
Big River Zinc Corporation
Jersey Miniere Zinc Company
ZCA
Location
Denver, CO
Sauget, IL
Clarksville, TN
Bartlesville, OK
B. Generalized Process Description
1. Discussion of Typical Production Processes
Cadmium is mainly a byproduct of the production of zinc metal from sulfide ore concentrates. The mined
zinc ores are crushed and ground to liberate the zinc sulfide particles from the waste host rock. The ground ore is
usually treated by a differential flotation process to separate the zinc-bearing particles from the waste rock, yielding a
high-grade zinc concentrate and waste tailings. About 90% to 98% of the cadmium present in zinc ores is recovered
in the mining and beneficiating stages of the extraction process. Zinc concentrate is converted from zinc sulfide to
zinc oxide by roasting, and at the same time most of the sulfur is removed as sulfur dioxide. The sulfur dioxide
1 Peter Kuck, "Cadmium," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995, pp. 36-37.
2 Thomas O. Llewellyn, "Cadmium," from Minerals Yearbook Volume1. Metals and Minerals. U.S. Bureau of
Mines, 1992, pp. 271-276.
3 Ibid.
173
-------
offgas is stripped of all entrapped dust and other impurities and then converted to sulfuric acid in an acid plant.4
Cadmium is recovered from zinc and zinc lead concentrates as precipitates from solution (hydrometallurgical
process) or as cadmium-lead fume (pyrometallurgical process), respectively, as shown in Exhibit 2. Cadmium may
also be recovered as a byproduct of beneficiating and refining lead ores or complex copper-zinc ores.
2. Generalized Process Flow
Cadmium from Zinc
Hvdrometallurgical Process
The hydrometallurgical process is used to recover cadmium as a precipitate. In this process, cadmium,
copper, and zinc are dissolved in the sulfuric acid leach of the roasted zinc ore. Copper and cadmium are among the
most common interfering impurities that are removed before the purified solution is subjected to electrolysis for zinc
recovery. Most of the cadmium is precipitated using a zinc dust addition. The purified zinc sulfate solution is sent
to the cellroom, and metallic zinc is recovered from the solution by electrowinning. The cadmium precipitate is sent
to the cadmium plant where it is filtered and pressed into a cake containing cadmium, zinc, and minor amounts of
copper and lead. Impurities are separated and a sufficiently pure cadmium sponge is dissolved in sulfuric acid.
Metallic cadmium is recovered by electrolysis of this solution where cadmium is deposited on cathodes. After
deposition, the cathodes are removed from the cells and stripped and the cadmium metal is melted and cast into
shapes. Exhibit 3 presents a process flow diagram of the production of cadmium from zinc.5
Pvrometallurgical Process
During the pyrometallurgical extraction of zinc, calcine from a roaster can be sintered with coke in a
sintering machine to give a dense desulfurized product. The sintering operation results in considerable volatilization
of cadmium and lead compounds, enhanced by the presence of chloride, leading to a 90-99% recovery of cadmium.
The fume and dust from the sintering machine are collected in a baghouse. Cadmium not removed during sintering
and subsequent operations follows the zinc metal and often is recovered during zinc metal purification by
distillation.6
The cadmium content in the feed to lead and copper smelters is lower than that generally encountered in
zinc plants, and this necessitates upgrading the initial cadmium level in the fume by one or more refuming steps in a
kiln or reverberatory furnace. The final fume may contain as much as 45% cadmium. Fumes usually require more
processing and purification steps for cadmium recovery than do purification residues from electrolytic zinc plants.
Galvanic precipitation is the most frequently adopted method for the final recovery of cadmium in pyrometallurgical
plants, but electrolysis may also be used.7
Exhibit 4 presents a process flow diagram of cadmium recovery from cadmium bearing fumes. Depending
on composition, the fume may have to be roasted with or without sulfuric acid or oxidized using sodium chlorate or
chlorine in order to convert cadmium into a water- or acid-soluble form and to eliminate volatile constituents.
4 U.S. Environmental Protection Agency, "Cadmium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. 3-64 - 3-71.
5 Ibid.
6 "Cadmium and Cadmium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. IV, 1993,
pp. 749-754.
7 Ibid.
174
-------
EXHIBIT 2
PRELIMINARY CADMIUM ROASTING PROCESSES
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1992, pp. 749 - 754.)
Zn Concentrates
Zn - Pb Concentrates
I
Cd
Pb Fumes
175
-------
EXHIBIT 3
HYDROMETALLURGICAL PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-64 - 3-71.)
High Cadmium Precipitate
o
>*
Spent Cadmium Electrt
Spent Zinc
Electrolyte
^
^
Wi-h Wnfrr ^-
i
Leaching Process
45 - 82 °C
1
Copper Removal
I
Filtration
1
Precipitation
+
Filtration
I
Cadmium Sponge
(80% Cd, <5% Zn)
1
Leaching Process
45 - 82 °C
1
Filtration
^- Filtrate
r Precipitation
1
7inr Dust ,-, •
1'llUdUuil
1
(to zinc plant)
1
Cadmium Sulfate Solution
(200 g Cd/L)
1 '
Electrolysis
_ 1
T
Melting Pot
1
Cast Shape
176
-------
EXHIBIT 4
PYROMETALLURGICAL PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-64 - 3-71.)
Concentrated ^
Sulfuric Acid ^
Iron Sulfate
Permanganate
Calcium Hydroxide ^
Sodium Carbonate
T
Roaster
450 - 600 °C
T
Crusher
T
I k T
T
1
1
._
Purification
1
T
*
n, -f
1
Filter
Fumes
^ Sciubbei ^- Wastewater
.^
j
f
Alternative # 1: Galvanic Precipitation
With Zinc
^ _
b^
9" v\ able Pmificdlioii Solution
^^ T _ _ , .
Purified Leach Solution
i
Alternative #2: Galvanic Precipitation with Zinc
Alternative #3: Electrolysis
177
-------
However the leach solution is obtained, it must generally be purified to remove arsenic, iron, copper, thallium, and
lead. The cadmium may also be galvanically precipitated from the leach solution and then redissolved (see Exhibit
5).8
Alternative 2 in Exhibit 5 indicates the most common method for the recovery of cadmium from purified
leach solution by galvanic displacement with zinc in the form of dust, sheets, or even rods or rectangular anodes.
The final processing depends on the grade of zinc. In most cases, the pH for galvanic precipitation is below 2,
although one plant operates at pH 6.2. In most plants, the final cadmium sponge is washed to remove soluble
impurities, and then compacted by briquetting. The briquettes may be melted under a flux of sodium hydroxide or
ammonium chloride or be distilled for final purification.9
Electrolysis is the third alternative for cadmium recovery. Exhibit 6 presents a process flow diagram of this
operation. The electrolysis may be operated on a semi-continuous basis with the cadmium eventually being stripped
completely from the electrolyte, which is then discarded after suitable treatment. Instead of the usual silver-lead
anodes, high silicon-iron anodes, such as Duriron, are commonly used.10
Cadmium from Lead
Cadmium may also be obtained from flue dust collected at lead or copper smelters. Concentrates of copper,
and especially lead, contain considerable amounts of cadmium. In copper smelters, the flue dusts are collected and
recycled through the smelter system to upgrade the cadmium content. At the lead smelters the cadmium is fumed off
and collected in the blast furnace baghouses. The baghouse dust is recycled to upgrade the cadmium content and is
later used as feed material for the cadmium refinery plant."
The cadmium upgraded dusts are charged into a tank and dissolved with sulfuric acid. The resultant
solution is filtered to remove impurities and to obtain a purified cadmium sulfate solution. Next, metallic cadmium,
called sponge because of its appearance, is precipitated from the solution using zinc dust. The sponge is usually
briquetted, remelted, and cast into ingots.
Some plants produce cadmium oxide and/or metallic cadmium powder. Cadmium oxide is produced by
melting the ingots and keeping a controlled oxidizing atmosphere in the retort. To produce metal powder, the melted
ingots in the retort are kept under an inert atmosphere while cadmium is distilled into a condenser as metallic
powder.12
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Beneficiation/Processing Boundaries
Since cadmium is recovered as a by-product of other metals, all of the wastes generated during cadmium
recovery are mineral processing wastes. For a description of where the beneficiation/processing boundary occurs for
this mineral commodity, see the reports for zinc and lead presented elsewhere in this document.
8 Ibid.
9 Ibid.
10 Ibid.
11 Thomas Llewellyn, 1992, Op. Cit.. pp. 271-276.
12 Ibid.
178
-------
EXHIBIT 5
ALTERNATIVES 1 AND 2
GALVANIC PRECIPITATION WITH ZINC
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-64 - 3-71.)
Purified Leach Solution
Wash Solution
(usually NaOH)
Galvanic Precipitation
pH = 2, 70 "C
I
Cadmium Sponge
Zinc
Precipitate
Waste Wash Solution
Cadmium Briquettes
179
-------
EXHIBIT 6
ALTERNATIVES
ELECTROLYSIS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-64 - 3-71.)
Purified Leach Solution
Electrolysis
High Silicon-Iron Anodes
Aluminum Cathodes
Spent Solution
Cast Shapes
180
-------
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Waste tailings.
2. Mineral Processing Wastes
Since cadmium is toxic to humans and certain other living organisms, care must be taken during the
production, use, and disposal of cadmium and its compounds to avoid the dispersal of cadmium fumes and dusts or
the release of cadmium-beariog effluents into the environment so that exposure is minimized.13 Listed below are
possible waste streams from cadmium production. Generally, all wastes are recycled or treated with other refinery
wastes.
Hydrometallurgical Process
Copper removal filter cake. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristic of
toxicity for cadmium. This waste may be recycled and is classified as a byproduct.
Post-leach filter cake. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristic of
toxicity for cadmium. This waste may be recycled to extraction/beneficiation units and is classified as a byproduct.
Spent electrolyte may contain thallic sulfate. Information regarding thallium removal from the spent
electrolyte remains unclear. However, according to the U.S. Bureau of Mines, there was no domestic production of
thallium metal in 1993; suggesting that thallium is not recovered domestically from cadmium production operations.
However, sludges from cadmium processing which are used for recovery of metals such as germanium may contain
thallium. Since there is no domestic production of germanium, the thallium contained in these sludges may be
recovered in other countries. '4 Although no published information regarding waste generation rate or characteristics
was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high
annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr, respectively. We
used best engineering judgement to determine that this waste may exhibit the characteristics of toxicity for cadmium
and corrosivity,
Pyrometallurgical Process
Copper sulfide and lead sulfate filter cakes. Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and
19,000 metric tons/yr, respectively. We used best engineering judgement to determine that this waste may exhibit
the characteristic of toxicity for cadmium and lead. This waste may be recycled and is classified as a byproduct.
Iron containing impurities. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
13 Patricia A. Plunkert, "Cadmium," from Mineral Facts and Problems, U.S. Bureau of Mines, 1985, pp. 111-119.
14 Personal communication between Peter Kuck, U.S. Bureau of Mines and ICF Incorporated, October 12, 1994.
181
-------
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristic of
toxicity for cadmium.
Lead sulfate waste (solid). Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium.
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr.
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristic of
toxicity for cadmium and lead. This waste may be recycled and is classified as a byproduct.
Spent leach solution. Although no published information regarding waste generation rate or characteristics
was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high
annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr, respectively. We
used best engineering judgement to determine that this waste may exhibit the characteristics of toxicity for arsenic,
cadmium, and lead and corrosivity. This waste may be recycled and is classified as a spent material,
Spent purification solution. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium.
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristics of
toxicity for cadmium and corrosivity.
Scrubber wastewater. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristics of
toxicity for cadmium and corrosivity. This waste may be recycled and is classified as a spent material.
Galvanic Precipitation
Caustic washwater solution. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr,
respectively. We used best engineering judgement to determine that this waste may exhibit the characteristics of
toxicity for cadmium and corrosivity. This waste may be recycled and is classified as a spent material.
Zinc precipitate. Although no published information regarding waste generation rate or characteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 190 metric tons/yr, 1,900 metric tons/yr, and 19,000 metric tons/yr, respectively. We used
best engineering judgement to determine that this waste may exhibit the characteristic of toxicity for cadmium. This
waste may be recycled and is classified as a byproduct.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
182
-------
BIBLIOGRAPHY
"Cadmium and Cadmium Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. 1992. Vol.
IV. pp. 749-754.
Kuck, Peter. "Cadmium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 36-37.
Llewellyn, Thomas. "Cadmium." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau
of Mines. 1992. pp. 271-276.
Personal communication between Peter Kuck, U.S. Bureau of Mines and ICF Incorporated, October 12, 1994.
Plunkert, Patricia. "Cadmium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 111-119.
U.S. Environmental Protection Agency. "Cadmium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-64 - 3-71.
183
-------
Page Intentionally Blank
784
-------
CALCIUM METAL
A. Commodity Summary
Pure calcium is a bright silvery-white metal. Under normal atmospheric conditions, however, freshly
exposed surfaces of calcium rapidly become covered with an oxide layer. The metal is extremely soft and ductile,
having a hardness between that of sodium and aluminum,1 Calcium is very reactive and reacts vigorously with water.
liberating hydrogen and forming calcium hydroxide, Ca(OH)2. Calcium does not readily oxidize in dry air at room
temperature, but is quickly oxidized in moist or dry oxygen at about 300° C.2
Calcium is an excellent reducing agent, and at elevated temperatures it reacts with oxides or halides of
almost all metallic elements to form the corresponding metal. Calcium is used in lead refining (for removal of
bismuth), steel refining (as a desulfurizer and deoxidizer), and as an alloying agent for aluminum, silicon, and lead.
Calcium is also used in the recovery of refractory metals (e.g., chromium, rare earth metals, and thorium) from their
oxides and in the reduction of uranium dioxide.3
Pfizer Chem (Quigley Company), located in Canaan, Connecticut is the only domestic producer of calcium
metal. Pfizer Chem uses the retort process. Calcium alloys, however, are produced by several companies, including
Elkem in Pittsburgh, Pennsylvania.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Calcium metal is produced by the aluminothermic method involving the high temperature vacuum reduction
of calcium oxide. The raw materials for this process are limestone and aluminum. In this process, aluminum metal
acts as the reducing agent. Exhibits 1 and 2 present flow diagrams for the typical process for producing calcium
metal.
2. Generalized Process Flow Diagram
Aluminothermic Process
As shown in Exhibit 1, high calcium limestone, CaCO3, is quarried and calcined to form calcium oxide. As
shown in Exhibit 2, the calcium oxide is then ground to a small particle size and dry blended with the desired amount
of finely divided aluminum. This mixture is then compacted into briquettes to ensure good contacts for reactants.
The briquettes are then placed in horizontal tubes, i.e., retorts, made of heat resistant steel and heated to 1100-
1200°C. The open ends of the retort protrude from the furnace and are cooled by water jackets to condense the
calcium vapor. The retorts are then sealed and evacuated to a pressure less than 13 Pa. After the reaction has been
allowed to proceed for approximately 24 hours, the vacuum is broken with argon and tJhe condensed blocks of about
99% pure calcium metal, known as crowns, and calcium aluminate residue are removed.4
1 "Calcium," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. IV, 1992, p. 777.
2 Ibid., p. 778.
I Ibid., p. 777.
4 Ibid., pp. 779-780.
185
-------
EXHTOITl
LIME AND LIMESTONE PRODUCTION
(Adapted from: Industrial Minerals and Rocks, 1994, p. 592.)
High Calcium and Dolomite Limestone
Quarry Stone
Quarry and Mine Operations
(Drilling, Blasting, and Conveying of Broken Limestone
6 - 8 in. Limestone for
Vertical Kilns
0.25 - 2.5 in. Limestone for
Rotary Kikus
r
Screening
1
r
Pebble and Lump
Quicklime
Crushing and Pulverizing
High Calcium
and
Dolomitic
Quicklime
Maximum Size 0.25 - 0.5 in.
Ground and Pulverized
Quicklime
Water
High Calcium and Dolomitic
Normal Hydrated Lime
Fuel
186
-------
EXHIBIT 2
ALUMINUM REDUCTION PROPCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. IV, 1992, pp. 777 - 782)
Limestone
Aluminum
Powder
Calcium
Residue
187
-------
Redistillation
In applications involving the reduction of other metal compounds, a purity greater than 99% calcium is
required. The necessary higher purities can be achieved through redistillation. For one method of redistillation.
crude calcium is placed at the bottom of a large vertical retort made of heat-resistant steel equipped with a water
cooler condenser at the top. The retort is sealed and evacuated to a pressure of less than 6.6 Pa while the bottom is
heated to 900-925°C. Under these conditions calcium quickly distills to the condensing section leaving behind the
bulk of the less volatile impurities. Any processing that takes place after this point must be in the absence of
moisture to avoid oxidation.5 Redistillation does not reduce those impurities that result from volatile materials, such
as magnesium. Volatile alkali metals can be separated from calcium by passing the vapors over refractory oxides
such as TiO2, ZrO2, CrO3 to form nonvolatile Na2O and K,O.6
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between briquet pressing of calcium oxide and retorting. EPA identified this point in the process sequence as where
beneficiation ends and mineral processing begins because it is here where calcium oxide undergoes a chemical
change to produce calcium metal. Therefore, because EPA has determined that all operations following the initial
"processing" step in the production sequence are also considered processing operations, irrespective of whether they
involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after
the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes.
EPA presents the mineral processing waste streams generated after the beneficiation/processing line in section C.2,
5 Ibid., pp. 780-781.
6 Ibid.
188
-------
along with associated information on waste generation rates, characteristics, and management practices for each of
these waste streams.
C, Process Waste Streams
1. Extraction/Beneficiation Wastes
Overburden. No waste characterization data or generation rates are available for overburden resulting
from the mining operations. However, the overburden is likely left at the mining site.
Off-gases. The gases that result from the calciner operation are generally vented to the atmosphere, and
consist primarily of CO2 and water vapor.
2. Mineral Processing Wastes
The aluminothermic process employed at the Pfizer plant in Connecticut generates two main sources of
mineral processing wastes. It is not clear whether the land surface is on or off site. The description of the wastes
does not specify'whether the terms reactive and non-combustible refer to RCRA definitions.
Calcium Aluminate Wastes. The calcium aluminate is a non-reactive waste and is generally disposed of in
a land surface storage area. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Dust with Quicklime. While dust collected from the system is recycled, some fugitive dust is accumulated
due to contamination concerns. The dust is reactive, non-combustible, and disposed of on the land surface. This
waste stream has a reported waste generation rate of 40 mt/yr. We used best engineering judgment to determine that
this waste stream may exhibit the characteristic of corrosivity. This waste stream is fully recycled and is classified as
a sludge.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
189
-------
BIBLIOGRAPHY
"Calcium." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992. pp. 777-782.
190
-------
CESIUM/RUBIDIUM
A.
Commodity Summary
The properties of cesium and its compounds are similar to those of rubidium and its compounds. As a
result, cesium and rubidium compounds are often used interchangeably. Although neither cesium nor rubidium is
recovered domestically from mined ores, according to the U.S. Bureau of Mines each is manufactured by primarily
one company domestically (Cabot Corp. - Revere, PA). Cesium products are manufactured from imported pollucite
ore and used commercially in electronics, photoelectric, and medical applications. Rubidium products are
manufactured from imported lepidolite ore and also used commercially in the electronic and medical industries.
Both cesium and rubidium were used in the form of chemical compounds in research and development endeavors.'
Exhibit 1 presents the names and locations of the facilities once involved in the production of cesium/rubidium.
EXHIBIT 1
SUMMARY Or CESIUM/RUBIDIUM FACILITIES
Facility Name
Cabot Corp
Callery Chem
Carus Corp
Corning Glass
Location
Revere, PA
Pittsburgh. PA
La Salle, IL
Corning, NY
Type of Operations
Recovery of both cesium and rubidium
Uncertain
Acid Digestion
Uncertain
B. Generalized Process Description
1. Discussion of Typical Production Processes
Cesium. The production of cesium metal from pollucite can be achieved through three basic methods:
direct reduction with metals, decomposition with bases, and acid digestion. Acid digestion is the primary
commercial process for cesium production and is described in further detail below.2 Exhibit 2 presents the
generalized process flow diagram for the production of cesium,
Rubidium, Rubidium is found widely dispersed in potassium minerals and salt brines, Lepidolite, a lithium
mica, is the principal source of rubidium. Because pollucite ore also contains some rubidium dioxide (RbO2), some
rubidium is processed as a by-product of cesium manufacture from this ore. The traditional methods for recovering
rubidium involve extraction of mixed alkali alums from the ore and are described in further detail below.3 Exhibits 3
through 6 present generalized process flow diagrams for the production of rubidium.
1 Robert G. Reese, Jr., "Cesium" and "Rubidium," from Mineral Commodity Summaries. 1995, pp. 40-41
and pp. 138-139.
2 "Cesium," Kirk-Qthmer Encyclopedia of Chemical Technology. 4th ed., Vol V, 1993, p. 753.
3 "Rubidium," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol XX, 1982,
p. 493.
191
-------
2. Generalized Process Flow Diagram
Cesium
As shown in Exhibit 2, the recovery of cesium from pollucite requires that the raw ore be crushed and
ground, and mixed with water to form a slurry.4 Some sources indicate that no further concentration is necessary at
this point and the pollucite can be digested with an acid.5 Other sources indicate that following the production of the
pollucite slurry, froth flotation can be used to yield a pollucite concentrate that is acidified through the addition of
sulfuric acid. Waste gangue is discarded and the acidified concentrate is treated with hydrofluoric acid, aluminum
sulfate, and a cationic reagent (e.g., cocoamine acetate) for conditioning. This conditioned pulp is then sent through
froth flotation for a second time and the resultant product is a relatively pure pollucite which is prepared for acid
digestion. Any non-pollucite minerals are separated through the froth filtration and discarded.6
Either hydrochloric, hydrobromic, hydrofluoric, or sulfuric acid can be used for the acid digestion step to
produce the cesium salt that can be evaporated to yield a dried cesium salt.7 Other sources suggest that hydrobionic
acid could be used as well.8
Rubidium
As shown in Exhibit 3, the recovery of rubidium from either pollucite or lepidolite ore requires that the ore
be leached for a prolonged period of time in sulfuric acid to form alkali alums. The alum solution is filtered from the
residue, which is washed with water. Calcination of the ore prior to leaching increases the yield. The other alkali
metals are separated from the rubidium solution by fractional recrystallization. The purified rubidium alum is
converted to rubidium hydroxide, by neutralization to precipitate the aluminum. The addition of barium hydroxide
precipitates the sulfate.
As shown in Exhibit 4, the chlorostannate method requires a partial separation of rubidium from the
potassium-bearing ore. The dissolved carbonates are converted to chlorides, and the solution is treated with enough
stannic chloride to precipitate cesium chlorostannate, which is less soluble than its rubidium counterpart. The
cesium-free chloride solution is treated with an excess of stannic chloride to precipitate rubidium chlorostannate
which may be decomposed to separate the rubidium and tin chlorides by pyrolytic, electrolytic, or chemical methods.
As shown in Exhibit 5, solvent extraction and ion exchange can also be used to separate rubidium from other alkali-
metal compounds.9
4 U.S. Environmental Protection Agency, "Cesium," from 1988 Final Draft Summary Report on Mineral Industry
Processing Wastes. Office of Solid Waste, 1988, p. 3-72.
5 "Cesium," 1993, Op. Cit.. p. 753.
6 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-72.
7 "Cesium," 1993, Op. Cit. p. 753.
8 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-73.
Q
"Rubidium," 1982, Op. Cit.. p. 493.
192
-------
EXHIBIT 2
CESIUM RECOVERY FROM POLLUCITE ORE
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Pollucite Ore
I
Water ^~
Sulfuric Acid ^»
Aluminum sulfate ^
Cationic Reagent — ^>
Hydrochioric,
Hydrobionic, or ^^
Sulfuric Acid
Ball Mill
Grinding
1 Slurry
Rotation
I Pulp
Mixing
J.
Froth
Rotation
^ Waste Solids
^ Non-Pollucite
Mineral Waste
Pollucite
^ Concentrate
Acid
Digestion
^^ Digestor
Waste
j CesiuiE Salt
v Solution
Evaporation
Dried Cesium Salt
193
-------
EXHIBIT 3
Rubidium Alums, Extraction
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes
1988, pp.3-179-3-186)
Rubidium
Bearing
Ores
Sulfutic_
Acid
Calciner
Calcined
Ore
i
Sulfuric
Leach
Residue
"Spent Ore
Alkali Alum
Solution
Neutralizing
Agent
Fractional
Recystalization
Rubidium
Alum
i
Neutralization
Unwanted Alkali Alums
Precipitated
Aluninum
Rubidium Hydroxide
in Solution
Barium
Hydroxide
Purification
Precipitated
Sulfate (BaSO4)
Pure Rubidium
Oxide
Source: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes. 1988, pp. 3-179-3-186.
194
-------
EXMB1T4
RUBIDIUM STANNIC CHLORIDE PREOP1TAHON
(Adapted from: 1988 Final Draft Summary Report of >fineral Industry Rwessmg Wastes, 1988, pp. 3-179 - 3-186.)
Potassium
Ores
Potassium
I Dissolved
Carbonates
t
Stannic
Chloride
Cesium
Precipitation
Cesium
Qilorostannate
I Cesium-free
I Chloride Solution
Stannic
Chloride
Spent Chloride
Solution
Rubidium Chlorostaimate (ppt)
I I
Purified
Rubidium Chloride
195
-------
EXHIBIT 5
RUBIDIUM FROM ALKALI METALS
(Adapted from: 1988 Final Draft Summary of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Rubidium Alkali Metal Compounds
Solvent Extraction
Spent Metals
Spent Solvent
Ion Exchange
Spent Solution
Rubidium
EXHIBIT 6
RUBIDIUM REDUCTION
(Adapted from: 1988 Final Draft Summary of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Active Metal
Pollucite or
Lepidolite -
Ores
Reduction
Spent Ore
Spent Metal
Pure Rubidium Metal
196
-------
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Cesium
In the process used by Cams Corp, the pollucite is digested with sulfuric acid to produce cesium alum that
is dissolved in an aqueous hydroxide solution to form cesium alum hydroxide and potassium sulfate. Cesium
permanganate can then be directly precipitated by the addition of potassium permanganate.10
Alternatively, if hydrochloric acid is used in the acid digestion, permanganic can be added to the resulting
cesium chloride after the removal of excess iron and alumina as hydroxides. The resultant cesium permanganate can
be converted to the carbonate or chloride by reduction with methanol.11
Rubidium
As shown in Exhibit 6, pure rubidium metal can be obtained by reducing either pollucite or lepidolite ores
with an active metal. Alternatively, pure rubidium compounds can be reduced thermochemically to yield pure
rubidium metal.12
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for the cesium recovery process within this specific mineral commodity sector, the
beneficiation/processing line occurs between froth flotation and acid digestion. EPA identified this point in the
process sequence as where beneficiation ends and mineral processing begins because it is here where the pollucite
ore undergoes a significant chemical change. For the stannic chloride precipitation process, EPA determined that the
beneficiation/processing line occurs between the production of rubidium chlorostannate and pyrolysis, electrolysis,
10 "Cesium," 1993, Op. Cit.. p. 753.
11 Ibid., p. 754.
12 "Rubidium," 1982, Op. Cit.. p. 493.
197
-------
or chemical addition. EPA identified this point in the process sequence as where beneficiation ends and mineral
processing begins because it is here where rubidium chlorostannate undergoes a significant chemical change to
produce rubidium chloride. EPA also determined that rubidium alum extraction and rubidium recovery from alkali
metals do not generate any mineral processing wastes. Also, all wastes generated during the rubidium reduction
process are mineral processing wastes. Therefore, because EPA has determined that all operations following the
initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents the mineral processing waste streams generated after the
beneficiation/proeessing line in section C.2, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
The wastes generated during the recovery of cesium and rubidium are listed below. Waste characterization
data, including information on generation rates and waste management are not available.
Cesium
Waste Gangue. Waste gangue is generated from froth flotation.
Non-Pollucite Mineral Waste
Rubidium
Alum Extraction
Calciner Residues
Spent Ore
Alkali Alums
Precipitated Aluminum
Precipitated Barium Sulfate
Stannic Chloride Precipitation
Cesium Chlorosonnate
Spent Chlorine Solution
Solvent Extraction
Spent Metal
Spent Solvent
Spent Ion-exchange solution
2, Mineral Processing Wastes
Existing data and engineering judgment suggest that the following materials do not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
198
-------
Acid Digestion
Digester waste
Stannic Chloride Precipitation
Pyrolytic Residue
Electrolytic Slimes
Chemical Residues
Reduction
Slag
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
199
-------
BIBLIOGRAPHY
"Cesium." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol V. 1993. pp. 749-754.
Reese, Robert G., Jr. "Cesium." From Mineral Commodity Summaries. 1995. pp. 40-41.
Reese, Robert G., Jr. "Rubidium." From Mineral Commodity Summaries. 1995. pp. 138-139.
"Rubidium." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol XX. 1982. pp. 492-494.
U.S. Environmental Protection Agency. "Cesium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-72-3-76.
U.S. Environmental Protection Agency. "Rubidium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-179-3-186.
200
-------
ATTACHMENT 1
201
-------
NJ
O
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT LIQUIDS - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0.008 0.008 0,008 1/1
0/0
0/0
0/0
0.03 0.03 0.03 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
. .
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
-
-
.
-
-
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT SOLIDS - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
20000 20000 20000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
20000 20000 20000 1/1
7500 7500 7500 1/1
0/0
2000 2000 2000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
110000 110000 110000 1/1
0/0
33 33 33 1/1
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
212 0
-
NJ
O
UJ
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
O
-ti
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT! AMMONIUM NITRATE PROCESSING SOLUTION - CERIUMU_ANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
0.046
0.229
0.0025
0.038
0.009
-
Q.OQ2S
0.009
0.054
0.005
0.053
0.001
0.005
0.005
0.0001
-
-
0.0025
0.005
-
-
0.001
0.005
0.025
69
-
-
-
1,126
-
0.1
107.13
0.38
10.11
0.01
0.07
0.01
-
0.03
0.06
4.93
0.04
0.05
0.02
56.08
0.02
0.00
-
-
0.01
0.04
-
-
0.02
0.09
0.34
595
-
-
-
11,108
-
7.07
109.17
0.97
20
0.025
0.11
0.009
-
0.095
0.24
9.8
0.085
0.053
0.03
221
0.045
0.0005
-
-
0.016
0.097
-
-
0.046
0.25
0.5
1,494
-
-
-
21,300
-
9.59
111.2
# Detects
3/3
2/2
4/5
5/5
1/1
0/0
4/5
3/5
2/2
2/3
1/1
4/4
6/6
3/4
2/3
0/0
0/0
1/3
3/5
0/0
0/0
3/4
0/3
0/3
3/3
0/0
0/0
0/0
3/3
0/0
9/9
2/2
EP Toxicity Analysis - PPM
Minimum Average Maximum
-
-
0.002 0.049
0.006 6.99
-
-
0.003 0.013
0.027 0.048
0.0005 0.065
.
-
0.005 0.014
-
-
0.0065 0.06
0,009 0.07
0.004 3.28
0.023 0.05
0.009 0.02
-
-
-
-
-
-
-
-
-
-
-
-
-
0.132
20
-
-
0.03
0.079
0.15
-
-
0.02
-
-
0.094
0.124
9.8
0.095
0.038
-
-
-
-
-
-
-
-
-
-
-
# Detects
0/0
0/0
3/3
3/3
0/0
0/0
3/3
a/3
2/3
0/0
0/0
2/3
0/0
0/0
2/3
3/3
3/3
3/3
3/3
0/0
0/0
0/0
0/0
o/o
0/0
0/0
0/0
0/0
0/0
0/0
TC ttValues
Level In Excess
.
-
5.0 0
100.0 0
.
1.0 0
5.0 0
-
-
.
5.0 0
-
-
0.2 0
-
.
1.0 0
5.0 0
-
.
.
.
.
.
.
-
.
-
-
212 1
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
3arium
3eryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Vlercury
Vtolybdenum
Nickel
Selenium
Sliver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH'
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
27,9
0.50
0.50
0.50
0.05
-
0.00050
0.00050
0.5
0.5
8.57
0,0005
154
3.68
0.00010
0.50
0.008
0.50
0.50
2.50
0.50
1.98
-
-
152
0.20
-
-
0.034
0.030
0.4
-
35.7
0,50
0.50
0.50
0.05
-
0.039
0.26
0.50
1.08
10.19
2.50
2,117
104
0.00010
0.50
1.25
0.50
0.50
2.50
0.50
8.09
-
-
786
15.10
-
-
1,675
4,740
0.7475
-
43.5
0,50
0.50
0.50
0.05
-
0.054
0.50
0.50
1.65
11.80
8.45
4,080
204
0.00010
0.50
4.00
0.50
0.50
2.50
0,50
14.20
-
-
1,420
30.0
-
-
6,490
9,480
1.1
-
Detects
2/2
0/2
0/2
0/2
0/2
0/0
1/4
1/4
0/2
1/2
2/2
3/4
2/2
2/2
0/2
0/2
2/4
0/2
0/2
0/2
0/2
2/2
0/0
0/0
2/2
2/2
0/0
0/0
4/4
2/2
4/4
0/0
EP Toxicity Analysis -
Minimum Average
23.2
0.50
0.50
0.50
0.05
-
0.05
0.50
0.50
0.50
7.55
0.63
1,020
2.52
0.0001
0.50
0.50
0.50
0.50
2.50
0.50
1.98
-
-
-
-
-
-
-
'
25.6
0.50
0.50
0.85
0.05
0.05
0.50
0.50
1.56
7.76
5.31
4,955
10.4
0.0001
0.50
0.50
0.50
0.50
2.50
0.50
7.24
PPM
Maximum #
28
0,50
0.50
1.20
0.05
0.05
0.50
0.50
2.62
7.97
10.0
8,890
18.3
0.0001
0.50
0,50
0.50
0.50
2.50
0.50
12.5
-
-
-
.
-
-
-
-
Detects
2/2
0/2
0/2
1/2
0/2
0/0
0/2
0/2
0/2
1/2
2/2
2/2
2/2
2/2
0/2
0/2
0/2
0/2
0/2
0/2
0/2
2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
-
5.0 1
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
,
.
.
.
.
-
-
212 . .4
-
NJ
O
U1
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
O
cn
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - SPENT ELECTROLYTIC CELL QUENCH WATER - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
2nc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Mawmum
-
0.005
0,006
-
0.001
-
0.001
0.001
-
0.01
-
0.14
-
-
0.0002
-
0.013
0.005
0.001
0.001
-
0.06
0.0003
-
-
-
-
-
-
-
-
-
-
0.0067
0.0177
-
0.0010
-
0.0073
0.0173
-
0.0230
-
0.2733
-
-
0.0008
-
0.0380
0.0110
0.0010
0.0057
-
0.1167
0.0075
-
-
-
-
-
-
-
-
-
-
0.01
0.025
-
0.001
-
0.02
0.033
-
0.033.
-
0.4
-
-
0.002
-
0.051
0.023
0.001
0.015
-
0.19
0.022
-
-
-
-
-
-
-
-
-
# Detects
0/0
373
3/3
0/0
3/3
0/0
3/3
3/3
0/0
3/3
0/0
3/3
0/0
0/0
3/3
0/0
3/3
3/3
3/3
373
0/0
3/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum f Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
.
5.0 0
100.0 0
-
.
1.0 0
5.0 0
-
-
.
5.0 0
-
-
0.2 0
-
,
1.0 0
5.0 0
-
.
-
-
,
.
.
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
CHROMIUM, FERROCHROMIUM, AND FERROCHROMIUM-SILICON
A,
Commodity Summary
Chromite ore, the starting material for chromium metal, alloys, and other chromium products, is not mined
in the United States.1 The metallurgical and chemical industry consumed 93 percent of the imported ehromite ore
used domestically in 1994; the refractory industry consumed the remainder. The major end uses of chromium metal
and ferroalloys were stainless and heat-resisting steel (78 percent), full-alloy steel (8 percent), superalloys (2 percent)
and other miscellaneous uses (12 percent).2 Exhibit 1 summarizes the producers of chromium products in 1992.
Only a small amount of the ehromite is processed to produce ductile chromium; the rest is used in an intermediate
form.3
EXHIBIT 1
SUMMARY OF PRODUCERS OF CHROMIUM PRODUCTS (IN 1992)"
Facility Name
American Chrome & Chemicals Inc.
Elkem AS. Elkem Metals Co.
Elkem AS, Elkem Metals Co.
General Refractories Co.
Harbison-Walker Refractories'1
Macalloy Corp.
National Refractories and Mining Corp.
National Refractories and Mining Corp.
North American Refractories Co. Ltd.
Occidental Chemicals Corp.
Satra Concentrates Inc.
Location
Corpus Christi, TX
Marietta, OH
Alloy, WV
Lehi, UT
Hammond, IN
Charleston, SC
Moss Landing, CA
Columbiana, OH
Womelsdorf, PA
Castle Hayne, NC
Steubenville. OH
Industry
Chemical
Metallurgical
Metallurgical
Refractory
Refractory
Metallurgical
Refractory
Refractory
Refractory
Chemical
Metallurgical
* - Papp, John. "Chromium." Minerals Yearbook Volume 1. Metals and Minerals 1992. United States Bureau of Mines. 1992. p. 355.
b - a division of Dresser Industries Inc,
Ferroehromium, an alloy of iron and chromium, is used as an additive in steel making. There are three
major grades of ferrochromium: low carbon, high carbon, and charge grade. In the past, low carbon ferrochromium
was required by steel makers to keep the carbon content of steel low. However, improved ladle refining techniques
1 John Papp, "Chromium," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995, p. 43.
2 Ibid, p. 42.
3 "Chromium and Chromium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. VI,
1993, p. 230.
207
-------
such as argon oxygen deearburization, have allowed the steel industry to use high carbon ferrochromium, which is
less expensive.4
Ferrochromium-silicon is used in the metallurgical industry to produce stainless, alloy, and tool steels and
cast irons.5 Ferrochromium-silicon is a smelted product of chromite ore; silicon is added during the smelting
process. Although a high silicon ferrochromium is sometimes produced as an intermediate in the production of low
carbon ferrochromium, no ferrochromium-silicon is being produced in the United States, and it is unlikely to be
produced domestically again.6-' Ferrochromium-silicon typically contains 34 to 42 percent chromium, 38 to 45
percent silicon and 0.05 to 0.06 percent carbon.8
B. Generaliied Process Description
1. Discussion of Typical Production Processes
Chromite ore is prepared for processing using several methods, depending on the ore source and the end use
requirements. Course clean ore is hand sorted, while fine clean ore is gravity separated. Lumpy ore mixed with host
rock may require heavy-media separation. If the chromite mineral occurs in fine grains intermixed with host rock.
crushing, gravity separation and magnetic separation may be used.9 Chromite ore is typically beneficiated before it is
sold, hence many of these operations may not be conducted in the United States.10 Exhibit 2 is a conceptual diagram
of chromite ore processing. Either ferrochromium or sodium chromate is produced, and may be sold or further
processed to manufacture other chromium compounds, as well as chromium metal.
2, Generalized Process Flow Diagram
Ferrochromium
Ferrochromium is made by smelting chromite ore in an electric arc furnace with flux materials (quartz.
dolomite, limestone, and aluminosilicates) and a carbonaceous reductant (wood chips, coke, or charcoal.) Lumpy
ore may be fed directly to the furnace, while finer ore must be agglomerated before it is added to the furnace. In
efficiently operated smelters, furnace dust is collected and resmelted, and slag is crushed and processed to recover
chromium. The chromium content of the ferrochromium is determined by the chromite ore's chromium to iron
ratio." The production of low carbon ferrochromium requires top blowing with oxygen. Aluminum, or more
frequently, silicon is used as the reducing agent. Extremely low carbon ferrochromium is made by the simplex
process, in which high carbon ferrochromium and oxidized ferrochromium are heated under high vacuum. The
4 John Papp, "Chromium," Minerals Yearbook Volume 1. Metals and Minerals 1992, U.S. Bureau of Mines,
1992, p. 325.
5 John Papp, "Chromium," Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 141.
6 Personal Communication between ICF Incorporated and John Papp, U.S. Bureau of Mines, March 1994.
7 "Chromium and Chromium Alloys," 1993, Op, Cit.. p. 232.
8 Ibid, p. 234.
9 John Papp, 1992, Op. Cit.. p. 327.
10 John Papp, "Chromite," Industrial Minerals and Rocks. 6th Ed., Society for Mining, Metallurgy, and
Exploration, 1994, p. 210.
11 John Papp, 1992, Op. Cit.. p. 328,
208
-------
EXHIBIT 2
CONCEPTUAL DIAGRAM OF CHROMTTE ORE PROCESSING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1993, p. 275.)
Chromite
(Fe, Mg)O . (Or. Fe, A1),O3
"5
Ammonium Chrome Alum
NH4Cr(SO4),,12H,O
Electrolysis
!Air Roast with
Na,CO,+CaO
HiC
LowC
Ferrochromium
Sodium Chromate
Leach and treat with
H,SO4orCO,
Sodium Dichromate
j- O
i 1
Ammonium Dichromate
(NH4)2Cr2O7
I
Chromic Acid
Cr03
Electrolysis
Chromic Oxide
Cr2O,
I i
C. A], Si Reduction
Electrolytic Chromium
PyrometallurgicaJ
Cr Metal
Purification Processes
in I
Vacuum with
Carbon
Ductile Chromium
(small quantities)
Various processes
Other Cr
Compounds
209
-------
carbon and oxygen form carbon monoxide, leaving a pure fenroehromium with a carbon content of about 0.01 weight
percent.12
Sodium Chronrate and Bichromate
Sodium chromate and dichromate are produced at two facilities by a hydrometallurgical process during
which ground chrome ore and soda ash are mixed (lime and/or leached calcine are sometimes added as well), roasted
in an oxidizing atmosphere, and leached with weak chromate liquor or water, as shown in Exhibit 3.'3 The resulting
leach liquor is separated from the remaining leach residue. At the American Chrome and Chemicals facility, the
roasting/leaching sequence is repeated, that is, two complete chromium extraction cycles are performed prior to
removal of the residue. The leach residue is then treated, as discussed below. The treatment residue from this
operation is classified as a RCRA special waste; it is disposed on-site at both facilities.14 The leach solution contains
unrefined sodium chromate; this liquor is neutralized and then filtered (not shown) to remove metal precipitates
(primarily alumina hydrate).15 The alumina-free sodium chromate may be marketed, but the predominant practice is
to convert the chromate to the dichromate form. Occidental Chemicals Corp. uses a continuous process that involves
treatment with sulfuric acid, evaporation of sodium dichromate, and precipitation of sodium sulfate (see left output
stream from leaching and precipitation operation in Exhibit 3.) Sodium sulfate may be sold as a byproduct or
disposed. American Chrome and Chemicals uses carbon dioxide (CO2) to convert the chromate to dichromate (see
right output stream from leaching and precipitation operation in Exhibit 3.) This process confers the advantage of
not generating a sludge. The dichromate liquor may be sold as 69 percent sodium dichromate solution or returned to
the evaporators, crystallized, and sold as a solid."
Chromium Oxide
Sodium dichromate can be converted into both anhydrous chromic oxide and hydrated chromic oxide.17 To
produce anhydrous chromic oxide (not shown), sodium dichromate, sulfur and wheat flour are blended with water,
and die resultant slurry is heated in a kiln. The material recovered from the kiln is slurried with water, filtered,
washed, dried, ground to size, screened and packaged. To produce hydrated chromic oxide (not shown), sodium
dichromate solution and boric acid are blended and heated in a kiln. The reacted material is slurried with water and
washed. Most of the washwater from the process is treated with sulfuric acid to recover boric acid. A waste stream
containing boric acid and sodium sulfate leave the boric acid recovery unit. The product with some of the final
washwater is filtered, rewashed, dried, ground, screened and packaged.18
12 "Chromium and Chromium Alloys," 1993, Op. Cit, p. 232.
13 Ibid., p. 275.
14 American Chrome and Chemicals and Occidental Chemical, 1989. Company Responses to the "National
Survey of Solid Wastes from Mineral Processing Facilities", U.S. EPA, 1989.
15 Marks, et ai, editors, Encyclopedia of Chemical Technology, Wiley Interscience, New York, NY, 1978, pp.
93-94.
16 U.S. Environmental Protection Agency, Report tQ..Congress on Special Wastes from Mineral Processing.
Volume II, Office of Solid Waste, July 1990, p. 4-2.
17 Processing of either form of chromic oxide, as well as chromium metal are not primary mineral processing, and
are therefore outside the scope of this report. Brief descriptions of these processes have been included for
completeness.
18 Versar, Inc., Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. II, Prepared for U.S.
Environmental Protection Agency, Industrial Environmental Research Laboratory, August 1980, pp. 3-13-3-16.
210
-------
EXHIBIT 3
SODIUM CHROMATE AND SODIUM DICHROMATE PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia ofChemical Technology, 1993, p. 275.)
Lime (optional) I
c
hrom
iu m
O
re
Soda Ash
Sulfuric Acid Option
Ore Residue Management
Mixing and Roasting
Leaching and Precipitation
To Sodium Sulfate Recovery
Sulfuric Acid
I
A cidification
and
E vaporation
Sodium Bisulfate
n
| To Sodium Chromate Manufacture ,
Sodium Bicarbonate
A cidification
and
E vaporation
Liquid Sodium Dichromate
Carbon Dioxide
Molten Chromic Acid
Production
Flaker
C ry stallization
Electrolytic Cell
+ Membrane -
D ryer
NaOH
Crystallization
Chromic Acid Flakes
Sodium Dichromate
Chromic Acid Crystals
-------
Chromium Metal
Chromium metal can be made either pyrometallurgically or electrolytically. In the pyrometallurgical
method (not shown), chromium oxide (Cr,O3) reacts with aluminum powder in a refractory lined vessel after being
ignited with barium peroxide and magnesium powder. Chromium metal may also be made from the oxide by
reduction with silicon in an electric arc furnace. The chromium from this process is similar to that obtained by the
aluminothermic process, except the aluminum content is lower and the silicon content may approach 0.8 percent.
Chromium may also be made by reducing chromium oxide briquets with carbon at low pressure and temperatures of
1,275 to 1,400CC.19
Exhibit 4 shows the production of electrolytic chromium by the chrome alum process conducted at the
Elkem Metals Company's Marietta Plant. High carbon ferrochromium is ground and leached with a hot solution of
reduced anolyte, chrome alum mother liquor, and makeup sulfuric acid. Cold mother liquor is added, and the slurry
is filtered to remove the undissolved solids, which are mostly silica. The filtrate is conditioned at elevated
temperature for several hours to convert the chromium to the non-alum form. The filtrate is then cooled to 5 = C,
allowing a crude ammonium sulfate to crystallize. This iron salt is further treated to form technical ferrous
ammonium sulfate, which can be sold as fertilizer and other purposes. The filtrate is clarified and aged, allowing
ammonium chrome alum to precipitate. The slurry is filtered, and the chrome alum is dissolved in hot water. The
chrome alum solution is clarified and fed to the electrolysis cell. After the electrolysis is complete, the cathodes are
removed, washed, and the metal is removed by air hammers. The metal is crushed, washed, and dehydrogenated.20
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Research is being conducted to investigate the feasibility of using plasma smelting both worldwide, as a
more efficient way of processing ferrochromium, and in the United States, to utilize low quality chromium bearing
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value typically does not occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
19 "Chromium and Chromium Alloys," 1993, Op. Cit.. pp. 232-234.
20 Ibid., pp. 234-236.
21 I.E. Goodwill, "Developing Plasma Applications for Metal Production in the USA," Iron and Steelmaking. 17,
No. 5, 1990, p. 352.
212
-------
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s). the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in Section B.
Ferrochromium and Ferrochromium-Silicon
EPA determined that for ferrochromium and ferrochromium-silieon, mineral processing first occurs when
the chromite ore undergoes smelting in an electric arc furnace and the physical/chemical structure of the chromite ore
is significantly altered. Therefore, because EPA has determined that all operations following the initial "processing"
step in the production sequence are also considered processing operations, irrespective of whether they involve only
techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial
mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA
presents below the mineral processing waste streams generated after the benefieiation/processing line, along with
associated information on waste generation rates, characteristics, and management practices for each of these waste
streams.
Sodium Chromate/Dichromate
EPA determined that for sodium chromate/dichromate, mineral processing occurs at the "leaching"
sequence of the process because the ore is vigorously attacked (digested) with a concentrated acid to significantly
change the physical structure of the ore. Therefore, because EPA has determined that all operations following the
initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents below the mineral processing waste streams generated after the
benefieiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
Chromium Oxide
Since chromium oxide is produced from sodium dichromate, all of the wastes generated during chromium
oxide production are mineral processing wastes. For a description of where the benefieiation/processing boundary
occurs for this mineral commodity, please see the sodium chromate/dichromate section above.
Chromium Metal
Since chromium metal is produced from either ferrochromium or chromium oxide, all of the wastes
generated during chromium oxide production are mineral processing wastes. For a description of where the
benefieiation/processing boundary occurs for this mineral commodity, please see the ferrochromium and chromium
oxide sections above.
C. Process Waste Streams
1. Extraction and Beneficiation Wastes
Wastes from the extraction and beneficiation of chromite may include gangue, and tailings. No information
on waste characteristics, waste generation, or waste management was available in the sources listed in the
bibliography.
213
-------
EXHIBIT 4
ELECTROLYTIC CHROMIUM METAL PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1993, p. 235.)
214
-------
2. Mineral Processing Wastes
The following waste streams have been associated with the production of sodium dichromate,
ferrochromium, and ferrochromium-silicon.
Ferrochromium
Dust or Sludge was a listed hazardous waste (K091) that has been remanded. EPA has decided not to "re-
list" this waste. Data from the Newly Identified Mineral Processing Waste Characterization Data Set indicate the
presence of chromium and selenium above toxicity characteristic levels for the remanded electrostatic precipitator
(ESP) dust. This waste is thus considered to be a characteristic hazardous waste under RCRA Subtitle C, At the
present time, there is only one generator of this characteristic D007 waste.22 The generator treats the material by
adding ferrous sulfate to reduce the teachable level of chromium to below regulatory levels. The non-hazardous
ESP dust is either disposed of in an off-site sanitary landfill or is used as a binding agent in Macalloy's briquetting
process. This facility reported producing approximately 3,000 metric tons of ESP dust annually. B
This facility also produces gas conditioning tower sludge (or GCT sludge) that it recycles back to the
electric arc furnace. The commenter stated that this sludge usually does not exhibit the toxicity characteristic for
chromium. Although no information was available on the generation rate of this waste, EPA estimated a low,
medium, and high annual waste generation rate of 30, 300, and 3,000 metric tons/yr, respectively. The GCT sludge
is fully recycled. This material formerly was classified as a sludge.
Slag and Residues. According to the Newly Identified Mineral Processing Waste Characterization Data
Set, approximately 47,000 metric tons of slag and residue are produced annually in the United States, and the
available data do not indicate that the waste is hazardous.24
Sodium Dichromate Production
Treated roast/leach residue is classified as a RCRA special waste. We note, however, that prior to
treatment, the roast/leach residue is not a RCRA special waste. Treatment of the leach residue consists of treating
the residue slurry with either a ferrous or sulfide ion to reduce hexavalent chromium followed by treatment with
sulfuric acid to lower the pH level. American Chrome and Chemicals pumps the leach residue directly to a dedicated
treatment unit, in which sulfuric acid and sodium sulfide are used to induce the desired chemical changes in the
residue, while at Occidental Chemicals Corp., the untreated residue is pumped to a wastewater treatment plant which
receives, and apparently combines, several other influent streams prior to treatment with several different chemical
agents. At both plants, the treated residue is pumped in slurry form to disposal surface impoundments.25
The treated residue from roasting/leaching of chrome ore, is a solid material, though it typically is generated
as a slurry containing particles between 2 mm and about 0.08 meters (3 inches) in diameter. The treated roast/leach
22 The Ferroalloys Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
23 Nexsen, Pruet, Jacobs & Pollard, LLP (Counsel to Macalloy Corporation). Comment submitted in response to
the Second Supplemental PropQsed.Rule Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral
Processing Wastes. May 12, 1997.
24 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Vol. I, Office of Solid Waste, August 1992, p. 1-3.
25 U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 4-2.
215
-------
residue is composed primarily of metallic oxides, such as those of iron, aluminum, silicon, magnesium, and
chromium, as well as sulfates.26 Using the available data on the composition of treated roast/leach residue, EPA
evaluated whether die residue exhibited any of the four characteristics of hazardous waste: corrosivity, reactivity.
ignitability, and extraction procedure (EP) toxicity. The limited available data indicated that the waste did not
exhibit any of the four hazardous waste characteristics.
According to the Newly Identified Mineral Processing Waste Characterization Data Set, approximately
102,000 metric tons of treated leach residue are produced annually in the United States.27
Ferrochromium-silicon
Dust or Sludge was a listed hazardous waste that has been remanded.28 EPA has decided not to re-list this
waste. According to the Newly Identified Mineral Processing Waste Characterization Data Set, there is presently no
domestic production of ferrochromium-silicon. Additional data is provided in Attachment 1.
D. Non-uniquely Associated Wastes
There are no non-uniquely associated wastes in this specific sector. However, standard ancillary hazardous
wastes may be generated at on-site laboratories, and may include used chemicals and liquid samples. Other
hazardous wastes may include spent solvents, and acidic tank cleaning wastes. Non-hazardous wastes may include
tires from trucks and large machinery, sanitary sewage, and waste oil and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Two commenters provided new factual information that has been included in the sector report (COMM 3,
COMM 48). Macalloy Corporation also provided comments on the May 1997 Second Supplemental Proposed Rule.
These comments also have been captured in the sector report.
Sector-specific Issues
One commenter indicated that it was encouraged to learn that the effort to obtain a chromium listing as
K091 would be eliminated. However, the commented believes that EPA's Proposed Rule circumvents the
remanding by Federal Court by calling the waste a so-called "newly identified" mineral processing waste, subject to
the even more stringent UTS criteria. The commenter believes that EPA has ignored the wishes of the courts and has
yielded to groups that desire only tougher regulations, apparently just for the sake of more regulation.29 EPA does
not agree that it is yielding to any influences and reaffirms that any solid waste that possesses one or more of the
TCLP characteristics is indeed a hazardous waste that must be regulated under Subtitle C of RCRA.
26 Occidental Chemical Corp., Company Responses to the "National Survey of Solid Wastes from Mineral
Processing Facilities", U.S. EPA, 1989.
27 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Vol. I, Office of Solid Waste, August 1992, p. 1-3.
28 Ibid.
29 Macalloy Corporation. Comment submitted in response to the Second Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. May 12, 1997.
216
-------
BIBLIOGRAPHY
Brown. R.E., and G.F. Murphy. "Ferroalloys." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985,
pp. 265-275.
"Chromium and Chromium Alloys." From Kirjc-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol VI.
1993. pp. 228-263.
Goodwill, J.E. "Developing Plasma Applications for Metal Production in die USA." Iron and Steelmaking. 17. No.
5. 1990. pp. 350-354.
Katayama, H. "Smelting Reduction Process with a Thick Layer of Slag for Producing Ferroalloys and Iron."
Materials Transactions. JIM. 33. No. 6. June 1992. pp. 531-542.
Papp, John. "Chromite." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. p. 210.
Papp, John. "Chromium." From Mineral Commodity Summaries. U.S. Bureau of Mines. 1995, pp. 42-43.
Papp, John. "Chromium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 139-155.
Papp, John. "Chromium." From Minerals Yearbook Volume 1. Metals and Minerals 1992. U.S. Bureau of Mines.
1992. pp. 325-378.
Personal Communication between ICF Incorporated and John Papp, U.S. Bureau of Mines. March, 1994.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. "Sodium Dichromate Production." From Report to Congress on Special
Wastes from Mineral Processing. Volume 2. Office of Solid Waste. July 1990. pp. 4-1-4-12.
Vazarlis, H.G., and A. Lekatou. "Pelletising-Sintering, Prereduction, and Smelting of Greek Chromite Ores and
Concentrates." Ironmaking and Steelmaking. 20. No. 1. 1993. pp. 42-53.
Versar, Inc. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. II. Prepared for U.S.
Environmental Protection Agency, Industrial Environmental Research Laboratory. August 1980.
217
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ATTACHMENT 1
218
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - DUST OR SLUDGE - FERROCHROME - SILICON
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
vlinimum Average Maximum #
12,100
0.60
50.00
138
0.52
-
0.15
41.00
1.00
3.50
1,270
273
121,000
1,510
0.049
0.145
16.20
5.50
0.15
23.90
1.50
3,270
-
-
-
-
-
-
-
-
-
-
12,100
0.60
50.00
138
0.52
-
0.15
801
1.00
3.50
1,270
273
121,000
1,510
0.049
0.145
16.20
5.50
0.15
23.90
1.50
3,270
-
-
-
-
-
-
-
-
12,100
0.60
50.00
138
0.52
-
0.15
1,560
1.00
3.50
1,270
273
121,000
1,510
0.049
0.145
16.20
5.50
0.15
23.90
1.50
3,270
-
-
-
-
-
-
-
-
-
-
Detects
1/1
0/1
0/1
1/1
1/1
0/0
0/1
2/2
1/1
1/1
'1/1
1/1
1/1
1/1
0/1
0/1
1/1
1/1
0/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis -
Minimum Average
1.39
0.023
0,40
0.60
0.00050
-
0.0015
2.07
0.0015
0.0015
0.0020
0.0010
954
5.08
0.00010
0.0082
0.033
0.069
0.0015
0.029
0.011
1.63
-
-
-
-
-
-
-
-
1.39
0.023
0.40
0.60
0.00050
0.0015
12.69
0.0015
0.0015
0.0020
0.02
954
5.08
0.00010
0.0082
0.033
0.069
0.0015
0.029
0.011
1.63
PPM
Maximum #
1.39
0.023
0.40
0.60
0.00050
0.0015
27.00
0.0015
0.0015
0.0020
0.03
954
5.08
0.00010
0.0082
0.033
0.069
0.0015
0.029
0.011
1.63
-
-
-
-
-
-
-
-
Detects
1/1
1/1
0/1
1/1
0/1
0/0
0/1
3/3
0/1
0/1
0/1
2/2
1/1
1/1
0/1
1/1
1/1
1/1
0/1
0/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
' -
1.0 0
5.0 2
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
M
O
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - DUST OR SLUDGE - FERROCHROME
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
28,100
3.85
2.65
75.60
0.66
-
0.70
3,390
9.20
9.20
6,240
300
188,000
5,750
0.26
3.20
128
37.00
5.60
27.10
17.70
13,600
0.59
5.05
-
485
-
-
-
-
-
-
29,200
11.43
2.85
76.00
1.33
-
0.78
5,360
9.20
24.35
15,170
1,290
188,500
5,770
0.32
3.75
130
42.90
5.95
130
19.35
14,300
0.59
5.05
-
485
-
'
-
-
-
-
30,300
19.00
3.05
76.40
2.00
-
0.85
6,470
9.20
39.50
24,100
1,860
189,000
5,790
0.38
4.30
131
48.80
6.30
232
21.00
15,000
0.59
5.05
-
485
-
-
-
-
-
-
Detects
2/2
1/2
0/2
2/2
2/2
0/0
0/2
3/3
1/1
2/2
2/2
3/3
2/2
2/2
1/2
2/2
2/2
2/2
2/2
2/2
2/2
2/2
1/1
0/1
0/0
1/1
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis -
Minimum Average
0.017
0.039
0.006
0.083
0.00050
-
0.0015
0.010
0.00150
0.0020
0.0020
0.0050
409
0.013
0.00010
0.022
0.003
0.02
0.0020
0.066
0.0015
0.0010
-
-
-
-
-
-
-
-
0.068
0.047
0.014
0.575
0.00050
0.0027
17.99
0.00150
0.0020
0.0020
0.57
880
0.72
0.00053
0.037
0.006
22.79
0.0050
0.077
0.0025
0.0015
PPM
Maximum
0.12
0.055
0.040
1.60
0.00050
-
0.0050
63.20
0.00150
0.0020
0.0020
4.73
1,350
1.43
0.00100
0.052
0.009
68.20
0.010
0.088
0.0035
0.0020
-
-
-
-
-
-
-
-
# Detects
2/2
2/2
1/4
4/4
0/2
0/0
0/3
18/21
0/2
0/2
0/2
10/17
2/2
2/2
0/3
2/2
1/2
2/3
2/4
2/2
1/2
1/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
5.0 0
100.0 0
-
-
1.0 0
5.0 12
-
-
-
5.0 0
-
-
0.2 0
.
-
1.0 1
5.0 0
-
-
.
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
COAL GAS
A.
Commodity Summary
In 1992, more than 997,545,000 short tons of coal were produced by 2,746 mines located in the United
States.' Coal is classified into four general categories: bituminous, subbituminous, lignite, and anthracite coal.
Nearly all coal is used in combustion or coking. At least 80 percent is burned directly in boilers for generation of
electricity or steam. Small amounts are used for transportation, space heating, and firing of ceramic products. The
rest is essentially pyrolyzed to produce coke, coal gas, ammonia, coal tar, and light oil products from which many
chemicals are produced. Combustible gases and chemical intermediates are also produced by the gasification of
coal, and different carbon products are produced by various heat treatments. A small amount of coal is used in
miscellaneous applications such as fillers, pigments, foundry material, and water filtration.2
Coal gasification produces a synthetic gas that is either further processed and sold as synthetic natural gas
or used to fire a gas turbine, generating electricity in an integrated gasification combined cycle (IGCC) system. As
shown in Exhibit 1, there is only one commercial scale synthetic gas producer, and two commercial scale IGCC
plants.3 The Tennessee Eastman facility is used in the production of acetic anhydride. There are also several
demonstration scale projects funded, at least in part, by the U.S. Department of Energy's Clean Coal Technology
(CCT) program, including two coal preparation technologies, one mild gasification project, and one indirect
liquefaction project, as well as six IGCC systems.4 Exhibit 2 lists the Clean Coal Projects, their sponsors, locations.
types of technology, and status. In addition to the CCT demonstration projects, there may be other planned or
operating private demonstration scale projects. The profitability of existing facilities and the potential for the
opening of new plants will be affected by the prices of traditional fuel sources such as oil and gas.
EXHIBIT 1
SUMMARY OF COMMERCIAL COAL GASIFICATION FACILITIES
Facility Name
Great Plains Coal Gasification Plant, Dakota Gasification Co.a
Louisiana Gasification Technology, Inc.3
Tennessee Eastman6
Location
Beulah, ND
Placamine, LA
NA
Type of Process
Synthetic Gas
IGCC
IGCC
' - U.S. EPA, Report to Congress on Special Wastes from Mineral Processing, July 1990, p. 5-1.
3 - "Coal Conversion Processes (Gasification)," Kirk-Othmer Encyclopedia of Chemical Technology. Vol 6. 4th. ed. 1993. pp. 543.
1 U.S. Department of Energy, Coal Production 1992. Energy Information Administration, October 1993, p. 18.
2 "Coal," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol VI, 1993, p. 424.
3 A fourth subsidized commercial scale facility (Cool Water) operated from 1982 to 1988 in Daggett, California.
This facility shut down after the Department of Energy funding ended.
4 U.S. Department of Energy, Clean Coal Technology Demonstration Program: Program Update 1993."
December 31, 1993, pp. 7-2 - 7-3.
221
-------
EXHIBIT 2
SUMMARY OF CLEAN COAL TECHNOLOGY DEMONSTRATION PROJECTS2
Project Name
Self-Scrubbing Coal: An
Integrated Approach to Clean
Air
Advanced Coal Conversion
Process Demonstration
ENCOAL Mild Coal
Gasification Project -
Commercial Scale
Demonstration of the Liquid-
Phase Methanol (LPMEOH)
Process
Combustion Engineering
IGCC Repowering Project
Camden Clean Energy
Demonstration Project
Pinon Pine IGCC Power
Project
Toms Creek IGCC
Demonstration Project
Tampa Electric Integrated
Gasification Combined Cycle
Project
Wabash River Coal
Gasification Repowering
Project
Sponsor
Custom Coals
International
Rosebud SynCoal
Partnership
ENCOAL
Corporation
Air Products and
Chemicals, Inc.
ABB Combustion
Engineering, Inc.
Duke Energy Corp.
Sierra Pacific
Power Company
TAMCO Power
Partners
Tampa Electric
Company
Wabash River Coal
Gasification
Repowering Project
Joint Venture
Location
Central City,
PA
Colstrip, MT
Near Gillette,
WY
Kingsport, TN
Springfield, IL
Camden, NJ
Reno, NV
Coeburn, VA
Lakeland, FL
West Terre
Haute, IN
Technology
Coal
Preparation
Coal
Preparation
Mild
gasification
Indirect
Liquefaction
IGCC
IGCC
IGCC
IGCC
IGCC
IGCC
Project Stage
Design/
Permitting
Operating
Operating
Project Definition
Assessing Project
Options
Negotiating
Cooperative
Agreement
Design
Project Definition
Design/
Permitting
Construction
* - U.S. Department of Energy, "Clean Coal Technology Demonstration Program: Program Update 1993," December 31, 1993, pp. 6-22, 6-23, &
6-27.
B. Generaliied Process Description
1. Discussion of Typical Production Processes
Coal gasification is essentially incomplete combustion of coal, producing a product gas and heat instead of
carbon dioxide and heat. In combustion, oxygen in stoichiometric excess reacts with the combustible matter in coal,
mostly carbon and hydrogen, to produce heat, the primary product of interest, as well as carbon dioxide and water.
Gasification involves the incomplete combustion of coal in the presence of steam. Only 20-30 percent of the oxygen
theoretically required for complete combustion to carbon dioxide and water is used; therefore, only a fraction of the
carbon in the coal is oxidized completely to carbon dioxide, the rest forms a mixture of gases including carbon
222
-------
monoxide, methane, hydrogen and hydrogen sulfide. The heat released by the partial combustion provides the bulk
of the energy necessary to drive the gasification reactions.5'6 When synthetic gas is produced as a product, lignite
coal is sized, and gasified with steam and oxygen producing raw gas, ash, and gasifier liquor. The gas is cooled.
purified in several steps, and sold. This process is described in greater detail below.
2. Generalized Process Flow Diagram
There is currently one facility, the Great Plains Coal Gasification Plant, which produces synthetic natural
gas on a commercial scale. Exhibit 3 illustrates the production of synthetic natural gas at this facility. The facility
employs 12 Lurgi Mark IV high pressure coal gasifiers, with two gasifiers on standby for spare capacity. Exhibit 4 is
a schematic diagram of a Lurgi Mark IV Gasifier. Lignite coal, which is taken from four mines that are co-located
with the facility, is crushed and fed to the top of individual gasifiers through a lock-hopper system; steam and
compressed oxygen are introduced at the bottom of each gasifier.7 The steam and oxygen travel up through the
coal/ash bed. As steam and oxygen contact the coal in the gasifier, the resulting combustion reactions produce two
major gases, carbon dioxide and carbon monoxide. The further reaction of these gases with carbon and steam results
in "gasification," the formation of carbon oxides, methane, and hydrogen.8
After gasification occurs, excess carbon remains in the form of "char." The char is combusted in a high-
temperature exothermic (heat releasing) reaction to provide energy for a series of reactions, including drying,
devolatization, and gasification, most, but not all, of which are endothermic (heat using) reactions. The char is then
converted to energy in the "combustion zone," roughly the middle of the gasifier. The residue of this combustion is
the gasifier ash. The gases formed in these reactions rise to the top of the unit, where their heat dries and drives off
volatiles liberated from the coal that has just entered the gasifier.9 Because not all of the flue gas constituents are
converted in the gasification process, the exiting gas stream contains both flue gas and product gas. These two
gaseous streams are separated downstream of the gasifiers and the product gas is converted to salable methane.10
The ash remaining in the bed after the reaction is removed by a rotating grate at the bottom of the gasifier
and is discharged through a gas lock. The ash is discharged into an enclosed ash sluiceway, where recirculating ash
sluice water is introduced to cool the ash and transport it to the ash handling and disposal area. The hot crude
product gas leaving the gasifiers goes through several operations, including quenching (to cool and clean), shift
conversion (to alter the ratio of hydrogen to carbon monoxide), further cooling of the gas, and processing through the
Rectisol unit (to remove sulfur compounds and carbon dioxide). The desulfurized crude gas is sent to the
methanation unit; the product gas is then compressed and dried for delivery to a pipeline for distribution."
5 "Coal Conversion Processes (Gasification)," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol.
VI, 1993, p. 551.
6 "Steam," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXI, 1983, pp. 543-544.
7 CDM Federal Programs Corporation, Draft Report American Natural Gas Special Study. Prepared for U.S.
Environmental Protection Agency, Office of Waste Programs Enforcement, March 19, 1987, pp.. 14-27.
8 Dakota Gasification Company, "Letter to Mr. Robert Tonetti and Mr. Bob Hall, Office of Solid Waste, U.S.
EPA", August 12, 1991, p. 5.
9 Ibid.
10 Dakota Gasification Company, "Lurgi Gasification and Flue Gas Scrubbing Simplified," Memorandum to D.
W. Peightal from T. G. Towers, July 29, 1991.
11 CDM Federal Programs Corporation, 1987, Op. Cit.. pp. 14-27.
223
-------
EXHIBIT 3
PROCESS FLOW DIAGRAM OF SYNTHETIC GAS PRODUCTION
Nitrogen (Adapted from : RTI Survey 100065, 1989)
^^ Oxygen
Production 1
T
Air ^ Air Oxygen
Compression Compression
T ^ '
Minecoa^ Coal Cs" »• „ .f. .
^^- „ . a Gasification
•^ Preparation ^
* i L
oo Sour >
. . | v
1 ' L,
Coal Fines to « ' ^- A sh
Antelope Valley
Electrical Generating Plant Handling
(Basin Electr c Power Cooperative)
A sh to Disposal
^^^ Lock Gas
^^ Recovery
Raw Gas
Cruide G as
-^- Shift
Conversion
Vater y
I
Gas Liquor
Separation
Product Gas SNG to Pipeline
and Drying
A L N aphtha to
Flash Gas Steam Generatio
1 *
knitted Mixed
Gas_ Gas Gas Rcctiso and
Cooling Refrigeration
Acid G as
Anhydrous Ammonia
^^ ^^ Ammonia ^^
W^t^r , ,
Crude Phenols to Steam Generation
Oil to Steam Generation ^^
Tar to Steam Generation
^.
^^ Rccozvery Fuc| Gas [0 Stcam Generation ^
Sulfur
-------
EXHIBIT 4
SCHEMATIC DIAGRAM OF LURGI MARK IV GASIFTER
(Adapted from: Dakota Gasification Company, July 29,1991.)
Coal from
Bunker
Wash Cooler Recycle
(Gas Liquor)
Boseman
Skirt
Steam
Scraper
Wash Cooler
Exit Gas
Rotating Grate
Oxygen
Ash
225
-------
The quenching operation described above, in addition to cooling the raw gas, serves to remove entrained
particles from the gas and to condense and remove unreacted steam, organic compounds, and soluble gases. This
cooling operation generates an aqueous stream known as quench liquor (labelled "sourwater" in Exhibit 3). This
quench liquor, along with similar streams from the shift conversion, gas cooling, and rectisol units, are sent to the gas
liquor separation unit (for removal of tar and oil), to a phenosolvan unit (for phenol recovery), and to a phosam-W
ammonia recovery unit (for ammonia recovery). The process water leaving the phosam-W unit, known as stripped
gas liquor, is classified as a RCRA special waste.
This process wastewater is used as makeup water for a water cooling system that is needed to cool the
gasifiers during operation. The hot water is routed to a cooling tower used to remove heat from the system.
Evaporation from the cooling tower exceeds the quantity of stripped gas liquor generated on an annual basis; hence,
all stripped gas liquor is used as makeup water. The stripped gas liquor passes through the cooling tower (not
shown) where it is concentrated, reducing the volume by a factor often, and through the Multiple Effects Evaporator
(not shown) where it is concentrated again, further reducing the volume by a factor of ten. This concentrate then
goes to the Liquid Waste Incinerator (LWI) for incineration. The blowdown water from the LWI is used as makeup
water to the ash sluice system.12'13
3. Identification/Discussion of Novel (or otherwise distinct) Processes
In an IGCC unit, oxygen, pulverized coal, and sometimes steam are gasified, and the syngas is cooled,
cleaned and combusted to power a gas turbine, to generate electricity. Excess heat is also recovered to generate
electricity using a steam turbine. IGCC, coking, and pyrolysis are considered to be energy producing operations
rather than mineral processing, and are therefore outside the scope of this report.
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
12 North Dakota State Department of Health, Letter to Robert L. Duprey, Director, Waste Management Division,
EPA, June 10, 1986. p. 1.
13 COM Federal Programs Corporation, 1987, Op. Cit. pp. 41-42.
226
-------
EPA determined that for the production of coal gas, the beneficiation/processing line occurs between coal
preparation and coal gasification due to the chemical reaction that occurs between oxygen, steam, and coal within the
gasification unit that significantly changes the physical/chemical structure of coal. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams
generated after the beneficiation/processing line, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Ejctraetion and Beneficiation Wastes
Wastes from the extraction and beneficiation of coal may include gangue, fines, baghouse coal dust, and
coal pile runoff. Run-of-mine lignite from neighboring mines is crushed to less than 2 inches. Fines are removed by
screening and are sent to an adjacent power plant. Baghouses collect the dust from crushing, conveying, sizing, and
storage operations. Coal dust collected in the baghouses is returned to the process. Coal pile runoff is handled by
the plant's storm drainage system, which includes a coal pile runoff retention pond. This pond provides sufficient
retention time to permit coal particles, soil sediments, and dust suspended in the stormwater to settle out. The
clarified water from the pond is discharged to the stormwater pond through an overflow weir.14
2. Mineral Processing Wastes
Gasifier Ash is classified as a RCRA special waste. This ash is removed from the bottom of the gasifier,
quenched, passed through crushers to reduce the maximum size to eight centimeters, and sluiced into ash sumps for
settling and dewatering. The dewatered ash is trucked to an on-site clay-lined landfill, where it is disposed of along
with ash from boilers, superheaters, and incinerators, and settled solids from process water management units (e.g.,
impoundments, API separators.)15 The North Dakota Department of Health reported that the Beulah facility had
considerable problems with their dewatering system which resulted in the disposal of large quantities of very wet
ash.l6 According to the Newly Identified Mineral Processing Waste Characterization Data Set, approximately
301,000 metric tons of gasifier ash are produced annually in the United States."
Process Wastewater is classified as a RCRA special waste.18 According to the Newly Identified Mineral
Processing Waste Characterization Data Set, approximately 5,143,000 metric tons of process wastewater are
produced annually in the United States.19 The management of the process wastewater (i.e., stripped gas liquor) is
reuse; the water is used as make-up water for the water-cooling system that cools the gasifiers. Specifically, the
process wastewater is routed from the cooling tower to the multiple effect evaporators, to the liquid waste
incinerator, and finally to the gasifier ash handling system.
14 Ibid., pp. 63-64.
15 U.S. Environmental Protection Agency, Report to Congress on Special Wastes from Mineral Processing,
Volume II, Office of Solid Waste, July 1990, p. 5-3.
16 North Dakota State Department of Health, 1986, Op. Cit.. pp. 1-2.
17 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set,
Vol. I, Office of Solid Waste, August 1992, p. 1-3.
18 U.S. Environmental Protection Agency, 1990, Op.Cit.. p. 5-3.
19 U.S. Environmental Protection Agency, 1992, Op.Cit.. p. 1-3.
227
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Surface Impoundment Solids (Cooling Tower Pond Sludge), When the supply of process wastewater
generated on a daily basis exceeds the need for cooling system make-up water, the process wastewater is stored in an
impoundment until it is needed. No long-term accumulation of waste occurs in this unit; the water is pumped to the
cooling tower and any settled solids are dredged (approximately 13 metric tons in 1988) and sent to the solid waste
disposal landfill.20 Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further,
Zeolite Softening PWW, Available data do not indicate that the waste exhibits hazardous characteristics.21
Therefore, the Agency did not evaluate this material further,
Cooling Tower Blowdown. Evaporation of water inside the cooling water system increases the
concentration of any impurities in the make-up water remaining in the cooling system; these impurities can lead to
scaling or other operational problems in the system. Therefore, the cooling water in the system is bled off at a rate of
360-500 gpm to prevent concentrations of impurities from reaching unacceptable levels. This concentrated bleed,
known as cooling tower blowdown, was generated at a rate of approximately 766,000 metric tons in 1988. The
cooling tower blowdown is treated in a multiple effects evaporator (MEE) unit.22
According to the Newly Identified Mineral Processing Waste Characterization Data Set, approximately
646,000 metric tons of cooling tower blowdown are produced annually in the United States.23 Existing data and
engineering judgement suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
die Agency did not evaluate mis material further.
Multiple Effects Evaporator Concentrate. Cooling tower blowdown is treated in a multiple effects
evaporator (MEE) unit. Distillate from this treatment is returned to the cooling system or used as other facility utility
water. The remaining residual, MEE concentrate, is returned as feed to the gasifier or is sent to an on-site liquid
waste incinerator (LWI). Separate surge ponds are used for storage of MEE distillate and concentrate.24 MEE
concentrate has been found to exhibit the characteristic of EP toxicity for arsenic and selenium. The arsenic levels
range from 3-29 ppm and the selenium levels from 15-44 ppm.25 This waste stream is partially recycled and
classified as a by-product. Although no published information regarding the waste generation rate was found, we
used the mediodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate of 0 metric tons/yr, 0 metric tons/yr, and 65,000 metric tons/yr, respectively.
Multiple Effects Evaporator Pond Sludge. Approximately 100 cubic yards of MEE pond sludge are
generated annually in the United States.26 Existing data and engineering judgement suggest mat this material does
not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Liquid Waste Incinerator Blowdown. Spent cooling water from the LWI unit, referred to as LWI
blowdown, is sent to the coal ash sluice area to be included as make-up water for ash handling. Any incinerator
20 U.S. Environmental Protection Agency, 1990, Qp.Cit.. p. 5-3.
21 U.S. Environmental Protection Agency, 1992, Op. Cit, p. 1-3.
22 U.S. Environmental Protection Agency, 1990, Op.Cit.. p. 5-4.
23 U.S. Environmental Protection Agency, 1992, Qp...Cit, p. 1-3.
24 U.S. Environmental Protection Agency, 1990. Op. Cit.. p. 5-4.
25 North Dakota State Department of Health, 1986, Op. Cit. p. 1.
26 Versar, Inc. Draft Site Visit Report on Dakota Gasification Company. Prepared for U.S. Environmental
Protection Agency, Office of Solid Waste, August 4, 1989. p. 3.
228
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ash/solids in the blowdown are, therefore, combined with the gasifier ash and managed as such.27 LWI blowdown
was found to exhibit the characteristic of EP toxicity for arsenic and selenium. The arsenic levels range from 6-16
ppm and the selenium levels from 7-54 ppm.28 Although no published information regarding the waste generation
rate was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high
annual waste generation rate of 0 metric tons/yr, 0 metric tons/yr, and 45,000 metric tons/yr, respectively. LW!
blowdown is recycled in process, therefore, it is not included in the analysis.
Liquid Waste Incinerator Pond Sludge. Approximately 300 cubic yards of liquid waste incinerator pond
sludge are generated annually in the United States.29 Existing data and engineering judgement suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Spent Methanol Catalyst. The rnethanation unit uses a nickel catalyst to upgrade the synthetic gas to
methane. The spent catalyst is recycled.30 Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 0 metric tons/yr, 5,000 metric tons/yr, and 45,000 metric tons/yr,
respectively. This waste stream is not hazardous, therefore, it is not included in the analysis.
Stretford Solution Purge Stream. The Stretford process uses a dilute solution of sodium carbonate,
sodium bicarbonate, sodium metavanadate, and anthraquinone disulfonic acid (ADA) to remove hydrogen sulfide
from a number of gas streams and convert it to elemental sulfur. After hydrogen sulfide removal, the treated gas
stream is incinerated in the boilers for its fuel value. The Stretford solution purge stream contains vanadium salts,
thiosulfate, thiocyanate, and ADA. The purge stream is collected in a wastewater tank, concentrated in a crystallizer,
and subsequently disposed of as a liquid. This liquid crystallizes into a solid during cooling after it is transported to
a secure disposal site. The liquid removed during concentration is used as cooling tower makeup water.31 Although
no published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 5,000
metric tons/yr, 17,000 metric tons/yr, and 45,000 metric tons/yr, respectively. This waste stream is not hazardous,
therefore, it is not included in the analysis.
Flue Dust Residues. Existing data and engineering judgement suggest that this material does not exhibit
any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Oily Water Treatment System
Oily water from all paved process areas drain to the oily water sewer. In addition, contaminated stormwater
and other contaminated waters may be diverted to the oily water sewer, which drains into the oily water treatment
system. This treatment system is intended to process contaminated water streams from the plant by reducing the oil
content from between 10 and 100 ppm free oils to less then 5 ppm free oils. The system consists of American
Petroleum Institute (APT) separators, dissolved air flotation units, vacuum filtration of sludges and froths, and
pressure media filtration. Effluent from this system is discharged to the cooling tower.
27 As reported by Dakota Gasification Company, approximately 32,000 metric tons of LWI blowdown was
generated in 1988 with a solids content of 5 percent; these approximately 1,600 metric tons of solids are assumed to
be included in the total volume of gasifier ash reported by the company.
28 North Dakota State Department of Health, 1986, Op. Cit.. p. 1.
29 Versar, Inc., 1989, Op. Cit.. p. 3.
30 COM Federal Programs Corporation, 1987, Op. Cit.. p. 6.
31 Ibid., pp. 52-58.
229
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The oily water is pumped to two API separators in parallel. Oils are skimmed off and sent to the slop oil
decanting tanks, while sludge is scraped off the bottom and transferred to the froth sump. The slop oil is used as fuel
for the boilers. Effluent from the API separators is transferred to the dissolved air flotation units where air.
coagulant aid, and caustic or acid are added to assist in removing any remaining oils. Under some plant operating
conditions, this API separator effluent is routed to cooling tower surge ponds following treatment.
Oils from the top and sludges from the bottom of the DAF unit are transferred to the froth sump. DAF
effluent is passed through sand filters before it is used as cooling tower makeup water. The API/DAF sludge in the
froth sump is sent to the vacuum precoat drum filter. This equipment is operated only when sufficient quantities of
sludge have accumulated. The filter cake is collected in hoppers for off-site disposal and the filtrate is returned to
the oily water sewer.32
API Water. Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
API Oil/Water Separator Sludge. Approximately 1,500 cubic yards of API oil/water separator sludge are
generated annually in the United States.33 These sludges are disposed of off-site.34 Existing data and engineering
judgement suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
Dissolved Air Flotation Sludge. Approximately 2,688 cubic yards of dissolved air flotation sludge are
generated annually in the United States.35 The DAF sludges are disposed of with the gasifier ash.36 Existing data
and engineering judgement suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Sludge and Filter Cake. Existing data and engineering judgement suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Vacuum Filter Sludge. The vacuum filter sludge is generated intermittently. This stream is disposed of
with the ash in the plant's ash handling system.37 Existing data and engineering judgement suggest that this material
does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated by cleaning operations that
generate up to 3,350 gallons of spent solvents each year; laboratory services that may generate 1,800 gallons of
hazardous waste (F002, F003, F004, and D002) each year; and container storage, which could generate hazardous
wastes from spills, and the associated clean up activities. Non-hazardous wastes may include tires from trucks and
large machinery, sanitary sewage, and waste oil (which has been analyzed and found to be non-hazardous).38
32 Ibid., pp. 36-37.
33 Versar, Inc, 1989, Op. Cit.. p. 3.
34 CDM Federal Programs Corporation, 1987, Op. Cit. p. 7.
35 Versar, Inc., 1989, Op. Cit. p. 3.
36 CDM Federal Programs Corporation, 1987, Pp. Cit.. p. 7.
37 Ibid., p. 39.
38 Ibid., pp. 73-76.
230
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E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
231
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BIBLIOGRAPHY
CDM Federal Programs Corporation. Draft Report American Natural Gas Special Study. Prepared for U.S.
Environmental Protection Agency, Office of Waste Programs Enforcement. March 19, 1987.
"Coal Conversion Processes (Gasification)." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. VI.
1993. pp. 541-568.
Dakota Gasification Company. "Letter to Mr. Robert Tonetti and Mr. Bob Hall, Office of Solid Waste, U.S.
Environmental Protection Agency." August 12, 1991. p. 5.
Dakota Gasification Company. "Lurgi Gasification and Flue Gas Scrubbing Simplified." Memorandum to D. W.
Peightal from T. G. Towers. July 29, 1991.
Energy Information Administration. Coal Data: A Reference. 1987.
National Research Council. Fuels to Drive our Future. National Academy Press: Washington, DC. 1990.
North Dakota State Department of Health. Letter to Robert L. Duprey, Director, Waste Management Division. U.S.
Environmental Protection Agency. June 10, 1986.
Personal Communication between ICF Incorporated and Stuart Clayton, U.S. Department of Energy, Fossil Energy
Division. September, 1994.
Personal Communication between ICF Incorporated and John Morris, U.S. Department of Treasury, Office of
Synthetic Fuels. September, 1994.
RTI Survey 100065. National Survey of Solid Wastes From Mineral Processing Facilities. Great Plains
Gasification Project. 1989.
"Steam." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXI. 1983. pp. 543-544.
U.S. Department of Energy. Clean Coal Technology Demonstration Program: Program Update 1993. December
31, 1993.
U.S. Department of Energy. Coal Production 1992. Energy Information Administration. October, 1993.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. Report to Congress on Special Wastes from Mineral Processing. Volume 2.
Office of Solid Waste. July 1990. pp. 5-1 - 5-20.
Versar, Inc. Draft Site Visit Report on Dakota Gasification Company. Prepared for U.S. Environmental Protection
Agency, Office of Solid Waste. August 4, 1989.
Versar, Inc. Trip Report: Dakota Gasification Company. Beulah. North Dakota. Prepared for U.S. Environmental
Protection Agency, Office of Solid Waste. January 12, 1990.
232
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COPPER
A. Commodity Summary
The physical properties of copper, including malleability and workability, corrosion resistance and
durability, high electrical and thermal conductivity, and ability to alloy with other metals, have made it an important
metal and production input to a number of diverse industries.1'2 Copper deposits are found in a variety of geological
environments, which are affected by the rock-forming processes that occurred at a particular location. These
deposits can be grouped in the following broad classes: porphyry and related deposits, sediment-hosted copper
deposits, volcanic-hosted massive sulfide deposits, veins and replacement bodies associated with metamorphic rocks,
and deposits associated with ultramafic, mafic, ultrabasic, and carbonatite rocks. The most commonly mined type of
copper deposit, porphyry copper, is found predominantly in areas along the western continental edges of North and
South America, as well as in the southwestern United States, associated with large granite intrusions.3>i
Copper occurs in about 250 minerals, only a few of these, however, are commercially important.5 Deposits
considered to be economically recoverable at current market prices may contain as little as 0.5 percent of copper or
less, depending on the mining method, total reserves, and the geologic setting of the deposit.6 Most copper ores
contain some amount of sulfur-bearing minerals. The weathering environment affecting the ore body following
deposition is determined mainly by the availability of oxygen. Ores exposed to air tend to be oxidized, while those
in oxygen poor environments remain as sulfides.7
The United States is the second largest copper producer in the world. Next to Chile, the United States had
the largest reserves (45 million metric tons) and reserve base (90 million metric tons) of contained copper. In 1994,
domestic mine production rose to slightly more than 1.8 million metric tons and was valued at about $4.4 billion.
The principal mining states, in descending order, Arizona, Utah, New Mexico, Michigan, and Montana, accounted
for 98 percent of domestic production; copper also was recovered at mines in seven other states. Eight primary and
five secondary smelters, nine electrolytic and six fire refineries, and 15 solvent extraction-electrowinning plants were
operating at the end of 1994. Refined copper and direct melt scrap were consumed at about 35 brass mills; 15 wire
rod mills; and 750 foundries, chemical plants, and miscellaneous consumers.8 Exhibit 1 presents the names and
locations of the mining, smelting, refining, and electrowinning facilities located in the United States. As available,
Exhibit 1 also presents information on potential site factors indicating whether the facility is located in a sensitive
environment.
1 "Copper," Kirk-Othmer Encyclopedia of Chemical Technology. 4th Ed., Vol. VII, 1993, p. 381.
2 U.S. Environmental Protection Agency, Technical Resources Document-Extraction and Beneficiation of Ores
and Minerals: Volume 4 Copper. Office of Solid Waste, 1993d, p. 3.
3 "Copper," 1993, Op. Cit.. p. 384.
4 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 7.
5 Ibid., p. 9.
6 Ibid., p. 7.
1 Ibid., p. 9.
8 Edelstein, Daniel L, from Minerals Commodities Summaries. U.S. Bureau of Mines, January 1995, pp. 50-51.
233
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EXHIBIT 1
Summary of Copper Mining, Smelting, Refining, and Eleetrowinning Facilities9
Facility Name
ASARCO
ASARCO
ASARCO
ASARCO
Burro Chief Copper Mine
Chino Mines Company
Copper Range
Cyprus Pinos Altos Mine
Cyprus
Cyprus Casa Grande Mine
Cyprus Miami Mining Corp.
Cyprus Mineral Park Corp.
Cyprus Sierrita/Twin Buttes
Cyprus Mining
Cyprus FMpdf&d Copper Minfi
Location
El Paso, TX
Amarillo, TX
Ray, AZ
Hayden, AZ
Tyrone, NM
Hurley, NM
White Pine, MI
Silver City, NM
Claypool, AZ
Casa Grande, AZ
Claypool, AZ
Kingman, AZ
Green Valley, AZ
Bagdad, AZ
Rapriad A7,
Type of Operations
Smelting
Electrolytic Refining
Electrowinning
Smelting and Electrowinning
Extraction and Electrowinning
Smelting/Fire Refining
Open Pit Mining, Smelting and
Refining
Extraction
Smelting, Refining, and Electrowinning
In-situ Extraction and Roasting
Heap Leaching
Dump Leaching
Heap Leaching
Electrowinning
Hp.ap 1 .p,af:hinjT nnt\ Milling
Potential Factors Related to Sensitive
Environments
1 00 year floodplain, karst terrain 1 ,000 feet below
surface, private wells within 1 mile10
fault area
fault area, private wells within 1 mile
9ICF Incorporated, Mining and Mineral Processing Facilities Database. August 1992.
1(1 Phelps Dodge Corporation. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land Disposal Restrictions to Newly
Identified Mineral Processing Wastes. January 25, 1996.
-------
EXHIBIT 1 (Continued)
Facility Name
Flambeau Copper Mine
Gibson Mine
Johnson Camp Mine
Kennecott
Kennecott13
Magma Mine (BHP Copper)
Magma (BHP Copper)
Mineral Park Mine
Mission Unit
Montanore Mine
Morenci Mine
Noranda
Oracle Ridge Mine
Phelps Dodge
Phelps Dorfpe.
Location
Wisconsin"
Mesa, AZ
Tucson, AZ
Garfield, UT
Magma, UT
Superior, AZ
San Manuel, AZ
Kingman, AZ
Sahuarita, AZ
Libby, MT
Morenci, AZ
Casa Grande, AZ
San Manuel, AZ
Morenci, AZ
Playas, NM
Type of Operations
Extraction
Strip and In-situ Extraction
Heap Leaching
Mining
Smelting and Refining
Undercutting and Filling (Mining)
Smelting, Refining, and Electrowinning
Extraction
Extraction
Extraction
Heap Leaching
Electrowinning
Extraction
Electrowinning
Smeltinp
Potential Factors Related to Sensitive
Environments
low pH and metals contamination of ground water
found hydraulically down-gradient from mine
operations12
public and private wells within 1 mile
UJ
Ul
"Ibid.
12 Ibid.
'•' Ibid.
-------
U)
cn
EXHIBIT 1 (Continued)
Facility Name
Phelps Dodge
Phelps Dodge
Pinos Altos Mine
Pinto Valley Operations
Pinto Valley
Ray Complex
San Manuel Div. Mine
San Pedro Mine
Silver Butte Mine
Silver Bell Unit
St. Cloud Mining Co.
Sunshine Mine
Tennessee Chemical
Tyrone Branch Mine
Western World Copper Mine
Yerington Mine
Location
El Paso, TX
Hurley, NM
Silver City, NM
Miami, AZ
Pinto Valley, AZ
Hayden, AZ
San Manuel, AZ
Truth or Consequence, NM
Riddle, OR
Marana, AZ
Truth or Consequence, NM
Kellog, ID
Copperhill, TN
Tyrone, NM
Marysville, CA
Tucson, AZ
Type of Operations
Refining
Smelting and Electrowinning
Extraction
Extraction and Electrowinning
Electrowinning
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Closed
Dump Leaching and Electrowinning
Extraction
Extraction
Potential Factors Related to Sensitive
Environments
fault area, public and private wells within I mile
-------
The majority of the copper produced in the United States is used in the electrical industry; it is used for a
wide range of wiring applications (from power transmission lines to printed circuit boards), in microwave and
electrical tubes, motors and generators, and many other specialized applications where its high electrical and thermal
conductivity can be employed. While copper has been replaced in some applications by aluminum (e.g., for
overhead power lines) and fiber optics (e.g., in telecommunications), its durability, strength, and resistance to fatigue
assure its continued use in the electrical industry. These latter three characteristics also make copper and copper
alloys a valued material in construction and containment (e.g., pipes and tanks), and in other activities where
endurance and resistance to corrosion are required.14
Primary production of copper in the United States steadily increased in the early 1990s. Total apparent
consumption rose from 2,170,000 metric tons in 1990 to 2,800,000 metric tons in 1994. Approximately 42 percent
of the 1994 domestic consumption of copper went to building and construction industries, while 24 percent was used
by the electrical and electronic products industries. Industrial machinery and equipment consumed 13 percent,
transportation equipment consumed 12 percent, and consumer and general products consumed the remaining 9
percent.13 Clearly, the development of new infrastructure in the United States and abroad would increase the
worldwide demand for copper, but consumption per unit of new gross product would be less than that in the past
because substitutes for copper are often used in a number of industries. For example, new telephone infrastructure is
largely based on fiber optics technology rather than copper. Continued re-opening of mothballed facilities,
expansion of existing facilities, and development of new mines could lead to copper supplies increasing faster than
demand.16-17
B. General Process Description
1. Discussion of the Typical Production Process
The two major processes employed in the United States to recover copper from ores are classified as either
(1) pyrometallurgical methods, or (2) hydrometallurgical methods. Pyrometallurgical methods consist of
conventional smelting technology, and are widely used. Hydrometallurgical methods involve leaching and recovery
by precipitation or electrowinning, and are gaining in popularity. For example, in 1984 100,180 tons of copper were
produced by solvent extraction and electrowinning (SX/EW). while in 1992 439,043 tons were produced by
SX/EW." Some within the industry believe that hydrometallurgical operations are only economically attractive for
producing 30,000 metric tons of copper product per year or less.19'20
2. Generalized Flow Diagram
Exhibit 2 presents a flow diagram of the typical pyrometallurgical operations involved in the production of
copper from ore. Exhibit 3 presents a flow diagram of the typical hydrometallurgical operations involved in the
production of copper from ore.
14 Edelstein, Daniel L, 1995, Op. Cit.
15 Ibid.
16 Ibid.
17 U.S. Environmental Protection Agency, "Primary Copper Processing," Report to Congress on Special Wastes
from Mineral Processing. Vol. II, Office of Solid Waste, July 1990, p. 6-2.
18 "Copper," 1993, Op. Cit.. p. 412.
19 Ibid., p. 408.
20 Keith R. Suttill, "Pyromet or Hydromet?" Engineering and Mining Journal. 191, May 1990, p. 31.
237
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U)
00
EXHIBIT 2
Process Flow Diagram for the Production of Copper
Pyrometallurgical Process
Bevill - Exempt Wastes
Disposal
Impoundment Tails
Overburden
Dilute Sulfurte
Acid Solution
-------
EXHIBIT 3
Process Flow Diagram for the Production of Copper
Hydrometallurgical Process
NJ
UJ
-------
Extraction and Beneficiation Operations
Prior to pyrometallurgical operations, sulfide ore (which often contains less than one percent copper) is
crushed and ground with water and placed in a concentrator.21 The rock/water slurry is subjected to physical and
chemical actions (i.e., air sparging and hydrophobic chemical reagents) inside a flotation tank. The chemical
reagents assist the flotation process by acting as frothing and collector agents. Methylisobutyl carbonal (MIBC) is a
typical frothing agent, and sodium xanthate, fuel oil, and VS M8 (a proprietary formulation) are typical collector
agents. As a result of the physical and chemical actions, the copper value rises to the surface of the flotation unit as a
froth."
The material remaining on the bottom of the flotation tank (spent ore or "gangue"), is partially dewatered
and then discharged to tailing ponds for disposal.23 In cases in which the copper ore contains a large amount of clay
minerals, "slime" (a mixture of clay minerals and copper values) often forms and is separated from the gangue for
further copper recovery. The slime is reground and subjected to flotation to remove the copper value. Once the
copper value is removed, the slime is ultimately managed/disposed with the gangue.24'25
The concentrate resulting from the flotation circuit contains approximately 30 percent copper and, in some
instances, may also contain significant recoverable concentrations of molybdenum. If molybdenum is readily
recoverable, as it is at Magma Copper (Arizona), the concentrate is sent to the molybdenum plant for recovery;
otherwise, the concentrate is ready for subsequent pyrometallurgical operations.26'27 Alternatively, the concentrate
can be dewatered and the dry product may either be stored for further processing or shipped to another facility for
processing. The collected water is usually recycled in the milling circuit.
All oxide ore and some low grade sulfide ores destined for hydrometallurgical beneficiation are not
crushed, floated, or sent to a concentrator. These ores are instead leached with copper values recovered by solvent
extraction and electro winning operations.28'29
At a molybdenum recovery plant, such as the one at Magma Copper (Arizona), the copper concentrate
contains approximately one percent molybdenum disulfide (which in itself is a saleable co-product). To isolate the
molybdenum from the copper concentrate, the concentrate undergoes additional flotation steps. The copper
concentrate is added to a rougher flotation cell where sodium cyanide is added to suppress the copper, thus causing
the molybdenum to float to the surface. Some operations, however, including the Chino Mines facility, do not
recover molybdenum disulfide using sodium cyanide. They instead use, sodium disulfide to suppress the copper and
21 Phelps Dodge Corporation. Op. Cit.
22 U.S. Environmental Protection Agency, Trip Report — Site Visit to Magma Copper and Cyprus Miami Copper
Mines." Draft Memorandum. Office of Solid Waste, April 1994b, p. 6.
23 Ibid., p. 6.
24 "Copper," 1993, Op. Cit.. pp. 388-92.
25 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 53.
26 "Copper," 1993, Op. Cit.. pp. 388-92.
27 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 53.
28 BHP Copper. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
29 Phelps Dodge Corporation. Op. Cit.
240
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float the molybdenum,30 The copper concentrate falls to the bottom and the underflow is sent for drying and
thickening prior to smelting. The molybdenum-containing overflow is sent to additional cleaner and recleaner
circuits. At the last recleaner circuit, 70 percent of the overflow is filtered and dried, and the remaining 30 percent is
returned to the filter at the beginning of the recleaner circuit. The filtered, dry molybdenum disulfide product (95
percent) is packed into 55-gallon drums and sold as molybdenite,31
Pyrometallurgical Processing
Pyrometallurgical processes employ high-temperature chemical reactions to extract copper from its ores and
concentrates. These processes generally are used with copper sulfides and in some cases high-grade oxides.32
Depending on the copper mineral and the type of equipment, pyrometallurgical recovery may take as many as five
steps: roasting, smelting, converting, fire refining, and eleetrorefming. The products from smelting, converting, fire
refining in an anode furnace, and electrolytic refining are copper matte, blister copper, copper anodes, and refined
copper, respectively.33 Roasting dries, heats, and partially removes the sulfur and volatile contaminants from the
concentrated ore to produce a calcine suitable for smelting.34 Modern copper smelters generally have abandoned
roasting as a separate step, and have combined this function with the smelting furnace. However, in older systems
using multiple brick hearths, the copper concentrate moves from the top of the hearth towards the base, while air is
injected counter-current to the concentrate. The roasted ore leaves through the bottom brick hearth and sulfur
dioxide (2-6 percent) exits through the top.33
Smelting involves the application of heat to a charge of copper ore concentrate, scrap, and flux, to fuse the
ore and allow the separation of copper from iron and other impurities. The smelter furnace produces two separate
molten streams: copper-iron-sulfide matte, and slag, as well as sulfur dioxide gas.36 The smelter slag, essentially a
mixture of flux material, iron, and other impurities, is a RCRA special waste. The slags from some smelting furnaces
are higher in copper content than the original ores taken from the mines, and may therefore be sent to a concentrator
for copper recovery.37'38 Tailings from flotation of copper slag are a second RCRA special waste. Reverberatory
furnaces are being replaced by electric or flash furnaces because reverberatory furnaces are not as energy efficient,
and they produce large volumes of low concentration SO2 gas, which is difficult to use in sulfur recovery.39
30 Phelps Dodge Corporation. Op. Cit.
31 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 7.
32 Office of Technology Assessment, Copper: Technology and Competitiveness. OTA-E-67, Washington, DC:
U.S. Government Printing Office, September 1988, p. 133.
' " U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 6-2.
14 Office of Technology Assessment, 1988, Op. Cit.. p. 134.
35 "Copper," 1993, Op. Cit.. p. 394-95.
36 Process upsets sometimes require the copper concentrate to be stored temporarily until the'smelter is
operational. In many cases, this temporary storage takes place in the pipeline. In other cases, such as at the Hidalgo
Smelter, concentrate is shipped by rail car, then stored in an enclosed building prior to being fed by a conveyor belt
to the smelter. (Phelps Dodge Corporation. Op. Cit.)
37 "Copper," 1993, Op. Cit.. p. 393.
38 U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 6-3.
39 K. Yoshiki-Gravelsins, J. M. Toguri, and R. T. Choo, "Metals Production, Energy, and the Environment, Part
II: Environmental Impact," Journal of Mines. 45, No. 8, August 1993, p. 23.
241
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Moreover, the gases produced by electric furnace smelting are smaller in volume, lower in dust (less than 1 percent),
and have a higher SO2 concentration, which allows better sulfur recovery in an acid plant.40 Gases from smelting
operations contain dust and sulfur dioxide. The gases are cleaned using a variety of paniculate control technologies.
including baghouses, scrubbers, settling chambers, and electrostatic precipitators.41 The gases are then sent to the
acid plant, which converts the sulfur dioxide-rich gases-to sulfuric acid (a useable and/or saleable product).42
In the converter (the most common being the Peirce-Smith converter, followed by the Hoboken converter
and the Mitsubishi continuous converter), a high silica flux and compressed air or oxygen are introduced into the
molten copper matte. Most of the remaining iron combines with the silica to form converter slag, a RCRA special
waste. After removing the slag, additional air or oxygen is blown in to oxidize the sulfur and convert the copper
sulfide to blister copper that contains about 99 percent copper; the sulfur is removed in the form of S02 gas, which
reports to an acid plant where it is converted to high grade sulfuric acid. Depending on the efficiency of the acid
plant, differing amounts of SO2 are emitted to the atmosphere. Some facilities have combined the smelting furnace
and converter into one operation, such as the one used by Kennecott (i.e., the Kenneeott-Outokumpo flash converting
process).43'44 In the interest of conserving energy and improving efficiency, many companies are now employing
flash smelting (such as the Outokumpo, Inco, Mitsubishi, or Noranda processes) to produce matte feed.45
Oxygen and other impurities in blister copper must be removed before the copper can be fabricated or cast
into anodes for electrolytic refining. Blister copper is fire refined in reverberatory or rotary furnaces known as anode
furnaces. When co-located with a smelter or converter, the furnace may receive the blister copper in molten form so
remelting is unnecessary. Air is blown in to oxidize some impurities; flux may be added to remove others. The
residual sulfur is removed as sulfur dioxide. A slag is generated during anode furnace operation. This slag is also a
component of the RCRA special waste. The final step in fire refining is the reduction of the copper and oxygen
removal by feeding a reducing gas such as ammonia, reformed gas, or natural gas into the copper while it is still in
the anode furnace. The molten copper then is cast into either anodes for further electrolytic refining or wire-rod
forms.46'47 Smelted copper typically retains metallic impurities at concentrations that can interfere with electrical
uses. Anode copper may be suitable for non-electric uses such as decorative copper or cooking utensils, but wire bar
is made specifically for electrical wire manufacturing and requires high grade electrowon or electrolytically refined
copper.48
At the Cyprus Amax Minerals Company, during the addition of oxygen into the converter furnace while
slag is present (slag blow), secondary copper materials may be added to recover copper and to cool the furnace
charge. Once the iron has been removed, the converter furnace switches to "copper blow" (the addition of oxygen
without the presence of slag), and at this point, very high copper content materials can be added to the furnace. For
example, reverts (a mixture of converter slag and matte which is frozen to the walls and bottom of a transfer ladle)
40 Ibid., p. 27,
41Phelps Dodge Corporation. Op. Cit.
42 U.S. Environmental Protection Agency, 1994b, Op, Cit.. p. 8.
43 "Copper," 1993, Op. Cit.. p. 396.
44 U.S. Environmental Protection Agency, 1990, Ojx_Cit., pp. 6-3 - 6-4.
43 "Copper," 1993, Op. Cit.. p. 396.
46 Ibid., p. 399-400.
47 U.S. Environmental Protection Agency, 1990, Qp.,.Cit., p. 6-4.
48
242
BMP Copper. Op. Cit.
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may be introduced at this point. Reverts are knocked loose and stored until they have cooled sufficiently to allow
equipment to move them to the crashing and sizing area. The material is chipped and then fed back into the furnace
for melting and then to the converters and eventually anode casting in order to continue copper production during
times when the Isamelt furnace is down. Reverts are accumulated in more than one area and are surveyed for
inventory control purposes and left undisturbed until ready to be reused in the furnaces. The matte is accumulated in
a slag accumulation area located on the ground.49
Electrolytic refining (or electrorefining) purifies the copper anodes by virtually eliminating the oxygen,
sulfur, and base metals that limit copper's useful properties. In electrorefining, the copper anodes produced from
fire-refining are taken to a "tank house" where they are dissolved electrolytically in acidic copper sulfate solution
(the electrolyte). The copper is electrolytically deposited on "starter" sheets of purified copper to ultimately produce
copper cathodes (relatively pure copper with only trace contaminants ~ less than a few parts per million) for sale
and/or direct use. The concentration of copper and impurities in the electrolyte are monitored and controlled. As
necessary, the electrolyte is purified and the resulting impurities (left on the bottom of the electrolytic cells — often
referred to as "anode slimes") are processed for recovery of precious metals (gold, silver, platinum, palladium),
bismuth, selenium, and tellurium.50 Electrorefining also produces aqueous waste streams (e.g., process wastewater,
bleed electrolyte) that must be treated and discharged, reused, or disposed of in some manner. Many of the facilities
use a wastewater treatment operation to treat these wastes. The solid residual from these treatment operations is a
calcium sulfate sludge, which is yet another RCRA special waste generated by the primary copper sector.51 The
exemption from RCRA regulation for calcium sulfate sludge, which has a variable water content, does not depend on
its water content.52
Hvdrometallurgical Beneficiation
Hydrometallurgical copper recovery is the extraction and recovery of copper from oxide ore and some low
grade suffide ores using aqueous solutions. Hydrometallurgical operations include the following: (1) acid extraction
of copper from oxide ores; (2) oxidation and dissolution of sulfides in spent ore from mining, concentrator tailings,
or in situ ore bodies (e.g., low grade oxide and sulfide mine wastes); and (3) dissolution of copper from concentrates
to avoid conventional smelting.55 In summary, the copper-bearing ore (and in some cases, the overburden) is
leached, then the copper is recovered from the pregnant leachate through precipitation, or solvent extraction and
electrowinning (SX/EW).54
The simplest form of hydrometallurgical beneficiation of low grade ore, practiced at large, open-pit copper
mines is dump leaching. In dump leaching, the raw material is leached using a dilute sulfuric acid solution. At
Phelps Dodge facilities, leaching is accomplished by applying raffinate (a weak aqueous acid solution) to the leach
ore stockpiles by standard sprinkler irrigation spray heads or drip emitters.55 There are several other types of
leaching operations (progressing from least capital intensive and inefficient — using the rock "as is" — to most capital
49 Cyprus Amax Minerals Company. Comment submitted in response to the Second Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. October 10, 1997.
50 "Copper," 1993, Op. Cit. pp. 401-404.
51 U.S. Environmental Protection Agency, 1990, Op. Cit. p. 6-4.
52 Phelps Dodge Corporation. Op. Cit.
53 "Copper," 1993, Op. Cit.. p. 408.
54 Office of Technology Assessment, 1988. Op. Cit.. p. 140.
55 U.S. Environmental Protection Agency Telephone Questionnaire. August 22, 1997. Facility Contact: Richard
N. Mohr, Phelps Dodge Morenci, Inc.
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intensive and efficient — using ground ore): in situ, heap or pile, dump, vat, and heat or agitation leaching. In some
cases, roasting is employed prior to leaching in order to enhance the leachability of the material. In roasting, heat is
applied to the ore, which enhances its amenability to leaching without destroying the physical structure of the ore
particles. The roasted material is then subjected to leaching (as described above). The copper-rich leachate
(referred to as "pregnant leachate solution") is subjected to further beneficiation while the waste material is either
left in place (in the case of dump, in situ, heap, or pile leaching) or managed in tailing ponds (in the case of vat, heat,
or agitation leaching).
Copper is removed from the pregnant leachate solution (PLS) through either iron precipitation (or
cementation) or solvent extraction and electrowinning. In cementation, which was once the most popular method for
recovering copper from the PLS, the leachate is combined with detinned iron in a scrap iron cone (such as the
Kennecott-Precipitation Cone) or vibrating cementation mill, where the detinned iron replaces the copper in the
solution. The copper precipitates are removed for subsequent hydro metallurgical refining (electrowinning) or
pyrometallurgical processing.56'57
In solvent extraction (now, the most popular process), an organic chemical (chelator) that binds copper but
not impurity metals is dissolved in an organic solvent (often kerosene58) and is mixed with the pregnant leachate
solution. The copper-laden organic solution is separated from the leachate in a settling tank. A weak sulfuric acid
(or lean) electrolyte59 is then added to the pregnant organic mixture, which strips the copper into an electrolytic
solution ready for electrowinning. The barren leachate (or raffinate) is sent back to the leaching system.
Electrowinning is the recovery of copper from the loaded electrolyte solution produced by solvent extraction,
yielding wire-grade60 copper metal. When the iron concentration in the electrolyte stream61 becomes too high, some
solution is bled off and sent to the SX unit for further copper recovery. The copper-poor (or lean) electrolyte from
electrowinning is returned to the SX plant. Excess lean electrolyte from the SX unit is returned to the raffinate pond
to later be recycled into the leaching circuit. Filter clay is used to filter the electrolyte.62 Impurities left on the
bottom of the electrowinning cells are referred to as "muds or slimes." BHP Copper refers to the impurities left on
the bottom of the electrowinning cell as "anode sludge." Both this anode sludge and lead anodes that are no longer
usable are periodically removed from the cells and send to lead smelting facilities for resource recovery.63
Electrowinning is functionally equivalent to electrolytic refining.64-65
56 "Copper," 1993, Op. Cit.. p. 410.
57 Office of Technology Assessment, 1988, Op. Cit.. pp. 140-142.
58 Phelps Dodge uses a petroleum distillate manufactured specifically for use in the solvent extraction process.
This petroleum distillate consists of longer chain hydrocarbons with a lower volatile organic content than kerosene.
(Phelps Dodge Corporation. Op. CiU
59 Phelps Dodge Corporation. Op. Cit.
60 Ibid.
61 Ibid.
62 Ibid.
63 BHP Copper. Op. Cit.
64 "Copper," 1993, Op. Cit. pp. 412-13.
65 Office of Technology Assessment, 1988, Op. Cit.. p. 142.
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We note that at Magma Copper (Arizona), the pregnant leach solution (PLS) is collected in the PLS feed
pond, where other inputs to the PLS feed pond include liquids from in-situ leaching, Gould Solution, and TNT filter
cake. Gould Solution is produced from the electrolytic refining of copper foil at one facility in Chandler, AZ. The
spent electrolyte solution (containing 100 g/L sulfuric acid and 60 g/L copper) is trucked to Magma Copper, where it
is added directly to the PLS feed pond. Magma Copper has proposed to accept filter cakes consisting of copper
oxide mud from copper chloride etching solution generated during the production of circuit boards. This material
(TNT filter cake) would be mixed with the PLS feed to the SX unit.66 At the Phelps Dodge Morenci site, PLS which
has been stripped of copper (acidic solution) from the SX process, copper-bearing bleed electrolyte and washdown
water from the EW process, and fresh water are transferred by pipeline to lined impoundments for reuse in the
leaching process. This "raffinate" is piped to the top of the leach stockpiles for reuse. In addition, water collected
behind dams in Rocky Gulch and Gold Gulch is piped for reuse in the leaching process. All reagents used in the SX
and EW processes are stored in above ground tanks.67
The Kennecott Corporation's new hydrometallurgical plant combines acid plant blowdown, refinery bleed
solutions, and electrostatic precipitator (ESP) dusts in a series of chemical reactions to produce a metal concentrate,
a sulfide cake, and non-hazardous tailings. The valued metals are returned to the smelter for recovery. Impurities
such as bismuth, that would have otherwise compromised the quality of the copper product, can thereby be removed
while extracting the maximum economic benefit in resource recovery from valuable metals contained in the dust,68
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Additional pyrometallurgical technologies still under development include the solid matte oxygen
converting (SMOC) process and continuous total pressure oxidation process. The SMOC process developed by
Kennrcott is a one-step smelting process designed to eliminate the hot matte and slag transfers between smelting and
convening, thereby reducing their attendant fugitive emissions. In the total pressure oxidation process, chalcopyrite
(CuFeS2) can be hydrothermally oxidized directly to digenite (CuS) inside a single, continuous, autoclave reactor.
The enriched solid residue (super concentrate) is separated from the liquor, containing ferrous sulfate and sulfuric
acid, and the upgraded concentrate can proceed directly to smelting. The acid solution can be used in heap or dump
leaching.69 Total pressure oxidization is especially well-suited for concentrates with a high copper to sulfur ratio.'°
Magma has constructed a new flue dust leaching (FDL) facility to recover copper from several smelter by-
product streams. Feedstocks to the FDL facility were to include flash furnace dust (20-25 percent copper, 1.3
percent arsenic), converter flue dust (80 percent copper, 0.01 percent arsenic), acidic bleed solution from die Lurgi
scrubbers (3.6 g/L copper, 0.4 g/L arsenic, 3.5 g/L acid pH 1.6). (Lurgi scrubbers are pollution control devices for
smelter converter offgas.) These feedstocks were to be stored in bins or slurry tanks prior to entering a series of
agitator leach vessels. Sulfuric acid (93 percent concentration) would be added to dissolve the copper into solution.
The copper rich leachate was to be purified in a dedicated solvent extraction unit, where an extremely concentrated
copper sulfate solution (one that could easily be crystallized into commercial grade copper sulfate crystals) would be
66 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 16.
67 U.S. Environmental Protection Agency Telephone Questionnaire. Op. Cit.
68 Kennecott Corporation. Comment submitted in response to the Second Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. May 12, 1997.
69 Robert W. Bartlet, "Copper Super-Concentrates-Processing, Economics, and Smelting," EPD Congress, 1992,
pp. 652-653.
70 J. A. King, D. A. Knight, and D. B. Dreisinger, "The Total Pressure Oxidation of Copper Concentrates," The
Minerals, Metals and Materials Society, 1993, p. 735.
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generated. The crystals could be either sold "as is" or sent to the main solvent extraction circuit.71 The remaining
solids would be thickened, washed, and filtered. The resulting filter cake was to be sent back to the flash furnace for
smelting. In a comment, Magma Copper wrote that this facility was originally designed to utilize BHP's existing SX
plant, not the dedicated plant described above. After evaluating the high operating costs of the dedicated SX as well
as the treatment plant, BHP determined that it could not economically operate die FDLP, and the plant has never
been operated.72 Kennecott Utah Copper's modernized smelter includes a pneumatic conveying system that allows
mineral-rich boiler and electrostatic precipitator (ESP) dusts to be re-introduced directly into the flash smelting and
flash converting furnaces without any additional handling. This dust on average contains approximately 35%
copper, as compared to less than 1 % copper in mined ore and less than 30% in virgin copper concentrate.
Additionally, this dust contains significant amounts of valuable precious metals.73
4. Benefieiation/Proeessing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this mineral commodity sector, depending on the specific process, the
beneficiation/processing line occurs between flotation and furnacing or between iron precipitation and furnacing
because furnacing (or smelting) significantly alters the physical/chemical structure of the beneficiated ore.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence also are considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below
information about process waste streams associated with both extraction/benefieiation and mineral processing
activities, along with associated information on waste generation rates, characteristics, and management practices for
each of these waste streams.
71 U.S. Environmental Protection Agency, 1994b, Op. Cit. p. 9.
72 BHP Copper. Qjx Cit.
73 U.S. Environmental Protection Agency, "Verbatim Comment Excerpts, Summary and Response Form, for
Kennecott Utah Copper Corporation." Excerpt number COMM1054-8-1.
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C. Process Waste Streams
As discussed above (and shown in Exhibits 2 and 3), the extraction, beneficiation, and processing of copper
leads to the generation of numerous solid, liquid and gaseous wastes, which depending on the material, may be
recycled or purified prior to disposal. The generation, treatment, and management of each of these wastes is
discussed below.
1. Extraction/Beneflciation Wastes
Wastes generated from the extraction and beneficiation of copper from copper-bearing ores are exempt
from RCRA Subtitle C and the scope of BOAT determinations. Wastes from the extraction/beneficiation of copper-
bearing ores are discussed below.
Spent ore. This waste from mining operations, along with overburden, is generated from the actual
removal of copper ore from the ground and contains little or no recoverable copper values. Overburden and spent
ore may be stockpiled for reclamation upon closure of the facility or to achieve contemporaneous reclamation of
leach piles and rock piles.74 These materials are typically hauled from the mine site and are disposed of in on-site
spent ore dumps. At Magma Copper (Arizona), spent ore is left in place; at other facilities, however, the spent ore
may be hauled to the surface and disposed.75 In 1980, more than 282 million tons of spent ore were disposed.76
Tailings (or gangue). This waste results from the flotation of ground ore/water slurry. The composition of
tailings varies according to the characteristics of the ore; this waste is comprised of very fine host rock and
nonmetallic minerals. Tailings are sent to tailings impoundments for disposal, but may first be dewatered in
thickeners. For example, at Magma Copper (Arizona) tailings from the copper and molybdenum flotation processes
are sent to a hydroseparator for dewatering. The hydroseparator underflow is sent to a repulper and the slurry is
discharged to the tailings ponds for disposal. The hydroseparator overflow is sent to a thickener, where the solids
(underflow) are sent to the repulper and the liquid stream (water overflow) is reused in the flotation circuit. Tailings
generated during the flotation processes are excluded from RCRA Subtitle C regulation under the Bevill
Amendment.77 In 1985, the industry disposed of more than 189 million tons of gangue.78
Slime. A clay/copper material called slime is often generated during the flotation of copper ore containing
a large amount of clay minerals. Slime is separated from the gangue and is reground and refloated to remove
additional copper value. The slime is ultimately disposed of along with the tailings. There is no information on the
quantity of slime generated annually.79 The term also has another meaning in the industry, usually referring to the
clay and silt fraction of the tailing that is separated from the coarser tailing materials by size classifiers (usually
cyclones) at the tailing disposal site. This separation, which can be accomplished by gravity separation as the tailing
slurry is deposited and flows toward the water decant area at the tailing ponds is encouraged in order to deposit the
sandier materials near the tailing embankment to provide higher embankment stability than die finer materials would
have created. The finer materials (slimes) are then deposited in the interior of the tailing impoundment.80 We note
74 Phelps Dodge Corporation. Op. Cit.
75 U.S. Environmental Protection Agency, 1994b, Op. Cit. p. 10.
76 U.S. Environmental Protection Agency, 1993d, Op. Cit.. pp. 50-51.
77 U.S. Environmental Protection Agency, 1994b, Op. Cit. p. 10.
78 U.S. Environmental Protection Agency, 1993d, Op. Cit. p. 53-54.
79 "Copper," 1993, Op. Cit.. p. 388-92.
80 Phelps Dodge Corporation. OjkCit.
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that this "slime" is much different in composition than the "slimes or muds" generated by electrolytic refining (see
below).
Process wastewaters. Various processing wastewaters result from conveyance, flotation, mixing, and
dissolution operations. Process wastewaters may either be treated on site at wastewater treatment facilities or
discharged to tailings ponds, surface impoundments, or to receiving streams. Process wastewaters are believed not
to be land stored and are fully recycled.81
Solvent extraction/electrowinning. These operations result in the generation of several liquid and semi-
liquid wastes. Often these materials are still either useful or rich in values and can be reused or recycled. The
following waste streams are uniquely associated with copper beneficiation activities and, therefore, are subject to the
Bevill Mining Waste Exclusion:
Slimes or "muds". These materials result from the deposition of sediment in electrowinning cells. These
materials often contain recoverable quantities of lead and are either processed on-site or are drummed and
sent off-site for recovery.82 Approximately 3,000 metric tons of slimes are generated annually.83
Crud (often referred to as "gunk," "grungies," or "grumos"). This waste is generated during solvent
extraction. Crud is solid particles associated with oil/water dispersions of varied complexity and typically
forms stable multi-phase emulsions. Crud is periodically removed from the system. The crud is centrifuged
or otherwise treated to remove the organics, which are returned to the solvent extraction circuit for reuse.
Site-specific management information is available for several companies. At the Chino Mines Company
(Santa Rita, NM), the recovered organic is filtered using Filtrol No.l montmorillonite clay84 and then
solids, mainly fine rock materials from the leach rock and particles of the clay used as a filter for the organic
solution, are returned to the leach system. Any aqueous solution is drained off and returned to the raffinate
pond and the leach circuit.85 In some cases, the resulting solids contain sufficient quantities of precious
metals to warrant recovery (off-site).86 We note that at both the Magma Copper Company's San Manuel,
AZ facility and the Cyprus Mines' Miami, AZ facility, crud is recycled into the raffinate pond which is
linked to, and forms, an integral part of the SX/EW processing circuit.87'88 Phelps Dodge Morenci generates
1,650 tons/year of copper bearing gunk. This gunk is smelted for flux values and to recover copper.89
Entire sector production rates for crud are currently not available.
81 Exhibit 1. Draft Technical Background Document Characterization of Mineral Processing Wastes and
Materials, March 18, 1997.
82 ii,
2 "Copper," 1993, Op. Cit.. pp. 401-404.
83 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Volume I, Office of Solid Waste, August 1992, p. 1-3.
84 Tom Burniston, James N. Greenshield, and Peter E. Tetlow, "Crud Control in Copper SX Plants," Engineering
and Mining Journal. 193, No. 1, January 1992, pp. 32-33.
85 Phelps Dodge Corporation. Op. Cit.
86 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 54.
87 RTI Survey 100750, National Survey of Solid Wastes from Mineral Processing Facilities. Magma Copper Co..
San Manuel, AZ, 1989.
88 Tom Burniston, James N. Greenshield, and Peter E. Tetlow, 1992, Op. Cit.. p. 34.
89 U.S. Environmental Protection Agency Telephone Questionnaire. Op. Cit.
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Raffinate or barren leachate. This waste is generated when the pregnant leachate is stripped and is
recycled back to the leaching circuit. Approximately 70,036,000 metric tons of raffinate is generated
annually.90'91 At the Phelps Dodge Corporation raffinate is recycled for its copper content and is reused in
the leach system because of its acidity.92
Spent kerosene. Commonly used as the organic material in solvent extraction, spent kerosene is purified
using filter clay. The resulting impurities or "grungies" are sent to the dump-leaching area, sent off-site for
precious metals recovery, sent to the raffinate pond, or are disposed of with tailings.93 The Phelps Dodge
Corporation recycles the spent kerosene for reuse in the solvent extraction operation.94
2. Mineral Processing Wastes
Smelting and Refining operations generate numerous solid, liquid, and gaseous wastes, several of which
are Bevill Exempt wastes including furnace slags, anode casting slags, and wastewater treatment sludges. Other
wastes are described below.
Spent bleed electrolyte. Spent electrolyte results from electrolytic refining in electrolytic cells. Normally,
spent electrolyte is purified in liberator cells. Liberator cells are similar to normal electrolytic cells, but they have
lead anodes instead of copper anodes. The electrolyte is cascaded through the liberator cells, and an electric current
is applied to strip the electrolyte of copper. Copper in the solution is deposited on copper starting sheets (cathodes).
As the copper in the solution is depleted, the quality of the copper deposited is lowered. Copper liberator cathodes,
which contain impurities, are returned to the smelter to be melted and cast into anodes. Purified electrolyte is
recycled to the electrolytic cells. Any bleed electrolyte can be neutralized with mill tailings and disposed of intailing
ponds or pumped to a raffinate pond, from which it is pumped to on-site copper leaching dumps. Sludge that settles
to the floor of the liberator cell is returned to the smelter or sold.95'96
Site-specific management information is available for several companies. Cyprus Miami Mining Corp. in
Claypool, AZ recycles the bleed electrolyte to the solvent extraction plant.97 Magma Copper Company's San Manuel
facility recycled the bleed electrolyte to the solvent extraction/electrowinning plant for copper recovery.98 At one
90 The 1992 NIMPW Characterization Data Set indicates that 70,036,000 metric tons of raffinate are generated
annually. We are currently trying to verify this number and will revise it in the near future (if appropriate).
91 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-3.
92 Phelps Dodge Corporation. Op. Cit.
93 U.S. Environmental Protection Agency, 1993d, Op. Cit.. pp. 114-115.
94 Phelps Dodge Corporation. Op. Cit.
95 U.S. Environmental Protection Agency, Revised Draft Wastes from Primary Copper Processing
Characterization Report for Cyprus Miami Mining Corporation. Clavpool. AZ. Office of Solid Waste, May 1991, p.
5.
96 U.S. Environmental Protection Agency, Draft Overview of Solid Waste Generation. Management, and
Chemical Characteristics in the Primary Copper Smelting and Refining Industry. Industrial Environmental Research
Laboratory, Office of Research and Development, October 1984, p. 3-12.
97 RTI Survey 100156, National Survey of Solid Wastes from Mineral Processing Facilities. Cyprus Miami
Mining Corp., Clay Pool, AZ, 1989.
98 RTI Survey 100750, 1989, Op. Cit.
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time Kennecott Utah Copper's Bingham Canyon, UT facility treated the bleed electrolyte in its wastewater treatment
plant." It is now routed to the hydrometallurgical plant where it is used as reagent/raw material for metal
recovery,100
At the Phelps Dodge Refinery in El Paso, electrolyte is withdrawn from tankhouse circulation and sent to
the nickel sulfate plant for copper and nickel recovery. The process Phelps Dodge uses is similar to the above
description except for the following steps. Liberator sludge is sent to the smelter for metal recovery and the copper-
free solution is evaporated to concentrate the nickel salts. The precipitated nickel sulfate is separated from the
concentrated sulfuric acid solution by centrifuging. While the nickel sulfate crystals are marketed, the concentrated
spent sulfuric acid is disposed off site at a permitted deep-well injection facility.101
Approximately 307,000 metric tons of bleed electrolyte are generated annually. Bleed electrolyte exhibits
the hazardous characteristics of toxicity (for arsenic, cadmium, chromium, lead, selenium, and silver) and
corrosivity.102 This partially recycled waste stream was formerly classified as a spent material. Additional data are
included in Attachment 1. Spent bleed electrolyte is believed not to be land stored.103
Tankhouse slimes. Often referred to as "anode slimes", tankhouse slimes are the result of material
deposition in electrolytic cells. Slimes contain the constituents in a copper anode that remain insoluble during the
electrorefining process and ultimately settle to the bottom of the cells.104 Generally, slimes generated from copper
refining of various ores have the same values and impurities, including gold, silver, platinum group metals, copper,
selenium, arsenic, tin, lead, and tellurium. However, their metals concentrations may vary widely, depending on the
ore from which the copper anodes have been obtained. The raw slimes always have high copper contents, and the
selenium content is also usually high. Therefore, normal slime treatment includes initial decopperization of the
slimes, followed usually by deselenization. Traditionally, these slimes are then sent to smelting in a dore furnace,
followed by refining.105 A new method of metals recovery gaining popularity is wet chlorination, which uses
chlorination and solvent extraction to recover these values.106 These materials often contain valuable quantities of
precious metals and are either processed on-site or are drummed and sent off-site for recovery. Approximately 4,000
metric tons of tankhouse slimes are generated annually.107 Although EPA found no published information regarding
waste characteristics, we used best engineering judgment to determine that this waste may exhibit the characteristic
of toxicity for selenium, silver, arsenic and lead. This partially recycled waste stream was formerly classified as a
by-product.
99 RTI Survey 100834, National Survey of Solid Wastes from Mineral Processing Facilities. Kennecott Utah
Copper, Bingham Canyon, UT, 1989.
100 Kennecott Corporation. Op. Cit.
101 Phelps Dodge Corporation. Op. Cit
102 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-3.
103 Exhibit 1. Qp.Cit.
104 James E. Hoffmann, "Advances in the Extractive Metal Metallurgy of Selected Rate and Precious Metals,"
Journal of Mines. 43, No. 4, 1991, pp. 22-23.
105 M. Devia and A. Luraschi, "A Study of the Smelting and Refining of Anode Slimes to Dore Metal," Copper 91
(Cobre 91). Ottawa. Ontario. Canada. 18-21 Aug. 1991. Pergamon Press, Inc., New York, 1992 p. 210.
10* James E. Hoffmann, 1991, Op. Cit. p. 23.
107 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-3.
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The Phelps Dodge Corporation's refinery in El Paso processes tankhouse slimes in its slimes treatment
plant. Treatment includes the removal of copper and tellurium, followed by deselenization through roasting. The
selenium-free calcine residue from the roasters is transferred to the precious metals plant, where it undergoes a wet
chlorination leach and solvent extraction for precious metals recovery. Recovery of precious metals involves
leaching with calcium nitrate to dissolve the contained silver, and electrowinning of the filtered silver nitrate solution
to produce high purity silver crystals. These crystals are melted in a silver-induction furnace and cast into silver
ingots. The silver-free calcine residue is leached. The residue is sent to the smelter for recycling and the liquor
containing dissolved gold is delivered to the solvent extraction process. The resulting high purity gold sand, which is
washed with dilute hydrochloric acid and alcohol, is melted in a gold induction furnace and cast into gold bars. A
platinum-palladium cake is produced from the raffinate, and the residual precious metals (gold, platinum and
palladium), rhodium, selenium and tellurium are removed by reduction with hydrazine. The hydrazine cake is
returned to the autoclave at the slimes plant for recycling until the concentrations of platinum and palladium give the
cake a red color, at which time it can be sold as platinum-palladium sponge.108 Tankhouse slimes are believed not to
be land stored.109
Acid plant blowdown. This waste originates in the gas cleaning section of the acid plant. It is generated
from the water spraying of smelter converter gases and consists largely of smelter feed carryover solids. Blowdown
has been reported to contain 14 percent sulfate, 15 percent total dissolved solids, 1 percent copper, 1 percent iron
and 70 percent water.110 Acid plant blowdown also may contain significant concentrations (i.e., >1,000 mg/L) of
arsenic, cadmium, lead, molybdenum, and selenium (additional data are included in Attachment I).111
Approximately 4,847,000 metric tons of acid plant blowdown are generated annually. This waste exhibits the
characteristics of toxicity (for arsenic, cadmium, chromium, lead, mercury, selenium, and silver) and corrosivity.112
This partially recycled waste was formerly classified as a by-product.
Site-specific management information is available for several facilities. Four of the seven primary copper
facilities generating acid plant blowdown (ASARCO Inc.'s Hayden, AZ and El Paso, TX plants; Cyprus Miami in
Claypool, AZ; and Phelps Dodge Corporation in Hurley, NM) beneficially recycle all of the acid plant material for
metals recovery, and thus do not generate K064. A fifth facility (Kennecott in Garfield, UT), currently generates
calcium sulfate wastewater treatment plant sludge, a special mineral processing waste excluded from RCRA Subtitle
C regulation under the Bevill Amendment, but is planning process changes that will result in the elimination of that
waste stream in favor of metals recovery from acid plant blowdown. The two remaining primary copper facilities
generating acid plant blowdown (Phelps Dodge in Hidalgo, NM; and BHP Copper (formerly Magma Copper) in San
Manuel, AZ) do not generate a sludge that meets the K064 listing description. Phelps Dodge treats its acid plant
blowdown with lime in a series of tanks, and discharges the resulting calcium sulfate wastewater treatment sludge to
double-lined surface impoundments equipped with monitoring wells, subject to the requirements of a state discharge
plan. 1I3
108 Phelps Dodge Corporation.;
109 Exhibitl. Op. Cit.
no
U.S. Environmental Protection Agency, 1991, Op. Cit.. pp. 5-7.
111 U.S. Environmental Protection Agency, Study of Remanded Mineral Processing Wastes Draft Report. Office
of Solid Waste, April 1994c, p. 19.
112 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-3.
113 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
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Cyprus Miami Mining Corp. in Claypool, AZ recycles the solid fraction to the smelter and the liquid
portion to the solvent extraction plant.114 At the Phelps Dodge Hidalgo Smelter, radial flow scrubbers have been
installed to minimize the volume of APB prior to neutralization of the APB with lime to create calcium sulfate
sludge. The calcium sulfate sludge is sent to a series of double-lined ponds where the liquid phase is decanted and
reused pursuant to New Mexico regulations.115 Chino Mining Company in Hurley, NM neutralizes the blowdown
with magnesium hydroxide in a settler. The solids are recycled to the smelter and the fluids are recycled to the
concentrator.116 At the Magma Copper Company's San Manuel, AZ facility, the blowdown is neutralized with
alkaline tailings,117 and the resulting mixture is sent to tailings dams.118 Kennecott Utah Copper in Bingham Canyon,
UT sends the blowdown to the hydrometallurgical plant where it is used as reagents/raw materials for metal
recovery. "9
Acid plant thickener sludge. This sludge results from the treatment of weak acid plant blowdown (see
above). In the past, this waste stream generally was discharged to either a tailings pond or an evaporation pond.
Recent site-specific information, addressing all Phelps Dodge facilities120 and several others, however, indicates that
this waste stream is no longer generated. Specifically, two facilities filter solids from the blowdown and blend the
recovered solids with incoming copper ore for beneficiation/processing. The filtered blowdown is routed to an on-
site electrowinning circuit for recovery of copper (and other metals). At a third facility, the blowdown is neutralized
with ammonia, then filtered, and the resulting solids are blended with incoming ore. The majority of the filtrate is
returned to the sulfuric acid plant for reuse as scrubber water, and the remaining portion of the filtrate is evaporated
to recover ammonium sulfate product. At a fourth facility, the blowdown is neutralized with magnesium hydroxide,
then filtered, and the resulting solids are blended with incoming ore. The filtrate is reused as make-up water in the
flotation circuit. At a fifth facility, the blowdown is first neutralized with alkaline tailings and then discharged to a
tailings pond (analysis of the neutralized blowdown indicates that it is not TC characteristic). At a sixth facility, the
blowdown is neutralized with lime and then sent to a double-lined, Subtitle C evaporation pond. At a seventh
facility, the blowdown is neutralized with lime, combined with other plant wastewaters, and then sent to an unlined
evaporation pond (analysis of the combined wastewater indicates that it exhibits the TC characteristic for arsenic,
lead, and selenium).121 Additional data are included in Attachment 1.
Waste contact cooling water. This waste results from heat exchanging operations, such as those taking
place at the smelter. The water used for anode cooling is reported to contain dissolved arsenic, copper, and zinc, and
also to pick up aluminum and chlorides, probably from mold dressing compounds.122 Site-specific management
information is available for several companies. The Magma Copper Company's San Manuel, AZ facility recycles the
114 RTI Survey 100156, 1989, Op. Cit.
115 Phelps Dodge Corporation. Op. Cit.
116 RTI Survey 100495, National Survey of Solid Wastes from Mineral Processing Facilities. Chino Mining Co.
Hurley, NM, 1989.
117 BHP Copper. Op. Cit.
ll* RTI Survey 100750, 1989, Op. Cit.
119 Kennecott Corporation. Op. Cit.
120 Phelps Dodge Corporation. Op. Cit.
121
U.S. Environmental Protection Agency, 1994c, Op. Cit., pp. 3-4.
122 U.S. Department of Commerce, Industrial Process Profiles for Environmental Use: Chapter 29 Primary Copper
Industry. Industrial Environmental Research Lab, July 1980. p. 89.
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copper anode cooling water to the concentrator.123 At Kennecott's facilities, waste contact cooling water is routed to
the KUCC process water system. The water is used for process water, and ultimately discharged to the tailings
impoundment, where it is pumped back into the process water system.'24 At Cyprus Miami Mining Corp., Claypool.
AZ. contact cooling water is returned to the Industrial Water System.ns According to the Phelps Dodge Corporation,
waste contact cooling water may be clarified or distilled in a brine concentrator prior to reuse in the production
process or as on-site irrigation water.126 Approximately 13,000 metric tons of contact cooling water is generated
annually.127 Although EPA found no published information regarding waste characteristics, we used best
engineering judgment to determine that this waste may exhibit the characteristic of toxicity for arsenic. This
recycled waste stream was formerly classified as a spent material.
WWTP liquid effluent. Treated effluent from the wastewater treatment plant is either disposed of in the
tailings surface impoundments or discharged through a NPDES permitted outflow, and therefore it is not included in
the analysis. The Phelps Dodge Corporation reportedly recycles WWTP liquid effluent back into its operations.128
Approximately 4,590,000 metric tons of WWTP liquid effluent is generated annually.129 We used best engineering
judgement to determine that this waste may exhibit the characteristic of toxicity for lead. Additional data are
included in Attachment 1.
Process wastewaters. Various processing wastewaters result from cooling and electrorefining operations.
Water is used for many things, including seal water in crushers and pumps, and for dust suppression in low grade
heat extraction from furnace cooling elements and acid plant coolers, sulfuric acid production, anode cooling, steam
production, electricity production, potable drinking water, and conveyance of sanitary sewage.130 Process
wastewaters may either be treated on site at wastewater treatment facilities or discharged to tailings ponds, surface
impoundments, or to receiving streams. At Claypool, process wastewater is limited to anode casting cooling water.
It is mixed with cooling tower effluent and stored for later recycling back to the process.131 At Magma Copper
Company's San Manuel site, process wastewater from both the electrolytic refinery and the flash furnace is sent to an
on-site tailings pond.132 At Copper Range Co.'s White Pine facility, process wastewater consists of contact and non-
contact cooling water. It is commingled with mill tailings and pumped to a tailings basin where the solids settle out.
The water is then discharged through permitted outfalls.133 Approximately 4,891,000 metric tons of process
123 RTI Survey 100750, 1989, Qp. Cit
124 Kennecott Corporation. Qp. Cit.
125 U.S. Environmental Protection Agency, 1991. Op. Cit. p. 3.
126 Phelps Dodge Corporation. Op. Cit.
127 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4.
128 Phelps Dodge Corporation. Op. Cit.
129
U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-4.
130 Christine P. Viecelli, "Comprehensive Water Management Program For a Primary Copper Smelter," Residues
and Effluents - Processing and Environmental Considerations," The Minerals, Metals and Materials Society, 1991, p.
82.
131 U.S. Environmental Protection Agency, 1991, Op. Cit. p. 5.
132 i
; RTI Survey 100750, 1989, Op. Cit.
133 RTI Survey 101782, National Survey of Solid Wastes from Mineral Processing Facilities. Copper Range Co.,
White Pine, MI, 1989.
253
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wastewaters are generated annually. This waste exhibits the hazardous characteristic of toxicity (for arsenic,
cadmium, lead and mercury) and corrosivity.134 We used best engineering judgement to determine that this waste
may also exhibit the characteristics of toxicity for selenium. This recycled waste stream was formerly classified as a
spent material. Additional data are included in Attachment 1, Hazardous process wastewaters are believed not to be
land stored prior to reclamation.135
Scrubber blowdown. This waste results when low volumes of high total dissolved solids (TDS) materials
are removed from the gas scrubbing system. At the Phelps Dodge Hidalgo smelter, electric furnace gases are
cleaned in a scrubber. The resulting effluent is either neutralized and recycled, or utilized as acid plant scrubber
liquor, and then neutralized with lime.136 Chino Mining Company in Hurley, NM neutralizes the blowdown with
magnesium hydroxide in a settler. The solids are recycled to the smelter and the fluids are recycled to the
concentrator.07 At Magma Copper company's San Manuel, AZ facility, Lurgi scrubber blowdown is usually
recycled back through the concentrator. Only during mechanical failure, or insufficient mill capacity does the
solution become mixed with acid plant blowdown and tailings for deposition on the tailings impoundments."8 At
Cyprus Mining Corporation, Casa Grande, AZ, scrubber blowdown resulting from tail gas cleaning operations using
a double-contact alkali scrubber generates a slurry that is discharged to a 40-mil lined lagoon.139 This waste exhibits
the characteristic of toxicity for arsenic, cadmium, and selenium, and may also be toxic for mercury.140 This partially
recycled waste stream was formerly classified as a sludge. Although no published information regarding the waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 49,000 metric tons/yr, 490,000 metric tons/yr, and
4,900,000 metric tons/yr, respectively. Additional data are included in Attachment 1, Scrubber blowdown is
believed not to be land stored.141
Discarded furnace and converter brick. This maintenance waste is periodically generated during
rebuilding of the furnace and converters. At one facility, bricks are crushed and stockpiled for recycling to the
sulfide mill where the copper is recovered through beneficiation. Furnace brick, at one location, was reported to
contain 7 percent iron, 6 percent copper, 2 percent magnesium, and 1 percent phosphorus.142 Approximately 3,000
metric tons of furnace brick is generated annually.143 Revert (molten matte that is spilled during its transfer in the
smelting process) also contains significant concentrations of copper and is returned to the crushing/grinding
134 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-4.
'"Exhibit 1. Op. Cit.
06 Phelps Dodge Corporation. Op. Cit
137 RTI Survey 100495, 1989, Op. Cit.
138
RTI Survey 100750, 1989, Op. Cit
139 j£p incorpOrated, Mineral Processing Waste Sampling Survey Trip Reports. Prepared for U.S. Environmental
Protection Agency, Office of Solid Waste, August 1989, p. 2.
140 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-4.
141 Exhibit 1. Op. Cit.
142 U.S. Environmental Protection Agency, 1991, Op. Cit.. p. 7. •
143 U.S. Environmental Protection Agency, 1992, Op. Cit, p. 1-4.
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circuit.144 At one facility, the converter bricks are re-processed through the smelter while the furnace bricks are
discarded. Some bricks may contain chromium above hazardous characteristic levels.145
APC dusts/sludges. Generated during smelting operations, these materials may contain significant
concentrations of copper. These dusts/sludges are typically fed back to the smelter.146 Site-specific management
information is available for several companies. At Kennecott Utah Copper, Bingham Canyon, UT, previously only
some of the copper-containing flue dust was returned to the smelting vessel; the majority of the flue dust was
stockpiled for future recycling.147 KUCC no longer stockpiles flue dust for future recycling. Formerly, stockpiled
material which could not be processed in the hydrometallurgical plant was disposed of at a properly permitted
disposal facility. Flue dust that is generated in the current process is automatically reprocessed for recovery of
mineral values in the hydrometallurgical plant.148 All APC dusts generated at Phelps Dodge have recoverable values,
and are recycled.149
Alternatively, bismuth can be recovered from air pollution control solids. Specifically, in copper smelting,
a portion of the bismuth is volatilized in the copper converter and captured along with such elements as lead, arsenic,
and antimony as a dust in a baghouse or cottrell system. The dust is then transferred to a lead smelting operation. A
major portion of the bismuth, however, also remains with the metallic copper. Therefore, during electrolytic refining
of the copper, the bismuth accumulates in the anode slime and can be reclaimed during recovery operations.150'151
Although no published information regarding waste generation rate or characteristics was found, we used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
of 100 metric tons/yr, 222,000 metric tons/yr, and 450,000 metric tons/yr, respectively. We used best engineering
judgement to determine that this waste may exhibit the characteristics of toxicity for arsenic. This fully recycled
waste stream was formerly classified as a sludge. APC dusts/sludges are believed not to be land stored and are fully
recycled.152
Surface impoundment waste liquids. The liquids sent to surface impoundments frequently contain
mixtures of tailings and process wastewater (such as slag concentrate filtrate), which may have been treated in a
wastewater treatment plant. Often the solids are allowed to settle out, and the liquids are discharged through
permitted outfalls. Approximately 615,000 metric tons of surface impoundment liquids are generated annually. This
144 U.S. Environmental Protection Agency, 1994b, Op. Cit. p. 11.
145 U.S. Environmental Protection Agency, Trip Report — Site Visit to Magma Copper and Cyprus Miami Copper
Mines." Draft Memorandum. Office of Solid Waste, April 1994b.
146 Gavin, P. Swayn, Ken R. Robilliard, and John M. Floyd, "Applying Ausmelt Processing to Complex Copper
Smelter Dusts," Journal of Mines. 45, No. 8, 1993, p. 35.
147ICF Incorporated, 1989, Op. Cit. p. 2.
148 Kennecott Corporation. Op. Cit.
149 Phelps Dodge Corporation. Op. Cit.
150 "Indium and Bismuth," ASM International Materials Handbook. Tenth Edition, Vol. 2: Properties and
Selection: Non-ferrous Alloys and Special-Purpose Materials, 1990, p. 753.
151 Funsho K. Ohebuoboh, "Bismudi-Production, Properties, and Applications," Journal of Mines. 44, No. 4,
1992. pp. 46-49.
'"Exhibit 1. Op. Cit.
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waste exhibits the hazardous characteristic of corrosivity.153 We used best engineering judgement to determine that
this waste may also exhibit the hazardous characteristic of toxicity for arsenic, lead, and selenium. Also, we used
best engineering judgement to determine that this waste stream is partially recycled. This waste was formerly
classified as a spent material. Additional data are included in Attachment 1.
Chamber solids/scrubber sludge. Approximately 31,000 metric tons of chamber solids and scrubber
sludges are generated annually from smelting on refining processes.154 Existing data and engineering judgment
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Spent black sulfuric acid sludge. This material is obtained from the vacuum evaporation of decopperized
electrolyte. The black acid liquor may also be used in leaching operations or be sold to fertilizer manufactures.153
Existing data and engineering judgement suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
WWTP sludge. This sludge results from the neutralization of process waters using magnesium hydroxide
or lime. This material is generated by the Phelps Dodge Hurley facility, which uses magnesium hydroxide, and the
Phelps Dodge Hidalgo smelter, which uses lime.156'157 Approximately 6,000 metric tons of solids and sludges are
generated annually.158 Although no published information regarding waste characteristics was found, we used best
engineering judgement to determine that this waste may exhibit the characteristic of toxicity for cadmium and lead.
This partially recycled waste stream was formerly classified as a sludge. Additional data are included in Attachment
1.
Attachment 2 contains a summary of the operational history and environmental contamination documented
at several former copper production sites that are now on the Superfund National Priority List.
D. Non-uniquely Associated Wastes
Non-uniquely associated hazardous wastes may be generated at on-site laboratories and include chemicals,
liquid samples, and ceramics/crucibles which are disposed of off-site at commercial hazardous waste facilities.
Other hazardous wastes may include spent paints and solvents (non-chlorinated solvents such as "140 Stoddard" and
petroleum naphtha, and "Safety Kleen" solvents) generated from facility maintenance operations, and spent
batteries. Waste oil also may be generated, and might be hazardous. Non-hazardous wastes are likely to include
sanitary wastewater, power plant wastes (such as run-off from coal piles and ash), and refuse.
Finally, spent catalysts (vanadium pentoxide) are generated in the acid plant. Acid plants at copper smelters
are ancillary operations that produce sulfuric acid from sulfur-rich smelter emissions. The spent vanadium pentoxide
153 Funsho K. Ohebuoboh, 1992, Op. Cit.
154 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4
155 U.S. Environmental Protection Agency, 1984, Op. Cit.. p. 3-12.
156
U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 13-74.
157 Phelps Dodge Corporation. Op. Cit.
158 U.S. Environmental Protection Agency, 1992, Op. Cit.
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catalyst is not unique to copper smelter acid plants, and is either sent off-site for recycling for the silica values,159 or
disposed of either on- or off-site.160
E. Summary of Comments Received by EPA
The Agency received information from nine public commenters on the MPSR's description of the copper
sector. (COMM36, COMM38, COMM40, COMM46, COMM58, COMM67, COMM73, COMM1085,
COMM1090) The Agency appreciates this information and has used it to update the summary of facilities, the
general process description, and the process waste streams description as included in sections B, C and D above.
New Factual Information
Three commenters provided new factual information that has been incorporated into sections B, C and D
above. One comrnenter identified the following materials as being recycled back into their processing operations:
raffinate, spent kerosene and WWTP effluent. (COMM38) One comrnenter stated that electrowinning produces lead
containing slimes and not precious metals laden slimes. (COMM67) One comrnenter stated that the process
wastewaters listed in the mineral processing section are actually beneficiation wastewaters. (COMM58) Seven
commenters provided new process description information. (COMM38, COMM40, COMM58, COMM67,
COMM46 ,COMM67, COMM40) One comrnenter provided a correction for the classification of scrubber
blowdown. (COMM67) Two commenters provided information on their sites' locations. (COMM38, COMM40)
One comrnenter corrected a description of the disposal of crad (COPMM38) Three commenters made the distinction
between sulfide ores which are pyrometallurgically processed versus oxide and low-grade sulfide ores which are
hydrometallurgically processed. (COMM38, COMM58, COMM67) One comrnenter clarified that calcium sulfate
sludge has a variable water content. (COMM38) One comrnenter included an alternate definition of slime.
(COMM38) One comrnenter stated that asbestos and PCBs are not hazardous wastes under RCRA. (COMM38)
Two commenters made corrections to the process flow diagram. (COMM58, COMM67) One comrnenter added to
the description of anode copper. (COMM67)
Sector-specific Issues
Seven commenters asserted that slimes, muds, crud, raffinate, barren leachate solution and spent kerosene
are uniquely associated. (COMM36, COMM38, COMM40, COMM46, COMM58, COMM67, COMM73) The
Agency agrees with these commenters and has changed the MPSR accordingly. One comrnenter criticizes the
generic nature of the process waste descriptions. The Agency acknowledges this fact and will modify the MPSR as
necessary. (COMM67)
The Agency received comments on numerous issues on which the Agency decided no action was required.
These issues include: the interpretation of the beneficiation/processing line (COMM40, COMM46); classifying
wastes on a site specific basis (COMM67); the reinterpretation of existing regulatory interpretations (COMM67);
report text about primary and secondary smelting that could be .interpreted incorrectly (COMM67); the basis for
determining beneficiation/processing line (COMM67); the Agency's use of best engineering judgment in making
toxicity determination of waste streams (COMM38, COMM58, COMM67); the validity that WWTP effluent is toxic
for lead (COMM38); surface impoundment wastes are not wastes since they are reused (COMM38); the aggregation
of process wastewater streams in determining hazardous characteristics (COMM67); the classification of converter
and anode slags (COMM38); relevance and basis for text in report regarding copper supply and demand
(COMM38); the classification of tankhouse slimes as wastes since they contain valuable mineral resources
(COMM38); the classification of waste contact cooling water as a waste discourages recycling (COMM38); the
classification of APC dusts as wastes, since they are reclaimed in smelters (COMM38); the recycling of process
related residues and sludges (COMM46); the classification of waste contact cooling water as a spent material
(COMM67); the classification of reused sulfurie acid as a spent material (COMM67); the classification of APC
159 Phelps Dodge Corporation. Op. Cit.
160 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 12.
257
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sludge should be as a by-product (COMM67); the "Surface Impoundment Waste Liquids" section duplicates
information in other sections (COMM67); the lack of identification of a waste referred to as "surface impoundment
waste liquid" on page 940 in Appendix D of the MPSR (COMM67); the multiple grinding and flotation of the clay
portion of ore is not recycling (COMM67); the Agency's distinction between tailings and slimes (COMM67); the
term "ancillary" as applied to vanadium pentoxide catalyst (COMM67); the case histories presented in attachment 2
(COMM67); the inadequate description of materials under the chamber solids/scrubber sludge heading (COMM67);
the importance of recycling water in the flotation circuit (COMM38);classification of converter and anode slag as
wastes (COMM38); the term waste rock (COMM38); the environmental impacts of leaching (COMM67); converter
slag, furnace brick, refinery bleed solution, wastewater sludge being reused within 48 hours of generation is
unpractical or impossible (COMM36, COMM67, COMM1085, COMM1090); containers are use to transport slag
but not for storage (COMM67); slags are not susceptible to weathering, blowing or erosion (COMM67, COMM40);
continuous closed loop recycling of spent electrolyte (COMM46); the alternative feedstock restriction ignores the
operation needs of copper smelters (COMM38); spent kerosene should not a waste (COMM67).
One commenter questioned how the generation rate of waste was used in determining the beneficiation/
processing line. (COMM67) The generation rate was applied to determine high volume/low toxicity wastes only
after primary mineral processing was determined to occur.
One commenter stated that slimes be reclassified as co-products and furnace and converter bricks be
reclassified as in-process materials. (COMM67) Because slimes require significant processing to recover the
precious metal values, they are not co-products. Bricks clearly are spent materials.
One commenter stated that the reuse of acid solution from the SMOC process might be a use constituting
disposal. (COMM67) This is not a use constituting disposal if the reuse is a legitimate operation and meets the
condition of recovering one or more of the following: metals, acid, water or cyanide.
One commenter cautions the Agency that ore should not be classified as having "high" or "low" value.
(COMM67) The Agency disagrees with this commenter because many facilities have written to state that they use
hydrometallurgical processes specifically on low grade sulfide ores. Without this terminology, it would be
impossible to make this distinction.
258
-------
BIBLIOGRAPHY
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1992, pp. 651-661.
Burniston, Tom, James N. Greenshield, and Peter E. Tetlow. "Crud Control in Copper SX Plants,"
Engineering and Mining Journal. 193, No. 1. January 1992. pp. 32-35
"Copper." Kirk-Qthmer Encyclopedia of Chemical Technology. 4th Ed. Vol. VII. 1993. pp. 381-419.
Draft Technical Background Document Characterization of Mineral Processing Wastes and Materials.
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Devia, M., and A. Luraschi. "A Study of the Smelting and Refining of Anode Slimes to Dore Metal."
Copper 91 (Cobre 91), Ottawa. Ontario. Canada. 18-21 Aug. 1991. Pergamon Press, Inc., New
York. 1992.
Driggs, Kenneth L, "Modern Converter Practices At Magma Copper." The Minerals, Metals, and
Materials Society, EPD Congress. 1991. pp. 265-269.
Eamon, Michael A., and Jackson G. Jenkins. "Plant Practices and Innovations at Magma Copper
Company's San Manuel SX-EW Plant." The Minerals, Metals, and Materials Society, EPD
Congress. 1991. pp. 239-252.
Edelstein, Daniel L. From Minerals Commodities Summaries. U.S. Bureau of Mines. January 1995. pp.
50-51.
Greenwald, Norman. Letter to Matt Straus, U.S. Environmental Protection Agency. June 4, 1992.
Hoffmann, James, E. "Advances in the Extractive Metal Metallurgy of Selected Rate and Precious Metals.'
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ICF Incorporated. Mineral Processing Waste Sampling Survey Trip Reports. Prepared for U.S.
Environmental Protection Agency, Office of Solid Waste. August 1989.
"Indium and Bismuth." ASM International Materials Handbook. Tenth Edition. Vol. 2: Properties and
Selection: Non-ferrous Alloys and Special-Purpose Materials. 1990. pp. 750-757.
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The Minerals, Metals and Materials Society. 1993. pp. 735-756.
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DC: U.S. Government Printing Office. September 1988.
Ohebuoboh, Funsho K. "Bismuth-Production, Properties, and Applications." Journal of Mines. 44, No. 4.
1992. pp. 46-49.
Public Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes, January 25, 1996.
Public Comment submitted in response to the Second Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes, October 10, 1997.
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259
-------
RTI Survey 100024. National Survey of Solid Wastes from Mineral Processing Facilities. Cox Creek
Refinery, Baltimore, MD. 1989.
'RTI Survey 100156. National Survey of Solid Wastes from Mineral Processing Facilities. Cyprus Miami
Mining Corp. Clay Pool, AZ. 1989.
RTI Survey 100487. National Survey of Solid Wastes from Mineral Processing Facilities. Hidalgo
Smelter, Playas, NM. 1989.
RTI Survey 100495. National Survey of Solid Wastes from Mineral Processing Facilities. Chino Mining
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RTI Survey 100750. National Survey of Solid Wastes from Mineral Processing Facilities. Magma Copper
Co., San Manuel, AZ. 1989.
RTI Survey 100834. National Survey of Solid Wastes from Mineral Processing Facilities. Kennecott Utah
Copper. Bingham Canyon, UT. 1989.
RTI Survey 101741. National Survey of Solid Wastes from Mineral Processing Facilities. Phelps Dodge
Refining Co., El Paso, TX. 1989.
RTI Survey 101782. National Survey of Solid Wastes from Mineral Processing Facilities. Copper Range
Co. White Pine, MI. 1989.
Sundstrom, John L. "Recycle of Tankhouse Solutions at Cerro Copper Products Electrolytic Copper
Refinery in Sauget, Illinois." Residues and Effluents - Processing and Environmental
Considerations. The Minerals. Metals and Materials Society. 1991. pp. 525-538.
Suttill, Keith R. "Pyromet or Hydromet?" Engineering and Mining Journal. 191. May 1990. pp. 30-35.
Swayn, Gavin, P., Ken R. Robilliard, and John M. Floyd. "Applying Ausmelt Processing to Complex
Copper Smelter Dusts." Journal of Mines. 45. No. 8. 1993. pp. 35-38.
U.S. Bureau of Mines. "Copper in November 1993." Mineral Industry Surveys. March 14, 1994,
U.S. Bureau of Mines. "Copper in October 1993." Mineral Industry Surveys. January 14, 1994.
U.S. Bureau of Mines. "Copper in September 1993." Mineral Industry Surveys. December 13,1993.
U.S. Department of Commerce. Industrial Process Profiles for Environmental Use: Chapter 29 Primary
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U.S. Environmental Protection Agency. Draft Overview of Solid Waste Generation. Management, and
Chemical Characteristics in the Primary Copper Smelting and Refining Industry. Industrial
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Set. Volume I. Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. "Primary Copper Processing." Report to Congress on Special
Wastes from Mineral Processing. Vol.11. Office of Solid Waste. July 1990. pp. 6-1 - 6-66.
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260
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U.S. Environmental Protection Agency. RCRA Mining and Mineral Processing Waste Outreach Support
Document - Draft. Office of Solid Waste. January 1994a.
U.S. Environmental Protection Agency. Revised Draft Wastes from Primary Copper Processing
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U.S. Environmental Protection Agency. Slag Reprocessing: Magma Copper Company's San Manuel
Facility Draft. Office of Solid Waste. March 1993b.
U.S. Environmental Protection Agency. Study of Remanded Mineral Processing Wastes Draft Report.
Office of Solid Waste. April 1994c.
U.S. Environmental Protection Agency, Summary of Cyprus Bagdad Copper Corporation's Pollution
Prevention Plan Draft. Office of Solid Waste. March 1993c.
U.S. Environmental Protection Agency. Technical Resources-Document Extraction and Beneficiation of
Ores and Minerals: Volume 4 Copper. Office of Solid Waste. 1993d.
U.S. Environmental Protection Agency. Trip Report — Site Visit to Magma Copper and Cyprus Miami
Copper Mines." Draft Memorandum. Office of Solid Waste. April 1994b.
Viecelli, Christine P. "Comprehensive Water Management Program For a Primary Copper Smelter."
Residues and Effluents - Processing and Environmental Considerations." The Minerals, Metals and
Materials Society. 1991. pp. 81-87.
Yoshiki-Gravelsins, K., J. M. Toguri, and R. T. Choo, "Metals Production, Energy, and the Environment,
Part II: Environmental Impact." Journal of Mines. 45. No. 8. August 1993. pp. 23-29.
261
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ATTACHMENT 1
262
-------
SUMMARY OF EPA/ORD, 3007, AND RT1 SAMPLING DATA - SPENT BLEED ELECTROLYTE - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Znc
Sulfate
Fluoride
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
6.20
23.20
0.02
0.25
0.03
-
0.03
0.84
1.90
10.00
54.30
0.25
9.13
0.62
0.0001
0.25
10.00
0.01
0.23
1.25
0.25
2.73
18,301
1.00
32.50
95,650
1.00
7.29
145.04
203.50
2,218.50
7.19
0.36
•
0.52
12.59
39.15
26,787
386.54
19.68
196.76
9.04
0.0050
62.58
6,357.30
4.25
2.75
17.92
3.58
25.84
218,273
1.00
121.63
224,330
1.93
153.63
356.00
565.00
11,500.00
18.00
1.00
-
1.00
38.00
124.00
120,380
1,360.00
90.60
503.00
32.60
0.0100
187.00
33,050.00
10.60
10.00
50.00
10.00
62.40
786,653
1.00
285.00
308,000
2.72
382.00
# Detects
5/5
9/9
10/10
3/4
2/3
0/0
3/4
4/4
4/4
14/14
8/8
6/6
4/4
4/4
3/4
2/3
10/10
5/5
3/4
2/3
2/3
5/6
11/11
1/1
6/6
5/5
4/4
3/3
EP Toxicity Analysis -
Minimum Average
10.00
20.50
10.00
0.40
0.05
-
0.02
0.80
1.69
485.00
89.40
0.25
14.40
0.79
0.0001
0.50
10.00
0.01
0.19
2.50
0.50
2.73
139.73
67.37
347.00
5.23
0.68
-
1.27
5.55
55.56
10,991.25
443.85
3.20
195.53
11.43
0.0019
67.83
200.67
7.18
5.17
34.17
6.83
28.48
PPM
Maximum
361.00
98.50
1,100.00
10.00
1.00
-
3.07
10.00
126.00
22,200.00
1,390.00
5.00
505.00
33.00
0.0062
193.00
365.00
10.00
10.00
50.00
10.00
63.00
# Detects
3/3
3/3
4/4
3/4
2/3
0/0
4/4
4/4
3/3
4/4
4/4
3/4
3/3
4/4
2/4
2/3
3/3
4/4
3/4
2/3
2/3
4/4
TC
Level
-
-
5.0
100.0
-
-
1.0
5.0
-
-
-
5.0
-
-
0.2
-
-
1.0
5.0
-
-
-
-
-
-
-
212
-
# Values
In Excess
-
-
4
0
-
-
3
2
-
-
0
2
-
-
0
-
-
3
2
-
-
-
-
-
-
-
3
-
NJ
cn
ui
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
tSJ
en
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - ACID PLANT SLOWDOWN - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organies (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum
1.16
0.26
0.05
0.05
0.005
-
0.20
0.10
0.02
1.80
7.90
0.20
2.10
0.05
0.00
0.50
0.01
0.00
0.00
0.25
0.05
5.10
766.00
20.60
0.10
170.00
0.99
1.39
870.32
36.44
855.76
1.38
0.07
-
62.93
3.62
3.35
3,151.86
2,402.62
1,061.28
638.49
40.61
0.32
70.68
221.33
78.97
11.52
1.38
1.39
1,737.16
23,198
761.02
793.01
13,593.70
2.21
436.30
5,200.00
140.00
5,800.00
5.90
0.13
-
620.00
21.00
9.00
40,000
10,000
17,900
2,070.00
140.00
1.50
390.00
1,450.00
1,000.00
124.00
2.50
2.72
10,000
135,570
1,780.00
2,740.00
58,600.00
5.00
1,300.00
# Detects
8/8
2/4
10/15
7/12
1/2
0/0
16/16
14/14
4/5
20/20
12/12
19/19
10/10
8/9
6/11
5/6
10/11
6/13
6/11
0/2
1/2
13/13
12/12
6/6
6/7
5/5
17/17
3/3
EP Toxieity Analysis -
Minimum Average
0.78
0.17
0.04
0.05
0.01
-
0.05
0.00
0.05
1.89
0.22
0.04
60.60
0.02
0.0001
5.91
0.02
0.01
0.01
0.25
0.05
3.16
750.39
2.58
884.35
2.54
0.25
-
4.28
0.41
5.03
144.53
103.82
2.83
1,015.30
10.20
0.0426
15.86
1.83
1.21
0.41
8.50
2.53
100.70
PPM
Maximum
1,500.00
5.00
12,800
10.90
0.50
-
24.50
5.00
10.00
1,190.00
1,010.00
6.74
1,970.00
100.00
0.3100
25.80
5.00
7.63
5.00
25.00
5.00
467.00
# Detects
2/2
1/2
12/15
8/15
0/2
0/0
14/15
11/15
1/2
9/9
10/10
13/15
2/2
7/10
8/15
2/2
2/3
11/15
6/15
0/3
0/2
10/10
TC # Values
Level In Excess
-
-
5.0 10
100.0 0
-
-
1.0 9
5.0 1
-
-
-
5.0 3
-
-
0.2 2
-
-
1.0 3
5.0 1
-
-
-
-
-
-
-
212 10
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - ACID PLANT THICKENER SLUDGE - COPPER
Constituents
Aluminum
Antimony
Arsenic
EJarium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
200.00
90.00
400.00
-
-
250.00
50.00
20.00
21,000
39,000
56,000
-
-
-
50.00
40.00
5.00
67.30
-
-
2,230
-
10.00
620.00
-
1.81
-
-
1,600.00
2,795.00
2,700.00
-
-
1,875.00
760.00
210.00
89,500
163,000
275,500
-
-
-
625.00
1,355.00
307.50
217.00
-
-
13,315
-
740.00
9,310
-
1.81
-
-
3,000.00
5,500.00
5,000.00
-
-
3,500.00
1,470.00
400.00
158,000
287,000
495,000
-
-
-
1,200.00
2,670.00
610.00
366.70
-
-
24,400
-
1,470.00
18,000
-
1.81
-
# Detects
0/0
2/2
2/2
2/2
0/0
0/0
2/2
1/2
2/2
2/2
2/2
2/2
0/0
0/0
0/0
2/2
2/2
1/2
2/2
0/0
0/0
2/2
0/0
2/2
2/2
0/0
1/1
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum
-
-
0.18
0.04
45.00
-
0.16
0.00
-
-
0.22
0.04
-
0.03
0.0003
-
-
0.03
0.02
-
-
3.16
-
-
52.44
3.69
45.00
-
7.97
0.03
-
-
23.50
1.94
-
0.36
0.1038
-
-
0.24
0.04
-
-
193.64
-
-
193.00
10.90
45.00
-
24.50
0.17
-
-
150.00
3.80
-
1.03
0.3100
-
-
0.61
0.10
-
-
500.00
# Detects
0/0
0/0
7/7
5/7
1/1
0/0
6/6
7/7
0/0
0/0
7/7
7/7
0/0
4/5
4/6
0/0
0/0
7/7
2/5
0/0
0/0
7/7
TC # Values
Level In Excess
-
-
5.0 5
100.0 0
-
1.0 4
5.0 0
-
-
-
5.0 0
-
-
0.2 2
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
212 1
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
01
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimim Average Maximum
0.798
-
-
-
-
-
0.002
0.023
-
130.00
-
0.050
0.354
0.060
-
0.011
0.014
-
-
-
-
0.600
1889.00
-
-
740.00
3.10
-
0.798
-
-
-
-
-
0,151
0.023
-
130.00
-
3.53
25.18
0.060
-
0.011
0.207
-
-
-
-
0.600
2744.50
-
-
1794.00
7.48
-
0.798
-
-
-
-
-
0.300
0.023
-
130.00
-
7.00
50.00
0.060
-
0.011
0.400
-
-
.
-
0.600
3600.00
-
-
2848.00
11.80
-
# Detects
1/1
0/0
070
0/0
0/0
0/0
2/2
1/1
0/0
1/1
0/0
2/2
2/2
1/1
0/0
1/1
2/2
0/0
0/0
0/0
0/0
1/1
2/2
070
0/0
2/2
5/5
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # [Meets
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
070
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
.
-
.
-
212
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - COPPER
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Crganics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
0,050
0.050
0,005
0.005
0.005
-
0.0003
0.005
0.010
0.050
0.090
0.003
0.221
0,050
0.0001
0.005
0.050
0.0005
0.004
0.250
0.050
0.01
216.00
5.40
28.40
1.50
1.35
0.60
1.23
0.73
14.90
27.57
0.02
-
1.26
1.86
0.15
227.31
957.33
36.39
485.67
8.03
0.0010
14.77
1.15
0.55
0.10
1.13
0.18
8.72
2,152.63
8.20
363.39
55,080
6.37
257.13
7,71
1.51
191.00
318.60
0.05
-
10.00
22.02
0.50
1,410.00
8,466.00
402.50
3,643.00
63.07
0.0050
100.30
5.30
7.00
0.50
4.00
0.50
42.00
7,519.00
11.00
1,862,00
270,800
8,50
1,280,00
i Detects
7/7
6/6
14/15
12/12
5/5
0/0
15/15
15/16
6/6
12/12
8/9
16/16
8/8
8/8
11/12
7/7
9/9
15/15
12/12
6/7
5/5
11/11
8/8
2/2
7/7
13/13
28/28
5/5
EP Toxicity Analysis -
Minimum Average
0.05
0.05
0.0003
0.0027
0.0050
-
0.0050
0.0001
0,0500
0.0500
0.0001
0.0020
3.3600
0.0250
8.00E-07
0.0500
0.0500
0.0002
1.50E-05
0.1000
0,0500
0.0170
1.02
0.38
4.75
0.26
0.01
-
7.31
0.12
0.05
159.88
33.69
1.39
24.39
1.22
0.1910
0.51
0.15
0.03
0.03
0.32
0.05
43.50
PPM
Maximum
4.91
0.95
23.20
1.20
0.01
-
32.00
0.53
0,05
664.00
139.00
7.30
59.00
8.00
1.0600
2.33
0.40
0,05
0.05
0.81
0.05
202.00
# Detects
5/5
5/5
11/12
12/12
5/5
0/0
12/12
12/12
5/5
7/7
9/10
12/12
5/5
10/10
5/11
1/5
3/6
5/12
11/12
6/6
5/5
12/12
TC # Values
Level In Excess
.
-
5.0 3
100.0 0
-
-
1.0 5
5.0 0
-
-
-
5.0 1
-
-
0.2 2
-
-
1.0 0
5.0 0
-
-
-
.
-
-
-
212 3
-
NJ
cn
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
(VI
CT>
00
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPUNG DATA - SCRUBBER SLOWDOWN - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
'/iagnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum
1,84
0.73
0.05
0.05
0.01
-
2.10
0.17
0.05
4.90
11.50
4.90
15.80
0.05
0.01
0.90
0,47
0.01
0.02
0.25
0.05
6.24
-
-
-
-
-
-
1.84
0.73
13.98
0.73
0.01
-
3,75
0.28
0.05
4.90
11.50
11.60
15.80
0.05
0.49
0.90
0.47
7.20
0.04
0.25
0.05
6.24
-.
-
-
-
-
-
1.84
0.73
27.90
1.40
0.01
-
5.40
0.40
0.05
4.90
11.50
18.30
15.80
0.05
0.98
0.90
0.47
14.40
0.05
0.25
0.05
6.24
-
-
-
-
-
-
# Detects
1/1
1/1
2/2
2/2
1/1
0/0
2/2
2/2
1/1
1/1
1/1
2/2
1/1
1/1
2/2
1/1
1/1
2/2
2/2
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis -
Minimum Average
1.63
0.65
27.40
0.05
0.01
-
1.93
0.17
0.05
3.05
9.50
4.88
14.80
0.05
0.022
0.85
0.44
7.71
0.05
0.25
0,05
6.28
1.63
0.65
27.40
0.05
0.01
-
1.93
0.17
0.05
3.05
9.50
4.88
14.80
0.05
0.022
0.85
0.44
7.71
0,05
0,25
0.05
6.28
PPM
Maximum
1.63
0.65
27.40
0.05
0.01
-
1.93
0.17
0.05
3.05
9.50
4.88
14.80
0.05
0.022
0,85
0.44
7.71
0.05
0.25
0.05
6.28
# Detects
1/1
1/1
1/1
1/1
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
1.0 1
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 1
5.0 0
-
-
-
-
-
-
-
212
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
2.20
0.06
0.001
-
-
0.01
0.02
-
0.01
0.63
0.03
0.10
0.02
0.0001
0.72
0.10
0.02
0.02
-
-
0.11
1,250.00
17.00
129.00
2,230.00
1.30
-
-
2.45
33.23
0.001
-
-
0.15
1.61
-
25.41
48.21
2.11
2.77
0.04
0.0001
1.76
0.97
3.08
0.02
-
-
0.57
6,908.25
17.00
1,573.50
11,742.50
6.36
-
-
2.70
150.00
0.001
-
-
0.30
4.00
-
90.00
88.00
7.00
4.20
0.06
0.0001
2.80
3.00
9.00
0.02
-
-
1.00
18,842.00
17.00
2,230.00
25,470.00
10.00
-
# Detects
0/0
2/2
5/5
1/1
0/0
0/0
2/2
3/3
0/0
7/7
3/3
4/4
3/3
2/2
1/1
2/2
4/4
3/3
1/1
0/0
0/0
3/3
4/4
1/1
4/4
4/4
9/9
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0.25 0.25 0.25 2/2
5.00 5.00 5.00 2/2
0/0
0/0
0.05 0.05 0.05 2/2
0.25 0.25 0.25 2/2
0/0
0/0
0/0
0.25 0.25 0.25 2/2
0/0
0/0
0.10 0.10 0.10 2/2
0/0
0/0
0.05 0.05 0.05 2/2
0.25 0.25 0.25 2/2
0/0
0/0
- 0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
212 2
-
NJ
cn
ID
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
-sj
O
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE - COPPER
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
50,000 225,000 400,000 2/2
150,000 150,000 150,000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0002/2
pH* 3.10 6.05 9.00 2/2
Organics (TOC) - - - 0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
212
0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
ATTACHMENT 2
MINING SITES ON THE NATIONAL PRIORITY LIST
271
-------
Name of Site:
Owner of Site:
Location of Site;
Climate Data:
Commodity Mined:
Facility History:
Waste(s) at Issue:
Disposal Sites:
Mining Sites on the National Priority List
Anaconda Smelter
Anaconda Copper Mining Company (merged with ARCO in 1977)
Mill Creek, Montana (26 miles west of Butte)
To be determined
Copper
The Anaconda Copper Mining Company first began copper smelting operations in 1884
at the "Upper Works" smelter. The Upper Works consisted of a concentrator and smelter
buildings, which housed roasters and reverberatory furnaces, all connected to masonry
flues and two smokestacks. By 1887, the company had expanded and built an additional
smelter 1 mile east of the Upper Works. The new smelter was known as the "Lower
Works". By 1889, aa electrolytic copper refinery had been built as well, and was located
between the two smelters. Due to shortage of smelling capacity, a larger, more efficient
copper smelter was completed in 1902, and known as "Smelter Hill" or "Washoe
Smelter". The Upper and Lower Works were subsequently demolished in 1903. The
Washoe Smelter operated from 1902 to 1980.
Copper ore processing has produced wastes that cover over 6,000 acres and contain
elevated levels of arsenic, cadmium, copper, lead, and zinc. Wastes include. 185 million
cubic yards of tailings (pond); 27 million cubic yards of granulated slag (pile); and 0.25
million cubic yards of flue dust. Stack emissions have contaminated the soils near the
smelter. Ongoing fugitive flue dust emissions (from piles) and fugitive dust emissions
(from soil) have contaminated the community for over 100 years.
This site has 12 Operable Units, but only two have been investigated:
Mill Creek Operable Unit — Mill Creek is an unincorporated community located
approximately 25 miles west-northwest of Butte, Montana. It covers 160 acres of land
and consists of 37 household with less than 100 people. The contaminants of concern in
this Operable Unit are arsenic, lead, and cadmium. Arsenic dust in the air, and arsenic,
lead, and cadmium in the soil and drinking water present public health risks.
Flue Dust Operable Unit — flue dust is a fine grained waste material which was formed in
the smelter flue. The dust contains high concentrations of arsenic, cadmium, copper.
lead, and other metals. The amount of flue dust stored onsite, as of December 1989, was
estimated to exceed 316,000 tons.
The other 10 Operable Units are as follows: Smelter Hill — former ore processing area.
This Operable Unit has soil and ground water contamination by metals. Old Works —
Wastes (tailings) are located in a 100-year floodplain along a 2.75 mile stretch of Warm
Springs Creek. This area is the focus of a removal operation. In addition, waste piles and
soils at the smelter site and surface water near the site will be sampled. Arbiter — a
copper refining plant that produced cathode copper from sulfide ores using an ammonia
leach process. Slurry wastes from this inactive plant contain arsenic, cadmium, lead, zinc,
and are located in a pond near the plant. Beryllium Disposal Areas — a beryllium flake-
metal pilot plant and a beryllium oxide pilot plant were operated on Smelter Hill between
1964 and 1968. Following closure, waste containing beryllium was disposed of in the
Opportunity tailings pond. Communityjioils — nearby community soils contaminated by
smelter emissions. Slag — slag is the material separated from the metal during refining
process; it consists of 85% silica dioxide (sand) and 15% iron oxide. Tailings/Alluvium
272
-------
Soil Pathway:
Ground Water
Pathway;
Surface Water
Pathway:
Air Pathway:
Environmental Issues:
— tailings make up the largest volume of waste at this site and are deposited in both the
Anaconda and Opportunity ponds. The Opportunity ponds stretch 3 miles across from
east to west. Regional Soils — contaminated agricultural lands surrounding the site.
Regional Ground Water — ground water which have been contaminated from sources
such as the Opportunity ponds, slag piles, tailings, and contaminated soils. Surface water
and sediment — tailings have migrated into streams near the site.
It was discovered that the soil contamination (by arsenic, cadmium, and lead) in Mill
Creek was widespread. The geometric mean concentration of arsenic in Mill Creek
surface soils is 638 mg/kg; for cadmium it is 25 mg/kg; and for lead it is 508 mg/kg. At a
depth of 18 inches, concentrations of arsenic are below 100 mg/kg and approach
background levels at 42 inches below the surface. High concentrations of cadmium and
lead are also found in the first 6 inches of the soil profile. However, lead and cadmium
concentrations decrease more rapidly with depth than arsenic concentrations. Cadmium
levels were found to be less than detection limits at a depth of 9 inches, and lead levels
reached background levels below 6 inches.
The water table underlying Mill Creek is 20 feet or deeper below the surface.
Domestic well water is drawn from this aquifer. In 1986, sampling showed that seven
household water supplies had detectable arsenic levels. Cadmium and lead levels were
mostly at or below detection limits.
Mill Creek is the major drainage system is the area of the Anaconda Smelter and
The Mill Creek community. Mill Creek was sampled four times and results showed that
arsenic was present in the creek. Total arsenic concentrations ranged form 12 to 32.2
ug/1. Zinc was also detected in the waters of Mill Creek. Until transport of contaminated
soil into Mill Creek is controlled or remedied, it is estimated that recontamination of Mill
Creek will occur at a rate of 1.5 mg/kg of soil per year.
In 1984, samples of airborne paniculate matter were collected at four different locations
near the smelter and tested for.total suspended particulates, respirable particulates, and
trace-metal content. Arsenic concentrations were found to be 0.1 mg/m3. The highest
arsenic concentration found at the Mill Creek station was 0.681 mg/m3. Elevated levels
of cadmium, lead, and arsenic were found in household dust samples as well. Residential
dust showed an average concentration of 264 mg/kg arsenic, and indoor respirable arsenic
concentrations were 0.019 ug/mj.
The Anaconda Smelter site is located in the Upper Clark Fork Basin above Warm Springs
Creek and the main stem of the Clark Fork River to the Bitterroot River below Missoula,
Montana. In addition, the community of Mill Creek is immediately adjacent to this site.
Therefore, contaminants from the Anaconda Smelter site (e.g., arsenic, lead) pose a
potential risk to human health and the environment (e.g, aquatic life, drinking water).
273
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Mining Sites on the National Priority List
Name of Site: Tex Tin Corporation
Owner of Site: Tex Tin Corporation
Location of Site: Texas City, TX (situated on 175 acres in an area of mixed land use)
Climate Data:
Not given
Commodity Processed: Secondary copper smelting
Facility History:
Waste(s) at Issue:
Disposal Site:
Originally operated by the U.S. Government during World Ward II as its primary tin
smelting operation, the site was then acquired by the Associated Metals and Minerals
Corporation from the Wah Chang Corporation in 1970 and became know as the Gulf
Chemical and Metallurgical Company (GC&M). Since 1985, the company has been
known as the Tex Tin Corporation. At one time, the facility was operated as an iron
recovery facility, but it is currently engaged in the secondary smelting of copper. The Tex
Tin site was added to the NPL in August 1990.
Heavy metals (arsenic, tin, lead and nickel) found in onsite surface and ground water, and
in ambient air sampled on and off the site.
In 1977, the Tex Tin had three metals reclamation circuits: nickel sulfate, ferric chloride.
and tin. Nickel sludge circuit - The nickel sludge was stored in drums in the north end of
the smelter building. After smelting, waste sludge was sold for other metals recovery. A
small quantity removed during vessel cleaning was dumped with the slag from the tin
process. Ferric chloride circuit - The company was sold iron sludge contaminated with
the herbicide Amiben. The material was stored in two areas (not specified). Runoff
would flow through the plant to the pond system, A small quantity removed from the
settling tank was disposed of in Acid Pond B. Tin ingots circuit - The product was
received in the form of ore sacks (imported from Bolivia) which were stored on pallets by
Ponds A and B, tin residues in 55-gallon drums which were stored in the ore storage
building, and tin ore which were piled along Highway 519. After primary smelting, rich
slag was stored onsite. End slag was produced after the electrolyte process and GC&M
planned to install a new rotary furnace for secondary tin smelting. In 1979, the nickel
circuit had been discontinued. Ferric chloride production had also decreased which
caused GC&M to cease buying Amiben-contaminated iron sludge for use in this circuit.
GC&M also stopped disposing of the settling-tank sludge in the acid pond. A rotary
furnace was added to the tin circuit which resulted in material dumped north of the acid
pond. Waste areas identified at the site have included wastewater treatment ponds, a
gypsum slurry pond, an acid pond which once contained ferric chloride and hydrochloric
acid, several drained acid ponds, slag, sludge, and ore piles. One of the slag piles is
contaminated with the herbicide Amiben. The facility also stored approximately 4,000
drums containing radioactive material. At one time, the facility stored piles of spent
catalyst in the anticipation of building a plant to extract metals such as tungsten. An
inactive, licensed, low-level radioactive landfill, containing uranium/antimony slag, is
also located onsite. The slag is from a pilot study on the extraction of bismuth from a
bismuth-uranium catalyst. One other area of possible contamination, an abandoned oil-
processing facility, has been identified on the Tex Tin property. The Morchem Resources
facility was located on the northwestern portion of the site (then owned by GC&M) from
1982 to 1983. Morchem processed Luwa bottoms (high boiling-point glycols with 1%
molybdenum) and waste oil from chemical and refining companies. The facility was
abandoned in 1984. No other information is known about this facility.
274
-------
Soil Pathway:
Ground Water
Pathway:
Surface Water
Pathway:
Air Pathway:
Environmental Issues:
Possible soil contamination is not well characterized. In 1980, EPA conducted a
Potential Hazardous Waste Site Inspection. Piles of tin slag, iron ore, and crushed empty
barrels were noted in the rear of the plant. A reddish material (possibly iron) was noted in
the drainage ditch located close to the area of the material piles. One soil sample was
collected by the Texas Department of Health's Bureau of Radiation Control near the low-
level radioactive landfill in December 1984. The four metals detected were found to be at
significantly elevated concentrations and considered a health concern. They include:
antimony (2,590 ppm), arsenic (720 ppm), copper (130 ppm), and lead (980 ppm). The
level of copper in the soil was not sufficiently elevated to represent a health concern.
The Chicot Aquifer underlies the site and extends from 60 feet to approximately
1,000 feet below the land surface. The flow is generally in a southeasterly direction
towards Galveston Bay, Ground water in die vicinity of the acid pond was monitored
from 1975 to 1980. The monitoring wells were screened at 37 to 47 feet below the
ground surface. The contaminant concentrations detected were much higher from the
downgradient wells' samples as compared to the upgradient well. Twelve metals were
detected and determined to exceed drinking-water standards and long-term health
advisories. The metals of concern and their maximum concentrations detected include:
arsenic (0,198 ppm), barium (6.5 ppm), cadmium (7 ppm), chromium (0.25 ppm), copper
(390 ppm), lead (200 ppm), manganese (357 ppm), mercury (0.011 ppm), nickel (7 ppm),
silver (1.02 ppm), tin (100 ppm), zinc (140 ppm).
Inspections by the Texas Water Quality Board concluded that dikes designed to
prevent discharges from two old outfalls and the acid pond were seeping, allowing
contaminated water to enter Wah Chang Ditch. The ditch is currently pumped into the
Texas City Industrial Channel, which enters Galveston Bay. Twelve surface water
samples were collected from various locations at the facility between 1975 to 1988. The
constituent of concern and their maximum detected levels include: arsenic (0.94 ppm),
chromium (81 ppm), copper (60 ppm), mercury (0.02 ppm), nickel (535 ppm), zinc (42.7
ppm).
In January 1986, air-quality monitoring samples were obtained along die site perimeter
using high-volume particulate samplers. The conclusion reached after me sampling was
that heavy metals and arsenic were being carried offsite by the wind. The maximum
values of the detected contaminants were: arsenic (2.34 ug/m3), cadmium (0.64 ug/m'),
chromium (0.40 ug/m3), lead (4.42 ug/m3), nickel (0,21 ug/m3), and tin (103.6 ug/m3).
Commercial businesses, residential areas, and petrochemical complexes are, all located
within 0.25 miles of the site. The saline Swan Lake is located approximately 2 miles from
the site and is used primarily for recreational fishing and crabbing. A principal concern is
the potential environmental contamination of surface waters through the transport of
heavy metals into Chicot Aquifer, and drainage of contaminated water into Galveston
Bay. Most drinking water is supplied municipally, however, a 1985 survey identified a
small beach house community located approximately one mile southwest of the Tex Tin
facility that uses private water wells. The community, consisting of approximately 60
homes, is supplied by 25 wells. While most of the wells are more than 200 feet deep, at
least three of the wells are less than 105 feet deep and are in the Chicot Aquifer. Possible
human routes of exposure were noted as ingestion, inhalation, and dermal contact with
contaminated media. Inhalation and incidental ingestion of airborne particles of Tex Tin
emissions or entrained dust have also been cited as potential pathways of concern. In
addition, low levels of radioactivity have been detected onsite in association with the tin,
copper, and antimony slags and with the company roads that have been graded with tin
slag. According to the Bureau of Radiation Control, the radiation levels are well below
Federal occupational exposure limits, but are approaching the upper limits of the range of
levels generally considered safe for the general public.
275
-------
Page Intentionally Blank
276
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Mining Sites on the National Priority List
Name of Site:
Owner of Site:
Location of Site:
Climate Data:
Commodity Mined:
Facility History:
Waste(s) at Issue:
Disposal Site:
Tailings:
Torch Lake
Not applicable
Keweenaw Peninsula of Upper Michigan (14 miles from Lake Superior)
Not given
Copper
For over 100 years, the area surrounding Torch Lake was the center of Michigan's copper
mining, smelting, arid milling activities. Over 10.5 billion pounds of copper were
processed in the area between 1868 and 1968. An estimated 5 million tons of copper
were produced in the Keweenaw Copper District of Michigan from the 1960's to 1968.
More than half of this was processed along the shores of Torch Lake. Mining activities in
the lake area peaked between the early 1900's and 1920. By 1986, only one small copper
recovery plant was still operating. Torch Lake was listed on the NPL in June 1988.
At the mills, copper was processed and the recovered copper was sent to a smelter, while
tailings were disposed of with process wastewaters into or on land around Torch Lake. In
1916, copper was recovered from previously discarded tailings in Torch Lake through an
ammonia leaching process. Further technological advances initiated a flotation process
using reagents consisting of 50 percent coal tar, 15 percent pyridine oil, 20 percent coal
tar creosote, and 15 percent wood creosote. In 1926, xanthates were added to the
reagents. Between 1868 and 1968, an estimated 200 million tons of tailings were pumped
into the lake, reducing its volume by approximately 20 percent.
The Torch Lake site has three operable units (OUs). OU1 includes surface tailings,
contents of buried and submerged drams along the western shore of the lake, and
industrial chemicals. OU2 includes potentially contaminated media in and around the
lake. OU3 includes other tailings sources in the mid-Keweenaw Peninsula, including the
North Entry, the northern portion of Portage Lake, and tributary areas.
Mine tailings are divided into two categories. The first involves tailings resulting from
crashing and gravitational separation processes. The resulting contaminants of concern
are; arsenic, copper, lead, and zinc. The second category of tailings is a result of flotation
reprocessing. The contaminants of concern associated with this category include: arsenic.
copper, lead, zinc, and industrial chemicals (lime, pyridine oil, coal tar creosotes, wood
creosote, pine oil, and xanthates). Surface and subsurface tailings samples were collected
and analyzed. Fifty eight surface samples were collected from a 0- to 6-inch depth and
density of 1 sample per 10 acres. Twelve subsurface samples were collected from a depth
of 0 to 3 feet and at a density of 1 sample per 20 acres. The sampling analysis indicated
that the concentration and distribution of metals appeared to be similar in both surface
and subsurface samples. Copper concentrations were elevated above background soil
concentrations (3,020 mg/kg surface and 5,540 mg/kg subsurface as compared to 100
mg/kg in native soils). In summary, however, neither organic or inorganic compound
levels in tailings from OU1 were found to be dramatically higher than background soils.
In 1989, the U.S. Bureau of Mines determined that leachate from Torch Lake mine
tailings was extremely low in comparison to leachate from 30 other sites and they
concluded that very little metal is being released from the tailings.
277
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Drums:
Soil Pathway:
Ground Water
Pathway:
In 1989, buried and submerged drums in tailings piles were discovered and determined to
have very low hazardous constituent concentrations as measured by EP Toxicity tests,
PCBs and pesticides were not found above the detection limits in the samples. The eighth
drum contained 4,000 ppm of trichloroethylene; and it is suspected that the contents of the
drum are related to illegal dumping.
A limited soil investigation found that traces of tailings and slag were evident. The
contaminants of potential concern and their maximum values detected include: aluminum
(7,600 mg/kg), arsenic (7 mg/kg), barium (101 mg/kg), chromium (20.1 mg/kg), copper
(459 mg/kg), lead (329 mg/kg), manganese (357 mg/kg), mercury (0.47 mg/kg), nickel
(33.7 mg/kg), and vanadium (26.30 mg/kg). Soil samples from residential locations
generally had concentrations of inorganic compounds an order of magnitude higher than
background concentrations. The EPA Technical Assistance Team (TAT) also collected
samples from the east side of Torch Lake and determined that the metals detected in the
samples were all within typical soil background concentrations and below maximum
concentrations for EP Toxicity.
The U.S. Geological Survey sampled well water in 1968 and 1977. Analysis of the
35 wells in Houghton County indicated that only 3 had specific conductance greater than
500 micromhos per centimeter. These results indicated Torch Lake as a high quality
water source for general use. Many Torch Lake communities and seasonal residents get
their water from municipal systems or from an independent supplier. In July 1989, EPA's
TAT sampled seven private wells and two municipal wells. Only one location sampled
had a concentration of either organic or inorganic compounds in excess of the Maximum
Contaminant Levels (MCLs). The sample collected from the Lake Linden municipal well
had an iron concentration of 0.33 ppm which is slightly greater than the Secondary MCL
of 0.3 ppm for iron. Ground water contamination is to be discussed further in the ROD
for OU2.
Surface Water
Pathway:
Air Pathway:
Environmental Issues:
Water enters Torch Lake from the Trap Rock River, and Hammell, Dover,
McCallum, and Sawmill Creeks. The Trap Rock River is the largest discharger into
Torch Lake, and the Trap Rock River Watershed covers approximately 58 percent of the
Torch Lake Drainage Basin, An estimated 2,000 kilograms per year of dissolved copper
is transported through Trap Rock River and its tributaries into Torch Lake.
Contamination of the surface water is to be addressed in the ROD for OU2.
The Michigan Department of Resources (MDNR) collected air samples from four
sampling locations (based on wind and population profiles) to monitor likely exposure
points, emissions sources, and background conditions. Total Suspended Particulates
(TSP) samples were collected for one month, for 24-hour periods every other day in
1989. Further analysis of the two samples indicating the highest concentration of TSP
were further analyzed for arsenic, chromium, copper, nickel, lead, and zinc. The analysis
indicated that mean ambient-air concentrations at the two sample stations exceeded
background ambient-air concentrations for aluminum, arsenic, barium, copper,
magnesium, iron, manganese, and TSP,
A century of mining waste deposition into Torch Lake created environmental concerns in
the 1970's. In 1971, a discharge of cupric ammonium carbonate leaching liquor from the
Lake Linden Leaching Plant occurred and MDNR reported discoloration of several acres
of lake bottom. Further investigations found 15 water quality parameters with acceptable
background ranges. Heavy metal concentrations in lake sediments were within
background ranges, except for arsenic, chromium, zinc, and copper, which were all at
elevated levels. Plant and benthic invertebrate analysis did not indicate any water quality
changes. Three months later, the spill was cited as the cause of temporary depletion of
oxygen, elevated copper levels, increased pH, and increased carbon alkalinity in the lake
278
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and bioassays indicated toxicity to some macroinvertebrates. Changes in the dominant
predator fish species and observance of abnormalities in certain fish species prompted a
fish consumption advisory in 1983 for Sauger and Walleye.caught in the lake. In the
same year, the lake was designated as a Great Lakes Area of Concern (AOC). In 1988,
the Agency for Toxic Substances and Disease Registry (ATSCR) concluded that the site
is a potential public health concern because of possible exposure to unknown etiological
agents that may create adverse health effects over time. The mine tailings contaminating
Torch Lake have not been determined to cause known health effects, and there is no
indication that human exposure is currently occurring or has occurred in the past.
279
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Page Intentionally Blank
280
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ELEMENTAL PHOSPHORUS
A, Commodity Summary
Phosphorus is the twelfth most abundant element, almost all of which occurs as salts of phosphoric acid.
Phosphate rock deposits occur as marine phosphorites, apatite-rich igneous rock, and modern and ancient guano.
Apatite minerals comprise the majority of phosphate constituents in phosphate rock. All domestic production is from
marine phosphorites. According to the U.S. Bureau of Mines, nearly 93 percent of the phosphate rock sold or used
by U.S. producers in 1991 was for the manufacture of wet-process phosphoric acid, single superphosphate, and triple
superphosphate; the balance (approximately 7 percent) was used to produce elemental phosphorus.1
Solid elemental phosphorus exists in several allotropic forms — white, red, and black. The most
commercially important is white (elemental) phosphorus. Red phosphorus is also important commercially. Black
phosphorus has been prepared only in a few laboratories.2
Phosphorus-based materials are used mostly in fertilizers, detergents, foods and beverages, and metal
treatment coating. Elemental phosphorus is used as a process input to produce a wide array of phosphorus
chemicals. Most phosphorus is converted to derivatives, including phosphorus sulfides and halides, phosphorus
pentoxide, and phosphoric acid. Elemental phosphorus is used in the deoxidation and alloying of copper; and
elemental phosphorus is used with ferrophosphorus in ferrous metallurgy. White phosphorus is also used in roach
and rodent poisons, chemical warfare, and other military purposes. Generally, red phosphorus is made from white
phosphorus. Red phosphorus is used for wooden and paper safety matches and in the manufacture of fireworks.3
According to the largest U.S. producer of phosphorus, there are four domestic producers of elemental
phosphorus. FMC operates a facility in Pocatello, ID and Monsanto operates a facility in Soda Springs, ID. The
remaining two facilities are owned and operated by the Rhone Poulenc Basic Chemical Company and the Occidental
Chemical Company.4 These are located Silver Bow, MT and Columbia, TN, respectively,
B. Generalized Process Description
1. Discussion of Typical Production Processes
Phosphate rock is mined using both surface and underground mining techniques. A modern electric furnace
process for the production of phosphorus consists of a sequence of four operations: preparing the furnace burden,
charging and operating the furnace, collecting the liquid products, and collecting the gaseous products.5
1 David Morse, "Phosphate Rock," from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines, 1992, pp. 977-980.
2 "Phosphorus and the Phosphides," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XVII,
1982, pp. 473-490.
3 Ibid.
4 FMC Corporation. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
5 Kirk-Othmer Encyclopedia of Chemical Technology. Op. Cit.
281
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2. Generalized Process Flow Diagram
White Phosphorus
Exhibit 2 presents a process flow diagram for the production of white elemental phosphorus. The furnace
burden must be porous enough to allow gases to escape from the reaction zone near the bottom of the furnace.
Several agglomeration methods must be employed to prepare phosphate rock fines for the electric furnace. The
fines must be sintered and then crushed to size and screened. Another agglomeration method is nodulizing. In this
process, phosphate fines are heated in a rotary kiln to incipient fusion. The tumbling in the kiln causes the material
to cohere and form spheroidal agglomerates. A final method of agglomeration is formation of pellets by tumbling.
The pellets can then be calcined in a rotary kiln.6
The agglomerated phosphate rock is charged to an electric arc furnace with coke as a reductant and silica as
a flux. The reduction generates a calcium silicate slag and ferrophosphorus, which are tapped, and carbon monoxide
offgases that contain volatilized phosphorus. Dusts are removed from the offgases using dry separation techniques
such as electrostatic precipitation, and phosphorus is removed by condensation in the presence of recirculation water
above the melting point of phosphorus. The carbon monoxide gases are subsequently burned, and phosphorus is
decanted from the water and stored for sale. The recirculating water is neutralized, and a purge of mud and soluble
impurities is removed and disposed.7
Red Phosphorus
Although red phosphorus is usually manufactured by a batch process, continuous methods are now being
used. In the batch process, white phosphorous is converted to red phosphorus in a steel or cast-iron vessel. The
liquid phosphorus, which is protected by a layer of water, passes into the vessel, which then is closed. The vessel is
heated gradually so that unconverted liquid phosphorus does not boil violently and erupt. A reflux condenser is used
to retain the phosphorus. The mass remains fluid until almost half of the phosphorus has turned into red phosphorus.
As the process continues, the mass thickens and solidifies. The mass is cooled and red phosphorus is removed. The
material is then wet-ground and boiled with sodium carbonate solution to remove any traces of white phosphorus,
which is flammable in air. The red phosphorus is sieved, washed on a rotary filter, vacuum dried, and stabilized by
one of two methods. In the first method, red phosphorus is suspended in a sodium aluminate solution and then
aerated. In the second method, magnesium oxide is precipitated onto the red phosphorus.8
FMC Facility Process9
FMC Corporation is the world's largest producer of elemental phosphorus, producing about 240 million
pounds of elemental phosphorus per year. Under normal operating conditions, this process operates 24 hours per
day, 365 days per year.10 Because of the large quantities of elemental phosphorus produced here and the importance
of this facility in the market, FMC's process is described below and a process flow sheet is presented in Exhibit 3.
This information was provided by FMC. The Agency may not necessarily agree with FMC's characterization of its
waste streams.
6 Ibid.
7 Ibid.
8 Ibid.
9 The processes discussed in this technical background document pertain to production at the FMC Pocatello, ID
plant, and may not be fully representative of industry practices employed by the other three domestic phosphorous
producers.
10 FMC Corporation. Op. Cit. January 25, 1996.
282
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Storage and Preparation of Raw Materials
Storage and preparation of raw materials consists of stockpiling; screening and crushing; briquetting;
calcining; and proportioning of the shale ore, coke, and silica. Shale ore arrives at the plant by railcar and is
unloaded by a rotary car dumper. The ore is conveyed to the stacker for distribution on one of two storage piles.
Ore is then collected from the piles by a reclaimer which deposits it on a conveyer belt. The conveyor belt carries
the ore to crushing and screening. Ore is first screened to remove oversized material and then crushed to a uniform
size and sent to the briquetting process. Fugitive dust from screening and crushing is collected by three baghouses.
The briquetting process presses the crushed material into briquettes similar to the size and shape of charcoal
briquettes, which are fed to the calcining process. FMC Pocatello's calciners are sintering operations in which the
briquetted shale is heated to form a coherent mass without melting. The calcining operation is therefore principally
an agglomeration method. The process occurs in grate calciners in which the briquettes are carried on moving grates
or pallets through the calcining zone where hot gases are pulled through the feed bed (the briquettes) and grate.
Because the briquettes ride on the moving pallets they undergo little or no tumbling or other motion during this
process. Water and carbon dioxide are given off during this process, but the temperatures are carefully controlled
below the fusion point of the phosphate shale. Temperatures above the fusion point result in a phenomenon known
as "fusing the bed" in which the briquettes on the pallets fuse into a single, rigid mass that cannot be handled in
FMC's downstream material handling equipment. FMC calcines the ore for two reasons: (1) to harden the
briquettes, thereby limiting briquette breakage; and (2) to drive off moisture content and carboniferous matter. (The
carbon is driven off as carbon dioxide.) Calcining does not chemically alter the phosphate shale.
It is important to harden the briquettes during calcining to reduce breakage and allow proper flow of
gaseous reaction products in the furnaces. Hardened (calcined) phosphate shale briquettes (nodules) are choke-fed
into the furnace following mechanical conveyance and mixing with coke and silica. Significant breakage can occur
to improperly hardened nodules during drops from one conveyor to the next and as the nodules are forced into the
tops of the'furnaces. Phosphate in the shale nodules, which is unchanged chemically during calcination from
phosphate in the as-received mined shale, is reduced in the furnaces with coke to form elemental phosphorus and
carbon monoxide. This occurs near the bottom of the furnaces in the plasma arcs at the tips of the carbon electrodes.
Gas-phase reaction products, primarily elemental phosphorus and carbon monoxide, percolate up from the reaction
zones through gas channels in the incoming bed of phosphate nodules, coke, and silica. Nodule fragments, formed
by breakage from broken or improperly calcined briquettes, can plug these gas channels, interfering with proper,
steady-state furnace operation.
It is also important to drive off water during calcining of the briquettes to prevent volatilization of steam in
die high temperature furnaces and to prevent an unwanted side reaction involving water and elemental carbon. In the
calciners, water content is reduced from about 11 percent in the incoming phosphate shale to less than 1 percent in
the hardened briquettes or nodules. The dried and hardened nodules are conveyed and fed to the phosphorus
furnaces, which operate at very high temperature. At the top, where the nodules, coke, and silica are being choke-
fed, the temperature is about 400"C, while near the bottom, temperatures can reach 1500°C in the plasma-arc zones.
If wet briquettes were allowed to enter the furnaces, steam would be uncontrollably and possibly explosively
volatilized. At these temperatures, and in the reducing conditions found inside the furnaces, water and elemental
carbon can undergo the watergas reaction to form hydrogen and carbon monoxide. This is a very destructive side
reaction that can consume both coke, a reagent necessary for the reduction of phosphorus shale to elemental
phosphorus, and the furnace electrodes and sidewall refractory bricks (both of which are solid carbon). Finally,
water generated in the furnaces can cause increased corrosion in downstream process equipment.
Although less important than water removal, it is also necessary to drive off carboniferous material during
calcination. Volatilization of these materials in the furnaces can create severe furnace pressure excursions. During
calcining of phosphorus shale, quantities of low boiling point metals may be volatilized."
FMC Corporation. Op. Cit. January 25, 1996.
283
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NJ
00
Coke, Silica
Phosphate Rock or
Sintered/Agglomerated Fines I
Slag to disposal
EXHIBIT 2
ELEMENTAL PHOSPHORUS PRODUCTION
(Adapted from: Phosphorus, A Mineral Processing Waste Generation Profile.)
Electric
Furnace
Reduction
Ferrophosphorus to Storage
Offgases
H2O
Dry
Dust
Separation
Dust
Conditioning
Phosphorus
Condensation
j
CO to
Combustion
H,0
1
'
Phosphorus
Separation
INd^'-'-
^
Phosphoru
-^- to
Sale
Phosphate Dust to
Fertilizer Blending
Phossy Water
Mud to Disposal
-------
EXHIBIT 3
PROCESS AT FMC FACILITY
(Adapted from: Elemental Phosphorus Processing Waste Characterization Report For FMC Corporation, 1991, pp. 1-4.)
Shale •
Shale
Stacker-
Reclaimer
Screening
1*4
Sumps
OO
Ul
FMC Plants
Lawrence, KS
Newark, CA
Green River, WY
Caneret, NJ
Niiro, WV
*-
Cak
Phos
Calcining
, I
«^.
;med 1 ^^
phafp. 1 —
*^
Nodule
Storage &
Reclaim
Electric
Furnace
1 1
^ ' '
Proport
- Coke
• Silica
Crushing
Screening
Sales
-------
Electrothermal Processing
The burden is then fed to one of four electric arc furnaces through feed chutes located on top of the
furnaces. There are 10 feed chutes per furnace to distribute burden uniformly about the electrodes. Each furnace is
equipped with three electrodes that heat the furnaces to reduce the phosphate to gaseous elemental phosphorus.
Silica is used as a fluxing agent to bind with the calcium present in the phosphate ore and form slag. The coke reacts
with the phosphate ore to form carbon monoxide and ferrophosphorus. The furnace offgas, which contains elemental
phosphorus, carbon monoxide and particulates, passes through an electrostatic precipitator (ESP) for paniculate
removal. The gas is then passed through a primary condenser where the phosphorus is cooled by water sprays and
condensed to a liquid. Each furnace is equipped with a precipitator and primary condenser. The majority of the
phosphorus is condensed in the primary condenser. The gas stream leaving the primary condenser is combined with
the gas streams from the other primary condensers at the carbon monoxide header. The combined gas stream, which
is primarily carbon monoxide, flows to a second condenser for additional phosphorus removal. The carbon
monoxide stream from the secondary condenser is used as fuel for the calciners. Excess carbon monoxide goes to
the roof flare and to the flare pit.
Elemental phosphorus is gravity fed from the condenser to sumps in the furnace building. Phosphorus in
the sumps is kept under water to prevent contact with air. Phosphorus is transferred from the sumps to one of seven
storage tanks at the phosphorus loading dock by pumping water into the top of the sumps to displace the phosphorus
and forced it out the bottom of the sump and into the bottom of the storage tanks. The phosphorus displaces water
from the top of the storage tank, and this water flows back to the sumps to form a closed-loop system. The combined
capacity of the seven storage tanks is 3,131,000 pounds of phosphorus. Phosphorus is pumped from the storage
tanks into railcars for off-site shipment. FMC also has 12 underground storage tanks for long term storage of
phosphorus. The phosphorus dock also processes sludge generated at the furnace building sumps, storage tanks, and
in the returning railcars. The sludge is dried in a centrifuge and stored before being pumped back to the furnaces for
phosphorus recovery.12
Air emissions from furnace operations result from normal furnace operation, furnace venting, and slag
tapping. The electrothermal process generates carbon monoxide which is used as fuel at the calciners or vented to
the flare pit. Furnace venting occurs during furnace maintenance/repair or process upsets. During maintenance/
repair, the furnace is vented to the roof flare. Emissions to the flare bypass the carbon monoxide header. These
emissions consist primarily of phosphorus pentoxide. Emissions from process upsets, such as furnace
overpressurization, are vented to a pressure relief valve. These emissions are also primarily phosphorus pentoxide.
Emissions from slag tapping are vented to the atmosphere through a Medusa scrubber followed by an Anderson
scrubber.13
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4, Beneficiation/Proeessing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In.essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement, Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
12 National Enforcement Investigations Center (NEIC), Multi-Media Compliance Investigation. FMC Corporation
• Phosphorus Chemicals Division. Pocatello. Idaho. January 1994.
13
Ibid.
286
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Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for the production of elemental phosphorus,.the beneficiation/processing line occurs
between agglomeration and electric arc furnace reduction because the agglomerated phosphate rock undergoes a
significant thermal reaction inside the electric arc furnace to yield gaseous phosphorus. Calcining is recognized as a
beneficiation activity in the production of phosphorous. It is one of the final activities performed prior to the
chemical change of phosphate ore into the elemental phosphoro\us product.14 Because EPA has determined that all
operations following the initial "processing" step (in this case, the introduction of proportioned ore into the electric
furnace) in the production sequence also are considered processing operations, irrespective of whether they involve
only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial
mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA
presents below the mineral processing waste streams generated downstream of the beneficiation/processing line,
along with associated information on waste generation rates, characteristics, and management practices for each of
these waste streams.
C. Process Waste Streams
1. Extraetion/Benefieiation Wastes
Fugitive dust is generated from screening and crushing. FMC collects this dust in baghouses.13
Calcining offgas solids. FMC sends air emissions from the calciners to scrubbers for removal of
particulates and radionuclides.16 It should be ruled that if calcining at FMC drivers off more than water and carbon
dioxide, it is not a beneficiation activity (See 40 CFR 261.4(b)(7).
2. Mineral Processing Wastes
Surface Impoundment waste solids are generated at a rate of 373 kg per kkg product.17 Existing data and
engineering judgment indicate that this waste does not exhibit characteristics of a hazardous waste. Therefore, the
Agency did not evaluate this material further. Waste characterization data are presented in Attachment 1.
14 FMC Corporation. Op. Cit. January 25, 1996.
ISNEIC. Op. Cit. 1994.
16 Ibid.
17 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals Industry, Volume
II, Chapter 8, 1980.
287
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Slag, a RCRA special waste, contains trace amounts of radioactive materials in a stable, calcium silicate
matrix. For every pound of white phosphorus produced, eight to ten pounds of slag are generated. In 1988. this
waste was generated at a rate of 2.6 million metric tons per year.18 At FMC, slag is tapped into the slag pit which is
located next to the furnace building. The slag is allowed to cool before it is loaded and hauled to the slag storage
piles. Some slag is screened and crushed for use in berm and road maintenance.19
Dust. Phosphatic dusts may contain slightly elevated levels of radioactivity as well as volatilized, reduced
heavy metals. Phosphatic dusts are normally sold for blending with fertilizer materials20 and formerly were classified
as byproducts. Past management practices have included storage in a waste pile and offsite landfill disposal.21 Dust
is generated at a rate of 4,400 metric tons per year (adjusted from a reported value to reflect changes in the sector).
Dusts may exhibit the characteristics of toxicity (for cadmium), ignitability, and reactivity.
Furnace offgas solids. This waste may contain cyanide. The generation rate for furnace offgas solids is
24,000 metric tons per year22 (adjusted from a reported value to reflect recent changes in the sector). Waste
characterization data are presented in Attachment 1. This waste may be recycled and formerly was classified as a
sludge.
Sludge is generated in the sumps and consists of a phosphorus/water emulsion and particulates not removed
by the ESPs. Generally, sludge is distilled in iron retorts of steam heated vessels to recover phosphorus. Recovered
phosphorus is added to the product and phosphorus free residues from the retorts are landfilled. Sludge is generated
at a rate of 25 kg per kkg product.23 At FMC, the sludge is sent to the phosphorus dock where it is processed with
sludge generated from furnace building sumps, storage tanks, and returning railcars. The sludge is dried in a
centrifuge and stored before being pumped back to the furnace for phosphorus recovery.24 Existing data and
engineering judgment suggest that this waste does not exhibit any characteristics of hazardous waste. Therefore, the
Agency did not evaluate it further.
Precipitator slurry scrubber water. FMC treats the scrubber water with lime and discharges it to calciner
ponds for settling. The water is recycled back to the scrubbers from the calciner ponds.25 Existing data and
engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further. Waste characterization data are presented in Attachment 1.
18 U.S. Environmental Protection Agency, Report to Congress on Special Wastes from Mineral Processing.
Volume II: Methods and Analysis. Office of Solid Waste, July 1990, p. 7-3.
19NEIC. 1994. Op. Cit.
20 .S. Environmental Protection Agency. "Phosphate Rock," from 1988 Final Draft Summary Report of Mineral
Industry Processing Waste. 1988, pp. 2-120 - 2-127.
21 U.S. Environmental Protection Agency, Technical Background Document. Development of Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, pp. 3-4-3-6.
22 Ibid.
23 U.S. Environmental Protection Agency, Op. Cit.. Volume II, Chapter 8, 1980.
;4NEIC, 1994. Op. Cit.
25 Ibid.
288
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Cooling water is generated from cooling of furnace domes by direct water spray. At FMC, this water is
discharged via a permitted outfall.26 Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Furnace scrubber blowdown. FMC generates this waste at the rate of 43.4 million gallons per year."
Management for this waste may include treating in a tank and sending the sludge to disposal impoundments.28 This
waste may exhibit the characteristics of toxicity for cadmium and corrosivity prior to treatment. Waste
characterization data for raw furnace scrubber blowdown are presented in Attachment 1.
Furnace building washdown. This waste is generated from numerous sources in the furnace building. The
term "furnace building washdown" is a generic term used at the FMC facility to designate water collected in the V-
3600 tank from numerous sources throughout the furnace building. The water is eventually discharged into a RCRA
Interim Status MTR pond. Water is used in condensing elemental phosphorus from the furnace off-gas stream, water
seals on pressure relief devices and overfill protection systems, electrical transformer and furnace cooling, furnace
tapping fume scrubber systems, conveying and storage operations to keep phosphorus under water cover, slurrying
and transporting electrostatic precipitator solids, cleaning (rinsing) of process equipment to ensure maximum
performance, and other miscellaneous uses such as pump packings and steam condensate. The V-3600 tank is the
back-up water collection point for some of these streams, which do not normally report to this tank. The discharge
from the V-3600 tank collectively has been known as "furnace building washdown" because waters from numerous
sources in the furnace building are the primary components of this stream. This stream is generated continuously
during process operations. Contaminants in this stream originate from the mineral feedstocks (phosphate shale,
silica, and coke) used at Pocatello to produce elemental phosphorus. This stream does not contain outside
contaminants such as solvents or acidic or caustic cleaning agents. The furnace building washdown occasionally
exhibits the Toxicity Characteristic for cadmium (D006). The TSS average is .08 percent, and it is also considered a
wastewater for LDR purposes. Furnace Building Washdown contains elemental phosphorus and NORM. The FMC
facility generates approximately 79 million gallons of this waste a year.29
WWTP sludge/solids. This waste is not expected to be hazardous. Waste characterization data are
presented in Attachment 1.
Surface impoundment waste liquids. This waste is not expected to be hazardous. Waste characterization
data are presented in Attachment 1. This waste is completely recycled at FMC.
Spent furnace brick. Existing data and engineering judgment suggest that this material does not exhibit
any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Waste ferrophosphorus is tapped from the furnaces. It is tapped into chill molds inside the furnace
building and allowed to cool. After cooling, the ferrophosphorus is crushed and screened before being sold as a raw
material to the steel industry.30 Based on existing data and engineering judgment, this waste is not expected to
exhibit characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material further.
26 Ibid.
27 FMC Corporation. Op. Cit. January 25, 1996.
28 U.S. Environmental Protection Agency, Technical Background Document. Development of Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, pp. 3-4 to 3-6.
29 FMC Corporation. Qp. Cit. January 25, 1996.
30 Ibid.
289
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WWTP liquid effluent is not expected to be hazardous. This waste may be discharged under NPDES.
The generation rate for this waste stream is 1,520,000 metric tons per year31 (adjusted from a reported value to
reflect recent changes in the sector). Waste characterization data are presented in Attachment 1.
Andersen Filter Media (AFM). Andersen Filter Media (AFM) is a felt-like material that is used in the
Andersen scrubbers to filter fine particulate. Andersen Cleanable Media High Efficiency Air Filter (CHEAP)
scrubbers are used in series with the Medusa Scrubbers to further clean fumes from furnace tapping and phosphorus
dock loading and operations. Andersen Filter Media is used in these scrubbers to filter fine particulates. The AFM is
generated at a rate of 420 cubic yards per year. The material fails the TCLP for cadmium and sometimes arsenic,
chromium, lead and selenium and is a RCRA hazardous waste.32
AFM rinsate. This waste stream has been eliminated by FMC as a waste reduction process modification.
FMC generates three additional waste streams, as described below, which may or may not be typical of
other phosphorus producers.33
Precipitator slurry. The elemental phosphorus product exits the furnaces as a gas along with the carbon
monoxide produced in the furnace reaction. The furnace off-gas also includes entrained solids and solids that have
volatilized in the furnace and condensed as the off-gas cools. Electrostatic precipitators are used to remove these
furnace off-gas solids prior to the water spray condensers that remove the elemental phosphorus as a liquid. At
FMC, these solids collect in a vessel at the bottom of the precipitator, known as the slurry pot, where water is added
with a mixer to form what is termed precipitator slurry. The slurry pot acts as a gas seal on the precipitators to
prevent in-leakage of air. Some elemental phosphorus condenses in the slurry pot and the solids contain low volatile
metals such as cadmium and zinc in elevated levels. Historically, precipitator slurry has been sent to ponds where
the solids settle out and the water is recycled. FMC produces 43 million gallons of precipitator slurry (may be
combined with NOSAP slurry as discussed below) each year. Although there are elevated levels of metals in the
precipitator slurry, the solids typically do not fail a Toxicity Characteristic Leaching Procedure (TCLP) test, unless
there are extenuating circumstances, in which case it will fail for cadmium (D006).
Based on preliminary data, EPA has indicated that precipitator slurry is ignitable (D001) and reactive
(D003). The slurry also contains NORM and elemental phosphorus and should be managed accordingly. The TSS
in the precipitator slurry typically exceed 1 percent, and the TOC concentration present in the precipitator slurry
does not exceed 1 percent. Therefore, the slurry is considered an LDR non-wastewater.
NOSAP Slurry. In 1994 and 1995 as part of its waste minimization efforts, FMC developed and installed
the NOSAP, which is a modification to the electrostatic precipitator and the slurry pot. Lime slurry is added to the
slurry pot to control the pH of the slurry to a set point of pH 12. The lime reacts with the phosphorus to form
phosphites and phosphine gas, thus reducing the concentration of phosphorus to below 1000 ppm. The lime also
prevents the metals from becoming leachable and ensures the slurry will not fail the TCLP test. The resulting slurry
that has gone through this process is known as NOSAP slurry. Based on preliminary data, EPA has indicated that
NOSAP slurry is reactive (D003). If all precipitator slurry went through the NOSAP process, FMC would produce
only 22 million gallons per year since the NOSAP slurry has a higher solids content. The solids in NOSAP slurry
are the same as precipitator slurry with the exception of the effect of the lime. The NORM content is the same and
there is still some residual phosphorus content. NOSAP slurry that does not meet specifications is a component of
precipitator slurry. The TSS in the NOSAP slurry typically exceed 1 percent, and the TOC in the NOSAP slurry does
not exceed 1 percent. Therefore, the NOSAP slurry is a non-wastewater for LDR purposes.
31 U.S. Environmental Protection Agency, Op. Cit.. Vol. II, pp. 14-45 - 14-59.
32 FMC Corporation. Op. Cit. January 25, 1996.
33 FMC Corporation. Comment submitted in response to the Second Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. May 12, 1997.
290
-------
The maximum volume of precipitator slurry and NOSAP slurry that would be generated in one year would
be 43 million gallons.
Phossy water. This water waste stream is called phossy water by FMC. Phossy water may carry the D003
RCRA waste code for reactivity. It is possible that phossy water could exhibit the TC for cadmium (D006) upon
process upset. As a result of its contact with phosphorus, phossy water contains suspended phosphorus and other
dissolved solids. In addition, the phossy water contains NORM. The majority of phossy water is recovered for
reuse, but excess phossy water is generated from two locations within the facility. Due to the presence of elemental
phosphorus, the solids in phossy water may spontaneously oxidize and ignite if dewatered. The TSS in the phossy
water typically exceed 1 percent, and the TOC in the phossy water does not exceed 1 percent Therefore, the phossy
water is a non-wastewater for LDR purposes. FMC generates 89 million gallons total of the phossy water per year.
Solids in phossy water settle out, and are considered to be mineral processing wastes, because the 1984 rule states
that a waste of a mineral process waste is a mineral process wastes. Based on available data, solids from phossy
water may be a hazardous waste.
Although other phosphorous manufacturers may generate the following waste streams, FMC does not do so
at its facility: phosphatic dust, condenser water discard, precipitator slurry scrubber water, WWTP liquid effluent.
and WWTP sludge/solids.
D. Non-uniquely Associated Wastes
Non-contact cooling water is generated by cooling of the ore calciner grates that transport the briquettes.
At FMC, the noncontact cooling water is discharged via a permitted outfall.34 This waste is a non-uniquely
associated waste. Ancillary hazardous wastes may be generated at on-site laboratories, and may include used
chemicals and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), and
acidic tank cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary
sewage, waste oil (which may or may not be hazardous), and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Three commenters provided additional factual information about the elemental phosphorous production
process (COMM 42, 70, 78)). This information, where appropriate, has been included in sector report.
Sector-specific Issues
Two commenters disagreed with the Agency's assertion that certain wastes generated during elemental
phosphorous production are RCRA ignitable and reactive (COMM 42, COMM 70). One of these commenters has
since agreed to treat certain wastes as ignitable and'reactive (COMM 70).
One commenter stated that water recycled from ponds on-site should not be considered a hazardous waste,
because it does not fit any one criteria that would make it a hazardous waste under the RCRA statute definitions
(COMM 70).
34NEIC, 1994.,
291
-------
BIBLIOGRAPHY
Barrels, James J., and Theodore M. Gurr. "Phosphate Rock." From Industrial Mineral and Rocks. 6th ed. Society
for Mining, Metallurgy, and Exploration. 1994. pp. 751-763.
Elemental Phosphorus Processing Waste Characterization Report for FMC Corporation. Pocatello. Idaho. 1991.
pp. 1-4.
FMC Corporation LDR presentation for EPA/OSW, December 1994.
Morse, David. "Phosphate Rock." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines. 1992. pp. 977-980.
National Enforcement Investigations Center. Multi-Media Compliance Investigation. FMC Corporation -
Phosphorus Chemicals Division. Pocatello.Idaho. January 1994.
"Phosphorus and the Phosphides." Kirk-Othmer Encyclopedia of Chemical Technology. 3rded. Vol. XVII. 1982.
pp.473-490.
U.S. Environmental Protection Agency. Technical Background Document. Development of Cost. Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processins
Wastes. August 1989. pp. 3-4-3-6.
U.S. Environmental Protection Agency. "Elemental Phosphorus Production." From Report to Congress on Special
Wastes from Mineral Processing. Vol. II. Office of Solid Waste. July 1990. pp. 7-1 - 7-24.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992. Vol. I. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992. Vol. II. pp. 14-45 -14-59.
U.S. Environmental Protection Agency. "Phosphate Rock, Phosphoric Acid, and Phosphorus." From 1988 Final
Draft Summary Report of Mineral Industry Processing Waste. 1988. pp. 2-120-2-127.
U.S. Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. Volume II,
Chapter 8. 1980.
292
-------
ATTACHMENT 1
293
-------
fO
to
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
10,000 10,000 10,000 1/1
200,000 386,667 480,000 3/3
50,000 50,000 50,000 2/2
0/0
0/0
5.00 5.53 5.80 3/3
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
.
.
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SLAG QUENCHWATER - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
11.60
0.50
0.50
0.05
0.005
-
0.012
0.050
0.050
0.050
3.60
0.35
5.72
1.54
0.00010
0.050
0.050
0.050
0.050
0.250
0.050
3.13
-
-
5.00
-
-
-
41.30
-
-
5.78
11.60
0.50
0.50
0.05
0.005
-
0.012
0.050
0.050
0.050
3.60
0.35
5.72
1.54
0.00010
0.050
0.050
0.050
0.050
0.250
0.050
3.13
-
-
5.00
-
-
-
41.30
-
-
8.29
11.60
0.50
0.50
0.05
0.005
-
0.012
0.050
0.050
0.050
3.60
0.35
5.72
1.54
0.00010
0.050
0.050
0.050
0.050
0.250
0.050
3.13
-
-
5.00
-
-
-
41.30
-
-
10.80
Detects
1/1
0/1
0/1
0/1
0/1
0/0
1/1
0/1
0/1
0/1
1/1
1/1
1/1
1/1
0/1
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/0
0/0
1/1
0/0
0/0
0/0
1/1
0/0
0/0
2/2
EP Toxicity Analysis -
Minimum Average
11.50
0.050
0.050
0.050
0.0050
-
0.011
0.050
0.050
0.050
3.34
0.17
5.72
1.52
0.00020
0.050
0.050
0.050
0.050
0.25
0.050
2.94
-
-
-
-
-
-
-
-
11.50
0.050
0.050
0.050
0.0050
0.011
0.050
0.050
0.050
3.34
0.17
5.72
1.52
0.00020
0.050
0.050
0.050
0.050
0.25
0.050
2.94
PPM
Maximum #
11.50
0.050
0.050
0.050
0.0050
0.011
0.050
0.050
0.050
3.34
0.17
5.72
1.52
0.00020
0.050
0.050
0.050
0.050
0.25
0.050
2.94
-
-
-
-
-
-
-
Detects
1/1
0/1
0/1
0/1
0/1
0/0
1/1
0/1
0/1
0/1
1/1
1/1
1/1
1/1
1/1
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
<£>
Ol
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - CONDENSER PHOSSY WATER DISCARD - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
0.424
0.016
0.0024
0.120
0.005
14
0.002
0.014
0.013
0.017
1.2
0.024
6.83
0.23
0.00010
0.035
0.046
0.002
0.02
0.0455
0.05
0.6
36.00
1.20
2.50
80.00
25.00
63.00
38.00
0.78
3.00
20.00
64.39
1.76
1.27
16.09
0.026
14.000
324
33.15
0.15
20.98
20.26
13.49
32.22
1.77
0.1506
0.17
6.93
2.58
1.36
24.88
2.27
5,794
36.00
1.20
363
3,934
1,833
63.00
364
12652
5.09
39.67
220
4
3
90
0.05
14
3200
250
0.5
100
53
48
64
3.8
1
0.5
45
13.9
4.47
120
10
53,000
36.00
1.20
964
25,900
9,070
63.00
1,250
50000
7.10
76.20
Detects
5/5
3/5
3/5
5/6
2/4
1/1
11/11
8/8
2/4
5/5
4/4
7/7
6/6
4/4
3/7
2/4
5/7
3/6
3/5
2/5
4/6
10/10
1/1
1/1
6/7
7/7
6/6
1/1
9/9
4/4
111
3/3
EP Toxicity Analysis -
Minimum Average
5.70
0.050
0.031
0.15
0.005
9.400
0.067
0.049
0.050
0.005
0.87
0.125
6.4
0.25
0.00010
0.05
0.02
0.002
0.01
0.25
0.05
6.47
-
-
41.00
155
591
-
69
-
11.90
0.71
0.12
0.86
0.014
9.400
0.17
0.23
0.15
0.08
4.02
0.64
13.23
0.95
0.000175
0.15
0.09
0.10
0.08
0^75
0.17
71.49
-
-
74.00
304
662
-
152
-
PPM
Maximum
16.10
1.30
0.25
3.20
0.025
9.400
0.40
0.40
0.25
0.25
6.49
1.80
17.00
1.85
0.0002
0.25
0.25
0.25
0.25
1.25
0.25
167
-
-
107
453
732
-
234
-
# Detects
3/3
3/4
3/5
5/6
1/3
1/1
6/6
5/6
0/2
1/4
3/3
2/4
3/3
2/4
1/4
0/2
2/5
0/3
0/4
0/2
1/3
5/5
0/0
0/0
2/2
2/2
2/2
0/0
2/2
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - FURNACE OFFGAS SOLIDS - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Vlercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
98.20
0.43
0.050
0.84
0.022
39.000
0.45
1.61
0.05
0.05
16.80
2.57
84.00
2.79
0.00010
0.050
0.050
0.050
0.050
0.25
0.64
1 5.70
52.00
-
173
941
13.38
50,000
510
988,200
5.00
20.00
4,290
9.68
12.78
34.18
1.29
185.50
60.74
14.04
12.78
37.64
7,744
136
687
337
0.00010
12.78
14.14
12.78
12.78
43.65
12.71
13,489
52.00
-
8,802
1,221
240,007
125,000
38,564
988,200
5.40
384,940 1
1 1 ,500
25.50
25.50
96.70
2.55
332.00
200
25.50
25.50
116
20,000
368
1,373
1,170
0.00010
25.50
29.00
25.50
25.50
128
25.50
61,665
52.00
-
17,616
1,500
480,000
200,000
150,000
988,200
5.80
,140,000
Detects
4/4
2/3
0/2
3/3
1/2
2/2
4/4
2/3
0/2
2/4
5/5
3/3
4/4
4/4
0/1
0/2
2/4
0/2
0/2
1/3
2/3
5/5
1/1
0/0
4/4
2/2
2/2
2/2
4/4
1/1
2/2
3/3
EP Toxicity Analysis -
Minimum Average
4.60
0.050
0.020
0.050
0.005
24.000
0.011
0.050
0.050
0.050
1.81
0.45
3.39
0.25
0.00010
0.05
0.10
0.010
0.020
0.25
0.05
6.07
-
-
-
-
-
-
-
-
11.22
0.76
0.56
0.14
0.015
24.000
8.05
0.33
0.15
0.15
6.67
0.90
5.84
0.74
0.00010
0.15
0.17
0.07
0.12
0.75
0.30
116
PPM
Maximum
24.10
1.32
1.30
0.25
0.025
24.000
27.00
0.90
0.25
0.25
13.00
1.40
7.10
1.55
0.00010
0.25
0.25
0.25
0.25
1.25
0.60
267
-
-
-
-
-
-
-
# Detects
3/3
2/3
5/7
2/4
0/2
1/1
7/7
6/8
0/2
0/2
3/3
4/4
3/3
2/3
0/1
0/2
2/3
3/5
4/6
0/2
1/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 4
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
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00
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PRECIPITATOR SLURRY - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
28
5
18
0.2
-
1300
60
-
-
-
130
-
-
1
-
11
8
1
650
60
11000
-
-
-
-
-
-
-
200000
-
-
-
28
5
18
0.2
-
1300
60
-
-
-
130
-
-
1
-
11
8
1
650
60
11000
-
-
-
-
-
-
-
200000
-
-
-
28
5
18
0.2
-
1300
60
-
-
-
130
-
-
1
-
11
8
1
650
60
11000
-
-
-
-
-
-
.
200000
-
-
# Detects
0/0
1/1
1/1
1/1
1/1
0/0
1/1
1/1
0/0
. 0/0
0/0
1/1
0/0
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
1/1
0/0
0/0
EP Toxicity Analysis -
Minimum Average
-
0.31
0.1
1
0.01
-
0.022
0.237
-
-
-
0.11
-
-
0.0005
-
0.08
0.2
0.02
0.2
0.3
69.9
-
-
-
-
-
-
-
-
0.31
0.1
1
0.01
0.022
0.237
0.11
0.0005
0.08
0.2
0.02
0.2
0.3
69.9
PPM
Maximum
-
0.31
0.1
1
0.01
-
0.022
0.237
.
-
-
0.11
-
-
0.0005
-
0.08
0.2
0.02
0.2
0.3
69.9
-
.
-
-
-
-
# Detects
0/0
1/1
1/1
1/1
1/1
0/0
1/1
1/1
0/0
0/0
0/0
1/1
0/0
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
.
-
-
-
-
.
.
.
-
212 0
.
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - FURNACE SCRUBBER SLOWDOWN - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
3.70
0.016
0.016
0.050
0.0020
25.00
0.0010
0.0005
0.0030
0.0005
0.030
0.004
5.40
0.50
0.00010
0.029
0.009
0.003
0.0010
0.040
0.015
0.023
0.900
-
18.10
51.60
6.40
-
0.38
0.49
1.10
-
2,360
1.31
1.46
41.94
0.17
25.00
2.37
110
38.81
46.66
10,382
25.69
174
3,464
0.019
11.06
68.89
0.12
0.48
1.52
83.25
79.11
0.90
-
3,167
2,481
959
-
177
2,667
4.38
-
18,000
4.80
8.70
280.00
0.93
25.00
9.60
940
260
310
63,000
150
1,300
26,000
0.10
71.00
530
0.50
1.60
4.50
710
211
0.90
-
18,600
20,200
3,700
-
420
8,000
6.61
-
Detects
8/8
2/8
4/8
4/7
3/7
1/1
10/13
7/10
3/7
. 3/7
8/8
8/8
10/10
7/8
2/8
4/7
5/8
3/7
1/7
1/8
7/9
12/12
1/1
0/0
8/8
9/9
7/7
0/0
10/11
4/4
10/10
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum
0.25
0.05
0.00125
0.050
0.0025
19
0.0050
0.005
0.03
0.005
0.0375
0.125
0.17
0.25
0.0001
0.010
0.015
0.0025
0.01
0.25
0.015
0.55
-
-
6.00
2.41
2.17
-
0.27
-
4.23
0.53
0.14
0.43
0.01
19.00
0.40
0.34
0.08
0.07
3.88
0.31
6.10
2.03
0.0001
0.074
0.079
0.071
0.074
0.53
0.25
44.38
-
-
7.00
5.66
4.02
-
0.47
-
11.40
1.60
0.54
1.20
0.03
19.00
2.07
0.90
0.25
0.25
6.86
0.42
10.70
6.50
0.0002
0.25
0.25
0.25
0.25
1.25
0.79
130
-
-
8.00
8.91
5.87
-
0.67
-
# Detects
5/6
3/7
3/6
4/7
1/6
1/1
4/7
4/7
0/5
1/5
5/6
2/6
5/6
5/6
1/6
0/5
2/6
1/6
1/6
1/6
3/7
111
0/0
0/0
2/2
2/2
2/2
0/0
2/2
0/0
TC # Values
Level In Excess
,
-
5.0 0
100.0 0
-
-
1.0 2
5.0 0
-
-
-
5.0 0
-
-
0.2 0
.
-
1.0 0
5.0 0
-
-
_
-
-
~
"
-
-
.
-
212 1
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Ul
o
o
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE/SOLIDS - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
54500 54,500
-
233 233
-
-
-
1143 1,143
.
-
-
17400 17,400
188 188
2775 2,775
-
-
-
-
-
.
.
.
10625 10,625
-
-
1507 1,507
150 2,575
200 200
50000 162,200
.
-
4 7.1
-
54,500
-
233
-
-
-
1,143
-
-
-
17,400
188
2,775
-
-
-
-
-
-
-
-
10,625
-
'
1,507
5,000
200
274,400
-
-
11.3
-
Detects
1/1
0/0
1/1
0/0
0/0
0/0
1/1
0/0
0/0
0/0
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
1/1
0/0
0/0
1/1
2/2
1/1
2/2
0/0
0/0
3/3
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
,
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
.
-
-
212 0
.
Non-detects were assumed to be present at 1/2 the detection limit, TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RT1 SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
Lead
Magnesium
Manganese
Mercury
vloiybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Ulinimum Average Maximum #
0.424
-
-
-
-
0,643
2.86
0.014
-
-
-
-
54.5
-
0.00012
0.084
-
0.045
-
-
0.21
0.29
-
-
118
122
100
47.70
38.00
240
4.00
-
0.42
-
-
-
-
0.64
2.86
0.04
-
-
-
-
54.50
-
0.00012
0.084
-
0.045
-
-
0.37
2.11
-
-
118
122
490
47.70
111
240
5.33
-
0.42
-
-
-
-
0.64
2.86
0.07
-
-
-
-
54.50
-
0.00012
0.084
-
0.045
-
-
0.53
3.94
-
-
118
122
1,000
47.70
183
240
6.80
-
Detects
1/1
0/0
0/0
0/0
0/0
1/1
1/1
2/2
0/0
0/0
0/0
0/0
1/1
0/0
1/1
1/1
0/0
1/1
0/0
0/0
2/2
2/2
0/0
0/0
1/1
1/1
3/3
1/1
2/2
1/1
4/4
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
- . - 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
.
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
.
-
-
-
-
.
212 0
-
U)
o
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
UJ
o
NJ
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOO)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
1.00 1.00 1.00 1/1
0/0
0/0
0/0
177 177 177 1/1
0/0
0/0
0/0
0/0
0/0
190 190 190 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
536 536 536 1/1
0/0
0/0
1,533 1,533 1,533 1/1
22,80 22.80 22.80 1/1
100 100 100 1/1
0/0
2,308 2,308 2,308 1/1
0/0
4.00 4.85 5.70 2/2
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
p/o
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
.
-
-
-
-
-
.
212 0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - AFM RINSATE - ELEMENTAL PHOSPHOROUS
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Vlinimum Average Maximum # Detects
0/0
0/0
1 1 11/1
0/0
0/0
0/0
4 4 4 1/1
1 1 11/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
1 1 11/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
20000 20000 20000 1/1
0/0
0/0
EP Toxicity Analysis -
Minimum Average
-
0,2
0.14
1
0.01
-
4.12
0.278
-
-
.
0.19
-
-
0.0005
-
0.08
1,03
0.02
0.03
0.19
37.2
-
-
-
-
-
-
-
,
0.2
0.14
1
0.01
4.12
0.278
0.19
0.0005
0.08
1.03
0.02
0.03
0.19
37.2
PPM
Maximum #
0.2
0.14
1
0.01
4.12
0.278
.
-
-
0.19
-
-
0.0005
-
0.08
1.03
0.02
0.03
0.19
37.2
-
-
-
-
-
-
.
-
Detects
0/0
1/1
1/1
1/1
1/1
0/0
1/1
1/1
0/0
0/0
0/0
1/1
0/0
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
.
5.0 0
100.0 0
-
-
1.0 1
5.0 0
-
.
-
5.0 0
-
-
0.2 0
-
-
1.0 1
5.0 0
-
-
-
-
-
-
,
-
-
.
.
212 0
-
uu
o
UJ
ISIon-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
304
-------
FLUORSPAR AiND HYDROFLUORIC ACID
A. Commodity Summary
In 1994, approximately 73 percent of the reported fluorspar (CaF,) consumed in the United States was used
in the production of hydrofluoric acid. About 10 percent of the fluorspar was used as a fluxing agent in steelmaking,
and in iron and steel foundries. The remaining 17 percent was consumed in aluminum fluoride manufacture, primary
aluminum production, glass manufacture, enamels, welding-rod coatings, and other miscellaneous end uses or
products.1 Fluorspar is sold in three grades: metallurgical (minimum 85 percent CaF2), ceramic (85-96 percent
CaF,), and acid (minimum 97 percent CaF2).2 While there are seven active domestic fluorspar mines, the majority of
fluorspar used in the U.S. is imported.3
Hydrofluoric acid is an aqueous solution of hydrogen fluoride produced by a reaction of fluorspar and
sulfuric acid. Hydrofluoric acid is the feedstock used to produce almost all of the organic and inorganic fluorine-
bearing chemicals. Hydrofluoric acid also is used in aluminum and uranium processing.4 As of 1989, three facilities
actively produced hydrofluoric acid. Although several other facilities produce hydrofluoric acid as an intermediate
product during the formulation of commercial chemicals or compounds, these facilities are not included as part of the
primary hydrofluoric acid industry. The names and locations of the three hydrofluoric acid production facilities are
shown in Exhibit 1.
EXHIBIT 1
SUMMARY OF HYDROFLUORIC Aero PRODUCERS (IN 1989)
Facility Name
Allied Signal
E.I. duPont
Attochemical, N.A.
Location
Geismar, LA
La Porte, TX
Calvert City, KY
B. General Process Description
1. Discussion of the Typical Production Processes
Hydrofluoric acid is produced by reacting acid-grade fluorspar and sulfuric acid in a kiln, and cooling and
purifying the product. This process is described in detail below.
1 M.M. Miller, "Fluorspar," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p. 58.
2 M.M. Miller, "Fluorspar," from Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines,
1992, p. 487.
3 U.S. Bureau of Mines, Randol Mining Directory 1994/1995. Randol International Ltd., Golden, CO, 1994, p.
165.
* M.M. Miller, 1994, Op. Cit.. p. 58.
305
-------
2. Generalized Flow Diagram
Before fluorspar can be used to make hydrofluoric acid, the raw ore must be physically concentrated and
purified. Ceramic and acid grades of fluorspar are concentrated (not shown) by crushing and grinding fluorspar, and
purified by froth flotation. First the fluorspar is crushed and ground. Then lead and zinc sulfides are preferentially
floated away from the fluorspar. The easily floating fluorspar is removed and sent to the cleaner circuit. The tailings
are discarded and the middling product is reground and passed through a cleaner circuit. The flotation process yields
acid grade concentrate, and sometimes lower grade concentrates, which are sold either as ceramic or metallurgical
grade fluorspar. Metallurgical grade fluorspar is produced by hand sorting, crushing and screening, and gravity
ration.5
Hydrofluoric acid is produced from acid-grade fluorspar (CaF2) which reacts with sulfuric acid in a heated
retort kiln to produce hydrogen fluoride gas, as shown in Exhibit 2. The acid grade fluorspar typically contains at
least 97 percent calcium fluoride, as well as silica, calcium carbonate, carbon, sulfur, phosphorus pentoxide,
chloride, mixed metal oxides, and a trace amount of arsenic. The sulfuric acid generally is between 93 and 99
percent pure. Both sulfuric acid and oleum (SO3) are commonly used.6 The residue remaining after retorting is
calcium sulfate anhydrite, commonly known as fluorogypsum, which is a RCRA special waste. This solid is slurried
in process water as it exits the kiln and is transported either to the waste management units7 or, at the duPont plant, to
a production operation for further processing for sale as a byproduct.8 The process wastewater, the second RCRA
special waste generated by this sector, is stored/treated in on-site surface impoundments and then either reused in the
process operations or discharged.
The crude product gas is handled differently by the various manufacturers, but cooling and scrubbing are
always involved. Exhibit 2 shows the gas being cooled, purified by scrubbing, and condensed. The crude product
may be diluted and sold as an approximately 70 percent hydrofluoric acid solution, or distilled to remove any
remaining water and impurities, and sold as anhydrous hydrogen fluoride, a colorless fuming liquid. The wastes
from the refrigerated condenser go to an acid scrubber. The sulfuric acid used in this process unit is then sent to the
acid feed, to react with the fresh fluorspar. The waste stream from the acid scrubber is sent to a water scrubber
which generates fluorosilicic acid and gases. The fluorosilicic acid may be recovered or disposed.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
No new novel processes have been utilized, however, a possible process under investigation involves
extracting fluorine as fluorosilicic acid from phosphate rock during the production of phosphoric acid. Also under
investigation is the production of calcium fluoride from calcium silicon hexafluoride (CaSiF6) produced by the
reaction of fluorosilicic acid and phosphate rock.9
5 MM. Miller, 1992, Op. Cit.. pp. 488-89.
6 "Fluorspar," from Kirk Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. XI, 1994, p. 364.
7 Allied Signal, Inc., 1989, Public comments from Allied Signal, Inc. addressing the 1989 Proposed
Reinterpretation of the Mining Waste Exclusion (Docket No. MW2P00020); November 8, 1989; pg. 1.
8 At the duPont facility, lime is added when the fluorogypsum is quenched in order to enhance the chemical
characteristics of the material for construction applications.
9 "Fluorspar," 1994, Op. Cit.. pp. 367-68.
306
-------
EXHIBIT!
HYDROFLUORIC ACID PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1994, p. 367
and Development Document, Section 12, Hydrofluoric Acid Industry.)
Water
•I
Vent
y
Wastewater
to
Treatment
To Sales
Condensate to Stoprage
(or Recycled to Kiln)
LEGEND:
Common Practice
Intermittent Process
(or process at only
some plants)
307
-------
4, Beneflciation/Proeessing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation,
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
when the beneficiated fluorspar is mixed with concentrated acid in the furnace/kiln where an intense exothermic
chemical reaction occurs and signficantly alters the chemical structure of the fluorspar. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams
generated after the beneficiation/processing line, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams,
C. Process Waste Streams
1. Extraction and Beneficiation Wastes
Gangue, lead and zinc sulfides, spent flotation reagents, and tailings are likely to be generated by the
beneficiation of fluorspar. The lead and zinc sulfides may be processed further to recover the lead and zinc. No
other information on waste characteristics, waste generation, or waste management was available in the sources listed
in the bibliography.
2. Mineral Processing Wastes
The hydrofluoric acid production process generates several waste streams. Two of these waste streams,
fluorogypsum and process wastewater, were classified as RCRA special wastes, and were studied in the July 1990
Report to Congress on Special Wastes from Mineral Processing.
Fluorogypsum. This waste is a solid material consisting primarily of fine particles of calcium sulfate,
usually less than 0.02 mm in diameter, that is slurried for transport from the kilns to waste management units. Using
available data on the composition of fluorogypsum, EPA evaluated whether the waste exhibits any of the four
characteristics of hazardous waste: corrosivity, reactivity, ignitability, and extraction procedure (EP) toxicity. Based
on analyses of four samples from two facilities (Geismar and Calvert City) and professional judgment, the Agency
308
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does not believe the fluorogypsum exhibits any of these characteristics. All eight of the inorganic constituents with
EP toxicity regulatory levels were measured in concentrations (using the EP leach test) that were at least two orders
of magnitude below the regulatory levels.10 According to the Newly Identified Mineral Processing Waste
Characterization Data Set, approximately 894,000 metric tons of fluorogypsum are produced annually in the United
States." The La Porte, TX plant sells its fluorogypsum for use as a filler for a road base, railroad subbase, and
paving material.12
Process wastewater. This waste is an aqueous liquid, the chemical constituents of which include fluoride,
calcium, and sulfate, with smaller amounts of iron and silicon, as well as many trace metals. Using available data on
the composition of hydrofluoric acid process wastewater, EPA evaluated whether the wastewater exhibits any of the
four characteristics of hazardous waste: corrosivity, reactivity, ignitability, and extraction procedure (EP) toxicity.
Based on available information and professional judgment, the Agency does not believe the wastewater is reactive,
ignitable, or EP toxic. All eight of the inorganic constituents with EP toxicity regulatory levels were measured in
concentrations (using the EP leach test) that were at most 0.6 times the regulatory levels. Some wastewater samples,
however, exhibit the characteristic of corrosivity. Analyses of the pH of hydrofluoric acid process wastewater at the
Geismar and Calvert City facilities indicate that the wastewater is corrosive in all of the nine samples analyzed,
sometimes with pH values as extreme as 1.00 (for comparison, pH levels below 2.0 are operationally defined as
corrosive wastes).13 According to the Newly Identified Mineral Processing Waste Characterization Data Set,
approximately 13.6 million metric tons of process wastewater are produced annually in the United States.14
Sludges. Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Off-Spec Fluorosilicic acid (H2SiF6). This waste is recovered from the water scrubber, and can be used in
water fluoridation after it is recovered. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 0 metric tons/yr, 15,000 metric tons/yr, and 44,000 metric tons/yr,
respectively. We used best engineering judgement to determine, that this waste may exhibit the characteristics of
corrosivity. This waste stream is partially recycled and classified as a by-product.
APC Dusts. Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
D, Non-unlquely AssociatedWastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from tracks and large machinery, sanitary sewage, and
waste oil other lubricants.
10 From the response of Allied Signal, Inc. and Pennwalt Corp. to EPA's "National Survey of Solid Wastes from
Mineral Processing Facilities", conducted in 1989.
11 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, August 1992, p. 1-5.
12 From the response of E.I. duPont to EPA's "National Survey of Solid Wastes from Mineral Processing
Facilities," conducted in 1989.
13 From the response of Allied Signal, Inc. and Pennwalt Corp. to EPA's "National Survey of Solid Wastes from
Mineral Processing Facilities", conducted in 1989.
U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-5.
309
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E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
310
-------
BIBLIOGRAPHY
"Fluorspar." Kirk Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. XL 1994. pp. 364-68.
. Fulton III, R.B., and G. Montgomery. "Fluorspar." From Industrial Minerals and Rocks. 6th ed. Society for
Mining, Metallurgy, and Exploration. 1994. pp. 509-522.
Miller, M. M.. "Fluorspar." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995, pp. 58-
59.
Miller, M.M., "Fluorspar," From Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992.
pp. 487-500.
MRI Inc. Draft Site Visit Report on Pennwalt Corporation, Calvert City. July 14, 1989.
U.S. Bureau of Mines. Randol Mining Directory 1994/1995. Randol International Ltd. Golden, CO. 1994.
U.S. Environmental Protection Agency. "Fluorspar." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 2-104-2-108.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. Report to Congress on Special Wastes from Mineral Processing. Volume
II. Office of Solid Waste. July 1990. pp. 9-1-9-29.
Weiss, N.L., Ed, SME Mineral Processing Handbook. Society of Mining Engineers. New York. 1985. pp. 23-1-
23-9.
311
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Page Intentionally Blank
312
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GEM STONES
A. Commodity Summary
The gem stone industry in the United States is extremely small and relies on foreign trade to meet most of
its source requirements. The United States has no known large resources of precious gem stones (i.e., diamonds,
rubies, sapphires, and emeralds) and reserves are generally limited to semiprecious stones. Several semiprecious
gem stone deposits are mined in the United States. In 1992, 91% of the total U.S. gem stone production (by value)
was made up by the following states: Arizona, Nevada, Oregon, Maine, California, and Montana. In 1994, domestic
natural gem stone production was approximately $51.6 million.1
Most gem stone mining appears to be done by hobbyists and amateurs in Mitchell County, NC; Judith Basin
County, MT; San Diego County, CA; Oxford County, ME; and Gila County, AZ where gems such as turquoise,
tourmaline, kunzite, emerald, and sapphire are found.
Gem stones are formed in nature in one of three ways: (1) from metamorphic processes, (2) by precipitating
from aqueous solutions, and (3) by crystallizing from magmas. There are three major compositional groups of gem
stones: silicate minerals comprise one-third; alumino-silicates comprise one-fifth; and oxides comprise one-seventh
of gem minerals. The remaining groups are sulfides, phosphates, borosilicates, and carbonates.
Some semi-precious stones are produced as by-products of other mining operations. For example, beryl,
tourmaline, spodumene, and gem quartz may be coproducts of mica, feldspar, quartz, or other pegmatite minerals.
Diamonds may be recovered from gold dredges, turquoise from copper mines, agate and petrified wood from gravel
pits, and gem garnet from abrasive garnet mines and mills.
Gem stones are used primarily for decoration. There are, however, some industrial applications for gem
stone material. For instance, industrial processes requiring clean homogeneous stones use low-quality diamond.
Tourmaline is used in laboratories to demonstrate the polarization of light, to measure the compressibility of fluids,
and to measure high pressures. Agate is made into mortar and pestle sets, knife edges for balances, textile rollers,
and spatulas. Gem stones are used as jewel bearings in timing devices, gauges, meters, and other applications
requiring precision elements.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Gem stone production includes three steps, (1) mining, (2) processing, and (2) enhancement. These steps
are discussed in greater detail below.
2. General Process Flow
Mining
Gem stone mining operations vary according to size and complexity. Small shallow deposits are generally
mined by a few people with prybars, picks, shovels, and buckets. Drilling, blasting, and timbering may or may not
be employed. Mechanized hauling and hoisting are done only at the largest mines.
Processing
In small operations, gem stone ores are broken, crushed, and concentrated, by hand picking, washing,
screening, or jigging. In larger operations, mechanized processes are employed. For instance, diamond processing
1 Gordon Austin, "Gemstones," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp.
64-65.
313
-------
involves standard gravity methods, grease belts, electrostatic separation, skin-flotation, magnetic separation,
separation by x-ray luminescence, and separation by optical sorting.
Enhancement
Gem materials are cut in four main operations: sawing, grinding, sanding, and polishing. An initial cut is
made with a diamond saw or blade to obtain a slice of desired thickness. Grinding of the stone may be done with
impregnated-diamond, silicon carbide, aluminum oxide wheels, or coated abrasive disks. Multiple grinding steps
ranging from 80 mesh through 600 mesh abrasives are used. Disk and belt sanders use abrasives bonded to cloth or
waterproof reinforced paper. Leather laps or hard felt are used with a polishing agent to obtain the final polish.
Polishing agents such as fine diamond compound, tin oxide, tripoli, chromium oxide, cerium oxide,
alumina, and rouge are typically used. These polished irregular shapes can then be further polished by tumbling
them in a rubber lined drum and using a grinding and polishing medium with or without water.
Finally, many gem stones are further treated to enhance their appearance. Several different chemical and
physical processes may be used, including bleaching, oiling, waxing, staining, dyeing, plastic and color impregnation
by diffusion or dyeing, surface modification with color coating, lasering, glossing, heat treatment to change color,
and irradiation by electromagnetic spectrum and by energetic particles to change color. Interference filters, foil
backings, surface decoration, and inscribing are used to alter the surface of gems. The most common method of gem
enhancement is heat treatment which can .change color, structure, and clarity. A newer method of gem enhancement
is diffusion treatment. This involves a chemical heat treatment in a bath of chemicals containing iron and titanium.2
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Synthesis of materials that can replace rare crystalline materials has been encouraged by industry. Synthetic
gem stones may be used in electronics and semiconductors or as frequency controllers, polarizers, transducers,
radiation detectors, infrared optics, bearings, strain gages, amplifiers, lasers, lenses, crucibles, and more.3
4. Berieficiation/Processing Boundaries
Based on a review of the process, there are no mineral processing operations involved in the production of
gem stones.
C. Process Waste Streams
Existing data and engineering judgement suggest that the wastes listed below from gem stone production
do not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
1. Extraction/Beneficiation Wastes
The extraction of gem bearing material in mines creates overburden. However, land disturbance due to
gem stone extraction is minimal since the number of underground mines in operation is minimal.4 Additional
miscellaneous wastes include spent chemical agents used to color the gem stones, spent polishing media, and
waste minerals.
2 Gordon T. Austin, "Gemstones," from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines, 1992, pp. 501-519.
3 Jean W. Pressler, "Gemstones," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp. 305-315.
4 Ibid.
314
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2. Mineral Processing Wastes
No wastes are identified,
D. Non-uniquely AssociatedWastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from tracks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
315
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BIBLIOGRAPHY
Austin, Gordon. "Gemstones." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
64-65.
Austin. Gordon T. "Garnet." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. pp. 523-528.
Austin, Gordon. "Gemstones." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 501-519.
Pressler, Jean. "Gemstones." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp.305- 315.
316
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GERMANIUM
A.
Commodity Summary
Germanium is recovered either as a minor byproduct of the refining of base metal ores, or as a constituent
of coal deposits.1 Germanium has a metallic grayish appearance and is hard and brittle. It is a semiconductor with
electrical properties between those of metal and an insulator.2 The Bureau of Mines estimated domestic consumption
at 25,000 kilograms during 1994.3 The domestic germanium industry is composed of three germanium refineries,
one each in New York, Pennsylvania, and Oklahoma and a mining operation located in Tennessee.4 Additional
information is provided on a recovery operation in Utah. Exhibit 1 presents the names and locations of the facilities
involved in the production of germanium.
EXHIBIT 1
SUMMARY OF GERMANIUM PROCESSING FACILITIES
Facility Name
Atomergic Chem
Cabot
Eagle-Picher
Jersey Miniere
Musto Exploration
Location
Plainview, NY
Revere, PA
Quapaw, OK
Clarksville, TN
St. George, UT
Type of Operations
Refining
Refining
Refining
Mining
Mining and Refining
Germanium is available commercially as a tetrachloride and a high purity oxide, and is commonly found in
the form of zone-refined ingots, single crystal bars, castings, doped semiconductors, and optical materials.* Some of
the major end uses for germanium include infrared optics, fiber-optics systems, detectors, and semiconductors.6
B. Generalized Process Description
1. Discussion of Typical Production Processes
Germanium is recovered as a by-product of other metals, mostly copper, zinc, and lead. The process
described in detail below refers to the recovery of germanium from residues at zinc ore processing facilities.
Exhibits 2 through 4 present process flow diagrams for the production of germanium.
1 Thomas O. Llewellyn, "Germanium," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, p. 531.
2 Ibid., p. 531.
3 Thomas O. Llewllyn, "Germanium," from Minerals Commodity Summaries. U.S. Bureau of Mines, 1995, p. 66.
4 Ibid.
5 Thomas O. Llewellyn, 1992, Op. Cit. p. 531.
6 Thomas O. Llewellyn, 1994, Op. Cit.. p. 70.
317
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EXHIBIT 2
RECOVERY OF GERMANIUM DURING ZINC ORE PROCESSING
(Adapted from: 1988 Final Draft Summary Report on Mineral Industry Processing Wastes, 1988, pp. 3-93 - 3-99.)
Zinc Recovery from
Zinc Ore Processing
Fumes from Zinc Sintering
Containing Germanium Oxide
I
Leaching
Reagents
Precipitation
Reagents —
Leaching
l
r
Precipitation
Leaching
Waste
Wastewater
Crude Germanium Oxide
318
-------
EXHIBIT 3
PRIMARY AND SECONDARY GERMANIUM PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines and Standards for Nonferrous
Metals Manufacturing Point Source Category, 1989, pp. 5231 - 5352.)
Either HC1 or C12 •
Still Liquor •
H,O
Purchased
GeO, —
Hydrofluoric and
Nitric Acid Solution,
Water rinse
Ge Scrap,
Concentrates
Chlorination
GeCl,
Purification
via Distillation
and Stripping
Hydrolysis
GeO,
Reduction
Ge
Melt and
Cast
Acid Wash
and
Water Rinse
it
Zone
Refining
High Purity
Ge Product
Water or Caustic
Solution
Chlorination Wet
Air Pollution
Control
•^ To
Atmosphere
Hydrolysis
Filtrate
Spent Acid
Solution and
Rinse Water
319
-------
tu
ISJ
o
EXHIBIT 4
PROCESS FLOW SHEET FOR GALLIUM AND GERMANIUM PRODUCTION
(Adapted from: 1988 Final Draft Summary Report on Mineral Industry Processing Wastes, 1988, pp. 3-93 - 3-99.)
Ore
Sulfuric Acid
SO
Iron
Germanium
Precipitation
Copper
Cement
(Product)
Sulfuric
Salt Acid
Tailings to Pond
Ferrous Sulfate
Solution
98% Pure
Germanium Oxide
(Product)
Cominco Ltd.
Proprietary
Technology
Gallium
^ Metal
(Product)
Zinc Sulfate
Solution
-------
2. Generalized Process Flow Diagram
As shown in Exhibit 2, germanium-bearing residues from zinc ore processing facilities are a main source for
germanium metal. In general, the ore is roasted and sintered. The sintering fumes, which contain oxidized
germanium are then collected and leached with sulfuric acid, yielding a solution that contains germanium.
Germanium can then be selectively precipitated from the solution through the addition of zinc dust. The remaining
solids can be recycled to maximize the recovery of germanium.7
Most germanium, regardless of the process by which it was recovered from ore, is refined using
chlorination. As shown in Exhibit 3, germanium concentrates are chlorinated with concentrated hydrochloric acid or
chlorine gas to produce germanium tetrachloride (GeCL,) in solution.8 Chlorine is usually added to the primary
distillation or subsequent fractionation, or both, to suppress the volatility of arsenic.9 Solid impurities and still liquor
are separated and discarded as waste or processed further, while the filtrates and other wash water are sent for further
germanium recovery.'0
The resultant purified germanium tetrachloride is then hydrolyzed with deionized water to produce a solid
germanium dioxide (GeO2). The germanium dioxide is removed by filtration, dried, and reduced to germanium
metal with hydrogen at approximately 760 °C. The metal can then be melted and cast into first reduction or as-
reduced bars.''
An alternative process, shown in Exhibit 4, is used at the Musto Exploration site in Utah to recover
germanium. Fluorspar and ore are leached with sulfuric acid and sulfur dioxide. The fluorspar forms hydrofluoric
acid which then helps leach both germanium and gallium. Copper can be removed from the leachate by cementation
on iron and can then be sold as a byproduct. Hydrogen sulfide is used to precipitate the germanium. Following this
precipitation, the remaining liquid is sent for further gallium recovery. The recovered germanium is refined via
leaching and distillation. Any still residues are discarded.12
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Benefieiation/Processing Boundary
Since germanium is recovered as a by-product of other metals, all of the wastes generated during
germanium recovery are mineral processing wastes. For a description of where the beneficiation/processing
boundary occurs for this mineral commodity, please see the reports for copper, zinc, and lead presented elsewhere in
this background document.
7 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for Nonferrous Metals Manufacturing Point Source Category. Vol. X, Office of Water Regulations
Standard, May 1989, p. 5256.
8 Ibid., p. 5256.
9 "Germanium," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed, Vol XI, 1994, p. 796.
10 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 5256.
" "Germanium," 1994, Op. Cit. p. 796.
12 U.S. Environmental Protection Agency, "Germanium," from 1988 Final Draft Summary Report on Mineral
Industry Processing Wastes. Office of Solid Waste, 1988, p. 3-96.
321
-------
C. Process Waste Streams
1. ExtraeMon/Beneficiation Wastes
Not applicable,
2, Mineral Processing Wastes
Exhibit 3 identifies the following wastes from the recovery of primary and secondary germanium and
gallium recovery. Although no published information regarding waste generation rate or characteristics was found.
we used the methodology outlined in Appendix A of this report to estimate low, medium, and high annual waste
generation rates.
Waste Still Liquor. As shown in Exhibit 3, plants which chlorinate germanium raw materials generate an
acidic still liquor containing arsenic, nickel, zinc and germanium, and suspended solids.13 Low, medium, and high
annual waste generation rates were estimated as 10 metric tons/yr, 210 metric tons/yr, and 400 metric tons/yr. We
used best engineering judgment to determine that this waste may exhibit the characteristics of toxicity (arsenic,
cadmium, chromium, lead, selenium, and silver) and ignitability. Waste characterization sampling data for this waste
stream is included as Attachment 1.
Chlorinator Wet Air Pollution Control Sludge. Plants chlorinating germanium use a wet scrubbing
system to control HC1 and H2 fumes. Waste from the scrubbing system contains cadmium, lead, nickel, germanium.
suspended solids, and an alkaline pH.14 Low, medium, and high annual waste generation rates were estimated as 10
metric tons/yr, 210 metric tons/yr, and 400 metric tons/yr. We used best engineering judgment to determine that this
waste stream may be partially recycled and may exhibit the characteristic of toxicity (arsenic, cadmium, chromium,
lead, selenium, and silver). This waste is classified as a sludge. Waste characterization sampling data for this waste
stream is included as Attachment 1.
Hydrolysis Filtrate. As shown in Exhibit 3, germanium tetrachloride is hydrolyzed to germanium dioxide
by adding deionized water. Germanium dioxide solids are separated from the liquid phase by filtration, and the
filtrate may be discharged. The filtrate contains nickel and germanium.15 Low, medium, and high annual waste
generation rates were estimated as 10 metric tons/yr, 210 metric tons/yr, and 400 metric tons/yr. We used best
engineering judgment to determine that this waste may exhibit the characteristic of toxicity (arsenic, cadmium,
chromium, lead, selenium, and silver). Waste characterization sampling data for this waste stream is included as
Attachment 1.
Waste Acid Wash and Rinse Water. Germanium ingots or bars are washed with a HF-HNO3 mixture and
then rinsed with water to remove residual acid from the bar. The discharged spent acid and rinse water contain
treatable concentrations of lead, germanium, and fluoride.16 Low, medium, and high annual waste generation rates
were estimated as 400 metric tons/yr, 2,200 metric tons/yr, and 4,000 metric tons/yr. We used best engineering
judgment to determine that this waste stream may be partially recycled and may exhibit the characteristics of toxicity
(arsenic, cadmium, chromium, lead, selenium, and silver) and corrosivity. This waste is classified as a spent
material. Waste characterization sampling data for this waste stream is included as Attachment 1.
13 U.S. Environmental Protection Agency, 1989, Op. Cit. p. 5273.
14 Ibid., p. 5273.
15 Ibid.
16 Ibid.
322
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Exhibits 2 through 4 also identify the following mineral processing wastes associated with the production of
germanium. No information on waste generation or management is available for these wastestreams.
Roaster off-gases. Off-gases containing sulfur dioxide are generated during roasting and sent to an acid
plant for treatment.
Leach Residues. Ferrous residues are removed and sent to disposal. Residues containing copper and
cadmium are sent to further treatment and distribution. This waste stream has a reported annual waste generation
rate of 10 metric tons/yr. We used best engineering judgment to determine that this waste may exhibit die
characteristic of toxicity (cadmium and lead).
Germanium-Oxides Fumes. As shown in Exhibit 2, fumes containing germanium oxide are generated
during sintering. From these fumes, scrubbing water or solids as well as air pollution control dusts may also be
generated.
Spent Acid/Leachate. Spent acid is generated by leaching the germanium oxide fumes from die zinc
sintering. The spent acid likely contains arsenic and other heavy metals, including lead and zinc. Low, medium, and
high annual waste generation rates were estimated as 400 metric tons/yr, 2,200 metric tons/yr, and 4,000 metric
tons/yr. We used best engineering judgment to determine that this waste stream may be partially recycled and may
exhibit the characteristics of toxicity (arsenic and lead) and corrosivity. This waste is classified as a spent material.
Wastewater. Some wastewater will result from the precipitation step. Existing data and engineering
judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, me Agency
did not evaluate this material further.
As shown in Exhibit 4, tailings are generated as a result of the initial leaching at the Musto Exploration
process. Still residues are generated as a result of further refining operations at Musto Exploration and sent to ponds
for further treatment.''
D. Non-unlquely AssociatedWastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Otner hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments dial address this specific sector.
17 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-96.
323
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BIBLIOGRAPHY
Llewellyn, Thomas O. "Germanium." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. pp. 531-
534.
U.S. Environmental Protection Agency. "Germanium." From 1988 Final Draft Summary Report on Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-93-3-99.
Germanium Specialist. "Germanium." From Mineral Commodity Summaries. January 1995. pp. 66-67.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for Nonferrous Metals Manufacturing Point Source Category. May 1989. Vol. X. Office of Water
Regulations Standards. May 1989. pp. 5231-5352.
"Germanium." Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed. VolXI. 1994. p. 796.
324
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ATTACHMENT 1
325
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Ul
CO
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTE ACID WASH AND RINSE WATER - GERMANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis -
Minimum Average
350
0.04
0.39
-
0.05
-
0.05
0.50
0.50
0.10
2.90
0.78
-
0.09
-
0.50
0.20
0.01
0.07
0.01
1.00
0.06
-
-
-
-
-
-
-
-
-
-
350
0.04
0.39
-
0.05
-
0.05
0.50
0.50
0.10
2.9
0.78
-
0.09
-
0.50
0.20
0.01
0.07
0.01
1.00
0.06
-
-
-
-
-
-
-
-
-
-
PPM
Maximum
350
0.04
0.39
-
0.05
-
0.05
0.50
0.50
0.10
2.9
0.78
-
0.09
-
0.50
0.20
0.01
0.07
0.01
1.00
0.06
-
-
-
-
-
-
-
-
-
# Detects
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Min. Avg. Max. # Detects
0/0
0/0
0/0
0/0
0/0
0/0
- - - 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - HYDROLYSIS FILTRATE - GERMANIUM
Constituents
Aluminum
Antimony
Arsenic
3arium
Sen/Ilium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis -
Minimum Average
0.78
0.01
0.20
-
0.05
-
0.05
0.50
0.50
0.10
0.37
0.20
-
0.05
-
0.52
1.00
0.12
0.00
0.02
1.00
0.05
-
-
-
-
-
-
-
-
-
-
0.78
0.01
0.20
-
0.05
-
0.05
0.50
0,50
0.10
0.4
0.20
-
0.05
-
0.52
1.00
0.12
0.00
0.02
1.00
0.05
-
-
-
-
-
-
-
-
-
-
PPM
Maximum
0.78
0.01
0.20
-
0.05
-
0.05
0.50
0.50
0.10
0.4
0.20
-
0.05
-
0.52
1.00
0.12
0.00
0.02
1.00
0.05
-
-
-
-
-
-
-
. -
-
-
i Detects
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Min. Avg. Max. # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- • - o/o
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1,0 0
5.0 0
.
-
-
-
-
.
-
-
.
.
.
212 0
-
u>
NJ
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
UJ
NJ
00
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTE STILL LIQOUR - GERMANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis -
Minimum Average
1.50
0.03
1.70
-
0.05
-
0.23
0.50
0.50
0.16
1.80
0.20
-
2.20
-
0.50
2.00
0.09
0.00
0.01
1.00
150.00
-
-
-
-
-
-
-
-
-
-
1.50
0.03
1.70
-
0.05
-
0.23
0.50
0.50
0.16
1.8
0.20
-
2.20
-
0.50
2.00
0.09
0.00
0.01
1.00
150.00
-
-
-
-
-
-
-
-
-
-
PPM
Maximum
1.50
0.03
1.70
-
0.05
-
0.23
0.50
0.50
0,16
1.8
0.20
-
2.20
-
0.50
2.00
0.09
0.00
0.01
1.00
150.00
-
-
-
-
-
-
-
-
-
-
# Detects
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Min. Avg. Max. # Detects
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
-
-
-
.
.
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - CHLORINATOR WET ARC - GERMANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis -
Minimum Average
4.10
0.02
0.10
-
0.05
-
0.46
0.50
0.50
0.20
11.00
0.45
-
0.25
-
0,50
1.80
0.04
0.00
0.02
1.00
0.17
-
-
-
-
-
-
-
-
-
-
4.10
0.02
0.10
-
0.05
-
0.46
0.50
0.50
0.20
11,0
0.45
-
0.25
-
0.50
1.80
0.04
0,00
0.02
1.00
0.17
-
-
-
-
-
-
-
-
-
-
PPM
Maximum
4.10
0.02
0.10
-
0.05
-
0.46
0.50
0.50
0.20
11.0
0.45
-
0.25
-
0.50
1.80
0.04
0.00
0.02
1.00
0.17
-
-
-
-
-
-
-
-
-
-
# Detects
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
0/0
1/1
0/0
1/1
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Min. Avg. Max. # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
_
-
0.2 0
-
-
1.0 0
5.0 0
.
.
-
-
.
.
-
-
.
-
.
212 0
-
uu
NJ
IO
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
330
-------
GOLD AND SILVER
A. Commodity Summary
Gold and silver are discussed together in this report since most of the processes used to recover one will
also recover the other. In addition, both metals are often found together in nature. A mine is generally classified as a
gold or silver mine based on which metal recovered yields the greatest economic value to the operator. Exhibit 1
presents the names and locations of known gold and silver smelters and refineries. Exhibit 2 presents the names and
locations of the 25 leading gold-producing mines in the United States.
EXHIBIT 1
SUMMARY Or KNOWN GOLD AND SILVER SMELTERS AND REFINERIES
Facility Name
ASARCO, Inc.
AURIC-CHLOR, Inc.
David Fell & Company, Inc.
Drew Resources Corp.
Eastern Smelting & Refining Corp.
Englehard Industries West, Inc.
GD Resources, Inc.
Handy & Harman
Johnson Matthey
Metalor USA Refining Corp.
Multimetco, Inc.
Nevada Gold Refining Corp.
Sunshine Mining Co.
Williams Advanced Materials
Facility Location
Amarillo, TX
Omaha, NE
Rapid City, SD
City of Commerce, CA
Berkeley, CA
Lynn, MA
Anaheim, CA
Sparks, NV
Attleboro, MA
South Windsor, CT
Salt Lake City, UT
North Attleboro, MA
Anniston, AL
Reno, NV
Kellogg, ID
Buffalo, NY
Source: Randol Mining Directory. 1994, pp. 741-743.
331
-------
EXHIBIT 2
TWENTY-FIVE LEADING GOLD-PRODUCING MINES IN THE UNITED STATES (IN ORDER or OUTPUT)
Mine
Nevada Mines Operations, Newmont Gold Company
Gold Strike, Barrick Mercur Gold Mines, Inc.
Bingham Canyon, Kennecott-Utah Copper Corp,
Jerritt Canyon (Enfield Bell), Freeport-McMoran Gold
Company
Smoky Valley Common Operation, Round Mountain Gold
Corp.
Homestake, Homestake Mining Company
McCoy and Cove, Echo Bay Mining Company
McLaughlin, Homestake Mining Company
Chimney Creek, Gold Fields Mining Company
Fortitude and Surprise, Battle Mountain Gold Company
Bulldog, Bond Gold, Bullfrog, Inc.
Mesquite, Goldfields Mining Company
Getchell, FMG, Inc.
Sleeper, Ansax Gold, Inc.
Cannon, Asamera Minerals (U.S.), Inc.
Ridgeway, Ridgeway Mining Company
Jamestown, Sonora Mining Corp.
Paradise Peak, FMC Gold Company
Rabbit Creek, Rabbit Creek Mining, Inc.
Barney's Canyon, Kennecott Corp.
Continental, Montana Resources
Zortman-Landusky, Pegasus Gold, Inc.
Golden Sunlight, Golden Sunlight Mines, Inc.
Wind Mountain, Amax Gold, Inc.
Foley Ridge & Amie Creek, Wharf Resources
Location
Elko and Eureka, NV
Eureka. NV
Salt Lake, UT
Elko, NV
Nye, NV
Lawrence, SD
Lander, NV
Napa, CA
Humboldt, NV
Lander, NV
Nye, NV
Imperial, CA
Humboldt, NV
Humboldt, NV
Chelan, WA
Fairfield, SC
Tuolumne, CA
Nye, NV
Humboldt, NV
Salt Lake City, UT
Silver Bow, MT
Phillips, MT
Jefferson, MT
Washoe, NV
Lawrence, SD
Source of Gold
Gold ore
Gold ore
Copper ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Copper ore
Gold ore
Gold ore
Gold ore
Gold ore
Gold ore
Source: Mining Industry Profile Gold. 1993, pp. 5.
332
-------
The United States is the second largest gold producing nation in the world. Gold lode and placer mines are
located mostly in western states and Alaska while production in Nevada and California accounts for 70 percent of
domestic production. The 1994 mine production value was over $4.1 billion. Uses of gold include jewelry and arts,
71 percent; industrial (electronic), 22 percent; and dental, 7 percent.1 The 1994 silver production was valued at S240
million. Nearly three-fourths of the 1994 silver mine production was in Nevada, Idaho, Arizona, and Montana.
Approximately 50 percent of the refined silver consumed domestically during 1993 was used in the manufacture of
photographic products; 20 percent in electrical and electronic products; 10 percent in electroplated ware,
sterlingware, and jewelry; and 20 percent in other uses.2
Silver occurs as native metal, but is usually found in sulfur-bearing minerals. About two-thirds of the world
silver reserves and resources are contained in copper, lead, and zinc deposits. Ores in which silver or gold is the
main component account for the remaining one-third of total world reserves and resources. The chief silver minerals
found in domestic reserves are native silver, argentite, ceragyrite, polybasite, proustite, pyrargyrite, and tetrahedrite.
Other ore minerals of silver are the tellurides, stromeyerite, and pearceite. Gold occurs mainly as native metal,
alloyed with silver and/or other metals, and as tellurides. A naturally occurring alloy of gold and silver is known as
electrum. Other gold minerals are rare. Gold is commonly associated with the sulfides of antimony, arsenic, copper,
iron, and silver.3
B, Generalized Process Description
Precious metals may be recovered from the ore or from refining processes of base metals such as copper
and lead. Because these are distinct and separate recovery methods, they are discussed separately in this report.
Section 1 describes precious metal recovery from ore, and Section 2 describes precious metal recovery from refinery
slimes. Section 3 is a discussion of precious metal refining operations.
SECTION 1: PRECIOUS METAL RECOVERY FROM ORES
1. Discussion of Typical Production Processes
Most domestic gold comes from surface lode mines. Silver is mined using open pit and underground
methods. Several processes may be used to recover gold and silver from their ores. These include gravity
separation, amalgamation, froth flotation, and cyanidation. Several processes may be combined at any given plant.
These processes are discussed in more detail below.
2. Generalized Process Flow Diagram
Gravity Separation
Gravity separation relies on density differences to separate desired materials from host rock. Devices used
include gold pans, sluices, shaking tables, and jigs. Gravity separation is used at most placer mines and at some lode
or vein deposits.4
1 John Lucas, "Gold," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1994, pp. 72-73.
2 Robert Reese, "Silver," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp. 154-
155.
3 John M. Lucas, "Gold," from Minerals Yearbook Volume 1 Metals and Minerals. U.S. Bureau of Mines, 1992.
pp. 535-561.
;*U.S. Environmental Protection Agency, "Gold and Silver." from, 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. Office of Solid Waste, 1988, pp. 3-100- 3-115.
333
-------
Amalgamation
Fine gold in placer deposits is often not separable from the ore minerals by density alone. The fine
concentrate stream from a gravity separator, called "black sand" because of its color, often contains several dense
minerals as well as fine gold. This fine gold may be recovered by amalgamation which involves the dissolution of
gold or silver in mercury. The resulting alloy, amalgam, is relatively soft and will adhere readily to other pieces of
amalgam or to mercury.5
Historically, amalgamation was widely used in the United States for recovery of gold and silver from their
ores. Although this method is still practiced in other parts of the world, amalgamation most likely occurs
domestically on a very limited scale.
Ore Preparation
Extracted ore must be milled to prepare it for further recovery activities. Uniformly sized particles may be
obtained by crushing, grinding, and wet or dry classification. The degree of milling performed on the ore depends
on the gold concentration of the ore, mineralogy and hardness of the ore, the mill's capacity, and the next planned
step for recovery. Milled ore is pumped to the next operation unit in the form of a slurry. Fugitive dust generated
during crushing and grinding activities is usually collected by air pollution control devices and recirculated into the
beneficiation circuit. Most mills use water sprays to control dust from milling activities.6
After milling, sulfide ores may be subjected to oxidation by chlorination, bio-oxidation, roasting, or
autoclaving. Chlorination is not commonly used to oxidize sulfide ores because of high equipment maintenance
costs caused by the corrosive nature of the oxidizing agent. Bio-oxidation of sulfide ores employs bacteria to
oxidize the sulfur-bearing minerals. Roasting of sulfide ores involves heating the ores in air to convert them to oxide
ores and break up their physical structure, allowing leaching solutions to penetrate and dissolve the gold. Roasting
oxidizes the sulfur in the ore, generating sulfur dioxide that can be captured and converted to sulfuric acid. Roasting
temperatures are dependent on the mineralogy of the ore, but range as high as several hundred degrees Celsius.
Roasting of carbonaceous ores oxidizes the carbon to prevent interference with leaching, which, in time, improves
gold recovery efficiency. Autoclaving (pressure oxidation) is a relatively new technique that operates at lower
temperatures than roasting. Autoclaving uses pressurized steam to start the reaction and oxygen to oxidize sulfur-
bearing minerals. Heat released from the oxidation of sulfur sustains the reaction. The Getchell and Barrick
Goldstrike Mines in Nevada, the McLaughlin Mine in California, and the Barrick Mercur Mine in Utah are currently
using pressure oxidation (autoclave) technology, totally or in part, to beneficiate sulfide or carbonaceous gold ores.7
Agglomeration
Because ores with a high proportion of small particles may retard the percolation of the lixiviate,
agglomeration is used to increase particle size. This operation includes mixing the crushed ore with portland cement
and/or lime, wetting the ore evenly with cyanide solution to start leaching before the heap is built, and mechanically
tumbling the ore mixture so fine particles adhere to larger particles.
Cyanidarion - Leaching
Cyanidation leaching is the primary means of recovery of fine gold and silver. In this process, solutions of
sodium or potassium cyanide are brought into contact with an ore which may or may not require extensive
preparation prior to leaching. Gold and silver are dissolved by cyanide in high pH solutions in the presence of
5 Ibid.
6 U.S. Environmental Protection Agency, Technical Resource Document. Extraction and Beneficiation of Ores
and Minerals. Vol. II, July 1994.
7 Ibid.
334
-------
oxygen. There are three general methods of contacting ores with leach solutions: (1) heap leaching, (2) vat leaching,
and (3) agitation leaching. Cyanidation heap leaching and agitation leaching account for most gold and silver
recovery.8'9 These leaching methods are discussed in detail below.
(1) Cyanidation - Heap Leaching
Heap leaching, shown in Exhibit 3, is the least expensive process and is used most often to treat low value
ores. In 1993, heap leaching accounted for 39 percent of gold production.10 In many cases, heaps are constructed on
lined pads and ore is sent directly from the mine with little or no preparation. However, at about half of the heap
leaching operations, ore is crushed and agglomerated prior to placement on die heap to increase permeability of the
heap and maintain the high pH (optimally 10.5) needed for leaching to occur.
Two types of pads used in gold heap leaching are permanent heap construction on a pad from which the
leached ore is not removed, and on-off pads, which allow the spent ore to be removed from die pad following the
leach cycle and fresh ore to be placed on the pad. Permanent heaps are typically built in lifts. Each lift typically is
composed of a 5- to 30-foot layer of ore, though lifts may be higher at times.11 On-off pads are not commonly used
in die industry.
After the ore is piled on a leaching pad, the leaching solution is applied to die top of die pile by sprinklers.
The solution generally has a concentration of 0.5 to 1 pound of sodium cyanide per ton of solution, though one major
gold producer reports that the leaching solution is generally in die range of 0.25 pounds of sodium cyanide per ton of
solution.'2J3 The precious metals are dissolved as the solution trickles through the pile, and the metal bearing
solution is collected on the impervious pad and pumped to the recovery circuit. Following rejuvenation, which
involves removing die metals, die solution is returned for reuse. The leaching process continues until no more
precious metal is extracted. Typical operations will involve leaching for several mondis on each heap. The process
is relatively inexpensive and can be operated for less than two dollars per ton of ore. However, as much as half of
the gold and silver may not be extracted either because die leach liquor never contacts die precious metal or because
die metal bearing solution is trapped in blind channels. At one facility, at least 60 percent (and often much higher14
percentages) of the gold contained in leach-grade ore is recovered through heap leaching,13 Waste streams from this
process include spent ore and leaching solutions as well as residual leach liquor in the pile.
* Personal communication between ICF Incorporated and Robert G. Reese, U.S. Bureau of Mines, September 23,
1994.
9 Newmont Gold Company. Comments submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
10 Personal communication between ICF Incorporated and John M. Lucas, U.S. Bureau of Mines, September 15,
1994.
11 Newmont Gold Company. Op. Cit.
12 U.S. Environmental Protection Agency, Technical Resource Document. Treatment of Cyanide Heap Leaches
and Tailings. Office of Solid Waste Special Waste Branch, 1994, pp. 2-4.
13 Newmont Gold Company. Op. Cit.
14 U.S. Environmental Protection Agency, 1988, Op. Cit., pp. 3-100 - 30-115.
15 Ibid.
335
-------
Ul
U)
EXHIBIT 3
GOLD-SILVER LEACHING
(Adapted from : 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-100 - 3-115.)
Heap or Vat
Ore
Heap or
Vat
Carbon
Colurn n
Spent Ore
Barren
liquor
Recycle
Carbon
Stripping
Gold
Electrom ining
Do re*
Refining
-------
(2) Cyanidation - Vat Leaching
Vat leaching, shown in Exhibit 3, is used when greater solution control than that afforded by heap leaching
is necessary. In this system, prepared ore is placed in a vat or tank and flooded with leach liquor. The solution is
continuously cycled through, draining from the bottom of the vat, proceeding to gold recovery, rejuvenation, and
returning to the top of the vat. The process is more expensive than heap leaching because the material must be
removed from the vat at the end of the leaching process. While the primary advantage of vat leaching is better
solution contact, channelization and stagnant pockets of solution still occur (almost as severely as in heap leaching)
when solution is drained from the vat. However, some of the trapped solution is recovered when the solids are
removed from the vat. Wastes from this process include spent ore and leaching solutions.16
(3) Cyanidation - Agitation Leaching
Agitation leaching is the most commonly used leaching process in gold beneficiation operations in the
United States.1' High value ores are treated by agitation leaching, shown in Exhibit 4, to maximize the recovery of
metal values. The ore is crushed and ground in water to form a slurry. Cyanide is usually added at the grinding mill
to begin the leaching process, and more cyanide may be added to the leaching tanks. Ores may be leached anywhere
from 24 to 72 or more hours. Silver ores tend to require longer leaching times. The method of recovering the
precious metal from solution determines how the solution is separated from the solids. If the Merrill-Crowe or
carbon-in-column metal recovery process is used, the leach liquor will be washed out of the solids, usually by a
combination of counter-current decantation and filtration washing with water. This produces a concentrated wash
solution and recovers the maximum pregnant liquor from the solids. The resultant slurry will contain very little
cyanide or gold and would not be expected to exhibit any hazardous characteristics. The carbon-in-leach and
carbon-in-pulp beneficiation processes are the most commonly used metal recovery processes used in gold
beneficiation operations.18 If carbon-in-leach or carbon-in-pulp metal recovery is practiced, the slurry may be
discarded without washing. The carbon should remove all of the precious metals, and the solution is recovered from
the tailings treatment and recycled back to the process.19
Cyanidation - Metal Recovery
In leaching operations, after dissolving the metal, the leach solution is separated from the ore, and the gold
and silver are removed from solution in one of two ways: (1) the Merrill-Crowe process, or (2) activated carbon
loading followed by activated carbon stripping.20 The primary difference between recovery methods is whether the
metal is removed by precipitation with zinc or by adsorption on activated carbon. Zinc cyanide is more soluble than
gold or silver cyanide and if pregnant liquor is contacted with metallic zinc the zinc will go into solution and the gold
and silver will precipitate.21 The two different recovery methods are described below.
16 U.S. Environmental Protection Agency, 1988, Op. Cit. 3-100 - 3-115.
17 Newmont Gold Company and National Mining Association. Comments submitted in response to the
Supplemental Proposed Rule Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing
Wastes. January 25, 1996.
18 Ibid.
19 U.S. Environmental Protection Agency, 1988, Op. Cit.. 3-100-3-115.
20 Newmont Gold Company and National Mining Association. Op. Cit.
21
U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-100 - 3-115.
337
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EXHIBIT 4
AGITATION LEACHING WITH MERRILL-CROWE RECOVERY
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-100 - 3-115.)
Ore
Tailings
-^-Solids
Zn CN Solution
338
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(1) Cyanidation - Metal Recovery - Merrill-Crowe
In the Merrill-Crowe process, the pregnant leaching solution is filtered for clarity, then vacuum deaerated to
remove oxygen and decrease precious metal solubility. The deaerated solution is then mixed with fine zinc powder
to precipitate the precious metals. The solids, including the precious metals, are removed from the solution by
filtration, and the solution is sent back to the leaching circuit. The solids are melted and cast into bars. If silver and
gold are present, the bars are called dore. In most cases, the metal is then sent to an off-site refinery. Most
operations using zinc precipitation in the United States use some variation of the Merrill-Crowe process.22
(2) Cyanidation - Metal Recovery - Activated Carbon Loading/Activated Carbon Stripping
Precious metal leach solutions can be brought into contact with activated carbon by carbon-in-column,
carbon-in-pulp, and carbon-in-leach processes.
Carbon-in-column systems are used at heap and vat leach operations and in other situations where the
leaching solution is separated from the solids being leached prior to precious metal recovery. The leaching solution
is passed through a series of columns containing beds of activated carbon. The gold and silver are adsorbed as
cyanide complexes on the surface of die carbon. After passing through the columns, the solution is returned to the
leaching circuit. When the carbon in a column is loaded with precious metals, the column is switched to a stripping
circuit.23
In many agitation plants, the gold is recovered from the leached material before the solution is separated
from the solids. In the carbon-in-pulp system, the leached pulp passes from the last stage of the leaching circuit into
another series of agitation tanks. Each tank contains activated carbon granules. The slurry flows from tank to tank
in series while the carbon is retained by screens. When die carbon in the first tank is fully loaded with precious
metals, it is removed and sent to the stripping and reactivation circuit; the carbon in the other tanks is moved ahead
one stage, and new carbon is added to the last stage. The carbon moves counter-current to the leached slurry and the
leached slurry is finally sent to the tailings area for dewatering.24 A process flow diagram of carbon-in-pulp metal
recovery is shown in Exhibit 5.
Carbon-in-leach is similar to carbon-in-pulp except that the carbon is in the leaching tanks instead of in a
separate recovery circuit. One advantage of carbon-in-leach over carbon-in-pulp is that some cyanide is released
when gold adsorbs on carbon, making it available for more leaching. Another advantage is that fewer agitation tanks
are necessary since the separate recovery circuit is eliminated. However, the agitation is more aggressive in the
leach circuit causing more attrition of die carbon than in die carbon-in-pulp. Thus, the finely abraded carbon and its
load of precious metals may be lost, reducing recovery and increasing costs due to increased carbon replacement.25
A process flow diagram of carbon-in-leach metal recovery is presented in Exhibit 5.
Gold stripping from loaded activated carbon is usually done with a hot, concentrated alkaline cyanide
solution, sometimes including alcohol. These conditions favor the desorbtion of the precious metals into the
stripping solution. The solution then goes into an electrowinning cell where the precious metals are plated out,
generally onto a steel wool cathode. The solution is recycled to the stripping stage and the cathode is sent on to
22 Ibid.
23 Ibid.
24 Ibid.
25 Ibid.
339
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U!
-t>
o
EXHIBIT 5
CARBON-IN-PULP AND GARBON-IN-LEACH METAL RECOVERY
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-100 - 3-115.)
CARBON-IN-PULP
Ground j
Ore
Slurry
Cyanide
I
y |
*l
A
t
d
1
D
t
d
1
D .
i
! !
—
^l1
i
t
d
f
b
'I1
Jo
|
^ . „
Waste
4 '
Carbon Tanks
CARBON-IN-LEACH
Ground
Slurry
Cyanide
t
Loaded Carbon
to Stripping
Loaded Carbon
to Stripping
f
t
d
D
4
t
C
D
t
t
C
1
D
4
"^ Waste
-------
refining. Some operations refine the steel wool on site to make dore while others ship it directly to commercial
refineries. The primary waste from carbon stripping is the spent stripping solution.26
The Anglo-American Research Laboratory (AARL) elution method is an alternative stripping process being
used by at least one facility. In the first step of the AARL method, the loaded carbon is rinsed with a dilute (i.e.,
three percent) hydrochloric acid solution and then flushed with water to render the gold more amenable to separation
from the carbon. The rinse waters resulting from this process are recycled by pipe to the carbon-in-leach circuit to
recover any loaded carbon that is flushed out by the acid wash (loaded carbon typically contains 150 ounces of gold
per ton). Following the acid wash/water rinse stage, desorption occurs. The loaded carbon is soaked in a
concentrated solution composed of six percent sodium hydroxide and three percent sodium cyanide. This soaking
loosens the bond between the carbon and gold. A fresh water rinse then picks up the gold. The resulting pregnant
gold-bearing solution is pumped to the electrowinning circuit.27
Carbon Regeneration
After stripping, the carbon is reactivated on- or off-site and recirculated to the adsorption circuit. Carbon
used in adsorption/desorbtion can be reactivated numerous times. The regeneration technique varies with mining
operations, but generally involves an acid wash before or after extraction of the gold-cyanide complex, followed by
reactivation in a kiln. The activated carbon is washed with dilute acid solution (pH of 1 or 2) to dissolve carbonate
impurities and metal-cyanide complexes that adhere to the carbon along with the gold. This technique may be
employed either immediately before or after the gold-cyanide complex is removed. Acid washing before the gold is
removed enhances gold recovery. The Barrick Mercur Mine in Utah, the Barrick Goldstrike Mine in Nevada, and
the Ridgeway Gold Mine in South Carolina are examples of facilities using acid prewash techniques. The Golden
Sunlight Mine in Montana and the Battle Mountain Mine in Nevada use acid postwash techniques.28
The specific acid used for carbon washing is determined by the types of impurities need to be removed.
Usually, a hydrochloric acid solution is circulated through 3.6 metric tons of carbon for approximately 16 to 20
hours. Nitric acid also is used in these types of operations, but is thought to be less efficient than hydrochloric acid
in removing impurities. The resulting spent acid wash solutions may be neutralized with a high pH tailings slurry.
dilute sodium hydroxide solution, or water'rinse. When the spent acid wash solution reaches a stable pH of 10, it is
sent to a tailing impoundment. Metallic elements may also be precipitated with sodium sulfide to remove them from
the carbon.29
The carbon is screened to remove fines and thermally reactivated in a rotary kiln at about 730 °C for 20
minutes. The reactivated carbon is subsequently rescreened and reintroduced into the recovery system. Generally,
less than 10 percent of the carbon is lost during the process because of particle abrasion.30 Recirculating the carbon
material gradually decreases performance in subsequent absorption and reactivation series. Carbon adsorption
efficiency is closely monitored, and fresh carbon is added to maintain efficiency at design levels.31
26 Ibid.
27 Newmont Gold Company. Op. Cit.
28 U.S. Environmental Protection Agency, July 1994, Op. Cit., pp. 1-12.
29 Ibid.
30 Newmont Gold Company. Op. Cit.
31 U.S. Environmental Protection Agency, July 1994, Op. Cit., pp. 1-12.
341
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3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Benefieiation/Processing Boundaries
EPA has determined that all of the activities discussed in Section 1 are classified as beneficiation activities.
SECTION 2: PRECIOUS METAL RECOVERY FROM REFINERY SLIMES
1. Discussion of Typical Production Processes
Gold and silver also are recovered from the refining processes for base metals, primarily lead and copper.
Smelting operations remove iron, sulfur, and other impurities from the ore and produce copper anodes for
electrolytic refining. In refining operations, the anodes produced from smelting are purified electrolytically to
produce copper cathodes. The refinery slimes from these operations are processed for precious metals recovery, as
portrayed in Exhibit 6. The recovery of precious metals in lead refineries is a normal part of the operation called
"desilverizing."
2. Generalized Process Flow Diagram
A major source of precious metals from the copper industry is electrolytic cell slimes. The slimes are
periodically removed from the cells in the refinery for treatment. The first stage of treatment removes the copper in
the slimes by acid leaching, either as is or after roasting. The decopperized slimes are then placed in a furnace and
melted with a soda-silica flux. The siliceous slag formed in this melting is removed, and air is blown through the
molten material. Lime is added, and a high lead content slag is formed which is combined with the siliceous slag and
returned to the copper anode casting furnace. Next, fused soda ash is added to the furnace and air is again blown
through the melt, forming a soda slag which is removed and treated to recover selenium and tellurium. The
remaining dore in the furnace is removed and sent to refining to recover the precious metals.32 See the selenium and
tellurium commodity reviews for a more detailed discussion of product recovery,
The desilverizing process takes advantage of the solubility of precious metals in molten zinc which is
greater than their solubility in molten lead. Lead from previous stages of refining is brought in contact with a zinc
bath, either in a continuous operation or in batches. The zinc absorbs the precious metals from the lead, and the lead
is then passed onto a dezincing operation. The zinc bath is used until it contains 5,000 to 6,000 troy ounces of
precious metal per ton of zinc. The zinc bath is then retorted to recover zinc by distillation. The zinc is returned to
the desilverizing process, and the "retort metal" is treated by cupellation to produce dore bullion. In the
cupellation,step, the base metals in the retort metal are oxidized with air and removed from the precious metals. The
oxides are all treated for the recovery of their various precious metals. The dore is then sent to refining.33
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Benefieiation/Processing Boundaries
Because the slimes from which gold is recovered are mineral processing wastes generated in the recovery of
other metals, all of the wastes generated during gold recovery from refinery slimes are, therefore, mineral processing
wastes as well.
32 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-100 - 3-115.
33 Ibid.
342
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EXHIBIT 6
OVERVIEW OF GOLD PRODUCTION FROM BASE METALS
(Adapted from: Technical Resource Document, Extraction and BeneficiatJon of Ores and Minerals, July 1994, pp. 1-12.)
Base Metal Production
(e.g., copper, lead)
Base Meta! Flotation
1
Base Meta!
Product
Slag Containing
Selenium and Tellerium
343
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SECTION 3: PRECIOUS METAL REFINING
1. Discussion of Typical Production Processes
The refining process used for gold and silver depends on the composition of the material in the feed. The
most basic operation is "parting" which is the separation of gold and silver. Parting can be done electrolytically or
by acid leaching. In either case, the silver is removed from the gold. Further treatments may be necessary to remove
other contaminants. These treatments have the potential to produce wastes with hazardous characteristics, primarily
corrosivity, since strong acids are used.3"
2. Generalized Process Flow Diagram
Like several other gold refineries, the Newmont facility in Nevada electrowins its gold cyanide solution
onto steel wool cathodes after carbon stripping. The barren cyanide solution is returned to the leach circuit for gold
recovery. Sludge from the bottom of the electrowinning cell is filtered and sent to the retort for mercury recovery.
The gold/steel wool cathode is placed in a vat containing a sulfuric acid solution. The solution dissolves the steel
wool from the gold and silver, leaving a solid gold and silver residue. The waste sulfuric acid and steel wool
solution is discharged to the tailings slurry. The gold and sislver solids are filtered under vacuum through
diatomaceous earth. The gold and silver filter cake is then sent to the retort furnace where it is subjected to 1,200 °F
for 14 hours. After retorting, a flux of silica and borax is added, and the gold and silver mixture is smelted in an
induction furnace. It is from this induction furnace that gold dore bars are poured. Within days of generation, the
slag generated from this smelting is sent to a ball mill for crushing and grinding and is then leached in tanks with
sodium cyanide. The resulting gold rich slurry is conveyed to the cyanidation/leaching circuit where it is processed
with primary gold-bearing slurries. In some cases, portions of the slag are recycled directly back into the induction
furnaces for gold recovery. The gold slag may have between 3 and 4 ounces per ton of recoverable gold.35 The slag
from one facility reportedly averages 150 ounces of gold per ton.36
Silver Chloride Reduction
Silver metal is produced from silver chloride by a dissolution and cementation process. The silver chloride
is dissolved in a dilute solution of ammonium hydroxide and recovered by cementation. The silver is replaced in
solution, causing the silver ions to be reduced and precipitated from solution as silver metal.
Mercury Recovery
Many gold-bearing ores from the western United States contain small quantities of mercury. The presence
of mercury decreases the gold-loading capacity of the activated carbon. During cyanidation of mercury-bearing
gold-silver ores, significant amounts of mercury are extracted. Addition of calcium sulfide to the cyanide leach
slurry precipitates the solubilized mercury and also some silver.3' Primary mercury is also produced from gold-
bearing ores by roasting or calcining. These processes are described in more detail in the chapter on mercury.
Exhibit 7 presents an overall process flow sheet for gold production from ores.
34 Ibid.
35 U.S. Environmental Protection Agency, Trip report for Newmont Gold Corporation, South Operations
Facilities, Carlin Nevada, May 17, 1995.
36 Newmont Gold Company. Op. Cit.
37 Simpson, W,W., W.L. Staker, and R.G. Sandberg, Calcium Sulfide Precipitation of Mercury From Gold-Silver
Cyanide-j?.each Slurries. U.S. Department of Interior, 1986.
344
-------
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Benefleiation/Proeessing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for recovering gold and silver from precious metal refining, the beneficiation/
processing line occurs between electrowinning and retorting because this is where a significant chemical change
occurs. Therefore, because EPA has determined that all operations following the initial "processing" step in the
production sequence are also considered processing operations, irrespective of whether they involve only techniques
otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral
processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents
below the mineral processing waste streams generated during the production of gold and silver, along with associated
information on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneflciatlon Wastes
Mining
Mine water is a waste stream generated from gold and silver production. This waste consists of all water
mat-collects in mine workings, both surface and underground, as a result of inflow from rain or surface water and
ground water seepage. If necessary, the water is pumped to allow access to the ore body or to keep the mine dry.
This water may be pumped from sumps within the mine pit or from interceptor wells. Mine water may be used and
recycled to the beneficiation circuit, pumped to tailings ponds, or discharged to surface water. Quantity and
chemical composition of mine water varies from site to site.38
38 U.S. Environmental Protection Agency, Mining Industry Profile. Gold. Office of Solid Waste, Special Waste
Branch, 1993, pp. 41-45.
345
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EXHIBIT?
OVERVIEW OF GOLD PRODUCTION FROM ORES
(Adapted from: Technical Resource Document, Extraction and Beneficiation of Ores and Minerals, July 1994, pp. 1-12.;
Cyanidalion-Leaching .
Agitation Leaching
Cyanidation-Metal Recovery
XX
Merrill-Crowe Carbon-in-Colunm Carbon-in-Pulp Memll-Crowe
(see Exhibit 4) I Carbon-in-Leach (see Exhibit 4)
Gold Adsorption
on Activated
Carbon
Gold Adsorption
on Activated
Carbon
i
346
-------
Waste Rock. Overburden and mine development is referred to by the industry as waste rock. This waste is
generally disposed of in waste rock piles or dumps. An estimated 25 million metric tons of overburden and mine
development rock was generated in 1980 and 39 million metric tons in 1982. At surface mines, 71 percent of all
material handled is discarded as waste. At underground mines, 20 percent is discarded as waste. The quantity and
composition of the waste rock varies by site. Depending on the composition of the ore body, this waste may contain
sulfides or oxides.
Amalgamation
Waste rock, clay, and sand may be disposed of in a tailings pond.
Black sand may contain residual mercury and be disposed of in a tailings pond.
Mercury bearing solution may be sent to mercury recovery or a tailings pond.
Ore Preparation
Sulfur dioxide may be routed to an acid plant and converted to sulfuric acid. This may be sold to other
mines or used on-site for carbon washing and regeneration. At least one facility, Newmont's operation in Nevada,
generates sulfuric acid,.39
Cyanidation
Spent Ore. The ore from leaching may contain residual cyanide. The ore in continuous or valley fill heaps
is stacked in lifts and left in place for subsequent leaching, detoxification, and closure. Ore removed from on-off
heap leaching pads is permanently disposed at waste or spent ore disposal sites. Typically, detoxification of the
spent ore involves rinsing with water until the cyanide concentration in the effluent is below a specific standard set
by the State regulatory agency. The heap may then be reclaimed with wastes in place. Spent ore from vat leaching
exists in the form of a slurry composed of gangue and process water bearing cyanide and cyanide-metal complexes.
The spent ore may be treated to neutralize cyanide prior to disposal. The slurry is typically disposed of in a tailings
impoundment with some of the liquid component being recirculated to the tank leach as make-up water.40
Spent Leaching Solution. During the leaching operations, most of the barren cyanide solution is recycled
to leaching activitie. On rare occasions, however, the build-up of metal impurities may interfere with the dissolution
and precipitation of gold and, therefore, require a portion of the solution volume to be bled off and disposed. These
solutions may contain free cyanide and metallo-cyanide complexes of copper, iron, nickel, and zinc, as well as other
impurities, such as arsenic and antimony, mobilized during the leaching. Management practices for these solutions
are unclear; however, they have been discharged to tailings impoundments.41
Merrill- Crowe
Filter cake resulting from zinc precipitation consists primarily of fine gangue material and may contain
gold-cyanide complex, zinc, free cyanide, and lime. The filter may be washed with water, which is disposed of as
part of the waste. The waste is typically sent to tailings impoundments or piles.
Spent leaching solution from zinc precipitation is often returned to the leaching process.
39 Newmont Gold Company. Op. Cit.
40 U.S. Environmental Protection Agency, 1994, Op. Cit.. pp. 1-12.
41
Ibid.
347
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Metal Recovery - Activated Carbon Stripping
Tailings in slurry form, composed of gangue (including sulfide materials and dissolved base metals) and
process water bearing cyanide and cyanide-metal complexes, are generated from carbon-in-pulp and carbon-in-leach
processes. The characteristics of this waste vary depending on the ore, cyanide concentration, and water source
(fresh or recycled). The characteristics of the gangue are dependent on the ore source. The slurry is typically
disposed of in a tailings impoundment with some of the liquid component being recirculated to the tank leach or
other water consumptive system.42
Waste sulfuric acid from elution is exempt under the Bevill Amendment because it is generated in a
beneficiation activity that is uniquely associated with mineral processing. This waste may be corrosive,
Waste steel wool solution may be corrosive.
Acid wash from carbon regeneration may be corrosive.
2. Mineral Processing Wastes
Smelting and Refining
Slag. Slag is typically generated at gold mining and milling operations.43 At one facility, metal-bearing
slag is broken off the molten dore and then placed into barrels inside the refinery building. The slag is then
processed for gold recovery, normally within several days of its generation. Specifically, the slag is ground and then
leached in tanks with sodium cyanide. The gold-rich slurry that results is then conveyed, by pipe, to the primary
gold-bearing slurries in the mill for mixing. The facility also reports that in the past, slag also was processed by
placing it directly back into the induction furnaces for gold recovery. Assays performed by Newmont Gold during
1995 and 1997 show that slag generated at its Nevada Mines Complex typically contains between 100 and 700
ounces of gold per ton. Tests also indicate that the slag may exhibit the characteristic of toxicity for cadmium.44 No
published information regarding waste generation rate or characteristics was found, though one facility reportedly
generates approximately 38 to 57 tons of slag per year.43'45 This facility also indicated that it takes weeks to
accumulate enough slag to constitute a large enough batch for cost effective metals recovery. The total industry
generation rate for slag is thus probably less than 500 metric tons per year. One facility also indicated that slag may
possess the characteristic of toxicity for cadmium,47 The slag is not stored or processed on the land, nor does it enter
the outside environment. Slag is believed to be fully recycled and was formerly classified as a byproduct.
WWTP Sludge, WWTP sludge is typically generated at gold refineries.48 Although no published
information regarding waste generation rate or characteristics was found, we used the methodology outlined in
Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 100 metric tons/yr,
360,000 metric tons/yr, and 720,000 metric tons/yr, respectively". We used best engineering judgment to determine
42 Ibid.
43 Precious Metals Producers. January 25, 1996. Op. Cit.
44
Newmont Gold Company. May 12, 1997. Op. Cit.
45 Newmont Gold Company. January 25, 1996. Op. Cit.
46 Newmont Gold Company. May 12, 1997. Op. Cit.
47 Ibid.
48 Precious Metals Producers. Op. Cit.
348
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that this waste may exhibit the characteristic of toxicity for silver. This waste may be recycled and was formerly
classified as a sludge,
Spent Furnace Dust, Spent furnace dust is typically generated at gold mining and milling operations.49 As
part of the smelting process, gold-bearing dust is generated in the induction furnaces. This dust is conveyed by pipe
to a baghouse located in the refinery building and collected in barrels. The barrels of baghouse dust are never stored
outdoors. At the Nevada Mines Complex, sealed barrels of baghouse dust are accumulated for up to four months
before being shipped off-site for smelting. At other facilities, smelting of baghouse dust may be done in the on-site
induction furnace. Assays performed by Newmont Gold in 1995 and 1996 show that the baghouse dust from its
Nevada Mines Complex contains approximately 2,200 ounces of gold per ton and that the dust may exhibit the
characteristic of toxicity for cadmium and selenium. This facility generated approximately 1,550 ounces of gold in
1996 by smelting baghouse dust, generating revenues of over $600,Q00.50 Thus, the facility generated less than one
ton of baghouse dust in 1996, suggesting an industry-wide generation rate of less than 9 tons per year. The dust is
entirely recycled and was formerly classified as a byproduct. At one facility, several months are required to
accumulate sufficient baghouse dust to constitute a large enough batch to ship off-site for smelting.51 We used best
engineering judgment to determine that this waste may exhibit the characteristic of toxicity for silver. At one facility,
the dust exhibits the characteristic of toxicity for cadmium and selenium. The dust is not land stored and never
enters the outside environment.52'53 This waste is recycled and was formerly classified as a byproduct.
Retort Cooling Water. The retorting process at Newmont Gold's Nevada Mines Complex generates
mercury-, silver- and gold-bearing gases. Water is used to cool and condense those gases. Through this process, the
cooling water becomes contaminated with gold, silver, and mercury. This water is conveyed by pipe to the main
beneficiation circuit to allow recovery of the metals and reuse of the water.54
Wastewater is typically generated at gold refineries and is generated from numerous sources, including the
smelter air pollution control (APC), silver chloride reduction, electrolytic cell wet APC, and electrolyte preparation
wet APC.35 Wastewater from electrolyte preparation wet APC, electrolytic cell wet APC, and smelter wet APC may
contain toxic metals, suspended solids, oil, and grease. This waste may be recycled.56 Although no published
information regarding waste generation rate or characteristics was found, we used the methodology outlined in
Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 440,000 metric
tons/yr, 870,000 metric tons/yr, and 1,700,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity for arsenic, silver, cadmium, chromium, and lead.
This waste was formerly classified as a sludge.
40 Ti * ,
Ibid.
50 Newmont Gold Company. May 12, 1997. Op. Cit.
" Ibid.
52 Newmont Gold Company. January 25, 1996. Op. Cit.
53 Newmont Gold Company. May 12, 1997. Op. Cit.
54 Ibid.
55 Precious Metals Producers. Op. Cit.
56 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. V, 1989, pp. 2185-2186.
349
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Refining Wastes. The most basic refining operation for the separation of gold and silver is "parting" which
can be done electrolytically or by acid leaching. Further treatments are sometimes necessary to remove additional
contaminants. Although no published information regarding waste generation rate or characteristics was found, we
used the methodology outlined in Appendix A of this report to estimate a low. medium, and high annual waste
generation rate of 100 metric tons/yr, 360,000 metric tons/yr, and 720,000 metric tons/yr, respectively. We used best
engineering judgment to determine that this waste may exhibit the characteristics of toxicity for silver and
corrosivity. This waste is recycled to extraction/beneficiation units.
D. Non-imiquely Associated Wastes
Ancilary hazardous wastes also may be generated at on-site laboratories, and may include used chemicals
and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), acidic tank
cleaning wastes, and polyehlorinated biphenyls from electrical transformers and capacitors. Non-hazardous wastes
may include tires from trucks and large machinery, sanitary sewage, waste oil (which may or may not be hazardous).
and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Three commenters submitted comments in response to the January 25, 1996 Supplemental Proposed Rule
(COMM43, COMM57, COMM58), and one commenter submitted comments in response to the May 12, 1997
Second Supplemental Proposed Rule (Newmont Gold Company). All four commenters provided new factual
information that has been incorporated into the gold and silver sector report.
Sector-specific Issues
Three commenters addressed sector-specific issues.
• Three commenters stated that'the retorting step is, in fact, a beneficiation activity (COMM43,
COMM57, COMM58). EPA has clarified in the report that the beneficiation/mineral processing
boundary for gold recovery from ores is between electrowinning and retorting. Therefore, retorting is a
mineral processing activity.
* One commenter stated that slag and spent furnace dust are not wastes because they are destined for
reclamation (COMM57). EPA recognizes that these materials contain high concentrations of precious
metals and that they are reclaimed. However, they are still considered to be wastes, and no change was
made to the report.
* One commenter expressed confusion over the status of acid washing solution (COMM43), while
another commenter stated that EPA incorrectly classified acid washing during the elution process as
non-uniquely associated with mineral processing (COMM57). The Agency clarified in the report that
the use of an acid solution to dissolve the steel wool from the gold/steel wool cathode is a beneficiation
activity that is uniquely associated with mining or mineral processing. Acid wash solution from carbon
regeneration activities after the gold is stripped, however, is not uniquely associated and, therefore, is
not exempt under the Bevill Amendment.
• One commenter requested that EPA clarify the status of sulfuric acid (COMM43). The report was
modified to indicate that waste sulfuric acid from elution is exempt under the Bevill Amendment
because it is generated in a beneficiation activity that is uniquely associated with mining or mineral
processing,
» One commenter noted an inconsistency in that spent carbon is identified as a beneficiation waste
whereas carbon fines are not uniquely associated with mineral processing (COMM43). One commenter
stated that spent carbon is routinely regenerated and reused and, therefore, is not a waste (COMM43).
350
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Another commenter stated that carbon fines generated at on-site carbon regeneration kilns as well as
other secondary materials generated during carbon regeneration are uniquely associated with mineral
processing (COMM57). Spent carbon after the gold has been stripped is, in fact, a waste. The Agency
clarified that spent carbon from cyanidation is a non-uniquely associated waste because spent carbon
results from carbon regeneration which is a non-uniquely associated operation because many industries
routinely regenerate carbon and generate wastes such as carbon fines. Therefore, carbon regeneration
and the resulting wastes are non-uniquely associated with mining or mineral processing.
351
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BIBLIOGRAPHY
Lucas, John. "Gold." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 68-69.
Lucas. John. "Gold." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992. pp.
535-561.
Personal communication between ICF Incorporated and Robert G. Reese, U.S. Bureau of Mines. September 23,
1994.
Personal communication between ICF Incorporated and John M. Lucas, U.S. Bureau of Mines, September 15,
1994.
Reese, Robert. "Silver." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 154-
155.
Reese, Robert. "Silver." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992.
pp. 1199-1211.
Simpson, W.W., W.L. Staker, and R.G. Sandberg. Calcium Solfide Precipitation of Mercury From Gold-Silver
Cyanide-Leach Slurries. U.S. Department of Interior. 1986.
U.S. Bureau of Mines. Randol Mining Directory. 1994. pp. 741-743.
U.S. Environmental Protection Agency, Trip report for Newmont Gold Corporation, South Operations
Facilities, Carlin Nevada. May 17, 1995.
U.S. Environmental Protection Agency. Technical Resource Document. Treatment of Cyanide Heap Leaches and
Tailings. Office of Solid Waste, Special Waste Branch. 1994. pp. 2-4.
U.S. Environmental Protection Agency. Technical Resource Document, Extraction and Beneficiation of Ores and
Minerals. Office of Solid Waste, Special Waste Branch. Vol. 2. 1994. pp. 1-12.
U.S. Environmental Protection Agency. Mining Industry Profile. Gold. Office of Solid Waste, Special Waste
Branch. 1993. pp.41-45.
U:S, Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume V. Office of Water
Regulations Standards. May 1989. pp. 2185-2186.
U.S. Environmental Protection Agency. "Gold and Silver." From 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988. 3-100-3-115.
352
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IODINE
A.
Commodity Summary
Iodine compounds are found In seawater, seaweed, marine organisms, and brines. Iodine and its
compounds are generally marketed in the form of crude iodine, resublimed iodine, calcium iodate, calcium iodide,
potassium iodide, sodium iodide, and numerous organic compounds.1 Final uses of iodine include animal feed
supplements, catalysts, inks and colorants, pharmaceuticals, photographic chemicals and film, sanitary and industrial
disinfectants, and stabilizers.
Japan and Chile are the largest producers of iodine in the world and account for 99% of the U.S. iodine
imports. All domestic iodine production is from iodine-rich natural brines in the deep subsurface of the Anadarko
basin of northwestern Oklahoma. Oklahoma production began in 1977 and at present, three companies operate a
total of four facilities (three major plants and one miniplant) for the recovery of iodine. The U.S. Bureau of Mines
estimates that domestic production was 2,000,000 kilograms in 1994.2 Exhibit 1 presents the names and locations of
the facilities involved in the production of iodine.
EXHIBIT 1
SUMMARY OF IODINE PROCESSING FACILITIES
Facility Name
Asahi Glass Company of Japan
lochem Corporation of Japan
North American Brine Resources (miniplant)
North American Brine Resources (major plant)
Location
Woodward, OK
Vici, OK
Dover, OK
Woodward, OK
B. Generalized Process Description
1. Discussion of Typical Production Processes
All three facilities (Asahi Glass Company of Japan, lochem Corporation of Japan, and North America Brine
Resources) obtain iodine-rich brines from the Morrowan sandstones. Asahi Glass Company operates 22 production
wells and 10 injection wells ranging in depth from 2,130 to 2,290 meters. The lochem facility has nine production
wells and four injection wells ranging in depth from 3,000 to 3,183 meters. The North American Brine Resources
facility operates two production wells and three injection wells drilled to about 1,800 meters.
North American Brine Resources also operates a mini facility near Dover, OK. At the Dover facility, North
American Brine Resources recovers iodine from oil-field brines collected from a number of oil and gas wells in
nearby parts of northwestern Oklahoma.
1 Kenneth S. Johnson, "Iodine," from Industrial Minerals and Rocks. 6th edition, Society for Mining, Metallurgy,
and Exploration, 1994, pp. 583-587.
2 Phyllis Lyday, "Iodine," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp. 82-83.
353
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Brines are separated from hydrocarbons by using the blowing-out process. lochem Corporation and North
American's Woodward facility both use this process.3 Exhibit 2 presents a typical process flow diagram for the
production of iodine from brines by the blowing-out process.
2. Generalized Process Flow Diagram
Exhibit 2 displays the blowing-out process. In the first stage of this process, hydrogen sulfide gas
(contained in the brine) is removed. This gas is reacted to form sulfur compounds which are sent to a hazardous
waste disposal facility. The second stage of processing is chlorine oxidation to convert iodide to iodine. The iodine
is then removed from the brine by air vapor stripping (air-blowout). The waste brine is treated with lime to adjust
pH and is reinjected into Class IV disposal wells. The iodine vapor is absorbed by a solution of hydriodic and
sulfuric acids. Sulfur dioxide is added to reduce the absorbed iodine to hydriodic acid. Most of the solution is
recirculated to the absorption tower, but a bleed stream is sent to a reactor for iodine recovery. In the reactor,
chlorine is added to oxidize and liberate the iodine which precipitates and settles out of solution. The settled iodine
is filtered to remove waste liquor and melted under a layer of concentrated sulfuric acid. The melted iodine is then
solidified either as flakes or ingots.4
Iodine is also recovered from oil well brines. In a settling tank, the iodine containing brine settles to the
bottom and the oil rises to the top. The oil is skimmed off and processed with other oil from nearby wells. The brine
is sent through a chlorinator which frees the iodine. It is then absorbed onto charcoal which is back-flushed with
potassium or sodium hydroxide when full. This solution is treated with hydrochloric acid which results in a 90%
crude iodine product. The spent brine is reinjected and the potassium/sodium hydroxide is recycled.5
3. Identification/Discussion of Novel (or otherwise distinct) Processes
While domestic iodine production employs the chlorine-oxidation air-blowout method for recovery of
iodine, three other brine clarification processes exist. In one process, silver iodide is precipitated by the addition of a
silver nitrate solution. The silver iodide is filtered and treated with scrap iron to form metallic silver and a solution
of ferrous iodide. The silver is redissolved in nitric acid and recycled, and the solution is treated with chlorine to
liberate the iodine. In a second process, chlorine is added after clarification to liberate the iodine as a free element in
solution. Passing the solution over bales of copper wire precipitates insoluble cuprous iodides. At intervals, the
bales are agitated with water to separate the adhering iodide; the bales are then recycled. The cuprous iodide
suspended in the water is filtered, dried, and sold. The third process uses ion-exchange resins on brines which have
been oxidized to liberate iodine. The liberated iodine, which is in the form of polyiodide, is absorbed on an anion-
exchange resin. When the ion-exchange resin is saturated, it is discharged from the bottom of the column and then
transferred to the elutriation column. Iodine is elutriated with a caustic solution followed by sodium chloride. The
regenerated resin is returned to the absorption column. The iodine-rich elutriant is acidified and oxidized to
precipitate iodine. The crude iodine is then separated in a centrifuge and purified with hot sulfuric acid or refined by
sublimation.6
3 Phyllis A. Lyday, "Iodine," from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines,
1992, pp. 609-612.
4 U.S. Environmental Protection Agency, "Iodine," from 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988, pp. 2-109 - 2-112.
5 Personal Communication between ICF Incorporated and Phyllis Lyday, U.S. Bureau of Mines. October 11,
1994.
6 "Iodine and Iodine Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., 1981, Vol.
XIII, pp. 655-656.
354
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EXHIBIT 2
THE BLOWING-OUT PROCESS
(Adapted from; 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-109 - 2-112.)
Brine from Wells
Sulfur Compounds
Waste Brine
Iodine Product
Waste Bleed Liquor
Filtrate Waste
355
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The Chilean nitrate industry employs another method for iodine recovery. Iodine is extracted from caliche
as sodium iodate, along with sodium nitrate. The iodate accumulates in mother liquors during crystallization of the
nitrate. Part is drawn off and treated with sodium bisulfite solution. Fresh mother liquor is added to the solution to
liberate the iodine. The precipitated iodine is filtered in bag filters and the iodine-free mother liquor is returned to
the nitrate leaching cycle after neutralization with soda ash. The iodine cake is washed, pressed, broken up. and
sublimed in retorts. The product is then crushed and packaged.7
4. Beneficiation/Processing Boundaries
Based on a review of the process, there are no mineral processing operations involved in the production of
iodine.
C. Process Waste Streams
Existing data and engineering judgement suggest that the wastes listed below from iodine production do not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
1. Extraction/Beneficiation Wastes
Sulfur compounds from hydrogen sulfide removal are sent to a hazardous waste disposal facility.
Waste brine. Waste brine contains 6,800 kkg of spent brine solids per kkg of product iodine. Waste brine
is processed for other solids recovery and then either used in chlor-alkali manufacture or returned to the source.
Bromine, calcium chloride and magnesium hydroxide may be recovered from these spent brines.8
Precipitation with Chlorine
Waste bleed liquor.
Filtration
Filtrate wastes may be recycled.
Sludge.
Waste Acid.
2. Mineral Processing Wastes
None are identified.
D. Non-uniquely AssociatedWastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
7 Ibid.
8 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals Industry. Volume
II, 1980, Chapter 9.
356
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E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
357
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BIBLIOGRAPHY
"Iodine and Iodine Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. 1981. Vol. XIII.
pp. 655-656.
Johnson, Kenneth S. "Iodine." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. pp. 583-587.
Lyday, Phyllis. "Iodine." From Mineral Commodity Summaries. January 1995. pp. 82-83.
Lyday, Phyllis. "Iodine." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992.
pp. 609-612.
Personal Communication between ICF Incorporated and Phyllis Lyday, Bureau of Mines. October 11, 1994.
U.S. Environmental Protection Agency. "Iodine." From 1988 Draft Report Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 2-109 - 2-112.
U.S. Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. 2,
1980. Chapter 9.
358
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IRON AND STEEL
A.
Commodity Summary
The iron and steel industry, including primary and secondary producers, is composed of 79 companies
that produce raw steel at 116 locations. Iron is generally produced from iron ore (taconite) in a primary mineral
production process, while steel is produced using both primary and secondary processes. Primary production refers
to those operations where the feedstock is composed of at least 50 percent ore (or ore that has been beneficiated).
Electric arc furnaces use a high percentage of scrap steel as the feedstock in their operations and are therefore
classified as secondary production and not considered primary minerals processing. Although the electric arc
furnace process is described in this section, some of the wastes generated from this operation are currently regulated
under RCRA Subtitle C. Specifically, electric arc furnace dust (K061) is a listed hazardous waste.
The annual aggregate raw steel production capacity is 99 million metric tons; 1993 production is reported to
be 87 million metric tons. According to the U.S. Bureau of Mines, the iron and steel producers and ferrous foundries
produced goods valued at $55 billion. Currently, pig iron (i.e., molten iron from iron blast furnaces) is produced at
15 companies operating integrated steel mills, with approximately 58 blast furnaces (of which 41 or 42 are in
continuous operation). Integrated companies accounted for approximately 67% of steel production, including output
of their electric arc furnaces (which are classified as secondary production).1
Pig iron production in 1994 is estimated at 49 million metric tons. Pig iron is sent to either basic oxygen
furnaces or electric arc furnaces for further processing at steel facilities. Basic oxygen furnaces (BOFs) and electric
arc furnaces (EAFs) account for 61 percent and 39 percent of steel production, respectively. Continuously cast steel
accounted for 89 percent of steel production. Lastly, open hearth furnaces (OHFs) have been phased out and were
not used domestically to produce steel in 1993. Exhibit 1 presents the names and locations of facilities involved in
the primary production of iron and steel.
EXHIBIT 1
SUMMARY OF PRIMARY IRON AND STEEL PRODUCERS IN 1989
Facility Name
Acme
Alleghany Ludlum
Armco Steel Co., L.P.
Armco Steel Co., L.P.
Bethlehem Steel
Bethlehem Steel
Bethlehem Steel
Geneva Steel
Location
Riverdale, IL
Brackenridge
Middletown, OH
Ashland, KY
Sparrows Point, MD
Bethlehem, PA
Chesterton, IN
Orem. UT
Type of Operations
Iron; BOF Steel
Iron; BOF Steel
Iron; BOF Steel
Iron; BOF Steel
Iron; BOF Steel
Iron; BOF Steel
Iron; BOF.OHF Steel
Iron: OHF Steel
Gerald Houck, "Iron and Steel," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p.
86.
2 Ibid.
359
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EXHIBIT 1 (continued)
SUMMARY or PRIMARY IRON AND STEEL PRODUCERS IN 1989
Facility Name
Gulf States Steel
Inland Steel
LTV
LTV
LTV
McLouth Steel
National Steel
National Steel
Rouge Steel
Sharon Steel
Shenango
US Steel
US Steel
US Steel
US Steel
US Steel/Kobe
Warren Steel
Weirton Steel
Wheeling-Pittsburgh Steel
Wheeling-Pittsburgh Steel
Location
Gadsden, AL
E. Chicago, IN
E. Cleveland, OH
W. Cleveland, OH
Indiana Harbor, IN
Trenton, MI
Granite City, IL
Escore, MI
Dearborn, MI
Farrell, PA
Pittsburgh, PA
Braddock, PA
Gary, IN
Fairless Hills, PA
Fairfield, AL
Lorain, OH
Warren, OH
Weirton, WV
Steubenville, OH
Mingo Junction, OH
Type of Operations
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
(shut down in November 1992)a
Iron
Iron; EOF Steel
Iron; EOF Steel
Iron; OHF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
Iron; EOF Steel
1 Gerald Houck, "Iron and Steel." from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines, 1992, p. 649.
On a tonnage basis, about nine-tenths of all metal consumed in the United States is iron or steel. Iron and
steel are used in the manufacture of transportation vehicles, machinery, pipes and tanks, cans and containers, and the
construction of large buildings, roadway superstructures, and bridges.3 According to the U.S. Bureau of Mines in
1993, steel consumption was divided amongst the following uses: warehouse and steel service centers, 26%;
3 Gerald Houck, "Iron and Steel," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 412.
360
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transportation (mainly for automotive production), 16%; construction 15%. cans and containers, 5%; and other uses.
38%.4
B. Generalized Process Description
1. Discussion of Typical Production Processes
The production of steel products from iron ore involves two separate steps: ironmaking and steelmaking.
Each of these is described in detail below. Iron blast furnaces produce molten iron (pig iron) that can be cast
(molded) into products; however, the majority of pig iron is used as the mineral feedstock for steel production. Steel
furnaces produce a molten steel that can be cast, forged, rolled, or alloyed in the production of a variety of materials.
Ironmaking
Iron is produced either by blast furnaces or by one of several direct reduction processes; blast furnaces,
however, account for over 98 percent of total domestic iron production.5 The modern blast furnace consists of a
refractory-lined steel shaft in which a charge is continuously added to the top through a gas seal. The charge consists
primarily of iron ore, sinter, or pellets; coke; and limestone or dolomite. Iron and steel scrap may be added in small
amounts. Near the bottom of the furnace, preheated air is blown in. Coke is combusted in the furnace to produce
carbon monoxide which reduces the iron ore to iron. Silica and alumina in the ore and coke ash are fluxed with
limestone to form a slag that absorbs much of the sulfur from the charge. Molten iron and slag are intermittently
tapped from the hearth at the bottom. The slag is drawn off and processed. The product, pig iron, is removed and
typically cooled, then transported to a steel mill operation for further processing in either an electric arc furnace or a
basic oxygen furnace, as depicted in Exhibit 2. As shown in Exhibit 2, the iron can also be directly reduced before it
is sent for further processing.
Recent changes in the process include modifications in the fluxing practices. Flux is often introduced
through fluxed sinter or fluxed pellets rather than by direct charging. The use of external desulfurization of hot
metals prior to steel making has also increased.6
Steelmaking
All contemporary steelmaking processes convert pig iron, scrap, or direct-reduced iron, or mixtures of
these, into steel by a refining process that lowers the carbon and silicon content and removes impurities (mainly
phosphorus and sulfur). Three major furnace types can be used for making steel:
« open hearth furnaces, no longer used for domestic steel production;
• basic oxygen furnaces, with 62 percent of the total; and
• electric arc furnaces, accounting for the remaining 38 percent.
The latter predominantly uses scrap (i.e., non-mineral material) as feedstock and is classified as a secondary
process. The open-hearth process was prevalent in the United States between 1908 and 1969, but it is no
4 Gerald Houck, 1994, Op. Cit. p. 90.
5 American Iron and Steel Institute, "Annual Statistical Report," 1984, p. 78.
6 Harold R. Kokal and Madhu G. Ranade, "Fluxes for Metallurgy," from Industrial Minerals and Rocks. 1994, pp.
668-669.
361
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ffiONMAKING
EXHIBIT 2
mONMAMNG AND STEELMAUNG PROCESSES
(Adapted from: USS Lorain flow diagram.)
Direct Reduction
p
(
.
Coke
1
Flux ^ Agglomeration
(sintering, pelletizing
Ore fe» briquetting)
nuT ^>.
Iron
Om -^ Fun
^^
JMAMNG
*
1
Blast
i-
Coob
Bk
Iron (Kg
^ BF Sludge/Slurry
^
Blast!
APCGas », Proces
1 dean
uas
T
lag (on-site landfill or sold)
ng Tower
>wdown
Iron, Hot Metal)
"umace
5 Water
Discharge
fkim
WWTP
'
Scrap
Electric Arc Furnace
(secondary production)
Basic Oxygen Furnace
Open Hearth Furnace
(no longer used)
f
Steel Furnace Slag
(sold as aggregate)
Alternate Process
APCDust
(on-site disposal)
362
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longer in use domestically. The basic oxygen process has supplanted it as the predominant primary steel-making
process, making up approximately 95 percent of domestic primary steel production in 1987.'
Modern steelmaking also includes treatment of steel in ladles. This use of ladles (1) improves the
cleanliness of the steelmaking process, (2) increases throughput in steel vessels, and (3) allows for shape control of
inclusions in continuous casting operations.8
2. Generalized Process Flow Diagram
A general flow diagram for the production of raw steel from iron ore is presented in Exhibit 2. In general,
the process involves (1) beneficiation of the iron ore, (2) either direct-reduction or reduction in an iron blast furnace,
(3) processing in steelmaking furnaces, and (4) casting.
Ironmaking
Beneficiation of the Iron Ore: Sintering, Pelletizing. or Briquetting
There are a variety of beneficiation methods that can be used to prepare iron ores, depending on the iron
content in the ores. Some ores contain greater than 60 percent iron and require only crushing and blending to
prepare them for further processing. In other cases, operations including screening and concentrating are necessary
to prepare the raw materials. The characteristics of the iron-bearing ores vary geographically. Specifically,
magnetite is the main iron-bearing ore in the Lake Superior district and in the northeastern United States, while
hematite and hematite magnetite mixtures tend to be found in ores in Alabama and the Southwest.
When magnetite occurs in lower grade deposits, the ore is ground, and the concentrate is separated
magnetically from the gangue with the ore in a water suspension. Ore containing hematite can be high in clay
content and requires washing to remove the clay and concentrate the iron. Low grade ores that can not be separated
magnetically may also need to be concentrated via washing, jigging, heavy media separation, or flotation.9
Ores that will be sent to blast furnaces for ironmaking need to be permeable to allow for an adequate flow
of gas through the system. Additionally, concentrates in raw ores that are very fine need to be agglomerated before
they can be used as feed stock for the blast furnaces. The three major processes used for agglomeration include:
• sintering;
• pelletizing; and
» briquetting.
Sintering. Sintering involves mixing the iron-bearing material such as ore fines, flue dust, or concentrate
with fuel (e.g., coke breeze or anthracite).10 The mixture is then spread on surface beds which are ignited by gas
burners. The heating process fuses the fine particles, and the resulting product is lumpy material known as sinter.
The sinter is sized and the fines are recycled. Sintering operations are used to recycle wastes from other iron and
steel manufacturing processes.
7 Frederick J. Schottman, "Iron an Steel," from Minerals Yearbook Volume I. Metals and Minerals. U.S. Bureau
of Mines, 1989, p. 511,
8 Harold R. Kokal and Madhu G. Ranade, 1994, Op. Cit. pp. 668-9.
9 U.S. Environmental Protection Agency, "Iron and Steel," from 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. Office of Solid Waste, 1988, p. 3-128.
10 Ibid.
363
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Palletizing. Pelletizing involves forming pellets from the raw ore or concentrates, then hardening the
pellets by heating. Solid fuel can be combined with the concentrate to promote the heating necessary to harden the
pellet. Common binders added to strengthen the pellets include limestone, dolomite, soda ash, bentonite, and
organic compounds. After the pellets are sized, any remaining fraction of materials are recycled back through the
sintering process.
Briquetting. Briquetting, another form of agglomeration, involves heating the ore and pressing it into
briquettes while the materials are still hot. Once the briquettes are cooled, they are sent directly to the blast furnaces.
Reduction of the Iron Ore
There are two basic methods for reducing iron ore:
• direct reduction; and
• reduction in a blast furnace.
Direct Reduction. Direct reduction involves the reduction of iron ore that is in the solid state - at less than
1000 °C." The solid primary metal produced by direct reduction of iron ores (DRI) can be used to supply electric
arc furnaces.
Blast Furnace. During ironmaking, agglomerated iron ore is combined with prepared limestone, silica, and
coke and placed into a blast furnace. Heated air is blown into the furnace and causes the limestone and silica to form
a fluid slag which combines with other impurities. The slag can be separated from the molten iron and sent to a slag
reprocessing unit. Generally, the molten iron from the blast furnace is transferred directly to the steelmaking
furnaces.
A number of integrated steelwork facilities in the United States have increased their use of fluxed pellets,
which are more easily reducible. The fluxed pellets are produced by adding limestone (CaCO3) and/or dolomite
[(Ca,Mg)CO3] to the iron ore concentrate during the balling stage. Flux is added until the ratio of calcium and
magnesium oxide to silicon dioxide and aluminum oxide ((CaO+MgO)/(SiO2+Al2O3)) in the pellet is above 0.6.
The most common ratio documented is approximately l.O.12
Steelmaking
Processing in Steelmaking Furnaces
There are three basic methods of steel production:
• open hearth furnaces (no longer in use domestically);
• basic oxygen furnaces; and
• electric arc furnaces (secondary production).
Open Hearth Furnace (no longer used). During the open-hearth process, a relatively shallow bath of
metal was heated by a flame that passed over the bath from the burners at one end of the furnace while the hot gases
resulting from combustion were pulled out the other end. The heat from the exhaust gas was retained in the exhaust
system's brick liners, which were known as checker-brick regenerators. Periodically the direction of the flame was
reversed and air was drawn through what had been the exhaust system; the hot checker-bricks preheated the air
before it was used for combustion in the furnace. Impurities were oxidized during the process and fluxes formed a
slag; this slag was drawn off and processed or discarded.
11 J. Astier, "Present Status of Direct Reduction and Smelting Reduction," from Steel Times. October 1992, pp.
453-458.
12 William S. Kirk, "Iron Ore," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, p. 618.
364
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Basic Oxygen Furnace. The basic oxygen process uses a jet of pure oxygen that is injected into the molten
metal by a lance of regulated height in a basic refractory-lined converter. Excess carbon, silicon, and other reactive
elements are oxidized during the controlled blows, and fluxes are added to form a slag. This slag, one of the RCRA
special wastes, is drawn off and processed or discarded.
The first step in the BOF process is charging the furnace. Hot metal (molten iron from the blast furnace)
which accounts for most of the metallic charge is added to the furnace by ladles. Once the furnace has been charged.
a water-cooled oxygen lance is lowered into the furnace and high purity oxygen is blown in the top of the furnace.
One modification to this process is the Q-BOP in which the oxygen and other gases are blown in from the bottom of
the furnace instead of the top. In the bottom blown process, oxygen is introduced through a number of tuyeres,
consisting of two concentric pipes in the bottom of the converter.13
In the furnace, oxygen combines with the carbon and other unwanted elements to oxidize the impurities in
the molten charge, and thereby converting the molten charge to steel. The lime and other fluxes help remove the
oxidized impurities as a layer of slag. The refined steel is then poured into ladles. At this point, any alloys can be
added to the steel to obtain the desired strength and characteristics required in the final product.
Electric Arc Furnace (secondary production). Electric arc furnaces are generally used for scrap
processing and have traditionally been used to produce alloy, stainless, tool, and specialty steels. Scrap steel is the
principal metallic charge to electric furnaces. Direct reduction of iron ore also produces pellets with high enough
iron content to be used. Limestone and other fluxes are charged after the scrap becomes molten. As in the blast
furnace operation, the impurities in the steel form a floating layer of slag that can be poured off. The molten steel is
then poured into ladles and sent to be cast.
In all steelmaking operations, gases from the furnace must be cleaned in order to meet air pollution control
requirements. Facilities may use dry collection (e.g., bag houses, filters, or electrostatic precipitators) or wet
scrubbers or, as is most often practiced, both types of controls. Large volumes of dust and scrubber sludge are
collected for either further processing or disposal. Some of these air pollution control residuals are RCRA special
wastes.
The molten steel, from whichever type of furnace is used, flows into ladles and is sent for further processing
at rolling mills to form the finished products.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
« Derincing and Detoxification of Electric Arc Furnace Steelmaking Dust via Ammonium
Carbonate Leaching. The use of ammoniacal ammonium carbonate (AAC) leaching for the treatment
of carbon steel making EAF dust has been investigated on a laboratory scale. The tests were performed
using dust samples from three European steel companies. The dusts were found to be toxic due to the
leachability of silver, mercury, lead, and cadmium. After treatment, the toxicity tests indicated
leachates below past and current EPA toxicity threshold limits.14
« Recovery of Manganese from Steel Plant Slag by Carbamate Leaching. The U.S. Bureau of Mines
investigated the feasibility of using ammonium carbamate leaching to recover manganese from steel
plant slag. It was found that treatment of the slag with hydrogen prior to the leaching increased the
13 Association of Iron and Steel Engineers, The Making. Shaping and Treating of Steel. 1985, pp. 539-652.
14 R.L. Nyirenda et al, "Dezincing and Detoxification of Electric Arc Furnace Steelmaking Dust via Ammonium
Carbonate Leaching," The Minerals, Metals, & Mining Society, 1993, pp. 894-906.
365
-------
amount of manganese recovered. Results indicated that the method cannot be applied satisfactorily to
all steelmaking slags.15
• Classification" of Electric Arc Furnace Dust. A new process has been developed to treat hazardous
materials, including electric arc furnace dust, slag, and spent refractories. The process, known as
Classification, utilizes electric arc furnace dust from both the steel and nonferrous metals industries to
produce glass products.17
• Treatment of Steel Plant Wastes by Magnetic Cyclones. Steel plants generate sludges containing
high concentrations of iron which display ferromagnetic properties. Methods of treating these wastes
to take advantage of these properties using magnetic cyclones have been evaluated. The results
indicated that the cycloning process creates an underflow with a high solids content and a clean water
overflow.18
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between agglomeration (sintering, pelletizing, and briquetting) and reduction of iron ore in a blast furnace. EPA
15 S.N. Mclntosh and E.G. Baglin, "Recovery of Manganese from Steel Plant Slag by Carbamate Leaching," U.S.
Bureau of Mines, 1992.
16 Classification is a registered trademark.
17 R.B. Ek and I.E. Schlobohm, "Classification of Electric Arc Furnace Dust," from Iron and Steel Engineer.
April 1993, pp. 82-84.
18 John L. Watson and Suren Mishra, "The Treatment of Steel Plant Wastes by Magnetic Cyclones," Conference
Paper from Symposium on Emerging Process Technologies for a Cleaner Environment, Phoenix, AZ, February 24-
27 1992.
366
-------
identified this point in the process sequence as where benefieiation ends and mineral processing begins because it is
here where a significant chemical change to the iron ore occurs. Therefore, because EPA has determined that all
operations following the initial "processing" step in the production sequence are also considered processing
operations, irrespective of whether they involve only techniques otherwise defined as benefieiation, all solid wastes
arising from any such operation(s) after the initial mineral processing operation are considered mineral processing
wastes, rather than benefieiation wastes, EPA presents the mineral processing waste streams generated after the
beneficiation/processing line in section C.2, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams,
C. Process Waste Streams
1. Extraetion/Beneflciation Wastes
Waste characterization data, waste generation data, and waste management data are not available for all of
the wastes identified as generated from the production of iron and steel.
Tailings. Wastes from magnetic separation include tailings consisting mostly of silicate rock. The
magnetite ore from lower grade deposits is ground, and the concentrate is separated magnetically from the gangue
with the ore in a water suspension. These wastes are typically managed in tailing impoundments.
Wastewater and Waste Solids. Ore containing hematite can be high in clay content and require washing
to remove the clay and concentrate the iron. The wastewater and waste solids generated from washing ores
containing clay are not expected to be hazardous. No information is available on management practices for these
2. Mineral Processing Wastes
Ferrous metal production operations generate four RCRA special mineral processing wastes that are exempt
from RCRA Subtitle C: iron blast furnace slag, iron blast furnace air pollution control dust/sludge, steel furnace
slag, and steel furnace air pollution control dust/sludge. The Agency did not evaluate the four RCRA special mineral
processing wastes further. Besides these RCRA special wastes, the only other types of wastes generated appear to be
various types of wastewater, including cooling water, wash water, and scrubber water.
Iron Blast Furnace Slag. In 1988, iron blast furnace slag was reported as generated at 26 of the 28 ferrous
metal production facilities in the United States surveyed by the U.S. Environmental Protection Agency in 1989 — all
24 integrated iron/steel facilities and two additional blast furnace operations.
Blast furnace slag contains oxides of silicon, aluminum, calcium, and magnesium, along with other trace
elements. There are three types of blast furnace slag: air-cooled, granulated, and expanded. Air cooled slag
comprises approximately ninety percent of all blast furnace slag produced. The physical characteristics of the slags
are in large part determined by the mediods used to cool the molten slag. In the surveys, all facilities characterized
their slags as solid, though slag is molten at the point of generation.20
The primary management practice for iron blast furnace slag is processing (e.g., crushing, sizing) and sale
for use as aggregate. In 1990, only one facility disposed its slag in an adjacent water body in order to build up a land
area that was intended for use managing other waste materials as part of an Army Corp of Engineers approved fill
project.21
19 U.S. Environmental Protection Agency, 1988, Op. Cit. p. 3-128,
20 U.S. Environmental Protection Agency, "Chapter 8," from Report to Congress on Special Wastes from Mineral
Processing. Vol II, Office of Solid Waste, July 1990.
21
Ibid.
367
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Iron Blast Furnace Air Pollution Control (APC) Dust/Sludge. In 1988, iron blast furnace APC
dust/sludge was generated at 26 of the 28 ferrous metal facilities in the United States submitting surveys, including
all 24 integrated iron/steel facilities and the two additional blast furnace operations.
Air pollution control (APC) devices treat the top gases emitted from iron blast furnaces. The air pollution
control devices generate either dusts or sludges. APC dust/sludge is composed primarily of iron, calcium, silicon,
magnesium, manganese, and aluminum.22
The two primary waste management practices at the iron facilities regarding APC dust/sludge are disposal
in on-site units and the return of the material to the production process via the sinter plant operation or blast
furnace.23
Steel Furnace Slag. In 1988, steel furnace slag was generated at 26 of the 28 ferrous facilities in the
United States that submitted surveys, including all 24 integrated iron/steel facilities and the two additional steel
production operations. Steel slag is composed primarily of calcium silicates and ferrites combined with fused oxides
of iron, aluminum, manganese, calcium, and magnesium. At the point of generation, the slag is in a molten form.
The molten slag is air cooled and is broken into varying sizes once processing (e.g., crushing) begins.24
The primary management practice for steel slag is processing (e.g., granulating, crushing, sizing) and sale
for use as aggregate, though several facilities dispose or stockpile their steel slag.
Steel Furnace Air Pollution Control (APC) Dust/Sludge. Steel furnace APC dust/sludge was generated
at 26 of the 28 domestic ferrous metal production facilities surveyed in 1989, including all 24 integrated iron/steel
facilities and the two additional steel production facilities. Steel APC dust/sludge consists mostly of iron, with
smaller amounts of silicon, calcium, and other metals.
Waste management practices were reported for only ten of the 26 facilities in 1989. Eight of the ten
reportedly dispose the APC dust/sludge on-site; the remaining two return the material to the production process via
the sinter plant operation.
Wastewater. Wastewater is generated from a number of sources during both the ironmaking and the
steelmaking processes. In addition to process wastewaters, wastewater streams also are generated from non-contact
operations (i.e., cooling tower water, cooling tower blowdown) and from non-process operations including
maintenance and utility requirements. However, the primary source of wastewater from ironmaking is water used for
the cleaning and cooling of gases. Most plants either recirculate or recycle their cooling process wastewater to
reduce the total pollutant load discharged from their facilities. The wastewaters from the blast furnace process
contain suspended particulate matter and cyanide, phenol, and ammonia. All of these pollutants are limited by
NPDES permit requirements. Other wastewaters contain toxic metals (predominantly zinc) and organic pollutants
which come from the raw materials or form during the reduction process.
Many of the pollutants in the process wastewaters are the result of compounds found in the charges and
fluxes added to the furnace. In both iron and ferromanganese blast furnaces operations, ammonia is present in the
exit gases and as a result is also present in the process wastewater. The ammonia is formed from the various nitrogen
compounds that are removed from the coke charge during blast furnace operations. Fluoride is also present in the
wastewater as a result of fluoride compounds, primarily calcium chloride from the limestone flux. Manganese is
present in wastewaters from ferromanganese production and other elements may be present depending on the various
22 Ibid.
23 Ibid.
24
Ibid.
368
-------
ores and alloys used in production. Lastly, cyanide is generated as a result of the reaction of nitrogen, in the blast
air, with carbon from the coke charge in the reducing atmosphere of the blast furnace.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Wastes
Wastes associated with the coke making process, stainless steel production, and steel finishings are
considered to be non-uniquely associated. In addition, ancillary hazardous wastes may be generated at on-site
laboratories, and may include used chemicals and liquid samples. Other hazardous wastes may include spent
solvents (e.g., petroleum naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical
transformers and capacitors. Non-hazardous wastes may include tires from trucks and large machinery, sanitary
sewage, and some waste oil and other lubricants. Other ancillary wastes associated with the coke making process,
stainless steel production, and the spent pickling liquors resulting from steel finishing at some integrated steel mills
are currently classified as listed and/or characteristic wastes and regulated under RCRA Subtitle C requirements.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
369
-------
BIBLIOGRAPHY
American Iron and Steel Institute, "Annual Statistical Report," 1984, p. 78.
Association of Iron and Steel Engineers. The Making. Shaping and Treating of Steel. 1985. pp. 539-652.
Astier, J. "Present Status of Direct Reduction and Smelting Reduction." From Steel Times. October 1992. pp. 453-
458.
Ek, R.B. and Schlobohm, I.E. "Classification of Electric Arc Furnace Dust." From Iron and Steel Engineer. April
1993. pp. 82-84.
Houck, Gerald. "Iron and Steel." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
86-87
Houck, Gerald. "Iron and Steel." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. p. 412.
U.S. Environmental Protection Agency. "Iron and Steel." From 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. Office of Solid Waste. 1988. pp. 3-125-3-145.
Houck, Gerald. "Iron and Steel." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 642-659.
Kirk, William S. "Iron Ore." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. p. 618-641.
Kokal Harold R., and Ranade, Madhu G. "Fluxes for Metallurgy." From Industrial Minerals and Rocks. 1994. pp.
668-669.
Mclntosh, S.N. and Baglin, E.G. "Recovery of Manganese from Steel Plant Slag by Carbamate Leaching." U.S.
Bureau of Mines. 1992.
Nyirenda R.L., et al. "Dezincing and Detoxification of Electric Arc Furnace Steelmaking Dust via Ammonium
Carbonate Leaching." The Minerals, Metals, & Mining Society. 1993. pp. 894-906.
Schottman, Frederick J. "Iron an Steel." From Minerals Yearbook Volume I. Metals and Minerals. U.S. Bureau of
Mines. 1989. p. 511.
U.S. Environmental Protection Agency. "Chapter 8." Report to Congress on Special Wastes from Mineral
Processing. Vol. II. July 1990.
Watson John L. and Mishra, Suren. "The Treatment of Steel Plant Wastes by Magnetic Cyclones." Conference
Paper from Symposium on Emerging Process Technologies for a Cleaner Environment. Phoenix, AZ.
February 24-27 1992.
370
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LEAD
A. Commodity Summary
Lead ore is mined domestically in several states. Seven lead mines in Missouri, along with mines in Alaska,
Colorado, Idaho, and Montana yield most of the total ore production. (BOM, 1995, p. 94) In 1990, primary lead was
processed at three integrated smelter-refineries in Glover, Boss, and Herculaneum, Missouri, a smelter in East
Helena, Montana, and a refinery in Omaha, Nebraska. (U.S. EPA, 1990, p. 10-1) The integrated plant in Boss.
Missouri is no longer operational. (BOM, 1995, p, 94; personal communication with Kenneth Buckley, Doe Run
Company, April 18, 1994)
Expected yield from domestic mines was 365,000 metric tons (mt) of lead (in concentrates) in 1994.
Expected primary lead production from domestic and imported ores totaled 330,000 mt and 30,000 mt, respectively,
in 1994. In addition, domestic secondary production from lead scrap totaled 880,000 mt in 1993, up from 842,000
mt in 1989. United States lead reserves totaled 10 million mt in 1993. (BOM, 1995, pp. 94-95)
In 1990, total domestic primary lead production capacity was estimated to be 577,000 mt per year.
However, this figure represented the aggregate of one smelter, one refinery, and three integrated smelter-refineries.
(U.S. EPA, 1990. p. 10-2) Only four primary lead facilities are currently operational (BOM, 1995, p. 94). Exhibit 1
presents the names and locations of the lead mining, smelting, and refining facilities located in the United States.
The lead mines shown were active as of 1990. As available, Exhibit 1 also presents information on potential site
factors indicating whether the facility is located in a sensitive environment.
Lead was consumed by approximately 200 domestic manufacturing plants in 1993. The major end use was
in transportation, with about 70 percent consumed in the manufacture of batteries, fuel tanks, solder, seals, and
bearings. Electrical, electronic, and communications uses (including batteries), ammunition, TV glass, construction
(including radiation shielding), and protective coatings consumed more than 25 percent. The remainder was used in
ballast and weights, ceramics and crystal glass, tubes and containers, type metal, foil, wire, and specialized
chemicals. Overall, lead acid batteries accounted for about 80 percent of lead consumption. (BOM, 1995, pp. 94^
95).
B. Generalized Process Description
1. Discussion of Typical Production Processes
Primary lead facilities in the United States employ pyrometallurgical methods to produce lead metal.
Treatment of lead ores begins with crushing, grinding, and concentrating. Pelletized concentrates are fed with other
materials (e.g., smelter material formerly classified as byproducts, coke) to a sinter unit. The sinter process
agglomerates fine particles, drives off volatile metals, converts metal sulfides to metal oxides and sulfates, and
removes sulfur as sulfur dioxide (SO2). The exit gas stream from the sinter machine is cleaned and routed to an acid
plant to produce concentrated sulfuric acid. The sintered material is then introduced into a blast furnace along with
coke and fluxes. (SAIC, 1991b, p. 2)
Inside the blast furnace, the lead is reduced (smelted), and the molten material separates into four layers:
lead bullion; "speiss" and "matte," two distinct layers containing recoverable quantities of copper and otner metals;
and blast furnace slag. The speiss and matte are sold to operators of copper smelters for metals recovery, and the
slag is stored and partially recycled. The bullion is drossed (agitated and cooled in a dressing kettle) to remove lead
and other metal oxides, which form a layer of dross that floats on the bullion. The dross, composed of roughly 90
percent lead oxide, along with other elements, is skimmed and sent to a dross furnace for recovery of non-lead
mineral values. Slag and residual lead from the dross furnace are returned to the blast furnace. The remaining
material is sold to operators of copper smelters for recovery of copper and precious metals. The lead bullion may
then be decopperized before being sent to the refining stages. (U.S. EPA, 1990, p. 10-2)
371
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EXHIBIT 1
SUMMARY OF LEAD MINING, SMELTING, AND REFINING FACILITIES
Facility Name
Location
Type of Operations
Potential Factors Related to Sensitive Environments
ASARCO
East Helena, MT
Smelting
Facility is partially located within a 100-yr. floodplain, a
wetland, and a fault area
Approximately 3,500 residents live within one mile of the
facility boundary
The nearest residence is located 100 yards from the facility
boundary
Depth from the bottom of special mineral processing waste
(slag) management units to water in the uppermost usable
aquifer is 38 feet
One aquifer is located between the ground surface and the
uppermost usable aquifer; this aquifer is contaminated
Surface water monitored upstream and downstream of the
slag management units has exceeded national ambient
surface water quality criteria for lead
Ambient air monitored near the slag management units has
exceeded the NAAQS for lead (arithmetic 3-month average,
-------
EXHIBIT 1 (Continued)
Facility Name
Location
Type of Operations
Potential Factors Related to Sensitive Environments
ASARCO
Glover, MO
Smelting and Refining
Facility is partially located in karst terrain
One residence is located within one mile of the facility,
approximately one-half mile from the facility boundary
Depth from the bottom of the slag management units to
water in the uppermost usable aquifer is 5 feet at its highest
seasonal level and 30 feet at the lowest seasonal level
Ground water monitoring wells located downgradient from
the slag management units have shown exceedanees of the
NPDWS for cadmium and the NSDWS for zinc and total
dissolved solids
ASARCO
Omaha, NE
Refining
Facility is partially located in a 100-yr. floodplain and a fault
area
Approximately 4,400 residents live within one mile of the
facility boundary
The nearest residence is located approximately three-
quarters of a mile outside the facility boundary
Ambient air monitored near the slag management units has
exceeded the NAAQS for lead (arithmetic 3-month average,
ASARCO Leadville Unit
Leadvilj_e,.CO
Mining
UJ
-J
UJ
-------
EXHIBIT 1 (Continued)
Facility Name
Doe Run Co.
Fourth of July Mine
Galena Mine
Glass Mine
Greens Creek Mine
Lucky Friday Mine
Magmont Mine
Montana Tunnels Mine
Red Dog Mine
Sunnyside Mine
Sweetwater Mine
Location
Herculaneum, MO
Yellow Pine, ID
Mullan, ID
Pend Oreille County,
WA
Admiralty Island, AK
Mullan, ID
Bixby, MO
Jefferson County, MT
Kotzebue, AK
Silverton, CO
Bunker, MO
Type of Operations
Smelting and Refining
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Extraction
Potential Factors Related to Sensitive Environments
» Facility located within 100-yr. floodplain
• Approximately 1 ,000 residents live within 1 mile of the
facility boundary
• Nearest residence is 21 yards from the facility boundary
• The active on-site surface impoundment is located 142 yards
from the nearest residence outside the facility boundary
» The depth from the bottom of the on-site solid waste
management units to water in the uppermost usable aquifer is
approximately 80 feet, at its highest and lowest levels.
-------
EXHIBIT 1 (Continued)
Facility Name
Viburnum Mines (6 mines):
Brushy Creek
Casteel
Fletcher
Viburnum 28
Viburnum 29
Buick
West Fork Mine
Location
Iron, Reynolds, and
Washington Counties,
MO
Bunker, MO
Type of Operations
Extraction and
Beneficiation
Extraction
Potential Factors Related to Sensitive Environments
-------
Lead refining operations generally consist of several steps, including (in sequence) softening, desilverizing,
dezincing, bismuth removal, and final refining. Various other saleable materials also may be removed from the
bullion during these steps, such as gold and oxides of antimony, arsenic, tin, and copper. During final refining, lead
bullion is mixed with various fluxes and reagents to remove remaining impurities (e.g., calcium, magnesium, and
lead oxide). The lead is cooled and the impurities rise to the surface and are removed as slag; this slag may be
recycled to the blast furnace. The purified bullion is then cast into ingots. (U.S. EPA, 1990, pp. 10-2, 10-3)
Recently, researchers at the former U.S. Bureau of Mines developed bench-scale alternative processes for
producing lead. These techniques consist of hydrometallurgical methods (e.g., leaching and solvent extraction).
Results of this research are discussed below, under Hydrometallurgical Beneficiation.
2. Generalized Process Flow Diagram
Exhibit 2 contains a process flow diagram that illustrates the steps used in primary lead production, and
includes several waste streams. Process variations are indicated by dashed arrows. Slag from primary lead
processing is a special waste, and hence is not subject to regulation under RCRA Subtitle C. In addition, material
flow diagrams showing the source and fate of materials for ASARCO's Glover, MO and Helena, MT facilities are
provided in Exhibits 3 and 4, respectively.
Extraction and Beneficiation
Lead is mined (extracted) almost exclusively in underground operations, though a few surface operations do
exist. The use of underground or surface mining techniques depends on the proximity of the ore body to the surface,
and the individual characteristics of each ore body determine the exact mining method. (U.S. EPA, 1993b, p. 14)
Lead ores are beneficiated in a series of steps, beginning with milling, a multi-stage crushing and grinding
operation. Crushing is usually a dry operation that utilizes water sprays to control dust. Primary crushing is often
performed at the mine site, followed by additional crashing at the mill. The crushed ore is mixed with water and
initial flotation reagents to form a slurry, then ground in rod and ball mills. The slurried ore may be ground in
autogenous mills (in which the ore acts as the grinding medium) or semi-autogenous mills (in which steel balls are
added to the ore). Hydrocyclones are used between each grinding step to separate coarse and fine particles; coarse
particles are returned to the mill for further size reduction. (U.S. EPA, 1993b, pp. 15-16)
Ground ores are further beneficiated by flotation. Flotation is a technique by which particles of a mineral or
group of minerals are made to adhere preferentially to air bubbles by the action of a chemical reagent. During or
after milling, ore may be treated with chemicals (known as conditioners and regulators) to modify the pH of the ore
pulp prior to flotation. Once conditioned, the ore is then slurried with fresh or salt water and various types of
chemical reagents that promote separation of different metals (collectors, frothers, activators, and depressants).
Flotation typically occurs in a series of steps, and multiple floats may be required to remove different mineral values
from a polymetallic ore. The residues (tailings) from one float are often used as the feed for a subsequent float to
concentrate another metal. (U.S. EPA, 1993b, pp. 16-20)
Flotation typically occurs in a series of cells, arranged from roughers to scavengers to cleaners (roughers
make a coarse separation of values from gangue, and scavengers remove smaller quantities of the remaining values).
Froth from the cleaner cells is sent to thickeners, in which the concentrate is thickened by settling. The thickened
concentrate is pumped out, dewatered by a filter press, and dried. The concentrate is then fed to a sintering
operation. (U.S. EPA, 1993b,pp. 18-23)
376
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Exhibit 2. Process Flow Diagram of Primary Lead Production in the U.S.
A *_
Granulator
_L
V_
Water
/
Thickener
V * , V <
\ / \
Slag and Lead
Recycled to
Blast Furnace
Bullion to
Softening
Slag
Water
1 Sludge
-------
Exhibit 2 (Continued).
Drossed,
Deeopperized
Bullion
Slag to
Sinter Feed
or
Blast Furnace
Desilverized
Bullion
Precious
Metal
Crusts
Flue Dusts
Recycled to ^ Zn°
Sinter Feed
Softening
Slag,
Sodium
Antimonate
Cooling
Water
HW Laad
Lead Oxide
Slag to
Softening Process
Flue Dusts and
Slag to
Blast Furnace
Contaminated
Cooling
Water
Slag to
Blast
Furnace
To Slag
Granulation
To Tailings
Pond
Sludge
-------
EXHIBIT 3
MATERIALS FLOW TO AND FROM ASARCO, GLOVER, MISSOURI
Big
River
Zinc
Zinc*
* Recovered Products
Cadmium*
Zinc-
Rich
Dusts
Leaded
Leach
Residues
Smelter
Refinery
Lead*
Slag
Copper
Speiss
to Hayden, AZ
Plant
ut
^i
ID
Amarillo
Plant
-------
U)
00
o
EXHIBIT 4
MATERIALS FLOW TO AND FROM ASARCO, HELENA, MONTANA
Canadian Ore
Ore Coeur D'Alene Ore
Lucky Friday +
One Other ASARCO
Owned Mine
Slag
Ore
Sunshine
Mine
Residual
Concentrate
with Lead,
Zinc, and
Bismuth
Silver*
Antimony*
Zinc Oxide*
Lead Bullion
Copper Speiss
(CuAs2)
to Hayden
„, „ f
Flue Dusts
Blister Copper
Recovery
Cadmium
Metal*
Leaded Slowdown
Solids to Hayden
' Waste
Thallium
Lead*
Lead Alloys*
-^ Antimony Oxide*
"^ Bismuth*
-^ Selenium*
"^ Tellurium*
"^ Copper*
Precious Metals*
(Gold)
* Recovered Products
-------
Liquid overflow from the thickeners, containing wastewater, flotation reagents, and dissolved and
suspended mineral products, may be recycled or sent to a tailings pond. Wastes from the rougher, scavenger, and
cleaning cells are collected and sent to a tailings thickener. Overflow from the tailings thickener (wastewater
containing high solids and some reagent) is often recycled to the flotation cells, and the underflow (containing
remaining gangue, unreeovered lead materials, chemical reagents, and wastewater) is pumped to a tailings pond.
Clarified water from the tailings pond may be recycled to the mill. (U.S. EPA, 1993b, p. 20)
Sintering occurs on a traveling grate furnace known as a "sinter machine." Ore concentrates are mixed with
fluxes, recycled sinter, and flue dusts. After moisture is added, the mixture is pelletized and fed to die sinter
machine. Inside the furnace, the mixture fuses into a firm porous material, known as sinter. Sintering converts
metallic sulfides to oxides, removes volatile metals, and converts most sulfur to sulfur dioxide (SO2). Product sinter
is sized for use in the blast furnace, and fine sinter particles are recycled to me sintering machine feed mixture. (PEI,
1979, pp. 232-234; U.S. EPA, 1993b, p. 23) Sintering is the final beneficiation step in the primary production of
lead (U.S. EPA, 1990).
Particulates emitted during sintering are collected using eidier baghouses or electrostatic precipitators
(ESPs) and recycled. (PEI, 1979, p. 234) The sinter plant off-gases are reacted in a contact acid plant to produce
concentrated sulfuric acid. Operation of the acid plant may generate wastewaters from scrubbing of the inlet SO2
stream (acid plant blowdown). These wastewaters may be routed to treatment plants or recycled. Treatment often
involves neutralization with lime, followed by thickening, filtering, and recycling of the effluent. (U.S. EPA, 1980,
pp. 31-34)
Blast Furnace
Sinter is charged to a blast furnace witii coke, limestone, and other fluxing materials and smelted. During
smelting, metallic oxides are reduced to metal. The mixture separates into as many as four distinct liquid layers,
depending on sinter composition, from the bottom up: lead bullion (94 to 98 percent lead by weight, and other
metals); speiss (arsenides and antimonides'of iron and other metals); matte (copper sulfides); and slag (flux and
metal impurities). The matte and speiss layers are sold to operators of copper smelters for metal recovery, and crude
bullion is fed to dressing kettles. Depending on its zinc content, the slag may be either disposed of or sent to a zinc
fuming furnace. (PEI, 1979, pp. 235-6; U.S. EPA, 1990, p. 10-2)
Inside a zinc fuming furnace, blast furnace slag and coal are mixed with air and heated. Zinc oxide (ZnO)
and lead oxide in the slag are reduced and volatilized, and then oxidized near the top of the furnace, forming
particulates. The particulates are recovered in a baghouse and sent to a zinc refinery for zinc recovery. The residual
slag is disposed of as described below. (PEI, 1979, pp. 237)
Disposal practices are similar for blast furnace slag and residual slag from zinc fuming operations. The slag
may be eimer dumped while hot onto a slag pile, or granulated with cooling water and then dumped. Some plants
dewater die slag; the granulating water may be cleaned in tiiickeners and recycled to the granulation unit. The
granulation water also may be discharged. Particulates emitted from the blast furnace are collected in a baghouse or
ESP, and can be recycled to the sinter feed or treated for cadmium recovery. If the cadmium content of the flue dust
reaches 12 percent by weight, die dust is roasted to recover cadmium. Fume emissions from the roasting operation
are cooled and recovered as a product (cadmium concentrate), and the residue is recycled to the sinter feed. Blast
furnace off-gases also contain small quantities of SO2 that may need chemical scrubbing, possibly generating a
waste. (PEI, 1979, pp. 236-253; U.S. EPA, 1980, p. 52; U.S. EPA, 1990, p. 10-3)
Lead bullion recovered from the blast furnace is fed to a dressing kettle, agitated with air, and cooled to just
above its freezing point. Oxides of lead, copper, and other impurities form a dross on die surface mat is skimmed.
Sulfur may be added to the dressing kettle to enhance copper removal, forming copper sulfide (Cu2S) that is
skimmed off witii the dross. Skimmed dross is sent to the dross reverberatory furnace for additional processing; off
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gases and particulates from the dressing kettle are combined with blast furnace off-gases for treatment. The lead
product is known as "rough-drossed" lead. (PEI, 1979, pp. 237-8; U.S. EPA, 1980, p. 47; U.S. EPA, 1990, p. 10-2)
Dross is fed into the reverberatory furnace with pig iron, silica sand, and possibly lime rock, and smelted.
The products separate into four layers: slag, matte, speiss, and molten lead. The slag and lead are returned to the
blast furnace, and the matte and speiss are removed separately, granulated, and shipped to copper smelters for metals
recovery. Off gases from the reverberatory furnace are combined with blast furnace off gases. (PEI, 1979, p. 238;
U.S. EPA. 1990, p. 10-2)
Decopperizing
Rough-drossed lead bullion is decopperized before refining, occasionally in the same kettle used for the
dressing operation. Sulfur is added while the lead is agitated, forming a layer of Cu2S that is skimmed and recycled
either to the dross reverberatory furnace or the dressing kettle (in two-stage drossing). (PEI, 1979, pp. 238-9; U.S.
EPA, 1990, p. 10-2)
Softening
Softening removes elements that make lead hard, and is accomplished using one of three techniques:
reverberatory softening, kettle softening, or Harris softening. In reverberatory softening, air is blown through molten
lead, causing metals such as antimony, arsenic, tin, and copper to form oxides. The oxides form a slag that is
skimmed and can be treated for metals recovery. Lead oxide (litharge) may be added to lead with hardness greater
than 0.3 to 0.5 weight percent antimony equivalent to increase the oxidation rate. (PEI, 1979, pp. 239-40)
Kettle softening can be used only on bullions with hardness less than or equal to 0.3 percent. The bullion is
melted and agitated, and sodium hydroxide (NaOH) and niter (NaNO3) are added as fluxes. The fluxes react with
impurities to form salts such as sodium antimonate (NaSbO3), resulting in a slag that is skimmed off and discarded.
(PEI, 1979, pp. 240)
Harris softening utilizes the same reagents as kettle softening and also requires low levels of impurities.
Harris softening occurs in two stages. The first stage is identical to kettle softening and generates a slag for further
processing. During the second step, the slag is crushed and leached with hot water to dissolve the sodium salts. The
solution is cooled to precipitate sodium antimonate (NaSbO3), which is filtered from solution and processed to
recover antimony. Calcium salts of arsenic and tin are then recovered separately by precipitation and sold. (PEI,
1979, p. 240)
Kettle softening slags and leached slags from Harris softening are discarded with blast furnace or zinc
fuming furnace slags. Reverberatory softening slag and sodium antimonate from Harris softening may be treated to
recover metal values. To recover antimonial lead ("hard lead"), the softening slag is heated in a furnace with a
reducing agent and fluxes, reducing lead and antimony. The antimonial lead is recovered and sold; the slag may be
sold if it is rich in tin or recycled to either the sinter feed or the blast furnace. To recover antimonial trioxide
(Sb2O3), the sodium antimonate is heated to volatilize antimonial trioxide and arsenic trioxide (As2O3), and these
compounds are separated by selective condensation. The antimony trioxide and arsenic trioxide are sent to antimony
and arsenic producers, respectively. The furnace residue is recycled to the blast furnace. Arsenic trioxide becomes a
waste if it cannot be sold. (PEI, 1979, pp. 240-1)
Parkes Desilverizing
This process is used to recover gold and silver from softened lead bullion. Gold and silver removal are
usually performed in two steps. First, a small amount of zinc is added to the molten bullion to generate a skim with
high gold content, because zinc alloys preferentially with gold and copper. After this layer is removed, more zinc is
added to form a zinc-silver skim, which is also removed. Other metallic impurities, including arsenic, must be
removed prior to this operation. The gold and silver-bearing crusts are retorted in furnaces to recover zinc, leaving
behind a purified gold-silver alloy (Dore). The zinc can be recycled to the process. Flue dusts from the furnaces can
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be cooled and collected with baghouses and recycled to the sinter feed. (PEI, 1979, pp. 241-2; U.S. EPA, 1980, p.
64)
Gold and silver are recovered by melting the alloy in a cupel and introducing air as well as oxidizing agents.
Several successive slags are produced, most of which are recycled to the blast furnace. Slag containing lead oxide is
recycled to the softening process. The remaining gold-silver alloy is cast and sold. Exhaust gases can be cooled and
routed to baghouses; collected dusts are then recycled to the blast furnace. Desilverized lead is sent to the dezincing
process. (PEI, 1979, p. 242: U.S. EPA, 1980. p. 65)
Dezincing
Excess zinc added during desilverizing is removed from lead bullion using one of three methods: Vacuum
dezincing; chlorine dezincing; or Harris dezincing. During vacuum dezincing, a vacuum is drawn on the molten lead
by submerging an inverted bell into the agitated metal. Vaporized zinc condenses on the inner surface of the bell,
and solid zinc is scraped from the dome after the vacuum is broken. The zinc is recycled to desilverizing. In
chlorine dezincing, molten desilvered lead is reacted with chlorine gas, forming a surface layer of zinc chloride
contaminated with small amounts of lead chloride. The layer is skimmed, treated with zinc for lead recovery, and
sold as ZnCl2. In Harris dezincing, caustic soda (NaOH) saturated with lead oxide is mixed with molten lead in a
reaction chamber, reducing lead oxide to lead and oxidizing zinc to zinc oxide. The zinc oxide reacts with the
caustic to form sodium zincate. The contents of the reaction chamber are fed to a granulator and then reacted with
hot water. Sodium zincate hydrolyzes to zinc oxide and sodium hydroxide. Zinc oxide (ZnO) precipitates from
solution, and is filtered, dried, and sold. The sodium hydroxide solution is evaporated to anhydrous caustic, which is
recycled. Antimony may also be recovered from spent granulated caustic. Dezinced lead is sent to a debismuthing
step or to the final refining stage. (PEI, 1979, pp. 242-3; U.S. EPA, 1980, pp. 67-71)
Debismuthing
Desilvered and dezinced lead bullion containing greater than 0.15 percent by weight bismuth must be
processed to remove bismuth before casting. Calcium and magnesium are mixed with molten lead, forming ternary
compounds (e.g., CaMg,Bi2) that rise to the surface when the lead is cooled to just above its melting point, forming a
dross, which is then skimmed. The purified lead is sent to a final refining step. Bismuth is recovered by melting the
dross in a furnace and then injecting chlorine gas. Magnesium, calcium, and lead contained in the dross form
chlorides, which are skimmed from the molten bismuth as a slag. Air and caustic soda are added to the melt to
oxidize any remaining impurities, forming a slag which is also removed. The nearly pure bismuth is cast and sold,
and the slags are disposed along with blast furnace slag. (PEI, 1979, p. 244; U.S. EPA, 1980, p. 74)
Final Refining and Casting
Lead bullion from dezincing or debismuthing is reacted with caustic soda and niter to remove lead oxide,
calcium, and magnesium before final casting. A slag forms, which is removed and recycled to the blast furnace or
disposed. The final refined lead is reheated and cast into ingots or pigs, which are cooled by direct contact with
water. The cooling water becomes contaminated with paniculate lead and lead oxides and can be recycled for use in
slag granulation or treated. Treatment may include liming to precipitate solids. (PEI, 1979, pp. 244-5; U.S. EPA,
1980, p. 75; U.S. EPA, 1990, p. 10-2)
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Hydrometallurgical Beneficiation
The U.S. Bureau of Mines developed a laboratory-scale method that combines oxidative leaching and
electrowinning to recover lead metal and elemental sulfur from lead sulfide (PbS) concentrates. Lead sulfide
concentrates were leached with fluosilicic acid (H,SiF6), using hydrogen peroxide (H,O2) and lead dioxide as
oxidants. After filtration to separate the lead fluosilicate (PbSiF6) leach solution and the sulfur-containing residue,
the PbSiF6 was electrowon to produce lead metal and H2SiF6. The H2SiF6 was recycled to the leaching step, and
sulfur was recovered from the leach residue by solvent extraction. (Lee et al., 1990, p. 2)
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Since H2O2 proved to be an expensive oxidant, the Bureau of Mines researchers developed and tested a
pressure leaching method for lead sulfide concentrates that utilizes oxygen gas (O2) in place of H2O2. This method
also utilizes H2SiF6 as the leach solution and electrowinning to recover lead metal. The researchers conducted
several experiments, varying O2 pressure, catalysts, temperature, acid concentration, and time. Lead metal with
99.96 percent purity was recovered by electrowinning from as-leached solution. Lead metal with at least 99.99
percent purity was recovered by electrowinning from leach solutions purified using either of two chemical methods.
Finally, elemental sulfur was recovered from the leach residue by solvent extraction, and methods were developed to
recover other valuable metals (e.g., Ag, Zn, and Cu) from the final residue. (Lee et al., 1990, pp. 2-3, 6)
The Bureau of Mines also conducted research on the leaching of mixed lead-zinc sulfide concentrates.
followed by electrowinning, to produce lead metal. Lead-zinc sulfide concentrates were leached with H2SiF6, using
either H2O2 or pure oxygen (O2) as an oxidant. Lead was selectively leached and zinc remained in the solid residue.
All experiments were performed on a bench-scale level. (Beyke, 1991, pp. 219-221)
The researchers conducted leaching experiments at both atmospheric pressure and at increased pressures.
At atmospheric pressure and at 95 degrees C, 85 percent of the lead was leached from the concentrate, and 87
percent of the zinc remained in the residue. Using pressure leaching, 78 percent of the lead was recovered from the
concentrate while 80 percent of the remained in the residue. After filtering the leach residue, the researchers
recovered pure lead metal by electrowinning from a purified PbSiF6 electrolyte produced from the leach solution.
The electrowinning step produced H2SiF6 that could be recycled to the leaching stage. In addition, once lead was
removed, the original leach solution could also be recycled to the leaching stage. (Beyke, 1991, pp. 219, 236) No
information was available on whether these hydrometallurgical methods developed by the Bureau of Mines have
been expanded to a pilot-scale or demonstration-scale process.
In the early 1980's, another experimental hydrometallurgical process was developed by the Bureau of Mines
in cooperation with four U.S. primary lead producers. Galena (PbS) concentrate was leached with ferric chloride
solution, and the lead chloride leachate was reduced by a process known as "fused salt electrolysis." The process
generated a lead product that required no further refining. The leachate was also processed to yield 99 percent pure
sulfur without sulfur dioxide emissions. The Bureau of Mines and the four primary lead producers concluded 18
months of testing in 1981, using a 500-pound-per-day demonstration unit. (BOM, 1985, p. 439) No information
was available on whether this method is used today.
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from primary mineral production arise
from mineral processing operations and which from beneficiation activities in the September 1989 final rule (see 54
Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically serve to separate and
concentrate the mineral values from waste material, remove impurities, or prepare the ore for further refinement.
Beneficiation activities generally do not change the mineral values themselves other than by reducing (e.g., crushing
or grinding) or enlarging (e.g., pelletizing or briquetting) particle size to facilitate processing. A chemical change in
the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or substantial chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
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ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between sintering and smelting in a blast furnace, EPA identified this point in the process sequence as where
beneficiation ends and mineral processing begins because it is here where the sintered ore is chemically reduced and
physically destroyed to lead metal. Therefore, because EPA has determined that all operations following the initial
"processing" step in the production sequence are also considered processing operations, irrespective of whether they
involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s)
following the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation
wastes. EPA presents the mineral processing waste streams generated downstream of the beneficiation/processing
line in section C.2, along with associated information on waste generation rates, characteristics, and management
practices for each of these waste streams.
C. Process Waste Streams
As discussed above (and shown in Exhibit 2), the extraction, beneficiation, and processing of lead generate
several solid, liquid, and gaseous wastes, that may be recycled or refined prior to disposal. The generation,
treatment, and management of these wastes are discussed below.
Attachment 2 contains a summary of the operational history of and environmental contamination
documented at a former lead production site that is now on the Superfund National Priority List.
1, Extraction/Beneficiation Wastes
Wastes generated from the extraction and beneficiation of lead from lead-bearing ores are exempt from
RCRA Subtitle C and the scope of BDAT determinations. These wastes are discussed below.
Waste Rock
Lead mining operations generate two types of waste rock, overburden and mine development rock.
Overburden results from the development of surface mines, while mine development rock is a material, formerly
labeled as a byproduct, of mineral extraction in underground mines. The quantity and composition of waste rock
generated at lead mines varies greatly among sites, but these wastes will contain minerals associated with both the
ore and host rock. Overburden wastes are usually disposed of in unlined piles, while mine development rock is often
used on-site for road or other construction. Mine development rock also may be stored in unlined on-site piles or in
underground openings. Waste rock piles may be referred to as mine rock dumps or waste rock dumps. Runoff and
leachate from waste rock dumps may contain heavy metals, and these piles may generate acid drainage if sufficient
amounts of sulflde minerals and moisture are present. EPA found no information on the quantities of waste rock
generated annually. (U.S. EPA, 1993b, pp. 25-26, 28, 105)
Mine Water
Mine water includes all water that collects in surface or underground mines, due to ground water seepage or
inflow from surface water or precipitation. While a mine is operational, water may be pumped out to keep the mine
dry and allow access to the ore body. The water may be pumped from sumps within the mine or from a system of
wells. The recovered water may be used in beneficiation, pumped to tailings or mine water ponds, or discharged to
surface water. EPA has no information on the quantities of mine water generated annually at all lead mining/milling
locations. One facility, however, the Doe Run mine/mill facility in Fletcher, MO, generates an average of 4.63
million gallons of mine water per day, which is pumped to an on-site mine water pond. (U.S. EPA, 1993b, pp. 26,
109)
The composition and quantity of mine water varies among mining sites, and the chemical composition of
mine water depends on the geochemistry of the ore body and the surrounding area. Mine water also may be
contaminated with small quantities of oil and grease from mining equipment and nitrates from blasting operations.
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When a mine is closed and pumping stops, the mine may fill with water. Through aeration and contact with sulfide
minerals, the accumulated water can acidify and become contaminated with heavy metals. (U.S. EPA, 1993b, pp.
26, 28)
Concentration Wastes
Beneficiation operations used to concentrate mineral ores generate various types of wastes. Flotation
systems discharge tailings consisting of liquids and solids. The solids include mostly gangue material and small
amounts of unrecovered lead minerals. The liquid component consists of water, dissolved solids, and reagents not
consumed during flotation. The reagents may include cyanide, which is used as a depressant in certain flotation
operations. Flotation wastes are generally sent to tailings ponds, in which solids settle out. The clarified liquid may
be recycled to the mill or discharged, provided it meets water quality standards. The characteristics of flotation
tailings vary considerably, depending on the ore, reagents, and processes used. Other types of beneficiation wastes
include waste slurries from milling and gravity concentration steps. These wastes also are disposed of in tailings
impoundments. Site-specific data on tailings generation were available for one facility, the Doe Run mine/mill
facility in Fletcher, MO. This facility generates approximately 1.4 million tons of tailings per year. (U.S. EPA,
1993b, pp. 28-29, 105) EPA has no information on the quantities of tailings generated annually at all lead
mining/milling locations.
2. Mineral Processing Wastes
Smelting and Refining operations generate numerous solid, liquid, and gaseous wastes. Slag generated
during primary lead smelting and refining is classified as a special waste, and is exempt from RCRA Subtitle C
controls and, consequently, BOAT determinations. Descriptions of the other wastes follow.
Process Wastewater
Primary lead production facilities generate various process wastewaters, including slag granulation water,
sinter plant scrubber water, plant washdown water, and plant run-off. (PEIA, 1984, p. 3-12; Doe Run Company,
1989b; Asarco, 1989a-c) Approximately 4,965,000 metric tons of process wastewater are generated annually (ICF,
1992). EPA/ORD sampling data, presented as Attachment 1, indicates that this waste stream exhibits the
characteristic of toxicity (arsenic, cadmium, lead, and selenium). In addition, the waste stream may be toxic for
mercury, based on best engineering judgment.
Site-specific information on process wastewater management practices were available only for one facility.
At the Doe Run plant in Herculaneum, MO, a mixture consisting of granulated blast furnace slag and the
accompanying slag granulation water are sent to a wastewater treatment plant (WWTP-3) for dewatering. The
granulation water is sent to a second wastewater treatment plant (WWTP-1) for additional treatment such as pH
adjustment and clarification. Other process wastewaters, including dross reverberatory furnace slag granulation
water; sinter plant scrubber water; clothes washing liquids; plant runoff; and washdown from the sinter plant, blast
furnace, dressing kettles, dross reverberatory furnace, refinery, baghouses, and pavement are sent directly to WWTP-
1 for treatment. (Doe Run Company, 1989b) This waste was formerly classified as a spent material and may be
partially recycled, based on best engineering judgment.
Surface Impoundment Waste Solids
Since 1980, the primary lead smelting industry has altered its management of process wastewaters, and the
solids that settle from those wastewaters. The three operating primary lead smelters (Asarco in Glover, MO; Asarco
in East Helena, MT; and Doe Run in Herculaneum, MO) no longer use surface impoundments and completely
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recycle all wastewater treatment solids. The industry now uses tanks to settle solids from lead process wastewater.
The collected solids are removed from the tanks for reintroduction to the smelting process.1
Spent Furnace Brick
Primary lead smelters generate used refractory brick during the reconstruction of blast furnaces. Some plant
operators crush and recycle the brick to the blast furnace, while others discard the brick in on-site disposal piles.
(PEIA, 1984, p. 3-10) Approximately 1,000 metric tons of spent furnace brick are generated annually (ICF, 1992).
The November 1984 PEI Associates study contains Jesuits of EP toxicity tests on two samples of used
refractory brick. The plants from which the samples were taken were not identified. Both samples exhibited EP
toxicity for lead (1,230 mg/L and 63.3 mg/L). (PEIA, 1984, pp. 5-16 to 5-17) This waste stream is recycled and
was formerly classified as a spent material.
WWTP Liquid Effluent
Wastewater treatment plants are utilized in primary lead production for treatment of acid plant blowdown
and other wastes, including slag granulation water, plant washdown, and ruh-on/run-off. These liquids may receive
some treatment prior to the WWTP, consisting of settling in lined basins. Treatment in the WWTP often consists of
lime neutralization and settling. Treated effluents may be either recycled within the plant or discharged through
NPDES outfalls. (PEIA, 1984, pp. 3-6 to 3-7; pp. 3-12 to 3-15; SAIC 1991b, pp. 8-10)
At the Doe Run plant in Herculaneum, MO, a portion of the WWTP-1 liquid effluent is recycled to the
sinter plant for use as scrubber water; the rest of the effluent is discharged through an NPDES outfall. Slag
granulation water from WWTP-3, as well as neutralized acid plant blowdown from another treatment plant (WWTP-
2) are routed to WWTP-1 for further treatment. (Doe Run Company, 1989b)
Approximately 3,500,000 metric tons of WWTP liquid effluent are generated annually (ICF, 1992). The
NIMPW Characterization Data Set contains data indicating that this waste stream may exhibit a hazardous
characteristic (ICF, 1992). Attachment 1 includes data from EPA/ORD sampling and shows that the waste stream
exhibits the characteristic of corrosivity. However, since the effluent is not managed in a land-based unit, and is
either recycled within the plant or discharged through a regulated outfall, this waste stream may not meet the
definition of a solid waste under RCRA, in which case it would not be subject to Subtitle C regulation. We used best
engineering judgment to determine that this waste may exhibit the characteristic of toxicity for lead. This waste
stream is fully recycled and was formerly classified as a sludge.
WWTP Sludges/Solids
Wastewater treatment sludges/solids are now completely recycled and reintroduced into the smelting
process. Thus, these materials are not considered to be within the definition of solid waste.2
Surface Impoundment Waste Liquids
Unlined surface impoundments are gradually being replaced by lined, engineered impoundments or
wastewater treatment systems. At the ASARCO facility in Glover, MO, existing unlined surface impoundments are
no longer used. Plant wastewaters (e.g., slag granulation water) are now clarified in two rubber-lined concrete
1 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
and The Doe Run Company. Comment submitted in response to the Second Supplemental Proposed Rule Applying
Phase IV Land Disposal RestrictionsiQ Newly Identified Mineral Processing Wastes. May 12, 1997.
2 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
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settling tanks. Overflow from the second tank collects in a lined retention pond; overflow from the retention pond is
treated with lime in a wastewater treatment plant and discharged through an NPDES outfall. In addition, the Doe
Run plant in Herculaneum, MO now continuously treats wastewaters that were formerly routed to unlined surface
impoundments. (SAIC 1991b, pp. 9-12) The remaining operational primary lead smelting facility, Asarco, East
Helena, MT, is reconstructing its wastewater management system. The modified system will allow the plant to
discontinue its use of surface impoundments. (U.S. EPA, 1994, pp. 22-23) The Asarco primary lead refinery in
Omaha, NE does not utilize any surface impoundments. (Asarco, 1989c)
The Newly Identified Mineral Processing Waste Characterization Data Set indicated that approximately
5,314,000 metric tons of surface impoundment liquids are generated annually. (ICF, 1992) However, this figure
may no longer be accurate, due to changes in management practices for primary lead plant wastewaters and the
closure of surface impoundments at several facilities. We used best engineering judgment to determine a waste
generation rate of 1,100,000 mt/yr. The waste generation rate is more than one million metric tons per year per
facility due to comingling of numerous waste streams.
The November 1984 PEI Associates study contains data on 4 samples of surface impoundment liquids
collected at various smelters (the plants were not identified). EP toxicity tests were conducted on one sample of slag
granulation water and one sample of granulated slag-pile run-off from separate impoundments at die same site. EP
tests were also conducted on two water samples from impoundments at separate facilities that receive miscellaneous
plant wastewaters (run-off, washdown, etc.). The samples of slag granulation water and slag pile run-off water did
not exhibit EP toxicity. Both samples from impoundments containing miscellaneous plant waters exhibited EP
toxicity. A sample from an impoundment that receives plant washdown and run-off (but not blowdown) exhibited
EP toxicity for lead (69.1 mg/L). The other sample, from an impoundment that collects acid plant cooling water,
sintering plant and concentrate storage area washdown, plant run-off, and personnel change-house water exhibited
EP toxicity for arsenic (69.8 mg/L). (PEIA, 1984, p. 5-14 to 5-16) The NIMPW Characterization Data Set contains
additional data indicating that this waste stream may exhibit a hazardous characteristic (ICF, 1992). We used best
engineering judgment to determine that this waste may be partially recycled and may exhibit die characteristic of
toxicity (arsenic, cadmium, and lead). This waste was formerly classified as a sludge.
Acid Plant Blowdown
This acidic liquid waste is generated from wet scrubbing of the sulfur dioxide gas stream that enters the
contact acid plant from the sinter plant. The purpose of the scrubbing is to remove particulate matter from the gas
before the gas is used to produce sulfuric acid. Some scrubbing solution is continuously purged to prevent a buildup
of solids in the recirculating scrubber water. The purged solution is known as acid plant blowdown. (PEIA, 1984, p.
3-6; U.S. EPA, 1994, p. 22)
Typically, acid plant blowdown (APB) is treated through some combination of lime neutralization and
settling. Some facilities treat APB with lime at the acid plant and then pump the resulting slurry to an on-site
WWTP. Other plants mix APB with other wastewaters, allow settling to occur, and then treat the clarified liquid
with lime. Solids derived from blowdown treatment are often recycled to the sinter feed preparation or to the
smelter, while the liquids are either discharged through NPDES outfalls or recycled within the plant. The solids may
also be sold for metals recovery. (PEIA, 1984, pp. 3-6, 3-7; SAIC, 1991b, pp. 8-12; ICF, 1989, pp. 2-3)
Approximately 556,000 metric tons of acid plant blowdown are generated annually (ICF, 1992).
At the Doe Run facility in Herculaneum, MO, acid plant blowdown is neutralized in a wastewater treatment
plant (WWTP-2), and the neutralized blowdown is sent to a second wastewater treatment plant (WWTP-1) for
additional neutralization and clarification. (Doe Run Company, 1989b)
The November 1984 PEI Associates study contains results of EP toxicity tests on two samples of lime-
neutralized acid plant blowdown collected at different smelters (the plants were not identified). Each sample
exhibited the characteristic of EP toxicity, one for lead (22 mg/L) and the other for arsenic (24.4 mg/L) and cadmium
(2.61 mg/L). The study also contains the results of an EP toxicity test on one sample of blowdown treatment
material formerly labeled as sludge. The material sample exhibited EP toxicity for arsenic (304 mg/L) and cadmium
(155 mg/L). (PEIA, 1984, pp. 5-14, 5-16, 5-17) The NIMPW Characterization Data Set contains additional data
388
-------
indicating that this waste stream may exhibit a hazardous characteristic (ICF, 1992). Attachment 1 includes
EPA/ORD sampling data which shows that this waste stream exhibits the characteristics of toxicity (arsenic,
cadmium, lead, and selenium) and corrosivity. We used best engineering judgment to determine that this waste
stream may exhibit the characteristic of toxicity for mercury. This waste is recycled and was formerly classified as a
spent material.
Slurried APC Dust
At one integrated smelter/refinery, ESP dust and scrubber underflow from the cleaning of sinter plant off-
gases destined for the acid plant were slurried into a thickener. The thickened solids were placed on the slag dump
along with other solids for air drying, and eventually recycled to the sinter feed preparation step. The facility at
which this practice occurred was not identified. (PEIA, 1984, p. 3-5) Approximately 7,000 metric tons of slurried
APC dust are generated annually. (ICF, 1992)
The 1989 RTI Survey for the Doe Run facility in Herculaneum, MO, suggests another source of this waste
stream. The flow diagram included with the survey shows that baghouses are used to collect particulates in off-gases
generated by the sinter plant, blast furnace, and the dross reverberatory furnace. The diagram also shows that a
liquid waste (process wastewater) known as "department washdown" flows from the baghouses to an on-site
wastewater treatment plant (WWTP-1), for treatment that includes pH adjustment and clarification, (Doe Run
Company, 1989b) However, the survey does not specify whether or not the department washdown contains
entrained baghouse dust.
The November 1984 PEI Associates study contains results of EP toxicity tests on one sample of solids from
sumps that collect slurried ESP dust, "cyclone underflow," and plant washdown. The study adds that the solids are
stockpiled on-site before they are recycled. The sample exhibited the characteristic of EP toxicity for lead (959
mg/L) and cadmium (22 mg/L). (PEIA, 1984, pp. 5-16, 5-17) This waste stream is fully recycled and was formerly
classified as a sludge.
Solids in Plant Washdown
At some plants, washdown liquids from storage and blending areas (sinter feed preparation) are typically
sent to concrete sumps and allowed to settle. The water is recycled, and the solids are stored to allow dewatering and
drying. The collected solids are returned to sinter feed piles or blending bins. (PEIA, 1984, p. 3-2)
Alternatively, plant washdown may be sent to on-site wastewater treatment plants. At the Doe Run facility
in Herculaneum, MO, washdown from the sinter plant, blast furnace, dressing kettles, dross reverberatory furnace,
refinery, and baghouses is sent along with other wastewaters, to a single treatment plant (WWTP-1) for
neutralization, clarification, and other treatment. Dewatered material formerly labeled as sludge from this treatment
plant is returned to the sinter feed. (Doe Run Company, 1989b) This washdown may contain entrained solids and
particulates.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Acid Plant Sludge
This waste stream was identified in a 1987 draft of an EPA Report to Congress on mineral processing
operations. The report provided an estimated annual generation rate of 14,600 metric tons per year, but did not
include any specific information on how the waste was generated or its composition. (ICF, 1987, pp. 3-41 to 3-44)
According to a process flow chart provided in the 1989 RTI survey, this waste stream was recycled to the sintering
machine. We used best engineering judgment to determine that this waste may exhibit the characteristic of
eorrosivity. This waste was formerly classified as a sludge.
389
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Solid Residues
This waste stream was identified in the 1989 RTI Survey for the Doe Run facility in Boss, MO. The waste
consisted of two types of material, "rice paddy" and "filter cake," and the facility reported generating the waste as a
residue from its sinter plant. (Doe Run Company, 1989a) According to the RTI Survey, this waste was recycled to
the sintering process. The Boss primary lead facility is no longer operational, and it is not known whether this waste
is generated by any other primary lead production facilities. This waste stream has a reported annual waste
generation rate of 400 metric tons/yr. The NIMPW Characterization Data Set contains data indicating that this waste
stream may exhibit a hazardous characteristic. (ICF, 1992) We used best engineering judgment to determine that
this waste may be recycled and may exhibit the characteristic of toxicity for lead. This waste was formerly classified
as a by-product.
Baghou.se Dust
Several components of the primary lead production process generate off-gases that contain dusts or
particulates. Particulates in off-gases from sintering operations are collected by baghouses and ESPs. These dusts
are returned to the sinter feed preparation. Particulates in off-gases from the blast furnace, dross kettle, the dross
reverberatory furnace, and silver/gold recovery operations are also collected using baghouses and ESPs and are
recycled to the sinter feed. (PEI, 1979) Approximately 46,000 metric tons of baghouse dust are generated annually
(ICF, 1992).
At the Doe Run facility in Herculaneum, MO, baghouses are used to collect particulates in off-gases
generated by the sinter plant, blast furnace, and the dross reverberatory furnace. However, ultimate destination of
the dust is unclear from the survey. The facility flow diagram indicates that a liquid waste (process wastewater)
known as "department washdown" flows from the baghouses to an on-site wastewater treatment plant (WWTP-1),
However, the survey does not specify whether or not the department washdown contains entrained baghouse dust.
(Doe Run Company, 1989b)
Dust collected in baghouses at one of ASARCO's facilities (a smelter) accumulates in cellars beneath the
baghouse. The baghouse is taken off-line every two to four weeks so that the dust can be removed from the cellar.
This material is then stored in a containment area to await further processing.3
The November 1984 PEI Associates study contains results of EP toxicity tests on one sample of baghouse
dust. The plant from which the sample was taken, the source of gas entering the baghouse, and the sample location
were not identified. This sample exhibited EP toxicity for cadmium (3,580 mg/L) and lead (61.7 mg/L). (PEIA,
1984, pp. 5-16 to 5-17) This waste stream is fully recycled and was formerly classified as a sludge.
Cooling Tower Slowdown
The 1989 RTI Survey for the Doe Run facility in Herculaneum, MO indicated that an on-site surface
impoundment received Acid Plant, Dross Furnace, and Blast Furnace cooling tower blowdown, (Doe Run Company.
1989b) However, the Herculaneum facility no longer uses surface impoundments as part of its wastewater
management system. It is not known whether any of these wastes are still generated at the Herculaneum facility.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Waste Nickel Matte
The 1989 RTI Survey for the Doe Run facility in Herculaneum, MO indicated that the dross plant
reverberatory generates a product known as nickel matte. (Doe Run Company, 1989b) It is not known whether this
3 ASARCO Incorporated. Comment submitted in response to the Second Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. May 12, 1997.
390
-------
material is still generated at the Herculaneum facility. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further,
SVG Backwash
The 1989 RTI Survey for the Doe Run facility in Herculaneum, MO indicated that an on-site wastewater
treatment plant (WWTP-1) received a liquid inflow known as "SVG Backwash." (Doe Run Company, 1989b) It is
not known whether this material is still generated at the Herculaneum facility. Existing data and engineering
judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
Baghouse Fume
The 1989 RTI Survey for the Doe Run facility in Herculaneum, MO indicated that in 1988, the sinter plant
received approximately 30,000 short tons of "baghouse fume" as a material input, but does not describe the
composition of this material or identify its source. (Doe Run Company, 1989b) No information is available on
whether this material is a waste stream, or its current annual generation rate. In addition, it is not known whether this
material is still generated at the Herculaneum facility.
Baghouse Incinerator Ash
At most primary lead production facilities, used bags from baghouses are fed to the blast furnace. At one
integrated smelter/refinery, however, the bags are washed and then incinerated in a small, on-site industrial
incinerator. The incinerator ash is landfilled on-site, and the bag washwater is sent to an on-site wastewater
treatment plant. (PEIA, 1984, pp. 3-5 to 3-6) The facility was not identified.
The November 1984 PEI Associates study contains results of EP toxicity tests on one sample of ash from an
incinerator that burned baghouse bags and other plant waste. The plant from which the sample was taken was not
identified. This sample exhibited EP toxicity for cadmium (5.76 mg/L) and lead (19.2 mg/L). (PEIA, 1984, pp. 5-
16, 5-17) Although no published information regarding waste generation rate was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 300 metric
tons/yr, 3,000 metric tons/yr, and 30.000 metric tons/yr, respectively.
Stockpiled Miscellaneous Plant Waste
This waste stream consists of a mixture of consolidated refractory brick, slag, matte, sweepings, and other
cleanup wastes. The November 1984 PEI Associates study contains results of EP toxicity tests on one sample of this
materials, which includes refractory brick, slag, matte, "cleanups," and plant "sweepings." The sample exhibited the
characteristic of EP toxicity for lead (1,380 mg/L) and cadmium (29.4 mg/L). (PEIA, 1984, pp. 5-16, 5-17) The
plant from which the sample was obtained was not identified. Although EPA found no published information
regarding waste generation rate, we used the methodology outlined in Appendix A of this report to estimate a low,
medium, and high annual waste generation rate of 400 metric tons/yr, 88,000 metric tons/yr, and 180,000 metric
tons/yr, respectively. We used best engineering judgment to determine that this waste may be partially recycled and
was formerly classified as a spent material.
D. Non-uniquely Associated Wastes
Non-uniquely associated wastes may be generated at on-site laboratories, and may include used chemicals
and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), acidic tank
cleaning wastes, and polyehlorinated biphenyls from electrical transformers and capacitors. Non-hazardous wastes
may include tires from trucks and large machinery, sanitary sewage, and waste oil and other lubricants. (U.S. EPA,
1993b, p. 110)
391
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The Asarco facilities in East Helena, MT, Glover, MO, and Omaha, NE each generate less than 100 kg of
solvents per month. These facilities hold RCRA identification numbers and are classified as conditionally exempt
small quantity generators. At the Glover and Omaha facilities, used solvents are collected by Safety-Kleen for
disposal. (ASARCO, 1989a-c) The Doe Run facility in Herculaneum, MO also holds a RCRA I.D. number, but no
information was available on the types of hazardous wastes that are generated. (Doe Run, 1989b)
E. Summary of Comments Received by EPA
New Factual Information
Two commenters indicated that the three operating primary lead smelters (Asarco in Glover, MO; Asarco in
East Helena, MT; and Doe Run in Herculaneum, MO) no longer use surface impoundments and completely recycle
all wastewater treatment solids (COMM 58, 1019). This new information was used to update the Surface
Impoundment Waste Solids section in the discussion of mineral processing wastes. One commenter mentioned that
baghouse dust accumulates in cellars beneath the baghouse and is removed every two to four weeks (COMM 1034).
This new information has been included in the Baghouse Dust section.
Sector-specific Issues
One commenter stated that certain operations downstream of sintering should be considered beneficiation,
not processing (COMM 36). EPA disagrees with this conclusion because it maintains that smelting is a processing
operation, while sintering (or other defined beneficiation operation preceding smelting) is a beneficiation activity.
Another commenter indicated that it no longer uses surface impoundments and completely recycles wastewater
treatment solids (COMM 58). Thus, the commenter believed that these wastes should not be considered as solid and
hazardous wastes. EPA agrees that wastewater treatment solids may not be considered hazardous wastes if they are
not stored on land and are reclaimed for their metal, acid, water, or cyanide values. The Agency has removed the
WWTP sludges/solids waste stream from the RIA.
392
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Doe Run Company, 1989b. National Survey of Solid Wastes from Mineral Processing. Doe Run Company
Smelting Division, Herculaneum, MO.
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Plant Wastes with Less than 2% Zinc Plus Lead," from Ironmaking Conference Proceedings. Vol.
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113-127.
Gritton, K.S. et al., 1990. "Metal Recovery from Copper Processing Wastes," (Abstract Only) from Second
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Incorporated. August 31.
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Wiley & Sons.
Khaidurov, V.P., et al., 1991. "The Production of Ferrite Complex Fluxes (FCF) at Novolipetsk Iron and
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Lenchev, A,, 1991. "Recovery of Heavy Non-Ferrous Metals and Silver by a Two-Step Roasting Process."
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396
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ATTACHMENT 1
397
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1X5
00
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfide
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
0.043
0.005
0.029
0.001
0.0003
-
0.002
0.001
0.006
0.009
0.035
0.002
0.008
0.010
0.0001
0.020
0.002
0.004
0.001
0,220
0.001
0.010
25.00
270.00
0.010
5.00
1.31
2.22
4.56
3.75
2.97
765.04
0.18
0.01
-
8.76
0.13
0.49
30.20
26.51
1,820.30
17.91
4.97
12.86
1.07
0.55
0.23
0.16
1.04
0.11
99.61
136.33
1,785.88
6.34
1,158.09
10,325.34
8.41
16.47
17.90
21.90
3,800.00
0.50
0.05
-
31.30
0.50
2.10
250
77.80
21000
61.30
33.60
90.00
4.62
1.90
1.66
0.50
2.50
0.50
690.00
207.00
5300
19.00
7000
73700
13.30
39.20
f Detects
8/8
9/9
9/9
7/7
6/6
0/0
13/13
7/7
9/9
10/10
9/9
13/13
9/9
8/8
7/7
6/6
9/9
9/9
9/9
7/7
9/9
11/11
3/3
8/8
3/3
9/9
8/8
17/17
5/5
EP Toxiclty Analysis -
Minimum Average
0.050
0.050
0.002
0.050
0.005
-
0.001
0.001
0.050
0.138
0.050
0.220
0.500
0.030
0.0001
0.050
0.050
0.001
0.005
0.250
0.050
0.500
4.85
7.82
530.41
0.25
0.03
2.78
0.19
0.28
0.72
1.38
15.54
22.43
0.93
0.0032
1.66
0.28
0.94
0.19
1.47
0.28
20.18
PPM
Maximum
18.80
30.20
3,160.00
0.50
0.05
-
8.96
0.50
0.50
1.75
5.69
84.00
54.00
2.86
0.0180
4.67
0.50
4.96
0.50
2.50
0.50
83.20
f Detects
4/4
4/4
6/6
5/5
4/4
0/0
6/6
6/6
4/4
4/4
5/5
6/6
4/4
5/5
6/6
4/4
4/4
6/6
6/6
4/4
4/4
5/5
TC # Values
Level In Excess
-
-
5.0 2
100.0 0
-
-
1.0 2
5.0 0
-
-
-
5.0 2
-
-
0.2 0
-
-
1.0 1
5.0 0
-
-
-
-
-
-
-
-
212 3
-
Non~detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - ACID PLANT SLOWDOWN - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
_ead
Vlagnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
0.05
0.05
0.05
0.05
0.0005
-
0.41
0.00
0.05
0.01
0.63
1.63
2.90
0.53
0.0010
0.05
0.05
0.05
0.01
0.25
0.00
0.32
536
57
3
21.30
0.62
8.81
1.82
29.57
785.14
0.14
0.02
-
77.21
0.20
0.55
2.85
29.19
115.30
23.92
1.71
1.23
0.22
0.61
1.91
0.18
47.77
0.21
47.43
1,126.83
364.50
1,250.56
7,965.06
3.91
125.90
7.68
148
2370
0.50
0.05
-
362.00
0.50
2.32
17.80
94.80
674.00
78.20
3.81
4.80
0.50
2.81
5.59
0.50
142.00
0.50
160
3150
672
4300
24730
9.04
350.00
# Detects
5/6
6/6
6/6
6/6
5/5
0/0
7/7
5/5
6/6
7/7
6/6
7/7
6/6
6/6
5/5
3/3
6/6
3/3
5/5
3/3
5/5
7/7
6/6
2/2
9/9
8/8
7/7
3/3
EP Toxicity Analysis -
Minimum Average
0.05
0.05
0.05
0.05
0.005
-
3.67
0.05
0.05
0.05
0.50
1.79
7.94
0.78
0.0001
0.05
0.05
0.05
0.05
0.25
0.05
0.29
0.58
30.72
840.18
0.35
0.035
-
126.78
0.35
0.35
0.35
14.21
4.14
25.88
0.99
0.0001
0.35
0.35
1.36
0.35
36.58
0.35
59.50
PPM
Maximum
1.18
91.60
2,520.00
0.50
0.050
-
368.00
0.50
0.50
0.50
39.20
7.29
54.00
1.17
0.0002
0.50
0.50
3.54
0.50
107.00
0.50
113.00
# Detects
3/3
3/3
3/3
3/3
3/3
0/0
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
3/3
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
-
1.0 3
5.0 0
-
-
-
5.0 1
-
-
0.2 0
-
-
1.0 1
5.0 0
-
-
-
-
-
-
-
212 2
-
(JU
ID
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
O
o
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - MISCELLANEOUS SOLIDS - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
O/o
0/0
0/0
10,000 10,000 10,000 1/1
100,000 100,000 100,000 1/1
500,000 500,000 500,000 1/1
0/0
0/0
0/0
0/0
0/0
O/o
0/0
0/0
o/o
50,000 50,000 50,000 1/1
0/0
o/o
- 0/0
0/0
o/o
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100,0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTi SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Selenium
Stiver
Thallium
Vanadium
Znc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum f Detects
0/0
0/0
18.00 18.00 18.00 1/1
0/0
0/0
0/0
0.05 5.53 20.70 4/4
070
- " 0/0
0.01 0.23 0.50 4/4
0.25 0.52 1.00 3/3
0.95 2.28 3.18 4/4
18.00 18.00 18.00 1/1
3.00 3.00 3.00 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
2.00 15.10 43.20 4/4
0/0
o/o
0/0
0/0
7.00 7.60 8.00 3/3
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
, - 0/0
0/0
0/0
0/0
0/0
0/0
070
0/0
0/0
0/0
0/0
0/0
0/0
070
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
.
1.0 0
5.0 0
-
.
.
5.0 0
-
.
0.2 0
-
-
1.0 0
5.0 0
-
-
-
.
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
-Pi
o
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE/SOLIDS - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Znc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
19.00 19.00 19.00 1/1
0/0
0/0
2,500 2,500 2,500 2/2
0/0
1,290 27,430 59,000 3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
68 64,689 98,000 3/3
0/0
0/0
0/0
0/0
0.00 7.55 13.00 5/5
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
212 1
'
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - LEAD
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
vlinimum Average Maximum # Detects
0/0
0/0
0/0
0/0
o/o
0/0
0.08 0.08 0.08 1/1
0/0
0/0
0/0
0/0
15.00 17.50 20.00 2/2
0/0
0/0
0/0
0/0
0/0
0/0
o/o
0/0
0/0
35.00 35.00 35.00 1/1
0/0
0/0
0/0
0/0
7.00 9.08 13.00 4/4
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
o/o
0/0
0/0
0/0
0/0
0/0
0/0
o/o
- 0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
.
.
.
-
-
-
212 1
-
o
UJ
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - LEAD
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Sulfate
Fluoride
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
640.00 670.00 700.00 212
28.00 44.00 60.00 212
0/0
0/0
0/0
115000 127500 140000 212
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
80000 106000 132000 2/2
0/0
0/0
0/0
0/0
4.80 6.29 11.20 6/6
O/o
EP Toxicity Analysis -
Minimum Average
-
-
0.00
0.15
-
-
0.01
0.00
-
-
0.05
0.22
-
0.03
0.0001
-
-
0.001
0.015
0.02
-
0.02
-
-
46.95
1.08
-
-
54.34
0.02
'
-
30.25
188.01
-
513.63
1.1313
-
-
0.077
0.018
0.02
-
65.66
PPM
Maximum
-
-
304.00
2.60
-
-
155.00
0.07
-
-
178.00
959.00
-
3,560.00
7.9000
-
-
0.420
0.030
0.02
-
184.00
# Detects
0/0
0/0
7/7
6/6
0/0
0/0
7/7
3/7
0/0
0/0
6/6
7/7
0/0
7/7
7/7
0/0
0/0
7/7
5/5
1/1
0/0
7/7
TC # Values
Level In Excess
.
-
5.0 2
100.0 0
-
1.0 6
5.0 0
-
-
-
5.0 3
-
-
0.2 1
-
-
1.0 0
5.0 0
.
-
-
.
-
.
.
212 0
.
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Name of Site:
Owner of Site:
Location of Site:
Climate Data:
Commodity Mined:
Facility History:
Waste(s) at Issue:
ATTACHMENT 2
Mining Sites on the National Priority List
Bunker Hill Mining and Metallurgical Complex
Bunker Limited Partnership
Kellogg, Idaho
To be determined
Lead and Zinc
The Bunker Hill Superfund Site is located in the Silver Valley of the South Fork of the
Coeur d'AJene River in Northern Idaho. It is approximately 60 miles east of Spokane,
Washington. The site is 3 miles wide and 7 miles long and bisected by Interstate 90. The
site includes the cities of Wardner, Kellogg, Smelterville, and Pinehurst, with a total
population of 5000. Lead and zinc mining began on the Bunker Hill site with the location
of the Bunker Hill and Sullivan claims in 1885 by Noah Kellogg, The first mill began
operations in 1886 and a larger mill was constructed in 1891. The lead smelter began
operation in 1917. An electrolytic zinc plant, capable of producing 99.99% zinc, began
operation in 1928. An electrolytic antimony plant was constructed in 1939, but it
operated only for a few years. In 1943, a slag fuming plant was constructed to recover
zinc from the blast furnace slag of the lead smelter. A cadmium recovery plant was added
in 1945. A sink-float plant operated from 1941 to 1953. A phosphoric acid plant began
operations in 1961. The plant used sulfuric acid from the zinc plant and phosphate rock
from southern Idaho or Wyoming to produce phosphoric acid and gypsum. Sulfuric acid
plants were added to the zinc facilities in 1954 and 1966. The lead smelting process was
changed in 1970 from a downdraft ore-roasting operation to a Lurgi updraft sintering
process with a sulfuric acid recovery plant. In 1976, a 715-foot stack was added to the
lead smelter, and a 610-foot stack was added to the zinc plant in 1977. In December
1981, the smelter complex was shut down.
The major environmental problems at the Bunker Hill site were caused by smelter
operations and mining and milling. Contaminants of concern are lead, zinc, cadmium,
antimony, arsenic, beryllium, copper, mercury, PCBs, selenium, silver, cobalt, and
asbestos.
During smelter operations (1917-1981) wastes and feed stock were stored onsite. In
addition, the smelter discharged heavy metal particulates and sulphur dioxide gas to the
atmosphere. In order to capture the heavy metal particulates, baghouse filtration systems
were installed at the lead and zinc plants. However, a 1973 fire severely damaged the
baghouses. Two of the seven baghouses were destroyed and the remaining five were shut
down for 6 months to be repaired. During this time, 20 to over 100 tons/month of
particulates containing 50 to 70 percent lead were emitted from the stacks (compared to
the normal 10 to 20 tons/month).
Originally, all liquid and solid residues from the milling operations were discharged
directly into the South Fork of the Coeur d'Alene River and its tributaries. Periodic
floods deposited contaminated wastes onto the valley floor. In the 1920's, mill tailings
were discharged to a small impoundment, and lead smelter slag was placed in what
became the slag pile. In 1928, the first impoundment at the Central Impoundment Area
(CIA) began operation. After 1961, me coarse fraction of mill tailings were used as sand
405
-------
Disposal Site:
Soil Pathway:
Ground Water
Pathway:
backfill in the Bunker Hill Mine. The CIA also received mine drainage beginning in
1965, gypsum from the phosphoric acid and fertilizer plant after 1970. and wastes from
the zinc plant and smelter after 1974. Decant from the CIA was discharged directly into
the river until 1974, when the Central Treatment Plant began operation. After 1974,
decant gypsum discharge was returned to the phosphate plant.
The Bunker Hill Mining Complex includes the Bunker Hill Mine (lead and zinc), a
milling and concentrating operation, a lead smelter, a silver refinery, an electrolytic zinc
plant, a phosphoric acid and phosphate fertilizer plant, sulfuric acid plants, and a
cadmium plant. Also included within the site boundary are the Page Mine (inactive), the
Page tailings disposal area known as the "Page Ponds" (currently the site of Silver Valley
water treatment facility), and numerous old mines, mill sites, and prospects.
Residual soil contamination with metals is a major concern at this site. During smelter
operation, metal-laden particulates were discharged from the smelter. In 1974 the top 0.5
inch of hillside soil had lead concentrations ranging from 1,000 to 24,000 ppm and
cadmium concentrations ranging from 50 to 236 ppm. On undisturbed areas, most of the
metals were found in the top 3 inches, while in severely eroded areas, airborne
contamination penetrated at least the top 10 inches. Soil near the smelting complex has
also been severely impacted by metals deposition. Around the smelter complex,
extremely high concentrations of lead (1,000 to 40,000 ppm) and cadmium (80 to 240
ppm) were detected. The upper 10 to 20 feet of soils on the valley floor were combined
with mine and mill tailings generated by the mineral processing industry in the early part
of the 20th century. These early milling practices resulted in the deposition of metals-rich
tailings in low-lying areas. Lead and cadmium levels in the valley area are similar to
those in the hillside soils. The Smelterville Flats encompass an area of approximately 2
square miles northwest of the City of Smelterville, where significant amounts of
unconfined tailings have accumulated over time. Surface metal concentrations ranged
from 6,000 to 25,000 ppm lead and 30 to 70 ppm cadmium. The Page Ponds and the CIA
cover 240 acres-and contain several million cubic yards of tailings. These areas are
located close to major residential areas and have lead concentrations ranging from 2,000
to 20,000 ppm (1974 and 1977 studies). In 1986 and 1987, a soil survey was conducted
in the communities of Smelterville, Kellogg, Wardner, and Page. Samples of the top 1
inch of mineral soil and litter were analyzed from 1,020 of 1547 homes (64%). Five
percent of all homes sampled had lead levels below 500 ppm; 11 percent had lead levels
between 500 and 1,000 ppm; and 84 percent had lead levels above 1,000 ppm.
Primary sources of ground water contamination include: seepage from the CIA
(estimated to be 1 ftVsec), infiltration and ground water flow through valley-wide deposits
of tailings, and ground water inflow upgradient of the site. Other sources of ground water
contamination include discharges from Magnet Gulch, Pine Creek, and Milo Gulch;
infiltration of incident precipitation through the CIA; and seepage from Sweeney Pond,
McKinley Pond, and other surface impoundments. Contaminants of primary concern
include: arsenic, cadmium, lead, cobalt, and zinc. Maximum zinc and cadmium levels
have been detected in wells adjacent to the CIA at 50 and 0.1 mg/L, respectively (1974).
These values appear to have reflected partly diluted direct seepage from the CIA. While
studies have been done to evaluate the seepage and metal transport to ground water from
the CIA, they have not specifically targeted the extent and degree of ground water
contamination, and thus, have not determined the spread of contaminants into, the
confined lower aquifer. Ground water in the Smelterville Flats area contain high levels of
heavy metals, but the concentrations generally decrease with depth and linear distance
from the South Fork. The ground water appears to be in hydraulic connection with
surface ponds in the flats. In 1979, it was estimated that the flats discharge about 5.3
kg/day of zinc to the ground water. The Page Ponds discharged 8 kg/day of zinc to the
ground water in 1975. The pones have subsequently been converted for sewage
406
-------
Surface Water
Pathway:
Air Pathway:
Environmental Issues:
treatment. Information on the potential of heavy-metal contamination of ground water
from these ponds remains unavailable.
The Bunker Hill site is situated in the Coeur d'Alene River basin. The main
surface water features at the Bunker Hill Complex include: the Coeur d'Alene River, the
CIA, which includes the central impoundment pond, the gypsum pond, and the slag pile.
Other smaller impoundments areas are located near the lead and zinc smelter, including
Sweeney Pond and the main reservoir in the lead smelter complex, and the main reservoir
and settling ponds in the zinc plant area. Major streams on the complex include
Government Creek, Bunker Creek, and Mile Creek. The streams in the vicinity of past
mining activities at this site have received a heavy sediment load of mine and mill
tailings. The South Fork of the Coeur d'Alene River has been receiving mine and mill
wastes for approximately 90 years. Even though the site was closed in 1981, discharges
to the South Fork still continue; including, for example, those from the operating
wastewater treatment plant. As of 1984, concentrations of several contaminants were still
significant in the South Fork: cadmium (28.6 ^g/L), iron (.1,146 /ug/L), manganese (1,507
/jg/L), and zinc (3,270 ,ug/L).
Lead, cadmium, zinc, mercury, and arsenic emissions from the lead smelter main stack
were calculated for the period of 1965 to 1981. In excess of 6 million Ibs of lead;
560,000 Ibs of cadmium; 860,000 Ibs of zinc; 29,000 Ibs of mercury; and 70,000 Ibs of
arsenic were emitted during this period. These figures do not include vent or fugitive
emissions, which were believed to total more than stack emissions. Since smelter closure,
ambient lead levels and total suspended particulates have generally been within primary
National Ambient Air Quality Standards (NAAQS). Ambient lead levels have ranged
from 0.1 to 0.5 /j-g/m3 (on a quarterly basis) and ambient levels of total suspended
particulates have ranged from 30 to 70 ym/m3 (on an annual basis) with daily values
ranging to 900 /.
-------
Page Intentionally Blank
408
-------
LIGHTWEIGHT AGGREGATE
A. Commodity Summary
Lightweight aggregates are minerals, natural rock materials, rock-like products, and byproducts of
manufacturing processes that are used as bulk fillers in lightweight structural concrete, concrete building blocks,
precast structural units, road surfacing materials, plaster aggregates, and insulating fill. Lightweight aggregates are
also used in architectural wall covers, suspended ceilings, soil conditioners, and other agricultural uses. Lightweight
aggregates may be classified into four groups:
• Natural lightweight aggregate materials which are prepared by crushing and sizing natural rock
materials, such as pumice, scoria, tuff, breccia, and volcanic cinders.
* Manufactured structural lightweight aggregates which are prepared by pyroprocessing shale, clay,
or slate in rotary kilns or on traveling grate sintering machines,
• Manufactured insulating ultralightweight aggregates which are prepared by pyroprocessing
ground vermiculite, perlite, and diatomite.
• Byproduct lightweight aggregates which are prepared by crushing and sizing foamed and
granulated slag, cinders, and coke breeze.
The first three groups of lightweight aggregates are produced from naturally occurring materials, while the fourth is
produced as a byproduct of iron and steel production. Lightweight aggregates are distinguished from other mineral
aggregate materials by their lighter unit weights. Exhibit 1 presents the names and locations of facilities involved in
the production of lightweight aggregates from naturally occurring raw materials. Exhibit 2 presents the names of
facilities involved in the production of lightweight aggregates from iron and steel slags.
B. Generalized Process Description
Lightweight aggregate materials are produced mainly by two methods. The first method of lightweight
aggregate production is from naturally occurring raw materials. The second method is byproduct production from
iron and steel production. These processes are quite different and are described separately below. Section 1
describes lightweight aggregate production from naturally occurring raw materials. Section 2 describes byproduct
lightweight aggregate production.
SECTION 1: Production From Naturally Occurring Raw Materials
1. Discussion of Typical Production Processes
While natural lightweight aggregates are prepared through basic operations including steps such as mining.
grinding, and sizing, manufactured lightweight aggregate and manufactured ultralightweight aggregate products are
produced by heating certain types of clay, shale, slate, and other materials in a rotary kiln which forces the materials
to expand or "bloat;" resulting in a porous product. The product will retain its physical strength despite its lighter
unit weight when cooled.1 The process is described in more detail below.
1 Bruce Mason, "Lightweight Aggregates," from Industrial Minerals and Rocks, 6th ed., Society for Mining,
Metallurgy, and Exploration, 1994, pp. 343-350.
409
-------
EXHIBIT 1
FACILITIES PRODUCING LIGHTWEIGHT AGGREGATES FROM NATURALLY OCCURRING RAW MATERIALS
Facility Name
Arkansas Lightweight Aggregate
Big River
Big River
Buildex
Buildex
Buildex
Chandler Materials Co.
Chandler Materials Co.
Dakota Block Co.
Featherlite
HP Brick Co.
HP Brick Co.
Jackson Concrete
Kanta
Lehigh Portland Cement Co.
Lorusso Corp.
Norlite
Parkwood Lightweight Plant
Porta Costa
Ridgelite
Solite
Solite
Northeast Solite
Carolina Solite
Kentucky Solite
Florida Solite
Strawn
Texas Industries
Utelite
Weblite
Location
West Memphis, AR
Livingstone, AL
Erwinville, LA
Dearborn, MO
Ottawa, KS
Marquette, KS
Tulsa, OK
Choctaw, OK
Rapid City, SD
Strawn (Ranger), TX
Brooklyn, IN
Independence, OH
Jackson, MS
Three Forks, MT
Woodsboro, MD
Plainville, MA
Cohoes, NY
Bessemer, AL
Porta Costa, CA
Frazier Park, CA
Cascade, VA
Arvonia, VA
Mount Marion, NY
Norwood, NC
Brooks, KY
Green Cove Springs, FL
Strawn, TX
Streetman, TX
Coalville, UT
Blue Ridge, VA
Source: Determination of Waste Volume for Twenty Conditionally Retained Bevill Mineral Processing Wastes. 1990, pp. 5-9, A10.
Facilities that burn hazardous waste fuels are shaded.
410
-------
EXHIBIT 2
BYPRODUCT LIGHTWEIGHT AGGREGATE PRODUCERS
Facilities
Waylite Corporation
Standard LaFarge Corporation
Edward C. Levy Company
Koch Minerals
Location
Bethlehem, PA
Cleveland, OH
Detroit, MI
Gary, IN
2. Generalized Process Flow Diagram
Naturally occurring lightweight aggregate raw materials, such as pumice and volcanic cinders, are normally
mined by open pit or quarry methods, depending on the degree of consolidation of the raw materials. Shale, clay,
and slate mined by open pit and quarry methods are dried in large sheds or open stockpiles to control water content
in the raw feed prior to high temperature pyroprocessing in either rotary kilns or sintering machines. The resulting
clinker may then be crushed before screening to yield proper gradation mixes for final use. Most lightweight
aggregate plants use coal as a primary source of fuel. Waste-derived fuels and solvents from various industrial
processes are also used as alternate fuel sources at a few locations (e.g., those operated by Solite and Norlite).
Exhibit 3 presents a typical process flow diagram for lightweight aggregate production for facilities using a wet
scrubber air pollution control technology or a dry collection method. All facilities currently use dry collection
systems.
3. Identification of Novel (or otherwise distinct) Processes
None identified.
4. Beneflciation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities.
411
-------
EXHIBIT 3
LIGHTWEIGHT AGGREGATE PROCESS FLOW DIAGRAM
Raw Materials (Clay, Shale, and/or Slate)
Landfill
t
I
Mining
Dry
Collection ^
1
Surface is
Impoundment ™ Dj
Solids
Drying
.. 1
Kiln or Sinter
Offcrases Machine
Clinker
PDES Screening
scharge & Sizing
1
Lightweight Aggrega
Product Storage
^, Tr>™rpr""fit1<">n in1r>
Fuel
(Coal, Waste
Derived Fuel)
End Product
412
-------
EPA determined that for the production of lightweight aggregates from naturally ocurring raw materials, the
beneficiation/proeessing line occurs after drying at the kiln/sinter machine because the elevated temperatures destroy
the physical structure of the raw material. Therefore, because EPA has determined that all operations following the
initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents below the mineral processing waste streams generated after the
beneficiation/proeessing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
SECTION 2: By-product Production
1. Discussion of Typical Production Processes
Both expanded slag and air-cooled slag are lightweight aggregate products produced as by-products from
iron and steel production. The process is described below.
2. Generalized Process Flow Diagram
Expanded slag and air-cooled slag are byproducts of iron and steel production. Expanded slag is
manufactured by spraying a stream of water through molten blast furnace slag as it is drawn from the furnace. The
resulting foamed slag is crushed and screened for use in concrete block or structural concrete. Air-cooled slag is
manufactured by pouring molten blast furnace slag into pits where it is cooled by water. It is then excavated,
crushed, and screened.2 Iron and steel slags are considered special wastes, and were addressed in the 1990 Report to
Congress on Special Wastes from Mineral Processing. Exhibits 4 and 5 present flow diagrams for expanded slag and
air-cooled slag, respectively.
3, Identification of Novel (or otherwise distinct) Processes
None identified.
4. Extraction/Beneficiation Boundaries
Because lightweight aggregates are recovered as by-products of mineral processing activities in the iron and
steel sector, all of the wastes generated during lightweight aggregate recovery also are mineral processing wastes.
For a description of where die beneficiation/proeessing boundary occurs for this mineral commodity, see the sector
report for iron and steel presented elsewhere in this document.
C, Process Waste Streams
1. Extraction/Beneficiation Wastes
The preparation of natural lightweight aggregate materials only generates extraction/beneficiation wastes
because no thermal processes are involved. However, production of manufactured lightweight aggregates generates
both extraction/beneficiation and mineral processing wastes. Overburden, waste rock, raw fines from primary
crushing operations, and sludge from rock washing operations are generated from the mining and extraction of
lightweight aggregate minerals. These materials likely are left in place at the original mining site.
: Bruce Mason, 1994, Op. Cit., pp. 343-350.
413
-------
EXHIBIT 4
EXPANDED SLAG PROCESS FLOW DIAGRAM
Ore, Coke, Limestone,
Oxygen, and Flux
Hot Water •
Furnace
1
Blast Furnace Slag
Crushing &
Screening
J
Expanded Slag Product
414
-------
EXHIBIT 5
AIR-COOLED SLAG PROCESS FLOW DIAGRAM
Ore, Coke, Limestone,
Oxygen, and Flux
Furnace
Blast Furnace Slag
Cooling Water
Pits
Crushing &
Screening
Air-Cooled Slag
415
-------
2. Mineral Processing Wastes
Hazardous waste fuels may be burned for use as a heat source in the production of lightweight aggregates.
Therefore, some of the waste streams discussed below would be considered hazardous through application of the
derived-from rule. Likely waste-derived fuels are high in Btu values and oily substances. Waste generated from this
process may contain metals, semivolatiles, and dioxins/furans. Six facilities burn listed hazardous waste as fuel in
their kilns. These facilities are Carolina Solite, Florida Solite, Kentucky Solite, Norlite, and the two Solite facilities
in Virginia.3 However, the Solite facility in Cascade, VA generates no solid waste because all the APC dust that is
generated is returned to the operation and the Florida Solite facility currently is inactive.4
Air pollution control scrubber water and solids. Most facilities now use dry collection systems and no
longer generate this waste. However, two wet scrubbers continue to be operated as kiln air pollution control devices
at Solites' North Carolina Plant.5 Kilns equipped with wet scrubbers generate scrubber wastewater which contained
particles from the kiln. In 1989, 18 of the active facilities used wet scrubbers for air pollution control. Lightweight
aggregate production for these 18 facilities ranged from 23,123 to 907,185 mt/y, and the volume of scrubber solids
generated ranged from 104 to 61,235 mt/y. Generally, the scrubber solids were managed in settling ponds, surface
impoundments, or landfills where dewatering occurred and the particulate matter settled out in the form of sludge.6
In 1989, this waste was generated at a rate of 2,420,000 mt/y.7 Attachment 1 presents waste characterization data for
this waste stream. Exhibit 6 presents facility specific management information as well as generation rates and waste
characteristics for the facilities that do not burn hazardous waste fuels in their kilns.
Because of the derived-from rule, scrubber water and solids are considered a hazardous waste at facilities
that use wet scrubbers and burn hazardous waste fuels in their kilns. Although this waste currently is generated at
only one facility, Exhibit 7 presents waste generation rates for five facilities that, in the past, have generated
hazardous scrubber water and solids.
Air pollution control dust/sludge. Lightweight aggregate facilities that use baghouses and other dry
collection systems generate APC dust that is collected in dry form. Some facilities using dry collection systems
recycle the dust to the process or use it in products (e.g., block mix). At Arkansas Lightweight Aggregate
Corporation, particulate matter that is too fine to continue on in the kilning process is exhausted in the mechanical
dust collector. After filtering, the waste dust drops into conical piles beneath the collector. Three piles collect
beneath the collector, one consisting of heavier particles and two consisting of lighter particles. This waste is
collected by a shovel loader and placed in a waste water impoundment onsite. The wet scrubber at the Arkansas
facility operates for particulate removal only; no chemical treatment of water occurs.8
3 U.S. Environmental Protection Agency, Addendum to the Technical Background Document. Development of
the Cost and Economic Impacts of Implementing the Bevill Mineral Processing Wastes Criteria. Office of Solid
Waste, 1990.
4 Solite Corporation. Op. Cit.
5 Ibid.
6 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
7 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, 1992, Vol. I, pp. 1-2 -1-8.
8 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
416
-------
EXHIBIT 6
APC SCRUBBERWATER AND SOLIDS AT FACILITIES NOT USING WASTE-DERIVED FUELS
Facility
Buildex, Dearborn, MO
Chandler Materials, Tulsa, OK
Chandler, Choctaw, OK
Featherlite, Strawn, TX
HP Brick, Brooklyn, IN
Texas Industries, Streetman, TX
Porta Costa, Porta Costa, CA
Parkwood, Bessemer, AL
Jackson Ready Mix Concrete,
Jackson, MS
Big River, Livingston, AL
Big River, Erwinville, LA
Arkansas Lightweight Aggregate,
West Memphis, AR
NE Solite, Mt. Marion, NY
RTI
ID#
100685
101725
101766
101659
100263
101808
100792
100180
100438
NA
NA
NA
NA
1988 Generation
Wastewater:
8,784,000 gallons
Wastewater:
17,900,000 gallons
Solids:
1 77 cubic yards
Wastewater:
14, 100,000 gallons
Wastewater:
4,535 mtons
Wastewater:
9,07 1 mtons
Wastewater:
250,000,000 gallons
Wastewater:
600 gallons
Wastewater:
8,981 mtons
Wastewater:
104 mtons
NA
NA
NA
NA
pH
5.8
5.5
5.6
NA
5.5
9.94
7.2
NA
NA
NA
NA
NA
NA
Management Practices
Sent to bedrock lined
surface impoundment for
settling
Sent to bedrock lined
surface impoundment for
solids precipitation
Sent to in-situ clay lined
surface impoundment for
solids precipitation
Sent to in-situ clay lined
surface impoundment for
solids precipitation
Sent to in-situ shale lined
surface impoundment for
dewatering
Sent to in-situ clay lined
surface impoundment for
solids precipitation
Sent to in-situ clay lined
surface impoundment for
water evaporation and
solids recycling
Sent to bedrock lined
surface impoundment for
solids precipitation and pH
adjustment with caustic
soda
Sent to recompacted local
clay lined surface
impoundment for solids
precipitation
NA
NA
NA
NA
SOURCE: 1988 RTI Surveys.
417
-------
EXHIBIT 7
1988 APC SCRUBBERWATER AND SOLIDS AT FACILITIES USING WASTE-DERIVED FUELS
Facility
Carolina Solite
Florida Solite
Kentucky Solite
Norlite
Solite
Location
Norwood, NC
Green Cove, FL
Brooks, KY
Cohoes, NY
Arvonia, VA
APC
Scrubberwater
and Solids (mt/y)
61,235
31,248
43,293
NA
NA
Percent
Solids
6.63
6.53
19.28
NA
NA
APC
Dust/Sludge
(mt/y)
4,060
2,040
8,347
NA
NA
Source: Results of EPA's Final Analysis (Exhibit 4). Lightweight Aggregate Production and Air Pollution Control Wastes. Technical
Background Document Supporting the Supplemental Proposed Rule Applying Phase IV Land Disposal Restrictions to Newly Identified
Mineral Processing Wastes. EPA, Office of Solid Wasts. December 1995.
At Solite's facilities that burn hazardous wastes, the lightweight aggregate APC dust/sludge (baghouse dust)
is collected in baghouses and conveyed to the finish end of Solite's lightweight aggregate plants where it is added to
crushed and sized clinker. In some cases, it is returned to the beginning of the manufacturing process and reinserted
into the kiln in extruded form, but the more usual practice is to incorporate the baghouse dust directly into a product
referred to as "block mix."
Block mix is comprised of lightweight aggregate ranging in size from 3/16 of an inch in diameter to very
fine material. The very fine material typically comprises no more than 12 to 16 percent of the block mix, and the
percentage of bag house dust in the very fine material varies. Usually, about 75 percent of Solite's total lightweight
aggregate output consists of block mix. However, this percentage can vary from plant to plant and in response to
customer demand. The fine material is a necessary component of block mix, and if it is not introduced in the form of
baghouse dust it must be produced by crushing the kiln clinker.
The finished block mix product is usually stored in an on-site pile prior to sale. It is kept damp during
storage and transportation to control fugitive dust emissions and because substantial moisture is needed to mix the
block mix with cement and other ingredients to make concrete. Block mix is transported by truck or rail car to
concrete block manufacturing plants where it is used as a primary ingredient in the manufacture of lightweight
concrete masonry units. The block mix confirms to ASTM Standard Number C 331 and individual customer
specifications.
Although Solite is not currently selling LAKD as a separate product, the company believes that LAKD
could be marketed as a mineral filler for asphalt and/or an ingredient in some concrete products. It may be necessary
to pursue this market if the demand for block mix is insufficient to absorb all of the baghouse dust.9
This waste would be considered a hazardous waste at facilities that burn hazardous waste fuels because of
the derived-from rule. These facilities are identified in Exhibit 1. The Solite facility in Cascade, VA does not
generate this waste because all APC dust is returned to the process at this facility. Exhibit 7 presents waste
generation rates for the remaining five facilities.
9 Solite Corporation. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
418
-------
Wastewater treatment plant (WWTP) liquid effluent. Attachment 1 presents waste characterization data
for this waste stream. In 1991, the waste generation rate for this waste stream was 1,094,000 metric tons per year.10
At the Carolina Solite facility in Norwood, NC, WWTP liquid effluent is discharged under an NPDES permit." This
waste is not expected to be hazardous.
Surface impoundment waste liquids. Attachment 1 presents characterization data for this waste stream.
The generation rate for this waste stream is 2,571,00 metric tons per year12 (adjusted from a reported value to reflect
recent changes in the sector). This waste is discharged under an NPDES permit at the Carolina Solite in Norwood,
NC and the Norlite Corporation in Cohoes, NY.13 This waste is not expected to be hazardous.
Byproduct Production
Waste streams from byproduct production of lightweight aggregate products from iron and steel production
include cooling water and slag. These wastes are not expected to be hazardous.
D. Non-uniquely Associated Wastes
Non-uniquely associated wastes and ancillary hazardous wastes may be generated at on-site laboratories,
and may include used chemicals and liquid samples. Other hazardous wastes may include spent solvents (e.g.,
petroleum naptha), and acidic tank cleaning wastes. Non-hazardous wastes may include tires from trucks and large
machinery, sanitary sewage, waste oil (which may or may not be hazardous) and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
One commenter addressed the lightweight aggregates sector report and provided new information about its
facilities that burn hazardous waste. This information has been included in the sector report, as appropriate.
Sector-specific Issues
None.
10 U.S. Environmental Protection Agency, 1990, Op. Cit. pp. 5-9, A10.
11 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, 1992, Vol. II, pp. 22-1 - 22-19.
12 U.S. Environmental Protection Agency, 1990, Op. Cit. pp. 5-9, A10.
13 U.S. Environmental Protection Agency, 1992, Op. Cit. Vol. II, pp. 22-1 - 22-19.
419
-------
BIBLIOGRAPHY
Mason, Bruce H., "Lightweight Aggregates." From Industrial Minerals and Rocks. 6th ed. Society for Mining,
Metallurgy, and Exploration. 1994. pp. 343-350.
U.S. Environmental Protection Agency. Lightweight Aggregate Production and Air Pollution Control Wastes.
Technical Background Document Supporting the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes. Office of Solid Waste, December
1995.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. Volume I. August 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set. Vol.
II. Office of Solid Waste. August 1992. pp. 22-1 - 22-19.
U.S. Environmental Protection Agency. Addendum to the Technical Background Document. Development of the
Cost and Economic Impacts of Implementing the Bevill Mineral Processing Wastes Criteria, Office of Solid
Waste. 1990.
U.S. Environmental Protection Agency, Mining Industry Profile. Lightweight Aggregate. Office of Solid Waste,
November 9,1990, pp. 31-33.
U.S. Environmental Protection Agency. Determination of Waste Volume for Twenty Conditionally Retained Bevill
Mineral Processing Wastes. Office of Solid Waste. 1990. pp. 5-9, A10.
U.S. Environmental Protection Agency. Mineral Processing Wastes Sampling Survey Trip Reports. Arkansas
Lightweight Aggregate Corporation, West Memphis, AR. August 1989.
420
-------
ATTACHMENT 1
421
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - APC SCRUBBER WATER AND SOLIDS - LIGHTWEIGHT AGGREGATE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
11.50
0,030
0.0040
0.21
0.0050
-
0.025
0.0025
0.25
0.025
1.16
0.013
90.60
13.50
0.0017
0.250
0.050
0.001
0.01
0.074
0,050
0.23
-
-
653
-
-
-
23.70
1,650
5.50
-
171
0.14
0.28
1.92
0.016
-
0.39
0.44
0.31
0.21
145
0,13
212
30.20
0.0018
0.250
0.30
0.092
0.090
0.52
0.31
1.33
-
-
653
-
-
-
25.35
4,525
5.50
-
330
0.25
0,81
3.62
0.025
-
1.08
1.08
0.36
0.34
289
0.35
334
46.90
0.0020
0.250
0.53
0.25
0.25
1.25
0,56
2,51
-
-
653
-
-
-
27.00
7,400
5.50
-
Detects
2/2
0/3
2/3
2/2
1/3
0/0
2/3
1/3
1/2
1/3
2/2
3/3
2/2
2/2
2/3
0/1
3/3
0/3
1/3
1/3
2/2
3/3
0/0
0/0
1/1
0/0
0/0
0/0
2/2
2/2
1/1
0/0
EP Toxicity Analysis -
Minimum Average
18.90
0.050
0.050
0.21
0.0050
-
0.0050
0.050
0.050
0.050
2.07
0.025
21.60
4.55
0.00010
0.050
0.050
0.050
0.050
0.25
0.050
0.34
-
-
-
-
-
-
-
-
18.90
0.050
0.050
0.21
0.0050
0.0050
0.050
0.050
0.050
2.07
0.025
21,60
4.55
0.00010
0.050
0.050
0.050
0.050
0.25
0.050
0.34
PPM
Maximum
18.90
0.050
0.050
0.21
0.0050
-
0.0050
0.050
0.050
0.050
2.07
0.025
21.60
4.55
0.00010
0.050
0.050
0.050
0.050
0.25
0.050
0.34
-
-
-
-
-
,
.
-
# Detects
1/1
0/1
0/1
1/1
0/1
0/0
0/1
0/1
0/1
0/1
1/1
0/1
1/1
1/1
0/1
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
.
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - AIR POLLUTION CONTROL DUST/SLUDGE - LIGHTWEIGHT AGGREGATE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum i
16,900
0.70
17.00
193
0.81
-
9.40
9.90
-
29.70
28,200
8.91
10,900
611
0.40
-
14.70
0.49
1.70
0.55
31.00
9.90
0.105
-
-
-
-
-
-
710,000
-
-
20,050
0.75
26.50
470
1.26
-
9.40
74.95
-
84.85
34,050
274
11,550
816
0.67
-
26.85
2.85
1.70
5.08
41.50
240
0.15
-
-
-
-
-
-
767,667
-
-
23,200
0.79
36.00
746
1.70
-
9.40
140
-
140
39,900
539
12,200
1,020
0.93
-
39.00
5.20
1.70
9.60
52.00
470
0.19
-
-
- '
-
-
-
830,000
-
-
Detects
2/2
1/2
2/2
2/2
2/2
0/0
1/1
2/2
0/0
2/2
2/2
2/2
2/2
2/2
2/2
0/0
2/2
2/2
1/1
1/2
2/2
2/2
0/2
0/0
0/0
0/0
0/0
0/0
0/0
3/3
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum #
-
.
0.00050 0.038 0.25
0.10 1.12 8.10
-
-
0.0025 0.18 0.78
0.0050 0.071 0.12
.
.
.
0.05 0.46 2.55
-
-
0.00020 0.0012 0.0050
-
.
0.00050 0.031 0.15
0.0050 0.029 0.25
.
.
.
0.50 0.50 0.50
0.50 4.75 9.00
-
,
.
.
.
550,000 673,440 756,400
Detects
0/0
0/0
8/13
7/13
0/0
0/0
9/13
3/13
0/0
0/0
0/0
7/13
0/0
0/0
3/12
0/0
0/0
6/13
1/13
0/0
0/0
0/0
0/2
1/2
0/0
0/0
0/0
0/0
0/0
5/5
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
.
-
-
-
-
,
-
212 0
-
NJ
OO
Non-detects were assumed to be present,at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
NJ
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - LIGHTWEIGHT AGGREGATE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
10.00 10.00 10.00 2/2
57.00 57.00 57.00 2/2
0/0
0/0
8.00 - - 0/0
12.00 12.00 12.00 2/2
0/0
0/0
0/0
11.00 11.00 11.00 2/2
0/0
0/0
0.100 0.100 0.100 2/2
0/0
0/0
0.700 0.700 0.700 2/2
0.400 0.400 0.400 2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - LIGHTWEIGHT AGGREGATE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
500 500 500 2/2
0/0
0/0
0/0
100 100 100 2/2
400 400 400 2/2
6 6.00 6.00 2/2
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
426
-------
LITHIUM AND LITHIUM CARBONATE
A. Commodity Summary
Primarily, lithium is produced in the United States by two companies: Cyprus-Foote Mineral Company and
FMC Corp. Cyprus-Foote produces lithium carbonate from its brine deposit in Silver Peak, Nevada and spodumene
concentrate at its mine in Kings Mountain, North Carolina. Cyprus-Foote also produces lithium chemicals and
metals at plants in Virginia and Tennessee, FMC purchased the Lithium Corporation of America assets and mines
and processes spodumene ores at the Bessemer City site.' Exhibit 1 presents the names and locations of all the
facilities involved in the production of lithium and lithium carbonate.
EXHIBIT 1
SUMMARY OF LITHIUM AND LITHIUM CARBONATE FACILITIES
Facility Name
Cyprus-Foote
Cyprus-Foote
Cyprus-Foote
FMC Corp
Location
New Johnsonville, TN
Sunbright, VA
Kings Mountain, NC
Bessemer City, NC
Lithium is found primarily in the mineral spodumene in pegmatites containing mineral assemblages which
are derived from the crystallization of post magnetic fluids or from metasomatic action by residual pegmatitic fluids.2
Lithium compounds are used primarily in ceramics, glass, and primary aluminum production. Lithium is
also used in the manufacture of lubricants and greases as well as in the production of synthetic rubbers.3
Specifically, lithium hydroxide is used in the production of lubricating greases and lithium carbonate is used as an
additive in aluminum refining. Lithium chloride and bromide are used in absorption refrigeration systems and
dehumidification systems.4 The consumption rate of lithium was estimated at 2,300 metric tons in 1994.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Lithium is obtained either from spodumene concentrates or from lithium-containing brines. It is chiefly
produced as lithium carbonate or as hydroxide salts. Each of these processes is described in detail below.
1 Joyce A. Ober, "Lithium," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, U.S. Bureau of
Mines, p. 754.
2 U.S. Environmental Protection Agency, "Lithium," from 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste, 1988, pp. 2-11-2-15.
3 Joyce A. Ober, "Lithium." from Mineral Commodity Summaries. 1995, pp. 98-99.
4 U.S. Environmental Protection Agency, 1988, Op. Cit. p. 2-11.
427
-------
2. Generalized Process Flow Diagram
Spodumene Concentrates
Exhibit 2 presents the process flow diagram for recovery from spodumene concentrates. After mining, the
spodumene is crushed and ground. Following this, the spodumene undergoes a flotation process (e.g., froth
flotation) to yield a spodumene concentrate. This concentrate is then heated to 1,075°C to 1,100°C (changing the
molecular structure of the mineral) to make it more reactive with sulfuric acid.5 Following the roasting and cooling,
the spodumene is treated with sulfuric acid and reroasted to yield lithium oxide. This calcine is then leached,
neutralized with limestone, and filtered to remove gangue constituents. The resulting lithium-containing filtrate is
treated with lime and soda ash to remove the soluble calcium and magnesium compounds. Following this, the
remaining solution is concentrated by evaporation to yield a lithium sulfate solution. Insoluble portions of ore are
removed by filtration and the purified solution is treated with soda ash to precipitate lithium carbonate. The
carbonate is separated, washed and dried for sale.6 The lithium can also be used as the feedstock in the production of
other lithium compounds.7
Lithium-containing Brines
Exhibit 3 presents the process flow diagram for the recovery of lithium from brines. In Nevada, brines
enriched in lithium chloride (300 ppm) are pumped from the ground into solar evaporation ponds, where in a year to
18 months, the concentration of the brines increases to 6,000 ppm.8 During the evaporation, halite and sylvite
crystallize and magnesium is precipitated as hydroxide by the addition of lime.9 When the proper concentration has
been reached, the liquid is pumped to a recovery plant and treated with soda ash to precipitate the lithium carbonate.
The carbonate can then be removed through filtration and dried for shipment.10
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
EPA determined that this mineral commodity sector does not generate any mineral processing wastes.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
From Spodumene Concentrates
Although generation rates are available for the wastes generated during the recovery of lithium carbonate
from spodumene, characterization and management data are not available for all of the wastes.
5 Joyce A. Ober, 1992, Op. Cit.. p. 753.
6 Ibid.
7 Ibid.
8 Ibid.
9 U.S. Environmental Protection Agency, 1988, Op. Cit. p. 2-11.
10 Joyce A. Ober, 1992, Op. Cit.. p. 754.
428
-------
Concentrate
EXHIBIT 2
LITHIUM CARBONATE FROM SPODUMENE
(Adapted from: Technical Background Document, 1989.)
Lime/Soda
Offgases
Offgases
A H2S04 A
Roasting/ f
Cooling
Na2SO4to ^
Sale
Acid
^^ Roasting
Drying,
Dehydration
-—
^-
Limestone
I
Leach,
Neutralization
'
'
Treatment
Filtration,
Washing
1
^
^
1
Mg, Ca
Removal
Gangue to Disposal
Na2CO3 j H2O Process
Wash
1 I \
Cooling/ ^
Filtration
Li2CO,
Precipitate
1
— —
1
Mg/Ca
Sludge
to Disposa
r
Evaporator
Reduction/
Conversion 1
LijCO, to
Sale
M
ID
-------
.fi
Ul
o
EXHIBIT 3
LITHIUM CARBONATE FROM BRINES
(Adapted from: Technical Background Document, 1989.)
1 Lime
W
Raw T Solar Evaporatio
Brine Sludge Settling
Lime/Soda
Treatment
1
n ^ Mg, Ca
Removal
1
Mg/Ca
Sludge
to Disposal
-^^- Evaporators
J
H2O Process
Wash
NajCO,
1
_^ Li2C03
Precipitation
J
Salt Solutes
to Disposal
to Sale
-------
Roaster Off-gases. Sources indicate the following generation rates: 600 ACF/lb, containing 0,0Lib dust/
Ib. The generated dusts-are concentrate fines."
Acid roaster gases. Sources indicate the following generation rates: 60 ACF/lb, containing 0,001 Ib dust/
Ib, The off-gases contain trace amounts of sulfuric acid and sulfur dioxide.12
Gangue. Sources indicate the following generation rates for gangue: 35 Ib/lb, aluminosilicate residues of
concentrate gangue. The solids generated contain 25 Ib/lb water with trace amounts of lithium and other salts.13
Magnesium/Calcium sludge. Sources indicate the following generation rates for Mg/Ca sludge: 0.1 Ib/lb
hydrous oxides/carbonates. The sludge contains trace amounts of lithium and other salts.14
Flotation Tailings. Solid residues are generated as a result of the froth flotation process. The solid
residues may be directly recovered and landfilled on-site. Characterization data are not available for either the
content or the generation rate for this waste.
Wastewater from Wet Scrubber. Wastewater generated as a result of wet scrubbing emissions may be
used for process make-up water. Wastewater from the wet scrubbing acid roaster emissions can be used for process
water after it has been neutralized. Alternatively, some plants may recycle the wastewater.15
From Brines
Magnesium/Calcium sludge. Sludge generated during recovery from brines, containing trace amounts of
lithium and other salts in addition to magnesium and calcium, is sent to disposal. Some magnesium hydroxide sludge
may be stored on-site.16 Generation rates are not available.
Salt Solutions. Spent brines containing sodium and potassium chlorides and trace amounts of other brines
are generated. These wastes may be sent to on-site evaporation ponds or reprocessed to recover potassium
chloride.17
2. Mineral Processing Wastes
None Identified.
11 U.S. Environmental Protection Agency, "Lithium: Mineral Processing Waste Generation Profile," Technical
Background Document: Development of me Cost. Economic, and Small Business Impacts Arising from
Reinterpretation of the Bevill Exclusion for Mineral Processing Wastes. 1989.
12 Ibid.
13 Ibid.
14 Ibid.
15 Versar, Inc., "Lithium Derivatives," Multi-media Assessment of the Inorganics Chemical Industry. 1980, p. 25-
7.
16 Versar, Inc., 1980, Op. Cit. p. 25-8.
17 Ibid-
431
-------
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Commented Received by EPA
EPA received no comments that address this specific sector.
432
-------
BIBLIOGRAPHY
Kunasz, Dior A. "Lithium Resources." From Industrial Minerals and Rocks. 1994. pp. 631-640.
Ober, Joyce A. "Lithium." From Mineral Commodity Summaries. 1995. pp. 98-99.
Ober, Joyce A. "Lithium." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. U.S. Bureau of
Mines, pp. 753-755.
U.S. Environmental Protection Agency. "Lithium." From 1988 Final Draft Summary Report Of Mineral Industry
Processing Wastes. 1988. p.2-11-2-15.
U.S. Environmental Protection Agency. "Lithium: Mineral Processing Waste Generation Profile." Technical
Background Document: Development of the Cost. Economic, and Small Business Impacts Arising from
Reinterpretation of the Bevill Exclusion for Mineral Processing Wastes. 1989.
Versar, Inc. "Lithium Derivatives." Multi-media Assessment of Inorganic Chemicals Industry. 1980.
pp. 25-1 - 25-8. Prepared for U.S. Environmental Protection Agency.
433
-------
Page Intentionally Blank
434
-------
MAGNESIUM AND MAGNESIA FROM BRINES
A. Commodity Summary
There are ten magnesium compound producers in the United States. Each of the facilities obtains its raw
source material from either magnetite, lake brines, well brines, or seawater. In addition, there are three facilities that
produce magnesium metal. Magnesia, the primary magnesium compound, is produced at three facilities. Exhibits 1
through 3 present the names and locations of facilities involved in the production of magnesium, magnesium metal.
and magnesia from brines, respectively.
Magnetite and dolomite, which have a theoretical magnesium content of 47.6% and 22%, respectively,
comprise the largest mineral sources of magnesium and magnesium compounds. Other sources of magnesium and its
compounds include seawater, brines, and bitterns.'
Magnesium and its alloys are used in the manufacture of structural components for automobiles, trucks.
aircraft, computers, and power tools. Because of its light weight and ease of machinability, magnesium is used by
the iron and steel industry for external hot^metal desulfurization and in the production of nodular iron. Producers of
several nonferrous metals often use magnesium as a reducing agent. Magnesium anodes are used for cathodic
protection of underground pipe and water tanks. Small quantities of magnesium are used as a catalyst in the
synthesis of organic compounds, as photoengraving plates, and in alloys (other than aluminum). Caustic magnesia
can be used as a cement if combined with magnesium chloride.
Refractory magnesia represents the largest use of magnesium in compounds. It is used principally for
linings in furnaces and auxiliary equipment used to produce iron and steel. Caustic-calcined magnesia (partially
calcined magnesite) is used in the agricultural, chemical, construction, and manufacturing industries,2
The most commonly used source for magnesia is magnesium carbonate, with the largest source being
magnesia-rich brines and seawater. Magnesite is one of the minerals directly and widely exploited for its magnesia
content. When pure, it contains 47.8% magnesia and 52.2% carbon dioxide. Sintered magnesia is used for
refractory manufacturing while lighter fired caustic magnesia is used in fluxes, fillers, insulation, cements,
decolorants, fertilizers, chemicals, in the treatment of wastewater including pH control, and in the removal of sulfur
compounds from gas exhaust stacks. In addition to naturally occurring magnesia, refractory grade magnesia can also
be produced synthetically. This involves the calcination of either magnesium hydroxide or magnesium chloride.3
B. Generalized Process Description
1. Discussion of Typical Production Processes
The two main operation types for recovery of magnesium are (1) electrolytic production, and (2) thermal
production. Each of these processes is described in more detail below.
1 Deborah A. Kramer, "Magnesite and Magnesia," from Minerals Yearbook Volume 1. Metals and Minerals.
U.S. Bureau of Mines, 1992, pp. 163-173.
2 Ibid.
3 L.R. Duncan and W.H. McCracken, "Magnesite and Magnesia," from Industrial Minerals and Rocks. 6th ed.
Society for Mining, Metallurgy, and Exploration, 1994, pp. 643-654.
435
-------
EXHIBIT 1
SUMMARY OF MAGNESIUM PROCESSING FACILITIES
Facility Name
Barcroft Co.
Dow Chemical Co.
Great Salt Lake
Marine Magnesium Co.
Martin Marietta Chemicals
Morton Chemical Co.
National Refractories & Minerals Corp.
Premier Services Inc.
Premier Services Inc.
Reilly Ind.
Location
Lewes, DE
Freeport, TX
Ogden, UT
South San Francisco, CA
Manistee, MI
Manistee, MI
Moss Landing, CA
Port St. Joe, FL
Gabbs, NV
Wendover, UT
Type of Operations
MgO from seawater
MgCl from seawater
MgCl from lake brine
MgO from seawater
MgCl from brine
MgCl from brine
MgO from seawater
MgO from seawater
Mine magnesium
carbonate and calcine
to MgO
Brine Extraction
EXHIBIT 2
SUMMARY OF MAGNESIUM METAL PROCESSING FACILITIES
Facility
Dow Chemical Co.
Magnesium Corp. of America
Northwest Alloys Inc.
Location
Freeport, TX
Rowley, UT
Addy, WA
EXHIBIT 3
SUMMARY OF MAGNESIA (McO) PROCESSING FACILITIES
Facility Name
Basic Incorporated
Dow Chemical Co.
Magnesia Operations
Location
Gabbs, NV
Freeport, TX
San Francisco,, CA
Type of Operations
Uncertain
Brine Extraction
Uncertain
436
-------
2. Generalized Process Flow Diagram
Electrolytic Production
Hydrous Magnesium Chloride Feed. The Dow Chemical Company is the only magnesium producer using
hydrous magnesium chloride as feed for the electrolytic cells. A flow sheet of the Dow process is presented in
Exhibit 4. In this process, magnesium is precipitated from seawater as magnesium hydroxide by addition of lime or
caustic in large agitated flocculators. The magnesium hydroxide is then settled in Dorr thickeners. The overflow
enters the plant wastewater system where it is neutralized and returned to the ocean. The thickened underflow is
pumped to rotary filters where it is dewatered, washed, and reslurried with wash water from the magnesium chloride
purification step. It is then pumped to the neutralizers where it is treated with hydrochloric acid and enough sulfuric
acid to precipitate excess calcium as calcium sulfate. The brine is filtered to remove calcium sulfate and other solids
such as clays and silica and is further purified to reduce sulfate and boron and forwarded to the dryer. The purified
brine is dried by direct contact with combustion gases in a fluid-bed dryer to produce granules of magnesium
chloride. The granules are stored in large tanks from which they are fed to the electrolytic cells. The cells are fed
semicontinuously and produce both magnesium and chlorine. The dilute, wet chlorine gas is drawn into refractory
regenerative furnaces and converted to HC1 which is recycled to neutralize magnesium hydroxide. The magnesium
collects in compartments in the front of the cell from which it is periodically pumped into a computer-controlled
crucible car operating at ground level. The crucible is conveyed to the casting house where it is emptied into a
holding furnace or into alloying pots from which the metal is pumped into molds on continuous mold conveyors.4
Surface Brine Feed, A second process for magnesium production, shown in Exhibit 5, utilizes surface brine
from the Great Salt Lake as feed to a series of solar evaporation ponds. This brine is further concentrated and treated
with CaCl2. Solids such as calcium sulfate and potassium and sodium chlorides are removed in a thickener. Further
concentration provides feed for the spray dryer whose waste gases provide heat for the concentration process. The
spray dryers convert the brine into a dry MgCl2 powder containing about 4% magnesia, 4% water, and other salts
which comprise the cell bath. The dryers are heated with exhaust gases from gas-fired turbines that generated some
of the power used to operate the cells. The spray-dried MgCi, powder is melted in large reactors and further purified
with chlorine and other reactants to remove magnesium oxide, water, bromine, residual sulfate, and heavy metals.
The molten MgCl2 is then fed to the electrolytic cells. Only a part of the chlorine produced is required for
chlorination, leaving up to 1 kg/kg magnesium produced available for sale as byproduct chlorine.5
Underground Brine Feed. A third process for magnesium recovery uses underground brines as its source of
raw material. Brine is pumped from below the ground into a large system of plastic-lined solar evaporation ponds,
where the magnesium chloride concentration is increased to 25% which reduces the solubility of sodium chloride to
1%. The brine is then moved by pipeline to the plant where it is further concentrated, purified, and spray dried. The
spray-dried feed is further purified by chlorination. The magnesium chloride is electrolyzed in diaphragmless cells
and the molten magnesium is removed by vacuum ladle. It is then transported to a refining furnace where it is cast
into ingots. The chlorine is collected, cleaned, and liquefied.6 Exhibit 5 presents a flow diagram of the process for
recovering magnesium from underground brines and surface brines.
Thermal Reduction
In the thermal reduction process, magnesium oxide, as a component of calcined dolomite, reacts with a
metal such as silicon to produce magnesium. The silicon is usually alloyed with iron. There are two principle
methods: (1) carbothermic, and (2) silicothermic.
4 Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XIV, 1981, pp. 576-586, 631-635.
5 Ibid.
6 Ibid.
437
-------
EXHIBIT 4
ELECTROLYTIC PRODUCTION USING HYDROUS MAGNESIUM CHLORIDE FEED
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 578.)
Dolomite
Rock
1
Kiln
I
Precipitation
to Mg(OH)2
|
T
Filters
1 Mg(OH)2
Neutralizer
I
MgCl2 Purifier
I
Dryer Dehydration
from 35% to 73% MgCl
Electrolytic Magnesium
Pells
1
1
Magnesium
Ingots
Seawater
Hfl from
Organic Chlorination
i
i
y
Cnlonne
Chlorine
Kirk-Othmer Encyclopedia of Chemical Technology. 1981, pp. 578.
438
-------
EXHIBITS
ELECTROLYTIC PRODUCTION USING SURFACE AND UNDERGROUND BRINES AS FEED
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 582.)
Subterranean Brine
il%Mgd2
Surface Brine
1.6%MgCl2
Dehydration I
(Solar)
Nad
Nad
Salt for Sale
Dehydration II
(Thermal)
Purification I
Dehydration ffl
(Thermal)
Purification
Electrolysis
Chlorine
Purification and
liquefaction
Liquid Chlorine
for Sale
Mg
Refining, Alloying
and Casting
Pure Mg Ingots
Alloy Mg Ingots
Source: Kirk-Othmer Encyclopedia of Chemical Technology. 1981, pp. 582.
439
-------
In the carbothermic process, magnesium oxide is reduced with carbon using modified shock cooling to
produce magnesium and carbon monoxide. Both products are in the vapor phase. In order to recover the
magnesium, the temperature must be dropped rapidly to prevent reversion. Shock cooling produces very finely
divided magnesium dust which is pyrophoric.7
The silicothermic process is based on the reaction of silica with carbon to give silicon metal which is
subsequently used to produce magnesium by reaction with calcined dolomite. The Pidgeon and Magnetherm
processes employ this procedure.
The Pidgeon process is a batch process in which dolime and silicon are sized, briquetted, and charged into
gas-fired or electrically heated retorts of nickel-chrome-steel alloy. The retort is equipped with removable baffles
and a condensing section that extends from the furnace and is water-cooled. High purity crowns are remelted and
cast into ingots.8 Exhibit 6 presents a flow diagram of the Pidgeon process.
In the Magnetherm process, sufficient alumina is added to melt the dicalcium silicate slag that forms at
around 1500° C. This permits the reactor to be heated by the electrical resistance of the slag and further allows the
reaction products to be removed in the molten state. About 0.45 kg calcined bauxite or alumina, 2.7 kg dolime, and
0.45 kg ferrosilicon are required to produce 0.45 kg metallic magnesium. As the reactants are fed to the furnace,
magnesium is evolved and passes through a large tuyere into the condensation chamber. Magnesium collects as a
liquid and runs down into a collection pot where it solidifies. The slag is tapped twice a day by introducing argon
into the furnace to break the vacuum. The slag outlet is electrically lanced and the molten calcium aluminum silicate
is quenched in water to stabilize the slag (which can be used as cement). About 5.9 kg slag are produced per kg
magnesium. The residual ferrosilicon containing 20% silicon is removed and can be used as low grade silicon alloy.
The magnesium collection crucible is removed once a day and the magnesium is remelted, alloyed if required, and
then cast into ingots.9
Magnesia from Brines
Magnesia, magnesium oxide, is usually produced by calcining the mineral magnesite or magnesium
hydroxide obtained from seawater or brine by liming. It is also produced by the thermal decomposition of
magnesium chloride, magnesium sulfate, magnesium sulfite, nesquehonite, and the basic carbonate.10 A flow
diagram of magnesia recovery from seawater is presented in Exhibit 7.
Magnesite ores contain varying amounts of silica, iron oxide, alumina, and lime as silicates, carbonates, and
oxides. The deposits are mined selectively and the ores are often beneficiated to reduce lime and silica
concentrations prior to calcining. Beneficiation methods include crushing and size separation, heavy-media
separation, and froth flotation. Magnetic separation reduces iron concentration, but is effective only when the iron is
present in the form of discrete ferromagnetic minerals rather than as ferrous carbonate."
In chemical beneficiation processes, the magnesium is dissolved as a salt, the insoluble impurities are
removed by filtration or sedimentation, and purified magnesia is recovered by thermally decomposing the clean salt
solution. Special processes are needed to separate out calcium due to its similarity to magnesium. Three of these
processes are discussed below.
7 Ibid.
Ibid.
9 Ibid.
10 Ibid.
"ibid.
440
-------
EXHIBIT 6
THE PIDGEON PROCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 584.)
Raw Materials
Dolomite Ore
(MgC03 + CaCOj)
Calcium Silicate
+ Iron
Magnesium Crystals
Source; Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 584
441
-------
EXHIBIT 7
PRODUCTION OF ELECTROLYTIC MANGANESE DIOXIDE
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-14.)
Vent Water
Reaction: (1) 2MnO, + C + 2MnO + CO2
(2) MnO + H2SO., + MnSO., + H20
Scrubber
500 Ore |
1 t 1 I
Kiln Leaching
1 10 Sulfuric Acid T
1 Coal Makeup
Filtration — —
1
800 Ore Residues
Mother Liquor
H2S(0- 10)
^^- Purification
I
Clarification
30 Graphite
Anodes
Vent
Dust
Collection
24 H9
t t 1
Grinding
^- Electrolysis ^~ and
Drying
1 1 I
20 FeS 30 Graphite Anodes ] ,000 Product
Waste Solids (Solid Waste) Manganese Dioxide
Landfilled
Source: Kirk-Othmer Encyclopedia of Chemical Technology. 1981. pp. 634.
-------
The first process to separate out calcium is the Pattinson process. In this process, a suspension of
magnesium hydroxide is carbonated to form a solution of magnesium bicarbonate. After the insoluble impurities are
separated, the solution is decarbonated by heating or aeration and the magnesium carbonate precipitates as the
trihydrate, the pentahydrate or the basic carbonate. The precipitate is recovered from the solution by filtration or
sedimentation and converted to the oxide by thermal decomposition. The highly reactive grades of caustic-calcined
magnesia are usually produced using a modified form of this process.12
In a second process for the separation of calcium impurities, magnesium is dissolved with the aid of sulfur
dioxide or a mixture of sulfur dioxide and carbon. One variation of this method can be employed to remove SO2
from flue gas. The flue gas is treated with a magnesium hydroxide slurry in a venturi scrubber to form MgSO, and
some MgSO4, which is subsequently calcined to recover the magnesium oxide and sulfur dioxide. The magnesium
oxide is recycled and the sulfur dioxide may be used to manufacture sulfuric acid.13
In a third process, magnesia is dissolved in hydrochloric acid. After the insoluble impurities are removed,
the magnesium chloride solution is thermally decomposed to recover the magnesia.14
There are several operations used to recover magnesium oxide from dolomite. Because calcite and
magnesite decompose at different temperatures, a stepwise decomposition permits a selective calcination in which
die magnesium carbonate is completely decomposed without decomposing the calcium carbonate. The magnesium
oxide is then separated mechanically from the half-calcined dolomite by screening or air separation. Another scheme
employs a modification of the Pattinson process in which the dolomite is calcined, slaked, and men carbonated in
steps to precipitate calcium carbonate and magnesium carbonate trihydrate. This is further carbonated to dissolve
the trihydrate as magnesium bicarbonate and the calcium carbonate is removed by filtration. The clean solution is
finally decarbonated to precipitate magnesium carbonate trihydrate which is thermally decomposed to produce
magnesia.15
Highly reactive grades of caustic-calcined magnesia are produced by calcining basic magnesium carbonate
or magnesium carbonate trihydrate in small batches under carefully controlled conditions. They generally have
magnesia contents above 99% and contain small quantities of carbon dioxide and moisture. The carbonates for these
grades are prepared by a variation of the Pattinson process described above. The less reactive grades are obtained by
calcining magnesium hydroxide or magnesite in multiple-hearth furnaces or rotary kilns.16
Dead-burned magnesia is used almost exclusively for refractory applications in the form of basic granular
refractories and brick. It is produced in a number of grades."
Fused magnesia is produced by melting calcined magnesia in an electric arc furnace. The furnaces have
water-cooled shells and no refractory linings. The material serves as its own refractory because only a small pool of
material in the center is actually melted. When magnesia is fused for the purpose of making grain, it is allowed to
13 „. ,
Ibid.
14 Ibid.
15 Ibid..
., . ,
Ibid.
"ibid.
443
-------
cool in the furnace after the electrodes have been removed. After cooling, it is removed from the furnace, separated
from the unfused material, and crushed.18
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4, Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
Electrolytic Production of Magnesium
EPA determined that for the production of magnesium through this process, the beneficiation/processing
line occurs when the dried MgCl2 undergoes electrolytic refining at the electrolytic magnesium cells and chlorine is
chemically removed to yield pure magnesium. Therefore, because EPA has determined that all operations following
the initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents below the mineral processing waste streams generated after the
beneficiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
Production of Magnesium Through Thermal Reduction
EPA determined that in the production of magnesium through thermal reduction, the
beneficiation/processing line is crossed when calcined dolomite ferrosilicon (CDF) pellets are introduced to the
furnace for retorting when magnesium crystals are produced through the thermal destruction of the CDF pellets.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
18
Ibid.
444
-------
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated after the beneficiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
Magnesia from Brines
EPA determined that for the production of magnesia from brines, the beneficiation/processing line occurs
between filtration or sedimentation and when trihydrates are converted to the oxide through thermal decomposition.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated after the beneficiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Ore Extraction and Beneficiation
Possible waste streams from ore extraction processes include tailings and offgases from calcining.
Brine Extraction and Beneficiation
Extraction waste streams from brines include calcium sludge, spent seawater, and offgases. .
2, Mineral Processing Wastes
Electrolytic Production
Casting plant slag. This waste stream was generated at a rate of 3,000 metric tons per year in 1991."
Existing data and engineering judgement suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
Smut (sludge and dross). This waste, generated at a rate of 26,000 metric tons per year, may be toxic for
barium.20 Management for this waste includes disposal in an unlined surface impoundment.21 Waste characterization
data are presented Attachment 1. This waste may be recycled and is classified as a byproduct.
Process wastewater is a possible waste stream from magnesium production. This waste was generated at a
rate of 2,465,000 metric tons per year in 1991.22 Process wastewater may contain calcium sulfate and boron and
19 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, Vol. I, August, 1992, pp. 1-2 -1-8.
20 Ibid.
21 U.S. Environmental Protection Agency, Technical Background Document. Development of Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, pp. 3-4-3-6.
22 U.S. Environmental Protection Agency, Op. Cit. Vol. I, August, 1992, pp. 1-2 -1-8.
445
-------
have a low pH. This waste is may be discharged to a waste pond.23 EPA determined in 1994 that the great majority
of process wastewater is comprised of two special wastes — scrubber underflow process wastewater and scrubber
liquor process wastewater.24
Thermal Reduction
Cathode scrubber liquor. Dissociation of magnesium chloride molten salt from magnesium produces
chlorine gas which is passed through a scrubber system. This produces a cathode scrubber liquor, which is
discharged to surface impoundments with other wastewaters.25 Existing data and engineering judgement suggest that
this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
APC Dust/Sludge is a possible waste stream from magnesium production.26 Existing data and engineering
judgement suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
Slag is a possible waste stream from magnesium production. Existing data and engineering judgement
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Casthouse dust. During the refining of magnesium metal, casthouse dust is produced. Although no
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 76 metric
tons/yr, 760 metric tons/yr, and 7,600 metric tons, respectively. We used best engineering judgement to determine
that this waste may exhibit the characteristic of toxicity for barium. This waste may be recycled and is classified as a
sludge.
Magnesia from Brines
Possible waste streams from magnesia production from brines include calciner offgases, calcium sludge,
and spent brines (which may be sold). Existing data and engineering judgement suggest that these materials do not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
U.S. Environmental Protection Agency. Mineral Processing Waste Sampling Survey Trip Reports. AMAX
Magnesium Company, Rowley, Utah. August 30, 1989.
U.S. Environmental Protection Agency, Memorandum
25 IMd.
26 U.S. Environmental Protection Agency, 1992, Op. Cit.. pp. 1-2 -1-8.
446
-------
BIBLIOGRAPHY
Duncan, L.R., and W.H. McCracken. "Magnesite and Magnesia," From Industrial Minerals and Rocks. Society for
Mining, Metallurgy, and Exploration. 6th ed. 1994. pp. 643-654
Kramer, Deborah. "Magnesite and Magnesia." From Minerals Yearbook Volume 1. Metals and Minerals.
U.S. Bureau of Mines. 1992, pp. 163-173.
"Magnesium and Magnesium Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XIV.
1981. pp. 576-586.
"Magnesium Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XIV. 1981. pp. 631-
635.
U.S. Environmental Protection Agency. Mineral Processing Waste Sampling Survey Trip Reports. AMAX
Magnesium Company, Rowley, Utah. August 30, 1989.
U.S. Environmental Protection Agency. Technical Background Document. Development of Cost. Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989. pp. 3-4-3-6.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol. I. August 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. "Magnesium Production." From Report to Congress on Special Wastes
from Mineral Processing. 1990. pp. 11-1 - 11-15.
447
-------
ATTACHMENT 1
448
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SMUT (SLUDGE AND DROSS) - MAGNESIUM
Constituents
Aluminum
Antimony
Arsenic
3arium
Sen/Ilium
Boron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis -
Minimum Average
-
-
0.1
14.9
-
-
0.01
0.023
-
0.025
0.22
0.043
-
0.03
0.0008
-
-
0.013
0.05
-
-
0.02
-
-
4
0.2
-
-
25600
-
0.375
81.95
0.0185
0.0385
1 ,2325
0.29
1.8415
0.1
0.0009
0.0145
0.095
0.355
4
1.3
27150
PPM
Maximum
0.65
149
0.027
0.054
2.44
0.36
3.64
0.17
0.001
-
-
0.016
0.14
.
-
0.69
-
-
4
2.4
-
-
28700
-
# Detects
0/0
0/0
2/2
2/2
0/0
0/0
2/2
2/2
0/0
1/2
2/2
2/2
0/0
1/2
2/2
0/0
0/0
2/2
2/2
0/0
0/0
1/2
0/0
0/0
0/2
2/2
0/0
0/0
2/2
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 1
-
.
1.0 0
5.0 0
-
-
-
5.0 0
-
• -
0.2 0
-
-
1.0 0
5.0 0
-
-
.
-
.
-
.
-
-
.
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
450
-------
MANGANESE, MANGANESE DIOXIDE, FERROMANGANESE, AND SILICOMANGANESE
A. Commodity Summary
Approximately 95 percent of all manganese ore is consumed in the manufacture of steel, primarily as
ferromanganese and silicomanganese, and other minor alloy-related industries. The other five percent is used by the
non-alloying industries, including the chemical, paint, fertilizer, and battery industries, and in the production of
manganese metal,1 Manganese ore was consumed mainly by about 20 firms with plants principally in the Eastern
and Midwestern United States. Metallic manganese is often too brittle and unworkable to be widely used.2
However, leading identifiable end uses of manganese were construction, machinery, and transportation, which were
estimated to be 14 percent, 9 percent, and 9 percent of total manganese demand, respectively. The other end uses
include a variety of iron and steel applications.3
Manganese ore containing 35 percent or more manganese was not produced domestically in 1993.4 The
manganese industry in the United States relies almost entirely on foreign ores containing 35 to 55 percent
manganese. The small amount of manganese ore produced in the United States is generally used as a pigment in the
manufacture of brick.5
As of 1992, there were four companies that produced manganese, manganese oxide, ferromanganese or
silicon manganese in six plants in the United States. Exhibit 1 presents the names, locations, products and types of
processes used by the facilities involved in the production of manganese, manganese oxide, ferromanganese, and
silicomanganese.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Almost all of the ore processed in the United States is imported as a concentrate. Nonetheless, typical
operations used to produce concentrates include crushing, screening, washing, jigging, and tabling, as well as
flotation, heavy-media, and high-intensity magnetic separation.6 Ferromanganese is made by smelting ore (which
contains both iron and manganese) with coke and limestone, and silicomanganese is produced by smelting the slag
from standard ferromanganese with additional ore and coke. Manganese metal is frequently produced by preparing a
solution of manganous sulfate from ore that has been reduction roasted, and electrolyzing this solution. Manganese
dioxide is prepared either chemically or electrolytically. Each of these processes is described in greater detail below.
1 R.A. Holmes, "Manganese Minerals," from Industrial Minerals and Rocks. 6th ed., Society for Mining,
Metallurgy, and Exploration, 1994, p. 657.
2 T.S. Jones, "Manganese," from Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines,
1992, p. 790.
3 T. S. Jones, "Manganese," from Mineral Commodity Summaries, U.S. Bureau of Mines, January 1995, p. 104.
4 Ibid.
5 R. A. Holmes, Op. Cit.. p. 656.
6 T. S. Jones, 1992, Op. Cit. p. 791.
451
-------
EXHIBIT 1
SUMMARY OF MANGANESE, MANGANESE DIOXIDE, FERROMANGANESE, AND SILICOMANGANESE PRODUCERS"
Facility Name
Chemetals Inc.
Chemetals Inc.
Elkem Metals Co.
Kerr McGee Chemical Corp.
Kerr McGee Chemical Corp.
Everready Battery Co.
Location
Baltimore, MD
New Johnsonville, TN
Marietta, OH
Hamilton, MS
Henderson, NV
Marietta, OH
Products
MnO,
MnO,
FeMn, SiMn, Mn
Mn
MnO,
MnO2
Type of Process
Chemical
Electrolytic
Electric Furnace and Electrolytic
Electrolytic
Electrolytic
Electrolytic
a - Jones, T. S., "Manganese." Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992. p. 802.
2. Generalized Process Flow Diagram
Ferromanganese and Silicomanganese
In the United States, electrothermy is the predominant method of manufacturing manganese ferroalloys,
using the submerged-arc furnace process. .Standard or high-grade ferromanganese is the principal intermediate form
into which manganese concentrates and other ore products are processed. Exhibit 2 shows a typical ferromanganese
production process. Typically, a charge of ore, coke, and limestone is smelted in a submerged-arc furnace. In the
manufacture of silicomanganese, an ore with a relatively high silica content, such as quartz or slag from standard
ferromanganese is included in the charge introduced into the submerged-arc furnace. Smelting economics favor an
integrated standard ferromanganese-silicomanganese electric-furnace operation, in which the high manganese slag
from ferromanganese production is used as part of the charge to the silicomanganese furnace, along with ore and
coke.7 If silicomanganese is not co-produced, ore containing lower concentrations of manganese or higher
concentrations of base oxides may be used, and the resulting slag is discarded.
Low carbon silicomanganese (or ferromanganese-silicon) is produced in a manner similar to standard
silicomanganese, using standard silicomanganese, quartz, and coke or coal as the charge. Both standard
ferromanganese and silicomanganese produce a slag and an off-gas containing CO2. Low carbon silicomanganese
manufacture is a slagless process, where the quartz is reduced to silicon and displaces the carbon in the remelted
silicomanganese.8 The gases are filtered through either wet scrubbers or baghouses. Ore fines are often sintered into
bulkier particles before charging them to the furnace to lower the CO2 concentration in the off-gas, and reduce
energy consumption.9
7 T.S Jones, "Manganese," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp. 487-88.
8 "Manganese and Manganese Alloys," Kirk-Othmer Encyclopedia of Chemical Technology, 3rd. ed., Volume
XIV, 1981, p. 833.
9 Ibid, p. 832.
452
-------
EXHIBIT 2
FERROMANGANESE AND SILICOMANGANESE PRODUCTION
Ore,
Coke, and
Limestone
Gas
Furnace
Standard
Ferromanganese
Ore
and
Coke
Slag
Furnace
Tt
Slag Gas
Quartz
Standard
Silicomanganese
Standard
Silicomanganese,
quartz, Coke or Coal
Gas
Furnace
Low Carbon
Silicomanganese
453
-------
Medium and low carbon ferromanganese are called refined ferromanganese. Silicon in silicomanganese or
low carbon silicomanganese reacts with manganese ore and lime to produce refined ferromanganese.10 Exhibits 3
through 5 illustrate three variations of this process.
Manganese Metal
Manganese metal is frequently produced by preparing a solution of manganous sulfate from ore that has
been reduction roasted, and electrolyzing this solution. Exhibit 6 depicts a typical production process of manganese
metal from ore. Manganese ore is roasted to reduce the higher oxides to manganese (II) oxide. Slag from the
production of high carbon ferromanganese may also supply manganese (II) oxide. The reduced ore or slag is leached
with sulfuric acid to produce manganese (II) sulfate. Impurities, such as iron and aluminum, are precipitated and
filtered. Other metal impurities are removed as sulfides, by introducing hydrogen sulfide gas. Either ferrous or
ammonium sulfide and air are added to remove colloidal sulfur, colloidal metallic sulfides, and organic matter. The
purified liquid is put into a diaphragm cell, and electrolyzed. The manganese metal deposits on the cathode in a thin
layer, which is brittle and extremely pure.11 Manganese metal can also be made electrolytically by fused-salt
electrolysis (not shown.) Manganese ore that has been reduced to the manganese(II) level is charged to an
electrolytic cell which contains molten calcium fluoride and lime. Fused electrolyte is periodically removed, as the
volume of fused electrolyte increases.12
Manganese Dioxide
Manganese dioxide is prepared either chemically or electrolytically. Exhibit 7 illustrates the electrolytic
production of manganese dioxide, which is similar to the electrolytic production of manganese metal. Manganese
ore and coke are reacted in kilns at 600 °C. The mixture is cooled and leached with a solution containing 50 grams
per liter of manganese sulfate and 67 grams per liter of sulfuric acid at 90 °C. After leaching, the solutions are
filtered to remove the insoluble ore residues, which are discarded as a waste. The filtered solution are treated with
hydrogen sulfide to precipitate iron salts and sulfides. These solids are removed by filtration and the purified
solutions are fed to electrolytic cells. The cells used are generally lead lined with graphite cathodes and anodes.
During electrolysis, manganese dioxide builds up a costing on the anodes as thick as 6 mm before it is removed. The
manganese dioxide is periodically stripped from the electrodes, recovered from the cells, crushed, washed, first with
dilute soda ash solutions and then with pure water, dried, pulverized and packaged. The hydrogen co-product from
the electrolysis is flared, and the spent process liquor containing mostly sulfuric acid is recycled to the ore leaching
step.
Manganese dioxide also may be prepared chemically, either by chemical reduction of permanganate (Type
I) or by thermally decomposing manganese salts, such as MnCO3 or Mn(NO3)2 under oxidizing conditions (Type
II).13 To produce Type I chemical manganese dioxide (not shown), the byproduct manganese dioxide from the
oxidation of organics using potassium permanganate, is treated with hydrochloric or sulfuric acid, followed by
MnSO4. This treatment removes the excessive quantities of adherent and bound alkali. KMnO4 is added to convert
the ion exchanged divalent Mn into MnO2. The product is washed and dried at low temperature, so as to avoid the
undesirable loss of water of hydration.I4
10 Ibid., pp. 834-837.
11 Ibid., pp. 835-836.
12 Ibid., p. 837.
13 Ibid., p. 863.
14 Ibid.
454
-------
EXHIBIT 3
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE RAW ORE PRACTICE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
Crushing
and Sizing
T
Tilting Furnace
Coal
Silicomanganese
Smelting Furnace
Slag
Discard
Medium-carbon
Ferromanganese
1
455
-------
EXHIBIT 4
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE FUSED ORE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
Medium-Carbon
Ferromanganese
Slag Discard
456
-------
EXHIBIT 5
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE FUSED ORE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
Tilting
Furnace
Mn Ore-Lime
Melt
Medium-Carbon
Ferromanganese
alien
mediate
Hoy
f
Molten
First Slag
t
Ladle
Molten
SiMn
Slag
Discard
Silicomanganese
Smelting Furnace
457
-------
EXHIBIT 6
MANGANESE METAL PRODUCTION
Manganese Ore
Roasting
Jv
Manganese (II) Oxide
Leaching
I
Manganese (II) Sulfate
Precipitation and
Filtration
Iron and
Aluminum
Hydrogen
Sulfide
Purification
Metal
Sulfides
Ferrous or
Ammonium
Sulfide
Purification
Electrolysis
Colloidal Sulfur,
Organic Matter, and
Colloidal Metallic Sulfides
Manganese Metal
458
-------
EXHIBIT 7
PRODUCTION OF ELECTROLYTIC MANGANESE DIOXIDE
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-14.)
Vent Water
Reaction:
(1) 2MnO, + C +2MnO + CO2
(2) MnO + H2SO, + MnSO,, + H,O
Scrubber Mother Liquor
00 Ore 1
1 t 1 1
Kiln Leaching
1 ^" H,S (0-10)
1 lOSulfuric Acid T T
1 Coal Makeup
Filtration ^- Purification _„ „ ,.
30 Graphite
Anodes
1 1 1
Vent
Dust
Collection
24 H9
_L _LJ
800 Ore Residues Grinding
Clarification ^~ Electrolysis ^~ and
Drying
I 1 1
20 FeS 30 Graphite Anodes 1,000 Product
Waste Solids (Solid Waste) Manganese Dioxide
Landfilled
-------
To make Type II chemical manganese dioxide, as shown in Exhibit 8, manganese ore is reacted with coke
in kilns at 600°C, then cooled and leached with 10 percent nitric acid at 85°C to generate a neutral manganese
nitrate solution. This solution is filtered to remove insoluble materials, treated with sulfides to precipitate iron
impurities and refiltered. The ore residues and iron sulfides are discarded as waste. The purified manganese nitrate
solution is evaporated to about half the original volume. Manganese nitrate crystals separate at this point and are
recovered by centrifugation. The mother liquor is recycled to the evaporators and the recovered crystals are heated
to 200°C to produce manganese dioxide and nitrogen dioxide, which is absorbed as nitric acid for reuse. The
manganese dioxide is recovered and packaged.
Type II chemical manganese dioxide can also be made from finely ground manganese dioxide ore that has
been reduced with H2—CO to manganese (II) oxide (not shown). This substance is leached with sulfuric acid and
the manganese sulfate solution neutralized to pH 4-6 to precipitate iron, aluminum, nickel, cobalt, and other
impurities. The solution is filtered to remove the precipitates, and (NH4)2CO3 is added to precipitate manganese
carbonate. The MnCO3 is filtered, dried, and roasted in air to produce manganese dioxide (MnO2) and carbon
dioxide (CO2).15
Other Manganese Products
Both manganese sulfate and manganese carbonate can also be prepared from ore. Manganese sulfate is
used primarily as an agricultural chemical, while manganese carbonate is used to prepare other manganese
compounds for specialty purposes. Both the sulfate and the carbonate production use less than five percent of total
manganese ore demand. Manganese sulfate can be prepared by either the hydroquinone process or the ore-coke
process.16
In the hydroquinone process, as shown in Exhibit 9, manganese ore, aniline, and sulfuric acid are reacted to
produce manganese sulfate, quinone and ammonium sulfate. The reacted mixture is steam distilled to separate
quinone, which is collected and processed on-site to hydroquinone. The remaining materials are filtered, and gangue
solids are removed as a waste material. The filtrate is partially evaporated and manganese sulfate crystallized from
solution is recovered as a solid. The spent liquor containing ammonium sulfate is sent to waste treatment and the
recovered manganese sulfate is dried and packaged. The ore-coke process for manufacturing manganese sulfate is
shown in Exhibit 10. Manganese ore and coke are reacted in a kiln and the product is leached with sulfuric acid.
The resulting slurry is evaporated to dryness to recover a 30 percent product for agricultural purposes. The insoluble
residues are left with the product.17
To produce manganese carbonate, as shown in Exhibit 11, manganese sulfate and soda ash are reacted in
solution to form the carbonate, which precipitates from solution and is recovered by filtration, dried and packaged.
The spent solutions containing by-product sodium sulfate are normally wasted.'8
15 Ibid.
16 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. II,
August 1980, p. 6-1.
17 Ibid., pp. 6-2 - 6-8.
18 Ibid., pp. 6-8 - 6-9.
460
-------
EXHIBITS
PRODUCTION OF CHEMICAL MANGANESE DIOXIDE (TYPE II)
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-16.)
Vent
Dry Dust
Collection
t 1
t t
1 Coke 1,800 Manganese
Ore
(Makeup) |
|
Filtration
1
Solids:
800 Ore Residues
10 Manganese Nitrate
.Nitric Acid
H2S (0 - 10)
_^^ Charcoal
Treatment
|
Filtration
0-20
Iron Su Ifides
Water Vapor
Evaporation
— ^
Water,
Oxygen
1
Nitric Acid
Regeneration
|N02
Calcination
I
1 ,000 Product
Manganese Dioxide
-Pi
en
-------
en
NJ
EXHIBIT 9
PRODUCTION OF MANGANESE SULFATE (HYDROQUINONE PROCESS)
(Adapted from: Multi-Media Assessment of the Inorganic Chemical!! Industry, 1980, pp. 6-5.)
879- 1,749
Manganese Dioxide Ore
(Contains 50 - 85% MnO2)
936 Quinonc
to Hydroquinone
Manufacture
Steam
l,265Sulfuric
Acid
Vent
t
Filter
1
^*-
Evaporator
and
Centrifuge
Product
^- Drier ^»
I Waterbome Wastes:
1 30 - 600 (NHJjSO, (Average 570)
W 60-500 MnSO4 (Average 300)
Solid Waste
130
- 1,000 Ore
Gangue
\
Waste
Treatment
63 - 660 Solid
Waste MnO2
CaSO4
-«( 23- 190 Lime
1
Effluent
30 - 500
(NH4)2S04
-------
EXHIBIT 10
PRODUCTION OF MANGANESE SULFATE (ORE-COKE PROCESS)
(Adapted from; Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-7.)
Vent
Reaction: 2MnO2 + C + 2MnO + CO,
MnO + HjSOj + MnSO4 +
650 Sulfuric
Add Water
700- 1,570
Manganese Ore
42 Coke
Product
l,OOOMnSO4
(in 30% Product
which includes
130- 1,000 of ore
residues.)
-------
EXHIBIT 11
PRODUCTION OF MANGANESE CARBONATE
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-9.)
Reaction: MnSO4 + Na3CO3 -> MnCO3 + Na2SO4
Water
I
946 ^
Soda Ash
1,321
MnSO4
Dust
Collection
1 ' T Jsolids
Reactor
Filtration
Solids
Drying, Storing
and Packaging
^ l.OOOMnCO,
Product
\
Wastewater Containing
l,268Na2SO4
-------
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Researchers are investigating how to increase recovery of manganese from refractory ores and steel
slag.1
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
Ferromanganese and Silicomanganese
EPA determined that for ferromanganese and silicomanganese, processing begins with smelting in a
submerged arc furnace because the ore undergoes physical/chemical reactions which significantly alter the
physical/chemical structure. Therefore, because EPA has determined that all operations following the initial
"processing" step in the production sequence are also considered processing operations, irrespective of whether they
involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after
the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes.
EPA presents below the mineral processing waste streams generated after the beneficiation/processing line, along
with associated information on waste generation rates, characteristics, and management practices for each of these
waste streams.
19 P. Comba, K.P.V. Lei, and T.G. Camahan, "CaFvEnhanced Leaching of a Manganese-Bearing Silicate Ore,"
U.S. Bureau of Mines, Report of Investigations 9372, 1991.
20 S.N. Mclntosh, and E.G. Baglin, "Recovery of Manganese from Steel Plant Slag by Carbamate Leaching," U.S.
Bureau of Mines, Report of Investigations 9400, 1992.
21 P. A. Rusin, I.E. Sharp, R.G. Arnold, and N.A. Sinclair, "Enhanced Recovery of Manganese and Silver from
Refractory Ores," Mineral Bioprocessing. The Minerals, Metals, and Materials Society, 1991.
465
-------
Since production of low carbon silicomanganese uses standard silicomanganese, all of the wastes generated
during silicomanganese production are mineral processing wastes.
Manganese Metal
EPA determined that for this specific mineral commodity, the beneficiation/processing line occurs between
reduction roasting and leaching because the ore (manganese (II) oxide) is converted to manganese (II) sulfate.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated after the beneficiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
Manganese Dioxide
Electrolytic Production
EPA determined that for manganese dioxide, mineral processing begins in the kiln because the ore reacts
with coal to produce manganese dioxide. Therefore, because EPA has determined that all operations following the
initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents below the mineral processing waste streams generated after the
beneficiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
Chemical (Type I) Production
Since this process begins with byproduct manganese dioxide, all of the wastes generated during the process
are mineral processing wastes.
Chemical (Type II) Production
EPA determined that for this specific process, mineral processing begins with the reaction of manganese ore
with coke in kilns because the reaction alters the chemical structure of the ore. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams
generated after the beneficiation/processing line, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
Other Manganese Products
Hydroquinone Process
EPA determined that for other manganese products produced via the hydroquinone process, mineral
processing begins with reacting the ore, aniline, and sulfuric acid because the resulting chemical reaction alters the
chemical structure of the ore. Therefore, because EPA has determined that all operations following the initial
"processing" step in the production sequence are also considered processing operations, irrespective of whether they
involve, only techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after
the initial mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes.
466
-------
EPA presents below the mineral processing waste streams generated after the beneficiation/processing line, along
with associated information on waste generation rates, characteristics, and management practices for each of these
waste streams.
Ore-Coke Process
EPA determined that for other manganese products produced via the ore-coke process, mineral processing
begins with the reaction of the ore and coke in kilns because the reaction alters the chemical structure of the ore.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated after the beneficiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
Manganese Carbonate
Since manganese carbonate is produced from manganese sulfate, all of the wastes generated during
manganese carbonate production are mineral processing wastes.
C. Process Waste Streams
1. Extraction/Beneticiation Wastes
The following wastes may be generated by extraction and beneficiation operations: gangue, flotation
tailings, spent flotation reagents, and wastewater.
2, Mineral Processing Wastes
Ferromanganese Production
Both Slag and APC Dust/Sludge are recycled where possible. Existing data and engineering judgement
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Electrolytic Manganese Dioxide and Metal
Waste Electrolyte. Available data do not indicate that waste electrolyte exhibits hazardous
characteristics.22 Therefore, the Agency did not evaluate this material further.
Spent Graphite Anodes. The spent anodes are directly recovered from the process and landfilled.23
Existing data and engineering judgement suggest that mis material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
22 U.S. Environmental Protection Agency, "Manganese," from 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988, p. 3-149.
23 U.S. Environmental Protection Agency, 1980, Op. Cit. pp. 6-13 - 6-15.
467
-------
Iron Sulflde Sludge. This waste is generated by solution purification prior to electrolysis and is
landfilled.24 Existing data and engineering judgement suggest that this material does not exhibit any characteristics
of hazardous waste. Therefore, the Agency did not evaluate this material further.
APC Water. Particulates generated during the calcination and product drying steps are collected by wet
scrubbers. The scrubber waters are used as process make-up waters.25 Existing data and engineering judgement
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Wastewater. This waste is generated during product washing and in slurring ore residues to disposal
lagoons, and may contain suspended ore residue and minor amounts of soda ash. Wastewater is treated with lime to
precipitate manganese salts and then discharges to lined evaporation ponds.26 Existing data and engineering
judgement suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
Chemical Manganese Dioxide
APC Dust. Dry particulate collection methods are used to reduce ore calcination and product handling
paniculate emissions. Collected materials are recycled.27 Existing data and engineering judgement suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate rnis
material further.
Ore residues. These wastes are generated in the leaching operations, which are acid insoluble material
such as aluminates and silicates, and in the purification of the intermediate manganese nitrate. There is also some
unrecovered manganese nitrate entrained in these wastes, which are slurried to treatment lagoons. Lime is added to
the lagoons to precipitate any soluble manganese present.28 Existing data and engineering judgement suggest that
this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate mis
material further.
Wastewater. This waste is generated by slurrying die ore residues to the treatment lagoons. After
treatment die slurry water is discharged.29 Existing data and engineering judgement suggest mat this material does
not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
24 Ibid.
25 Ibid., p. 6-13.
26 Ibid.
27 Ibid., p. 6-17.
28 Ibid., p. 6-17.
29 Ibid., p. 6-17.
468
-------
Other Manganese Products - Manganese Sulfate (Hydroquinone Process)
APC Dust. This dust consists of particulates generated in the calcination and drying operations, which are
captured and recycled.30 Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent Process Liquor, This waste contains ammonium sulfate and unrecovered manganese sulfate. This
waste, along with washings from the ore residues are lime treated to precipitate residual manganese, settled, and
discharged.31 Existing data and engineering judgement suggest that this material does not exhibit any characteristics
of hazardous waste. Therefore, the Agency did not evaluate this material further.
Wastewater Treatment Solids. These solids formed by wastewater treatment (i.e., manganese oxides and
calcium sulfate) are left in ponds. Solid ore residues wastes are washed free of soluble manganese and land
disposed.32 Existing data and engineering judgement suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further,
Other Manganese Products - Manganese Sulfate (Ore-Coke Process)
APC Dust. This dust consists of particulates generated in the calcination and drying operations, which are
captured and recycled.33 Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Other Manganese Products - Manganese Carbonate
APC Dust. This dust consists of particulates generated in the drying operation, which are captured and
recycled.3" Existing data and engineering judgement suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent Process Liquor. This waste contains sodium sulfate and small amounts of unrecovered product.
This waste is lime treated to precipitate residual manganese salts, settled, neutralized, and discharged.35 Existing
data and engineering judgement suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Wastewater Treatment Solids. The solids formed by wastewater treatment (i.e., manganese oxides and
calcium sulfate) are left in ponds.36 Existing data and engineering judgement suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
30 Ibid., pp. 6-2 - 6-6.
31 Ibid.
32 Ibid., p. 6-6.
33 Ibid., p. 6-8.
34 Ibid., pp. 6-8-6-10.
35 Ibid., p. 6-10.
36 Ibid.
469
-------
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
470
-------
BIBLIOGRAPHY
Brown, R.E., and G,F. Murphy. "Ferroalloys." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985.
pp. 265-275.
Comba, P., K.P.V. Lei, and T.G. Carnahan. "CaF:-Enhanced Leaching of a Manganese-Bearing Silicate Ore," U.S.
Bureau of Mines. Report of Investigations 9372, 1991.
Holmes, R.A. "Manganese Minerals." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy,
and Exploration. 1994. pp. 655-660.
Jones, T. S. "Manganese." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1994, pp. 108-
109.
Jones, T. S. "Manganese." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 483-497.
Jones, T, S. "Manganese." From Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 789-812.
"Manganese," An Appraisal of Minerals Availability for 34 Commodities. U.S. Bureau of Mines. 1987. pp. 177-
184.
"Manganese and Manganese Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XIV.
1981. pp. 824-868.
Mclntosh, S.N., and E.G. Baglin. "Recovery of Manganese from Steel Plant Slag by Carbamate Leaching." U.S.
Bureau of Mines. Report of Investigations 9400. 1992.
Rusin, P. A., J.E. Sharp, R.G. Arnold, and N.A. Sinclair. "Enhanced Recovery of Manganese and Silver from
Refractory Ores." Mineral Bioprocessing. The Minerals, Metals, and Materials Society. 1991.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. "Manganese." From 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988. pp. 3-143 - 3-151.
U.S. Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. II.
August 1980.
Weiss, Norman L., Ed. "Manganese." SME Mineral Processing Handbook. Volume II. Society of Mining
Engineers. 1985. pp. 27-6 - 27-10.
471
-------
Page Intentionally Blank
472
-------
MERCURY
A. Commodity Summary
Mercury, also known as quicksilver, is a liquid metal at room temperature. It is used in batteries, lighting,
thermometers, manometers, and switching devices. Mercury compounds are used in agriculture as bactericides and
disinfectants, in pharmaceutical applications in diuretics, antiseptics, skin preparations, and preservatives, and in the
production of caustics, such as sodium and potassium hydroxide. Mercury also is used as a catalyst for production of
anthraquinone derivatives, vinyl chloride monomers, and urethane foams. Mercury can be found in nature in more
than a dozen minerals, including cinnabar, which is the most common. No mercury is mined in the United States,
although mercury is recovered in small quantities as a coproduct of gold mining.1'2 Seven gold mining operations in
California, Nevada, and Utah recovered mercury as a result of gold retorting in 1994, as shown in Exhibit I.3
EXHIBIT 1
Summary of Mines Producing Mercury as a Coproduct in 1994a-b
Company Name
Barrick Mercur Gold Mines Inc.
FMC Gold Co.
FMC Gold Co.
Homestake Mining Co.
Independence Mining Co. Inc.
Newmont Gold Co.
Placer Dome U.S.
Mine
Mercur
Getchell
Paradise Peak
McLaughlin
Enfield Bell
Carlin Mines Complex
Alligator Ridge
Location
Toole, UT
Humboldt, NV
Nye, NV
Napa, CA
Elko, NV
Eureka, NV
White Pine. NV
* "Mercury," Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1991. p. 989.
b Personal Communication between ICF Incorporated and Steven M. Jasinski, U.S. Bureau of Mines, November 1994,
B. Generalized Process Description
1. Typical Production Processes
Mercury can be produced from mercury ores and gold-bearing ores by reduction roasting or calcining. The
primary mercury production process is described below.
1 U.S. Environmental Protection Agency, "Mercury, Hg," from 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988, pp. 1-2.
2 Newmont Gold Company, Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
3 Jasinski, S.M., "Mercury," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p. 108.
473
-------
2. Generalized Process Flow Diagram
Exhibit 2 is a typical production flow diagram, illustrating the primary production of mercury. Although
currently not in use domestically, mercury is recovered from primary mining operations by crushing the ore, and
concentrating the mercury by flotation (not shown). The flotation operation produces a tailings stream. The
concentrate is heated in a furnace to vaporize the mercury, and the resulting vapor is condensed.4'3 The sulfur in the
ore is oxidized to sulfur dioxide (SO2). Some water may condense with the mercury and is discharged as a waste
stream (labeled stream No. 4 in Exhibit 2). The mercury is recovered from the condenser and may be washed before
being sold (creating wastewater stream No. 5). The sulfur dioxide and other gaseous emissions from the mercury
roasting furnace are controlled with a multistage scrubber (creating stream No. 1). After SO2 removal, the clean
stack gases are cooled with contact cooling water and discharged to the atmosphere (stream No. 3). Waste streams
may also result from the quenching of calciner wastes to reduce the temperature prior to disposal (stream No. 5).6
The process for recovering mercury from gold ore is shown in Exhibit 3, and it is similar to recovery from
cinnabar ore. If the gold ore is a sulfide ore, it typically is sent to a roasting step prior to leaching. This roasting
operation is similar to primary mercury ore roasting in that the mercury and sulfide are both volatilized. The exhaust
gases are passed through wet electrostatic precipitators (ESPs), and if necessary, through carbon condensers. The
sulfur dioxide is removed by lime prior to venting. If the treated sulfide ore has a high mercury content, the primary
mercury recovery process occurs from the wet ESPs. However, if the concentration is sufficiently low, no attempt is
made to recover mercury for sale.7
If the gold ore is an oxide-based ore, the crushed ore is mixed with water and sent to a classifier, followed
by a concentrator, which reduces the water content. The concentrate is sent to an agitator containing cyanide leach
solution. The slurry from the agitators is filtered, the filter cake is disposed, and the filtrate, which contains the gold
and mercury, is transferred to the electrowinning process. If the carbon-in-pulp process is used, the cyanide pulp in
the agitators is treated with activated carbon to adsorb the gold and mercury. The carbon is filtered from the agitator
tanks and treated with an alkaline cyanide alcohol solution to desorb the metals. This liquid is then transferred to the
electrowinning tanks. In the electrowinning process, the gold and mercury are electrodeposited onto a stainless steel
wool cathode, which is sent to a retort to remove mercury and other volatile impurities. The stainless steel wool
containing the gold is transferred from the retort to a separate smelting furnace where the gold is melted and
recovered as crude bullion.8 The exhaust gas from the retort, containing mercury, SO2, particulates, water vapor, and
other volatile components, passes through condenser tubes where the mercury condenses as a liquid and is collected
under water in the launders. Slag quenchwater is stored prior to being recycled to the carbon-in-leach circuit (CIL).
From the launders, the mercury is purified and sent to storage.9
4 Personal communication between ICF Incorporated and Steve Jasinski, U.S. Bureau of Mines, March 1994.
5 Cameo, L.C., "Mercury," from Mineral Facts and Problems. U.S. Bureau of Mines. 1985, p. 501.
6 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume V, Office of Water Regulations
and Standards, May 1989, pp. 2167-68, 2178.
7 Personal Communication between ICF Incorporated and Steven M. Jasinski, November 1994.
8 U.S. Environmental Protection Agency, Technical Resources Document: Extraction and Beneficiation of Ores
and Minerals. Volume 2: Gold, Office of Solid Waste, July 1994, p. 1-31.
9 Personal Communication between ICF Incorporated and Steven M. Jasinski, November 1994.
474
-------
EXHIBIT 2
PRODUCTION OF METALLIC MERCURY FROM PRIMARY MERCURY ORES
(Adapted from; Development Document for Effluent Limitations Guidelines, 1989, p, 2175.)
(No primary mercury mining is now conducted in the U.S.)
To Atmosphere
H,O
H,O
Beneficiated
Ores
H,O
I
Stack
Gas
Cooling
1
t
Calciner Wet Air
Pollution Control
(Multistage)
I
Stack
Gas
i
Condenser
I
i Hg Vapo
Calcining or
Roasting
Furnace
Calcine
Quench
J
Calcined Ore
Waste Product
3
1 H,O
1
Liquid Mercury
Product ^^ Cleaning
^ Bath
1
H- i,
Condenser
Slowdown
2
Clean
• Mercury
Product
475
-------
•vl
01
EXHIBIT 3
PRODUCTION OF METALLIC MERCURY FROM GOLD ORES
(Source: Personal Communication Between ICF Incorporated and Steven M. Jasinski, November 1994.)
Mercury
Storage
Purification
•^"8
•
Condenser
Tubes,
Launders
•HjO
Cyanide Solution
Crushed
Ore
t
H2O
_^^ Ove
c,,,,,fa
rflow
Potential Mercury Emission Sources
f
Agitators
Multiple
— -
Filter
— *•
Electro-
winning
— *
Re
Hg
*
on
-------
Mercury is also recovered from industrial scrap and waste materials, such as discarded dental amalgams,
batteries, lamps, switches, measuring devices, control instruments, and wastes and sludges generated in laboratories
and electrolytic refining plants. Scrap products are broken down to liberate metallic mercury or its compounds,
heated in retorts to vaporize the mercury, and cooled to condense the mercury,10 This secondary recovery of mercury
is outside primary mineral processing and is, therefore, outside the scope of the this report,
3. Identification/Discussion of Novel (or otherwise distinct) Processes
There are several alternative processing options, including leaching with sodium sulfide and sodium
hydroxide, followed by precipitation with aluminum or electrolysis. Alternatively, mercury can be dissolved in
sodium hypochlorite solution, then passed through activated carbon to adsorb the mercury. The mercury is
recovered from the carbon by heating, producing elemental mercury. Neither of these processes are in use today. A
third option, also not in use, is electrooxidation." Research is continuing on the best way to recover mercury from
gold and silver solutions for coproduct mercury production.12'13'14
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in die production sequence, and waste generation points and
quantities presented above.
10 "Mercury," Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., Vol. XV, 1981, pp. 147-48.
11 Carrico, L.C., 1985, Op. Cit.. p. 501.
12 "Mercury," 1981, Op. Cit.. p. 148.
13 Simpson, W.W., W.L. Staker, and R.G. Sandberg, "Calcium Sulfide Precipitation of Mercury From Gold-Silver
Cyanide Leach Slurries," from Report of Investigations 9042. U.S. Bureau of Mines, 1986. p. 1.
14 Sandberg, E.G., W.W. Simpson, and W.L. Staker, "Calcium Sulfide Precipitation of Mercury During Cyanide
Leaching of Gold Ores," from Report of Investigations 8907. U.S. Bureau of Mines, 1984. p. 1.
477
-------
Production of Metallic Mercury from Primary Mercury Ore
EPA determined that for the production of metallic mercury from primary mercury ore, the
beneficiation/processing line occurs between calcining/roasting and condensing since there is no leaching directly
after the roasting step and the resulting product undergoes further beneficiation (i.e., cleaning). Therefore, because
EPA has determined that all operations following the initial "processing" step in the production sequence are also
considered processing operations, irrespective of whether they involve only techniques otherwise defined as
beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing operation are
considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing
waste streams generated after the beneficiation/processing line, along with associated information on waste
generation rates, characteristics, and management practices for each of these waste streams.
Production of Metallic Mercury from Gold Ores
Because mercury is being recovered as a co-product of other metals obtained during mineral processing
operations, all of the wastes generated during mercury recovery also are mineral processing wastes. For a
description of where the beneficiation/processing boundary occurs for this mineral, see the gold and silver sector
reports.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
The following wastes may be generated by extraction and beneficiation operations: gangue, flotation
tailings, spent flotation reagents, and wastewater.15
2. Mineral Processing Wastes
Primary Retorting is not currently used in the United States, due to the economics of mining primary
mercury ores. Therefore, the wastes associated with primary retorting are not included in the tables summarizing
waste stream generation rates and waste characteristics. The following three primary retorting waste streams are
included in this report for completeness.
Furnace Calcines. Approximately 10 metric tons of furnace calcines were produced annually in the United
States in 1992. Available data do not indicate the waste exhibits hazardous characteristics.16 No other information
on waste characteristics, waste generation, or waste management was available in the sources listed in the
bibliography.
SO2 Scrubber Effluent. Approximately 3,000 metric tons of SO2 scrubber effluent were produced
annually in the United States in 1992. Available data do not indicate the waste exhibits hazardous characteristics.17
No other information on waste characteristics, waste generation, or waste management was available in the sources
listed in the bibliography.
15 Harty, D.M., and P.M. Terlecky, Characterization of Wastewater and Solid Wastes generated in Selected Ore
Mining Subcategories. (Sb. Hg. Al. V. W, Ni. Til. U.S. Environmental Protection Agency, August 21, 1981, pp. II-
36 -11-40.
16 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Volume I, Office of Solid Waste, August 1992, p. 1-6.
17 Ibid.
478
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Participate Control Effluent. Approximately 2,000 metric tons of particulate control effluent were
produced annually in the United States in 1992. Available data do not indicate the waste exhibits hazardous
characteristics.18 No other information on waste characteristics, waste generation, or waste management was
available in the sources listed in the bibliography,
Co-product Retorting. The wastes produced in coproduct retorting will vary greatly depending on the
input materials. The wastes also may contain other metals.
Dust. Approximately 7 metric tons of dust are produced annually from the mercury sector in the U.S.19
Although no published information regarding waste characteristics was found, we used best engineering judgment to
determine that this waste may exhibit the characteristics of toxicity for mercury. We also used best engineering
judgment to determine that this waste stream is not believed to be recycled. This waste stream was formerly
classified as a sludge.
Furnace Residues. Approximately 77 metric tons of furnace residues are produced annually from the
mercury sector in the United States.20 Although no published information regarding waste characteristics was found,
we used best engineering judgment to determine that this waste may exhibit the characteristics of toxicity for
mercury. This waste stream is not recycled.
Quenchwater. During the retorting process, mercury gas is vaporized from the gold filter cake. The
mercury gas is quenched with a direct contact water spray and condensed to form liquid mercury, which is collected
for sale. Waste mercury quenchwater is generated at a rate of 20 to 30 gallons per minute at the facility, and is
recycled to the CIL circuit. This waste generation rate corresponds to low, medium, and high sector-wide generation
rates of 63,000 mt/y, 77,000 mt/y, and 420,000 mt/y, respectively. This waste may be toxic for lead and mercury.
This waste stream is believed to be fully recycled and was formerly classified as a spent material.
D. Non-uniquely Associated Wastes
Non-uniquely associated wastes may be generated at on-site laboratories and may include used chemicals
and liquid samples. Other hazardous wastes may include spent solvents, tank cleaning wastes, and polychlorinated
biphenyls from electrical transformers and capacitors. Non-hazardous wastes may include tires from trucks and large
machinery, sanitary sewage, and waste oil and other lubricants.
E. Summary of Comments Received By EPA
New Factual Information
Newmont Gold Company was the sole commenter on the mercury sector report. This commenter
(COMM57) provided new factual information to be added to the mercury sector report, stating that the flow diagram
depicting the mercury production process for recovery of mercury from gold ores and the accompanying narrative
did not resemble the process used at Newmont Gold nor at other gold producers. The commenter did not provide
any suggested changes and, therefore, the flow diagram was not revised.
18 Ibid.
19 Ibid.
20
Ibid.
479
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Sector-specific Issues
The commenter also provided several suggestions related to sector-specific issues. The commenter stated
that mercury is a "co-product," not a "by-product" because the mercury in question is not a secondary stream that is
discarded or recycled for further mercury recovery. Therefore, it is not a RCRA Subtitle C byproduct. The same
commenter stated that they were unaware of any statutory/regulatory language or EPA interpretive guidance that
would lead to the conclusion that all wastes generated during mercury recovery as a coproduct of other metals are
mineral processing wastes. In addition, this commenter stated that retort quenchwater can be a by-product or a spent
material, depending on the circumstances. EPA has revised the report to indicate that mercury is recovered and may
be a co-product of gold processing. EPA also has clarified that all wastes generated during mercury recovery from
gold ores are mineral processing wastes because the mercury recovery process occurs during mineral processing
operations for recovery of other metals. The report was not modified with respect to retort quenchwater because the
distinction between by-product and spent material is made irrelevant by today's Rule.
480
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BIBLIOGRAPHY
Carrico, L.C. "Mercury." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 499-508.
Harty, D.M., and P.M. Terlecky. Characterization of Wastewater and Solid Wastes generated in Selected Ore
Mining Siibcategories. (Sb. Hg. Al. V. W. Ni. Ti). U.S. Environmental Protection Agency. August 21,
1981. pp. 11-36 -11-40.
Jasinski, S.M. "Mercury." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 108-
109.
"Mercury." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd Ed. Vol. XV. 1981. pp. 143-148.
Personal Communication between ICF Incorporated and Steve Jasinski, U.S. Bureau of Mines. March 1994.
Personal Communication between ICF Incorporated and Steve Jasinski, U.S. Bureau of Mines. November 1994.
Sandberg, R.G., W.W. Simpson, and W.L. Staker. "Calcium Sulfide Precipitation of Mercury During Cyanide
Leaching of Gold Ores." From Report of Investigations 8907. U.S. Bureau of Mines 1984. pp. 1-13.
Simpson, W.W., W.L. Staker, and R.G. Sandberg. "Calcium Sulfide Precipitation of Mercury From Gold-Silver
Cyanide Leach Slurries." From Report of Investigations 9042. U.S. Bureau of Mines. 1986. pp. 1-9.
U.S. Bureau of Mines. "Mercury." From An Appraisal of Minerals Availability for 34 Commodities. 1987. pp.
185-190.
U.S. Bureau of Mines. "Mercury." From Minerals Yearbook. Volume 1. Metals and Minerals. 1991. p. 989.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Volume V. Office of Water Regulations
and Standards. May 1989.
U.S. Environmental Protection Agency. "Mercury," 1988 Final Draft Summary Report of Mineral Industrial
Processing Wastes. 1988. pp. 3-9-3-13.
U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, August 1992.
U.S. Environmental Protection Agency. Technical Resources Document: Extraction and Beneficiation of Ores and
Minerals. Volume 2: Gold. Office of Solid Waste. July 1994.
481
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Page Intentionally Blank
482
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MOLYBDENUM, FERROMOLYBDENUM, AND AMMONIUM MOLYBDATE
A. Commodity Summary
Almost all molybdenum is recovered from low-grade deposits of the mineral molybdenite, naturally
occurring molybdenum disulfide (MoS2), mined either from a primary deposit, or as a byproduct of copper
processing,1 In 1993, one mine extracted molybdenum ore, and nine mines recovered molybdenum as a byproduct.
Two plants converted molybdenite concentrate to molybdic oxide, which was used to produced ferromolybdenum,
metal powder, and other molybdenum compounds.2 Exhibit 1 presents the names and locations of molybdenum
mines and processing facilities.
EXHIBIT 1
SUMMARY OF MOLYBDENUM, MOLYBDIC OXIDE, AND FERROMOLYBDENUM PRODUCERS"
Facility Name
Cyprus-Climax - Henderson
Cyprus-Climax
Cyprus-Climax
Cyprus-Climax - Green Valley
Cyprus-Climax
Kennecott
Molycorp Inc.
Montana Resources Inc.
Phelps Dodge
San Manuel
San Manuel
Thompson Creek
Thompson Creek
Location
Empire, CO
Fort Madison, IA
Clear Water, MI
Tucson, AZ
Baghdad, AZ
Bingham Canyon, UT
Washington, PA
Butte, MT
Chino, NM
San Manuel, AZ
Morenci, AZ
Chalis, ID
Langeloth, PA
* - Persona) Communication between ICF Incorporated and John W. Blossom, U.S. Bureau of Mines, October 1994.
Molybdenum metal is a refractory metal used as an alloying agent in steels, cast irons, and superalloys.3
Ferromolybdenum is an alloy of iron and molybdenum used primarily as an alternative additive in producing alloy
steels, cast irons, and nonferrous alloys. The two most common grades of ferromolybdenum are low carbon- and
high carbon ferromolybdenum. Ammonium molybdate is an intermediate in manufacturing both molybdenum metal
and molybdic oxide, although it can also be sold as a product. Purified MoS2 concentrate also is used as a lubricant.
1 J.W. Blossom, "Molybdenum," from Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines, 1992, p. 849.
2 J.W. Blossom, "Molybdenum," Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p. 114.
3 J.W. Blossom, 1992, Op. Cit. p. 847.
483
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B. Generalized Process Description
1. Discussion of Typical Production Processes
Molybdenum and molybdenum products, including ammonium molybdate, are made by roasting
concentrated ore, followed by purification and/or reduction. Ferromolybdenum is typically produced by reaction of
technical grade molybdic oxide and iron oxide with a conventional metallothermic process using silicon and/or
aluminum as the rcductant. These processes are described in greater detail below.
2, Generalized Process Flow Diagram
Molybdenum Metal and Ammonium Molybdate
Molybdenum metal and ammonium molybdate are made by roasting concentrated molybdenite ore, as
shown in Exhibit 2. The concentration operations, which are not shown, include crushing, grinding, and flotation of
either primary or copper ores. Molybdenite is recovered from either primary molybdenite or copper sulfide ore by
flotation, after the ore has been crushed and ground to a suitable size. Several stages of grinding and reflotation
concentrate the molybdenite in the primary ore to a 90 to 95 percent purity concentrate.4 The remainder of the
concentrate is primarily silica.5 Copper, iron and lead are die impurities removed as tailings by this flotation process.
Several sequential stages of flotation also are used for the copper ore, first to separate the gangue, and then the
copper. The molybdenite concentration is usually 70 to 90 percent purity, when recovered from copper ores.6
Technical grade molybdic oxide, consisting of 90 to 95 percent MoO3, is produced by roasting molybdenite
concentrate in a multiple hearth furnace at temperatures up to 650°C.7 Molybdenum concentrates may be leached
with nitric acid prior to roasting to reduce the alkali concentrations in die concentrates.8 The roasting process
removes sulfur and converts die sulfide to oxide. The flue gas contains products of combustion, SO2, and may
contain rhenium or selenium. The SO2 in die flue gas is converted to sulfuric acid (H2SO4).9 More information on
the processing of the flue gas, and die production of sulfuric acid can be found in die Rhenium and Selenium sections
of this document.
Pure molybdic oxide can be produced from technical grade molybdic oxide through sublimation and
condensation or by leaching. In sublimation, the technical grade oxide is heated to approximately 1,100°C in a
muffle type furnace. The oxide is vaporized and carried in a stream of forced air through cooling ducts and
4 Ibid., p. 850,
5 "Molybdenum and Molybdenum Alloys," from Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed.,
Vol. XV, 1981, p. 670.
6 Blossom, J. W., 1992, Op. Cit.. p. 850.
7 Ibid, p. 848.
8 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume VI, Office of Water Regulations
and Standards, May 1989, p. 3364.
9 "Molybdenum and Molybdenum Alloys," 1981, Op. Cit.. p. 670.
484
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Gas
EXHIBIT 2
MOLYBDENUM PRODUCTION
(Source: Development Document for Effluent Limitations Guidelines, 1989, p. 3370.)
Molybdenum
Sulfidc
Concentrate ^
Molybdenum
Sulfidc
Concentrate
SO2 Scrubber
or Acid Plant
|Gas
Rhenium
Scrubber
t
t
Leaching
1
i
Wastewater
>
*• Wastewater
Solvent Wastewater
„, . Ion Exchange
Wastewater b
t T"^
Scrubber Dissolving,
Tcchmcal Crystallization
Grade
Oxide A Crude
| H2 Gas 1 Ammonium
1 » ., i i_j Perrhcnate
1 T Molybdenum , .
Pure Molybdic Mctal
^ Oxi.ir .^ Reduction Powder • •
"^ ~^ Furnace Purification,
, ,. Rp.Hnrlinn
Acid 1 A
1 Water Ammonium A I
v Molybdatc 1
„ ..,..• Ammonium W
Pure Molybdic T
. , . Oxide ^ Dissolution, Molybdatc^ Rhenium Meta
1 ^ L^a^l-uB ^ Cryslaliizalion ^r Fleming
II f 1 U
m m Pure Molybdic Water m Ammonium W Molybdic
Wastewater T T Oxide N1I.,OH | T Molybdate T Oxide
00
Ul
-------
the condensed oxide particles are collected in a fabric filter. The purified oxide contains greater than 99.5 percent
MoO3. Technical grade oxide may also be purified by leaching with a hydrochloric acid-ammonium chloride
solution (not shown). The impurities are dissolved and separated from the solid molybdic oxide by filtration. The
pure oxide may be sold as a product, reduced to molybdenum metal powder, or used to produce various
molybdenum chemicals.10
Ammonium molybdate is formed by reacting technical grade molybdic oxide with ammonium hydroxide
and crystallizing out the pure molybdate. The ammonium molybdate may be sold as product, calcined to form pure
molybdic oxide, or reduced to form molybdenum metal powder.1'
Hydrogen is used to reduce ammonium molybdate or pure molybdic oxide to molybdenum powder, at 500-
1150°C, in a boat- or tube-type furnace. The metal powder is sintered and cast into ingots or bars.12
Ferromolybdenum
Exhibit 3 illustrates the production of low carbon and high carbon ferromolybdenum. Low carbon
ferromolybdenum is produced by mixing technical grade molybdic oxide, aluminum, ferrosilicon, iron oxide,
limestone, lime, and fluorspar, and igniting the aluminum (not shown). A metal button and a slag are formed,
allowed to solidify, and then are separated.13 One firm added that when it produces low carbon ferromolybdenum no
furnace is necessary, only a sand bed.1'1 High carbon content ferromolybdenum is made by reducing technical grade
molybdic oxide, calcium molybdate, or sodium molybdate with carbon in the presence of iron in an electric furnace
(not shown). The impurities from a slag which is discarded.15 Low carbon ferromolybdenum produced by the
thermite process is more common than the high carbon alloy.
3. Identification of Novel or Distinct Processes
One researcher has investigated the separation and recovery of critical metals (including molybdenum) from
mixed and contaminated superalloy scrap.16
10 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 3364.
11 Ibid.
12 "Molybdenum and Molybdenum Alloys," 1981. Op. Cit., p. 674.
13 U.S. Environmental Protection Agency, "Molybdenum," 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988, p. 3-154.
14 Molycorp, Inc. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
15 Ibid., p. 3-154.
16 Hundley, G.L., and D.L. Davis, "Recovery of Critical Metals from Superalloy Scrap by Matte Smelting and
Hydrometallurgical Processing," U.S. Bureau of Mines Report of Investigations 9390, 1991, p. 1.
486
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EXHIBIT 3
FERROMOLYBDENUM PRODUCTION
Aluminum, Technical Grade Molybdic Oxide,
Ferrosilieon, Iron Oxide, Limestone, Lime and Fluorspar
Furnace
Low Carbon Ferromolybdenum
Technical Grade Oxide, Iron, Calcium or
Sodium Molybdate, Carbon
i
Furnace
High Carbon Ferromolybdenum
487
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4, Extraction/Benefleiation Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes. The idea that beneficiation wastes are earthen in character is only a guide, and
not a standard. There may be instances where beneficiation operations produce a waste that is "not" earthen in
character. In such instances, the operation is not considered a processing operation, because of the waste's non-
earthen characteristics, and instead remains a beneficiation operation.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
Molybdenum Powder
EPA determined that for the production of molybdenum powder, the beneficiation/processing line occurs
between the roasting and sublimation steps because leaching does not follow and because the molybdenum disulfide
is chemically roasted to pure molybdic oxide.17 Therefore, because EPA has determined that all operations
following the initial "processing" step in the production sequence are also considered processing operations,
irrespective of whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from
any such operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather
than beneficiation wastes, EPA presents below the mineral processing waste streams generated after the
beneficiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
Ammonium Molybdate and Pure Molybdic Oxide
Based on a review of the process, there are no mineral processing operations involved in the production of
either ammonium molybdate or pure molybdic oxide.
Ferromolybdenum
EPA determined that for ferromolybdenum, the beneficiation/processing line occurs at the furnace where
the technical grade molybdic oxide and other materials are charged and undergo thermal reduction to form
17 Molycorp, Inc. Op. Cit.
488
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ferromolybdenum. One firm, Molyeorp Inc., reported that in their operations furnaces were restricted to high carbon
ferrornolybdenum production.18
C, Process Waste Streams
1. Extraction/Beneficiation Wastes
The following wastes may be generated by extraction and beneficiation operations: gangue, flotation
tailings, spent flotation reagents, and waste water.19'20 The tailings from molybdenite concentration are not expected
to exhibit any hazardous characteristics, although metal leaching and acid formation may take place.21
2, Mineral Processing Wastes
Ammonium Molybdate Refining
Refining Wastes. Available data do not indicate that ammonium molybdate refining wastes exhibit any
hazardous characteristics,22 Therefore, the Agency did not evaluate this material further.
Technical Grade Molvbdic Oxide Production
Liquid Residues. Approximately 1,000 metric tons of liquid residues are generated annually in the United
States. Available data indicate that this waste is potentially TC toxic. Potentially hazardous constituents include
arsenic, cadmium, lead, and selenium.23 The waste is not recycled. Liquids from the quench and scrubber
towers/thickener contained the following constituents: arsenic - 60 ppm; cadmium - 1.2 ppm; chromium - 1.8 ppm;
lead - 5.8 ppm; molybdenum -100 ppm; and selenium - 32 ppm.24 Additional data is provided in Attachment 1. No
other information on waste characteristics, or waste management was available in the sources listed in the
bibliography.
Treatment Solids. Available data do not indicate that treatment solids exhibit any hazardous
characteristics.23 Silicon was found at a concentration of 10 percent in solids from the quench and scrubber
towers/thickener.26 Therefore, the Agency did not evaluate diis material further.
18 Ibid.
19 PEI Associates, Site Specific Data Summary Forms: Facilities Involved in the Extraction and Beneficiation of
Ores and Minerals. Prepared for U.S. Environmental Protection Agency, Office of Research and Development,
November 1986.
20 Weiss, Norman L., Ed. "Molybdenum," SME Mineral Processing Handbook. Volume II, Society of Mining
Engineers, 1985, pp. 16-1 - 16-36.
21 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-152.
22 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set,
Volume I, Office of Solid Waste, August 1992, p. 1-2.
23 Ibid..... p. 1-6.
24 Ibid, Vol. II, p. 28-11.
25 Ibid.. Vol. I, p. 1-6.
26 Ibid.. Vol. II. p. 28-8.
489
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Solid Residues. Available data do not indicate that solid residues exhibit any hazardous characteristics (see
Attachment I).27 Therefore, the Agency did not evaluate this material further.
Roaster Gas Blowdown Solids. Approximately 100 metric tons of roaster gas blowdown solids are
generated annually in the United States. Available data do not indicate that this waste exhibits any hazardous
characteristics.28 Therefore, the Agency did not evaluate this material further.
Molybdic Oxide Refining Wastes. Approximately 2,000 metric tons of molybdic oxide refining wastes
are generated annually in the United States.29 This waste is believed to not exhibit any hazardous characteristics30
and has not been evaluated further by the Agency.
Flue Dust/Gases. The flue gases produced during the roasting of molybdenite concentrates could contain
volatile metals in the flue dust, in addition to the SO2. These metals may include lead, zinc, tin and others.31
Although no published information regarding waste generation rate was found, we used the methodology outlined in
Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 1,100 metric tons/yr,
250,000 metric tons/yr, and 500,000 metric tons/yr, respectively. We used best engineering judgment to determine
that this waste may exhibit the characteristic of toxicity for lead. This waste typically is not recycled. However,
Molycorp Inc. reported that flue dust is recycled at its Washington, PA facility. It also reported that in its operations
there was no difference between flue dust/gases and roaster gas blowdown solids.32
Metal. Refining
Refining Wastes. Available data do not indicate that metal refining wastes exhibit any hazardous
characteristics.33 Therefore, the Agency did not evaluate this material further.
H2 Reduction Furnace Scrubber Water. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste (see Attachment 1). Therefore, the Agency did not
evaluate this material further.
Ferromolybdeiium Production
APC Dust/Sludge. This waste is generated by the baghouse or other APC device receiving the fumes from
the ferromolybdenum furnace. Available data do not indicate that APC dust/sludge exhibits any hazardous
characteristics.34 Therefore, the Agency did not evaluate this material further.
27 Ibid.. Vol. II, p. 1-6.
28 Ibid.
29 Ibid.
30 Molycorp, Inc. Op. Cit.
31 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-153.
32 Molycorp, Inc. Op. Cit.
33 U.S. Environmental Protection Agency, 1992, Op. Cit. Vol. I, p. 1-6.
34 Ibid., p. 1-4.
490
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Slag. This waste, formed in either the production of low carbon ferromolybdenum or high carbon
ferrornolybdenum, is not expected to exhibit any hazardous characteristics. The slag is usually discarded.33
Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Hazardous Wastes
Ancillary hazardous wastes may be generated at on-site laboratories, and may include used chemicals and
liquid samples. Other hazardous wastes may include spent solvents, and tank cleaning wastes. Non-hazardous
wastes may include tires from trucks and large machinery, sanitary sewage, and waste oil and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Two commenters provided new information on facility specific operations and processes (COMM40,
COMM69). This new information has been incorporated into the Agency's sector report.
Site-specific Issues
None.
; U.S. Environmental Protection Agency, 1988, Op. Cit. p. 3-154.
491
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BIBLIOGRAPHY
Blossom, J. W. "Molybdenum." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
114-115.
Blossom, J. W. "Molybdenum." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 521-534.
Blossom, J. W. "Molybdenum." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 847-862.
Hundley, G.L., and D.L. Davis. "Recovery of Critical Metals from Superalloy Scrap by Matte Smelting and
Hydrometallurgical Processing." From Report of Investigations 9390. U.S. Bureau of Mines. 1991. pp. 1-
11.
ICF Incorporated. Amax Incorporated. Fort Madison. IA: Mineral Processing Waste Sampling Visit — Trip Report.
August 1989.
ICF Incorporated. Magma Copper Company. San Manuel. AZ: Mineral Processing Waste Sampling Visit — Trip
Report. August 1989.
"Manganese." From An Appraisal of Minerals Availability for 34 Commodities. U.S. Bureau of Mines. 1987. pp.
191-199.
"Molybdenum and Molybdenum Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. Vol. XV. 3rd ed.,
1981. pp. 670-690.
PEI Associates. Site Specific Data Summary Forms: Facilities Involved in the Extraction and Beneficiation of Ores
and Minerals. Prepared for U.S. Environmental Protection Agency, Office of Research and Development.
November 1986.
Personal Communication between ICF Incorporated and John W. Blossom, U.S. Bureau of Mines. October 1994.
RTI Survey 100214. National Survey of Solid Wastes From Mineral Processing Facilities. Climax Molybdenum
Company, Fort Madison, IA. 1989.
RTI Survey 102145. National Survey of Solid Wastes From Mineral Processing Facilities. Molycorp, Inc.,
Washington, PA. 1989.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Volume VI. Office of Water Regulations
and Standards. May 1989.
U.S. Environmental Protection Agency. "Molybdenum." From 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988. pp. 3-152 - 3-157.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency. Technical background Document. Development of Cost. Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989. pp. 3-5 - 3-6.
Weiss, Norman L., Ed. "Molybdenum." SME Mineral Processing Handbook. Vol. II. Society of Mining Engineers.
1985. pp. 16-1 - 16-36.
492
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ATTACHMENT 1
493
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U3
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SOLID RESIDUES - MOLYBDENUM OXIDE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
100,000 100,000 100,000 1/1
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5,0 0
100.0 0
.
-
1,0 0
5,0 0
-
.
-
5.0 0
-
.
0.2 0
-
.
1.0 0
5.0 0
.
,
.
-
.
-
.
-
-
.
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - H2 REDUCTION FURNACE SCRUBBER WATER - MOLYBDENUM OXIDE
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
vlagnesium
Manganese
Mercury
Vlolybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
ylinimum Average Maximum #
-
0.001
0.002
-
0.001
-
0.001
0.001
-
0.004
-
0.001
-
-
0.0002
-
0.024
0.001
0.001
0.001
-
0.51
0.01
-
-
-
-
-
-
-
-
-
-
0.0090
0.0107
-
0.0023
-
0.0010
0.0040
-
0.3947
-
0.0657
-
-
0.0002
-
1.1613
0.0010
0.0053
0.0010
-
0.5733
0.0100
-
-
-
-
-
-
-
-
-
-
0.024
0.024
-
0.005
-
0.001
0.006
-
0.64
-
0.17
-
-
0.0002
-
2.8
0.001
0.014
0.001
-
0.63
0.01
-
-
-
-
-
-
-
-
-
Detects
0/0
3/3
3/3
0/0
3/3
0/0
3/3
3/3
0/0
3/3
0/0
3/3
0/0
0/0
3/3
0/0
3/3
3/3
3/3
3/3
0/0
3/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1,0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
. .
.
-
-
-
.
-
-
.
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
496
-------
PHOSPHORIC ACID
A.
Commodity Summary
Most phosphoric acid facilities are co-located with other manufacturing facilities.' The primary product
from phosphoric acid facilities is commercial-grade wet process phosphoric acid, approximately 95 percent of which
is used at co-located facilities to produce fertilizers and animal feed. Most of the remaining portion is used as a
feedstock in chemical processing operations. Phosphoric acid producing facilities are listed in Exhibit 1.
EXHIBIT 1
SUMMARY OF PHOSPHORIC Aero PRODUCING FACILITIES
Facility Name
Agrico Chem
Albright & Wilson
Arcadian
Car gill
Central Phosphates
CF Ind.
Chevron
Conserv
Farmland
FMC
Gardinier, Inc.
Hydrate
IMC
Locations
Pierce, FL
Uncle Sam, LA
Donaldsonville, LA
Fernald, OH
Charleston, SC
Geismar, LA
Riverview (Tampa), FL
Plant City, FL
Bartow, FL
Rock Springs, WY
Nichols, FL
Pierce (Bartow), FL
Carteret, NJ
Lawrence, KS
Newark, CA
Riverview, FL
Milwaukee, WI
Mulberry, FL
Type of
Operations
Wet Process
Wet Process
Wet Process
Furnace
Furnace
Wet Process
Wet Process
Wet Process
Wet Process
Wet Process
Wet Process
Wet Process
Furnace
Furnace
Furnace
Wet Process
Furnace
Wet Process
Potential Factors Related to
Sensitive Environments
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Located in 100-year floodplain,
within 1 mile of wetland
Located in 100-year floodplain,
located in wetland
Within 1 mile of wetland,
located in area of karst terrain
Uncertain
Uncertain
Within 1 mile of wetland
Within 1 mile of wetland
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Located within 1 mile of
wetland
1 U.S. Environmental Protection Agency, "Phosphoric Acid Production," from Report to Congress on Special
Wastes from Mineral Processing. Vol. II, Office of Solid Waste, July 1990, pp. 12-1-12-61.
497
-------
EXHIBIT 1 (continued)
Facility Name
JR Simplot
Mobil
Monsanto
Nu West
Nu South
Occidental
Royster
Seminole
Stauffer
Texasgulf
US Agri-Chemicals Corp
(USAC)
Locations
Pocatello, ID
Pasadena, TX
Trenton, MI
Augusta, GA
Carondelet, MO
Long Beach, CA
Soda Springs (Conda), ID
Pascagoula, MS
Jeffersonville, IN
Columbia, TN
White Springs, FL
Dallas, TX
Palmetto (Piney Ft), FL
Mulberry, FL
Bartow, FL
Morrisville, PA
Nashville, TN
Richmond, CA
Chicago Heights, IL
Chicago, IL
Aurora, NC
Ft. Meade, FL
Type of
Operations
Wet Process
Wet Process
Furnace
Furnace
Furnace
Furnace
Wet Process
Wet Process
Furnace
Furnace
Wet Process
Furnace
Wet Process
Wet Process
Wet Process
Furnace
Furnace
Furnace
Furnace
Furnace
Wet Process
Wet Process
Potential Factors Related to
Sensitive Environments
Located in 100-year floodplain.
located in fault zone
Located in 1 00-year floodplain
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain '
Located within 1 mile of
wetland
Uncertain
Located within 6.5 miles of
endangered species habitat,
within 1 mile of wetland,
located in area of karst terrain
Located within 1 mile of
wetland
Located in endangered species
habitat, located in 100-year
floodplain, within 1 mile of
wetland
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Located in 100-year floodplain,
located in wetland
Within 1 mile of wetland
Uncertain
498
-------
B, Generalized Process Description
There are two processes for producing phosphoric acid: (1) the wet process, and (2) the furnace process.
Wet process acid, produced directly from phosphatic ores, is characterized by relatively high production volume, low
cost, and low purity. It is used primarily in fertilizers. Furnace or thermal acid, manufactured from elemental
phosphorus, is more expensive and considerably purer than wet-process acid. It also is produced in much smaller
quantities, almost exclusively for applications requiring high purity.2 As shown in Exhibit 1, there are 22 facilities
that use the wet process and 18 that use the furnace process. There are significant differences in these processes and
therefore, this report is divided into two sections. The wet process, as described in Section 1, is the main focus of
this chapter. A brief discussion of the furnace process is provided in Section 2. (The furnace process uses a saleable
mineral commodity as a primary raw material (element al phosphorous) and as such, is completely outside the scope
of the Mining Waste Exclusion.) Finally, Section 3 describes several related processes such as ammoniated fertilizer
production, animal feed production, superphosphoric acid production, fluoride recovery, and sulfuric acid
production.
SECTION 1: The Wet Process
1. Discussion of the Typical Production Processes
Wet process steps include digestion, filtration, and concentration. Phosphate rock is dissolved in
phosphoric acid, to which sulfuric acid is added. The slurry from this operation is sent to filters where solids are
collected, washed, and sent to phosphogypsum stacks. The acid is concentrated by evaporation. The wet process is
described in more detail below.
2. Generalized Process Flow Diagram
During digestion, the first step in phosphoric acid production, beneficiated phosphate rock is dissolved in
phosphoric acid; sulfuric acid, which chemically digests the calcium phosphate, is added to this solution. The
product of this operation is a slurry that consists of the phosphoric acid solution and a suspended solid, calcium
sulfate, commonly known as phosphogypsum. The slurry is routed to a filtration operation where the suspended
phosphogypsum is separated from the acid solution. The acid isolated during filtration is concentrated through
evaporation to produce "merchant grade" (54 percent) phosphoric acid. The phosphogypsum is re-slurried, this time
in recycled process wastewater, and sent to disposal in phosphogypsum stacks.3 Exhibit 2 presents a process flow
diagram of phosphoric acid production.4
Only five percent of raw product acid is purified. Purification of wet-process acid is accomplished by two
primary methods: (1) solvent extraction, and (2) chemical precipitation. Exhibit 3 presents a typical flow diagram
for solvent extraction purification of wet-process phosphoric acid. (Purification steps are outside the scope of
mineral processing.) In the production of sodium phosphates using chemical precipitation, almost all wet-process
acid impurities may be induced to precipitate as the acid is neutralized with sodium carbonate or sodium hydroxide.
The main exception, sulfate, may be precipitated as calcium or barium sulfate. Most fluorine and silica can be
removed with the sulfate filter cake as sodium fluorosilicate by the addition of sodium ion and control of the Si/F
ratio in the process.5
2 "Phosphoric Acid and the Phosphides," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol.
XVII, 1982, pp. 426-442.
3 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 12-1 - 12-61.
4 Ibid.
5 Kirk-Othmer Encyclopedia of Chemical Technology. 1982, Op. Cit.. pp. 426-442.
499
-------
EXHIBIT 2
PHOSPHORIC ACID TREATMENT
(Adapted from: Report to Congress on Special Wastes from Mineral Processing, July 1990, pp. 12-1 -12-61.)
Process
Sulfuric Add
Beneficiated
Phosphate
Rock(BPR)
i i
Phosphoric Acid
Production
Process Wastewater
Phosphogypsum
Process
Wastewater
Hydrofluosilicic Acid
(Optional)
BPR
Phosphoric
Acid
Non-Ammoniated
Animal Feed
(Optional)
BPR
Limestone
and/or
Soda Ash
Animal Feed
Super
Phosphoric
Acid
Process •_
Wastewater ;
Merchant Grade
Phosphoric Acid
Special Waste
Management
I Gjpsum
| Stack
! Process •
| Wastewater:
i
Storage i
Surface
Impoundment'
f
Return
to
Production
NPDES
Discharge
Production Operation
i j Special Waste
f i Waste Management Unit
500
-------
EXHIBIT 3
SOLVENT EXTRACTION PURIFICATION OF WET PROCESS PHOSPHORIC ACID
(Adapted from: Krk-Othmer Encyclopedia of Chemical Technology, 1982, pp. 426 - 442.)
.Solvent.
Wet Process
Acid
Fertilizer
Product
501
-------
In the double-neutralization process for wet process acid purification, sodium fluorosilicate is precipitated
and removed by filtration at a pH of 3-4. Upon raising the pH to 7-9, insoluble phosphates of iron, aluminum.
calcium, and magnesium form and separate. Iron can be precipitated as hydrous ferric oxide, reducing the phosphate
loss in the second filter cake. Both the fluorosilicate and metal phosphate filter residues tend to be voluminous cakes
that shrink when dewatered; recovery of soluble phosphates trapped within the cakes is difficult.6
The double-neutralization process is used in the production of high volume detergent-builder phosphates
because the phosphate precursor solutions occur at pH 7-9. More acidic salts, however, require an additional
filtration to eliminate discoloration caused by remaining traces of ferric oxide that precipitate at higher pH.7
The increasing cost differential between the sulfur used in manufacture of wet-process acid and the
electricity needed for thermal acid has encouraged the development of new processes for purifying wet-process acid.
These are based mostly on solvent extraction using organic solvents with low miscibility in water. Crude wet-
process acid is typically concentrated and clarified prior to extraction to remove sludge-forming components and
improve partition coefficients. Chemical precipitation of sulfate, silicate, and fluoride may also be used as a
prepurification step preceding solvent extraction.8
Organic-phase extraction of H3PO4 is accomplished in a series of countercurrent mixer-settlers, with
extraction generally limited to 50-75 percent of the feed acid P2O5 content. Higher extraction results in sludge
precipitation in the settlers and in the depleted raffinate stream. Raffinate is stripped of residual solvent and used in
fertilizer production.9
The acid is washed from the organic stream by water or aqueous alkali in another series of countercurrent
mixer-settlers, stripped of residual solvent, and concentrated to the desired P2O5 level. The solvent is recycled to the
extraction section. Many variations of this basic scheme have been developed to improve extraction of phosphate
and rejection of impurities to the raffinate stream, and numerous patents have been granted on solvent extraction
processes.10
Processing phosphate rock to produce phosphate fertilizer is water-intensive. At larger wet process
phosphoric acid plants, water use can reach 50,000 gallons per ton of phosphoric acid. At one phosphoric acid plant
with a rated capacity of 4,500 tons per day, 155,000 gallons of water per minute are used. Water uses include
phosphogvpsum transport, phosphoric acid concentration, and phosphoric acid temperature control and cooling.11
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
6 Ibid.
7 Ibid.
8 Ibid.
9 Ibid.
10
Ibid.
11 The Fertilizer Institute. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1995.
502
-------
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed, Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for the production of phosphoric acid via the wet process, the beneficiation/
processing line occurs between beneficiation of phosphate rock and digestion, because the beneficiated phosphate
rock undergoes a complete acid digestion, which destroys the physical matrix of the rock to yield phosphoric acid
and phosphogypsum. Therefore, because EPA has determined that all operations following the initial "processing"
step in the production sequence are also considered processing operations, irrespective of whether they involve only
techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial
mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA
presents below the mineral processing waste streams generated after the beneficiation/processing line, along with
associated information on waste generation rates, characteristics, and management practices for each of these waste
streams.
SECTION 2: The Furnace Process
1. Discussion of the Typical Production Processes
In the furnace process, elemental phosphorus is burned to phosphorus pentoxide which is sent to hydration
for the production of phosphoric acid. This entire operation uses a saleable mineral commodity as a primary raw
material (elemental phosphorus) and therefore is completely outside the scope of the Mining Waste Exclusion.
2. Generalized Process Flow Diagram
In the manufacture of phosphoric acid from elemental phosphorus, phosphorus is burned in excess air, the
resulting phosphorus pentoxide is hydrated, the heats of combustion and hydration are removed, and the phosphoric
acid mist is collected. There are three principal process unit types used to deal with the very high combustion-zone
temperatures, the reactivity of hot phosphorus pentoxide, the corrosive nature of hot phosphoric acid, and the
difficulty of collecting the very fine phosphoric acid mist. These process unit types are (1) wetted wall, (2) water-
503
-------
cooled, and (3) air-cooled; depending on the method used to protect the combustion chamber wall.12 Exhibit 4
presents process flow diagrams for the three furnace-grade phosphoric acid production process units.
In wetted-wall units, the walls of a tall circular, slightly tapered combustion chamber are protected by a high
volume curtain of cooled acid flowing down inside the wall. Phosphorus is atomized by compressed air or steam
into the top of the chamber and burned in additional combustion air supplied by a forced or induced draft fan. Acid
sprays at either the bottom of the chamber or in a subsequent, separate spraying chamber complete the hydration of
phosphorus pentoxide.13
When all the acid is to be converted into sodium phosphate salt, a variation of the wetted-wall acid plant is
used. In this case, a relatively noncorrosive, neutral sodium phosphate solution is circulated in lieu of phosphoric
acid. Phosphorus pentoxide absorption is rapid and over 95 percent is collected by the circulating stream. Alkali
and make-up water are added through a tail scrubber as dilute caustic soda, soda ash, or sodium sesquicarbonate
solution adjusted to maintain the system materials balance.14
Air-cooled plants are characterized by a large refractory-lined combustion chamber from which waste heat
is removed by radiation and convection. The combustion chamber is constructed of carbon steel lined with a single
layer of high alumina refractory brick.15
Hot combustion gases from both the air-cooled combustion chamber and the water-cooled combustion
chamber are quenched and saturated with water in a hydrator. An absorber bed of carbon or graphite rings may be
mounted above the hydrator in the same structure to obtain more complete absorption of P2O5 and to assure that the
gas stream is cooled to about 100°C. Weak acid from mist collection is sprayed on the absorber bed, and product
acid at 75-85 percent H3PO4 leaves the hydrator through a heat exchanger.16
The P2O5 initially is hydrated and absorbed in the hot gas stream by direct contact with relatively strong
acid. This is often followed by successive stages of scrubbing with progressively more dilute acid and finally, with
incoming make-up water.17
Since most furnace grade phosphoric acid is used to make food-grade acid, the arsenic it contains must be
removed in a purification step. The phosphoric acid is reacted with a small amount of hydrogen sulfide to precipitate
arsenic sulfide which is removed by filtration.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
12 Kirk-Othmer Encyclopedia of Chemical Technology. 1982, Op. Cit.. pp. 426-442.
13 Ibid.
14 Ibid.
15 Ibid.
16 Ibid.
17 Ibid.
504
-------
EXHEBU4
FURNACE-GRADE PHOSPHORIC ACID PROCESSES
(Adapted from Krk-Othrrer Ereydopediaof Charieal Tedmology, 1982, pp. 426 - 442.)
Atomizing
Air
Phosphorous
Combustion
Air
R-oductArid
(a) Wetted-Wall Combustion Chamber
Hwsphorous
_ Combustion
Air
Exit Gas
to
rfydrator
(b) Air-CooledCcxnbustionCharnber
Atonizmg
Air
To Mst Collector
(c) Water-Cooled Combustion Chamber
(d) rfydrator/Absorber
505
-------
4. Extraction/Beneficiation Boundaries
The furnace process uses a refined mineral commodity and as such, is completely outside the scope of the
Mining Waste Exclusion.
SECTION 3: Ancillary Processes
Feed and fertilizer plants, as well as sulfuric acid plants, often are co-located with phosphoric acid facilities.
This section describes production of many products related to phosphoric acid. Exhibit 5 presents an overview of
phosphoric acid and related product manufacturing operations. All of these ancillary processes use a saleable
commodity (merchant grade phosphoric acid) as the primary raw material and, therefore, are outside the scope of the
Mining Waste Exclusion.
Fertilizer Operations
About 95 percent of commercial phosphoric acid is used to make ammoniated fertilizer and animal feed.
Several facilities produce ammoniated fertilizers such as DAP (diammonium phosphate), MAP (monoammonium
phosphate), and GTSP (granular triple superphosphate). MAP and DAP are generated by ammoniating phosphoric
acid and GTSP manufacturing involves reacting phosphate rock and phosphoric acid.18
Animal Feed Production
Ammonia is reacted with defluorinated P2O5 to produce the defluorinated ammonium phosphates Monofos
and Duofos. Limestone is reacted with defluorinated P2O5 to produce the defluorinated calcium phosphates Dynafos
and Biofos. IMC in Mulberry, FL produces up to 2,500 tons per day of these products.19
Superphosphoric Acid Operations
Superphosphoric acid is produced from concentrated (54 percent) acid by heating it in a shell and tube heat
exchanger, routing it to an evaporator to remove the remainder of the free water, and concentrating the acid to 70
percent. This product can be sold or further filtered. Metallic phosphates are filtered out and routed to the
granulated fertilizer feed.20
Liquid fertilizer may be produced by first diluting the Superphosphoric acid back to 54 percent then
ammoniating the acid. Liquid fertilizer is a low volume specialized product produced only on a limited basis.21
Silicofluoride Recovery
In order to produce low-fluorine animal feed supplements, P2O5 must be defluorinated. IMC in Mulberry,
Florida defluorinates 600 tons per day of 54 percent P2O5 in a batch tank using silica to remove fluoride. IMC uses
18 U.S. Environmental Protection Agency, Supplemental Information on Phosphoric Acid Production: Alternative
Management of Process Wastewater at Phosphoric Acid Facilities. Office of Solid Waste, December 1990, pp. A1-5.
19 Ibid., pp. A2-6.
20 Ibid.
21 Ibid.
506
-------
EXHIBITS
OVERVIEW OF PHOSPHORIC ACID AMD RELATED PRODUCTS PRODUCTION
(Adapted from: Supplemental Information on Phosphoric Acid Production, 1990, pp. A2 -11.)
H,O
I
H,0
H,O
Rock
^
Wet Rock
Grinding
^~
•^
Attack
Sulfunc
Acid
Manufacture
^ Air
- Sulfur
Uranium
^K
Uranium
Recovery
Filter
•«-
PA
^
^
Gypsum
Waste
to Pond
Animal
Feeds
Soda Ash
75%BPLRock
507
-------
16,000 gallons per minute of cooling pond water to condense vapors, which contain SiF4 and P2O5, from two
evaporators using barometric condensers. Upon condensing, the SiF4 is converted to H2SiF6. IMC sends 6,000
gallons per minute of the flow to the Multifos plant; the remainder is returned to the cooling pond.22 USAC in Ft.
Meade, Florida recovers 25 percent fluosilicic acid (FSA) as a by-product from the phosphoric acid evaporators and
from reaction vapors evolved from the reaction stage. Fluorine compounds are recovered from the vapor in
fluosilicic absorption towers at a rate of 55 tons per day. Seventy-five percent of the fluoride present in the vapors is
removed. USAC sells its recovered fluosilicic acid to a nearby ALCOA plant that manufactures aluminum
fluoride.23 Gardinier in Riverview, Florida also recovers FSA and in 1992 supplied 70 percent of the domestic
market for drinking water fluoridation.24 Agrico in Uncle Sam, Louisiana collects FSA and either sells it or
processes it in an on-site plant to produce silicon tetrafluoride.25 Agrico in Donaldsonville, LA sells the recovered
FSA.
Multifos Plant
IMC reacts non-defluorinated 54 percent P2O5, soda ash, and phosphate rock in a high temperature
calcining kiln to produce 300 tons per day of tricalcium phosphate, also known as Multifos, another low fluorine
animal feed supplement. Wastewaters from this process are returned to the cooling ponds at IMC.26
Sulfuric Acid Production
Phosphate rock is reacted with sulfuric acid to make phosphoric acid. At many plants, sulfuric acid is
produced on-site by burning sulfur. This process is exothermic and the heat generated is often used to run the plant.
At Texasgulf in Aurora, North Carolina, fresh water is used to make sulfuric acid after being purified in a lime
softening and ion exchange operation. Texasgulf has five sulfuric acid manufacturing process lines using double
absorption with vanadium pentoxide catalysts. This produces 3.4 million tons of 95 percent acid annually.27 IMC in
Mulberry, Florida produces 13,000 tons per day of 98.5 percent sulfuric acid.28 U.S. Agri-Chemicals in Fort Meade,
Florida (USAC) produces sulfuric acid in two double absorption contact sulfuric acid manufacturing plants. Each
plant has a capacity of 2,000 tons per day of 98 percent sulfuric acid.29 Gardinier in Riverview, Florida also
manufactures sulfuric acid for the wet process.30
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
22 Ibid., pp. A2-6.
23 Ibid., pp. A3-4.
24 Ibid., pp. A4-3.
25 Ibid., pp. A5-4.
26 Ibid.
27 Ibid., pp. A1-3.
28 Ibid., pp. A2-3.
29 Ibid., pp. A3-2.
30 Ibid., pp. A4-2.
508
-------
4. Extraction/Beneflciation Boundaries
These processes use a saleable mineral commodity as the primary raw material and as such, are completely
outside the scope of the Mining Waste Exclusion.
C. Process Waste Streams
1, Extraction/Beneflciation Wastes
None are identified,
2. Mineral Processing Wastes
Wet Process
Process wastewater and phosphogypsum are the primary waste streams from the wet process. These
wastes have been classified as RCRA special wastes, and are exempt from Subtitle C regulation.
The fertilizer industry typically manages its waste streams in the aggregate. Aggregation allows heat that
has built up in the system to assist natural evaporation in water management. Aggregate management of waste
streams also is essential to maintaining the water balance at phosphate rock processing facilities. Control of the
water balance requires close consideration of a number of factors, including the amount of rainfall, the watershed
area, and evaporation rates. Generally across the industry, more than 90 percent of the water used is recycled.
Because production and cooling are primary uses, water is generally recycled through cooling ponds. The constant
reuse and recycling of water results in buildup of acidity to the point that the recirculating water has significant acid
values that make it valuable for reuse and causes it to exhibit the corrosivity characteristic.31
Waste scale. This waste is generated at a rate of 41,700 to 208,300 metric tons per year and is generally
sent to a cooling pond.32 This waste is not expected to be hazardous.
Furnace Process
The furnace process uses a refined mineral commodity (elemental phosphorus) and therefore is completely
outside the scope of the Mining Waste Exclusion.
Arsenic sulflde sludge. Approximately 0.28 kg per kkg of product of arsenic sulfide is formed during
product purification.33
Spent filter cake is a possible waste stream generated from the production of phosphoric acid by the
furnace process.
31 The Fertilizer Institute. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1995.
32 U.S. Environmental Protection Agency, Technical Background Document. Data and Analyses in Support of the
Regulatory Determination for Special Wastes from Phosphoric Acid Production. Office of Solid Waste, Special
Waste Program, 1991.
33 U.S. Environmental Protection Agency, Supplemental Information on Phosphoric Acid Production: Alternative
Management of Process Wastewater at Phosphoric Acid Facilities. Office of Solid Waste, December 1990, pp. Al-5.
509
-------
3. Other Related Wastes
The other related wastes described below are commonly found at phosphoric acid facilities, but are outside
of the scope of the Mining Waste Exclusion because they are associated with activities that are downstream of
mineral processing and use a saleable commodity as the primary raw material.
Ammoniated Fertilizer Production
Process wastewater is a likely waste stream from ammoniated fertilizer production. In 1991, the waste
generation rate for process wastewater from ammoniated fertilizer production was 132,517,000 metric tons per
year.34 This wastewater may be discharged to a cooling pond and may have a low pH.
Sludge is a likely waste stream from ammoniated fertilizer production.
Animal Feed Production
Process wastewater is a likely waste stream from animal feed production.
Sludge is a likely waste stream from animal feed production. The 1991 waste generation rate for this waste
stream was 400 metric tons per year.35
Superphosphoric Acid Production
Sludge is a likely waste stream from superphosphoric acid production.
Silicofluoride Recovery
Filter cake and process wastewater are the waste streams likely to result from silicofluoride recovery
operations.
Sulfuric Acid Production
Process wastewater is a likely waste stream from sulfuric acid production. This waste is generated from an
ancillary process and as such is outside the scope of this report. At Texasgulf in Aurora, North Carolina, this process
wastewater from sulfuric acid production has a pH of about 10 and goes to a neutralization plant. In 1990, the
wastewater was discharged via an NPDES outfall at a rate of 80-100,000 gpd.36 IMC in Mulberry, Florida and
US AC in Ft. Meade, Florida create a cooling tower blowdo wn of pH 7 and a boiler blowdown of pH 11-12. US AC
sends these wastewaters to a cooling pond. At IMC, sulfuric acid plant blowdown is kept separate from other
process wastewater and is sent to a utility pond.37
34
Ibid.
35 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, Vol. I, August 1992, pp. 1-2 -1-8.
36 U.S. Environmental Protection Agency, Op. Cit.. 1990, pp. Al-3.
37 Ibid., pp. A2-3.
510
-------
On-site production of sulfuric acid for acidulation of phosphate rock also generates secondary materials
such as sulfuric acid production vessel cleanout residues. About once a year, small amounts of secondary materials,
such as precipitates are removed from sulfuric acid process vessels and product storage tanks.3B
D. Non-uniquely Associated Wastes
Wastes associated with the ancillary processes often found at phosphoric acid plants are not uniquely
associated because they are generated from chemical manufacturing activities, not from mineral processing. These
wastes include the wastewaters, sludge, and filtercake (described above) resulting from the production of
ammoniated fertilizer, animal feed, sulfuric and superphosphoric acid, and silicofluoride recovery.
Ancillary hazardous wastes may be generated at on-site laboratories, and may include used chemicals and
liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, waste
oil (which may or may not be hazardous) and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
One commenter provided additional factual information about the phosphoric acid production process
(COMM 45). This information, where appropriate, has been included in the sector report.
Sector-specific Issues
The commenter also addressed the potential negative implications of the Bevill mixture rule at phosphoric
acid production facilities. The commenter noted that materials such as precipitates removed from sulfuric acid
vessels and sulfuric acid spills may contain significant acid and sulfur values that can be useful in the phosphoric
acid production process. The same may be true for wastes generated by recharging spent ion exchange resins
(H2SO4 and NaOH). According to the commenter, the Bevill Mixture Rule requires these materials to be neutralized
before being reused, resulting in a loss of the sulfur and acid values (COMM 45).
38 The Fertilizer Institute. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1995.
511
-------
BIBLIOGRAPHY
Bartels, James J., and Theodore M. Gurr. "Phosphate Rock." From Industrial Minerals and Rocks. 6th ed. Society
for Mining, Metallurgy, and Exploration. 1994. pp. 751-763.
Morse, David E. "Phosphate Rock." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines. 1992. pp. 977-980.
"Phosphoric Acids and Phosphates." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XVII.
1982. pp. 426-442.
U.S. Environmental Protection Agency. Supplemental Information on Phosphoric Acid Production: Alternative
Management of Process Wastewater at Phosphoric Acid Facilities. Office of Solid Waste. December 1990.
Appendix A.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Vol.1. Office of Solid Waste. August 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Vol.111. Office of Solid Waste. August 1992. pp. 29-1 - 29-18.
U.S. Environmental Protection Agency. Technical Background Document. Data and Analyses in Support of the
Regulatory Determination for Special Wastes from Phosphoric Acid Production. Office of Solid Waste,
Special Waste Program. 1991.
U.S. Environmental Protection Agency. "Phosphoric Acid Production." From Report to Congress on Special
Wastes from Mineral Processing. Vol. II. Office of Solid Waste. July 1990, pp. 12-1-12-61.
U.S. Environmental Protection Agency. "Phosphate Rock." 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 2-120 - 2-127.
U.S. Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. 2.
1980. Chapters.
512
-------
PLATINUM GROUP METALS (PGM)
A. Commodity Summary
The platinum-group metals refer to six metals: platinum, palladium, rhodium, ruthenium, iridium, and
osmium. Commercially, the two most important metals are platinum and palladium. All of the platinum-group
metals are valued for their corrosion resistance and their catalytic activity.1 According to the U.S. Bureau of Mines,
ore containing the platinum-group metals is mined, concentrated, and smelted in Montana. The resulting platinum-
group matte is sent to Belgium to be refined and separated. Additionally, platinum-group metals are recovered as
byproducts of copper refining by two companies in Texas and Utah. Approximately 30 firms refine secondary metal
domestically. Platinum-group metals are used by the following industries: automotive, electrical and electronic,
chemical, dental, and medical. The metals are primarily used as catalysts in the automotive and petroleum refining
industries.2 Domestic production was reported as 60,000 kilograms in 1994 (sales as reported to industry) and
apparent domestic consumption was estimated at 127,000 kilograms during the same period,3 Exhibit 1 presents the
names and locations of all the facilities involved in the production and refining of platinum-group metals.
The six platinum-group metals can be separated into three pairs: platinum and palladium, ruthenium and
osmium, and rhodium and iridium. Each pair exhibits similar physical and metallurgical properties. Platinum and
palladium are corrosion resistant and the most malleable. Ruthenium and osmium have the strongest abrasion
resistance. Osmium alloys are used as pen tips and ruthenium is used as an electrical contact and as a titanium
coating alloy. Rhodium and iridium are the least abrasion resistant and often used as alloying elements for platinum.
Rhodium, palladium, and platinum are also used as an automotive catalyst for NOX reduction1, and platinum is used
in both automobile oxygen sensors and spark plugs.5
EXHIBIT 1
SUMMARY OF PLATINUM-GROUP METALS PROCESSING FACILITIES
Facility Name
Stillwater Mine
Allied Signal
Allied Precious Metals
ASARCO
AT & T Metals
Colonial Metals
Degussa Corp.
Location
Nye, MT
Tulsa, OK
Tucson, AZ
Amarillo, TX
Staten Island, NY
MD
South Plainfield, NJ
Type of Operations (source)
Mining and Beneficiation"
Secondary (spent automotive catalysts)
Secondary (solutions and sludges)
Secondary
Secondary (electronic scrap)
Secondary (spent industrial catalysts)
Secondary (solutions, electronic scrap, catalysts)
1 J. Roger Loebenstein, "Platinum-Group Metals," from Minerals Yearbook Volume 1. Metals and Minerals. U.S.
Bureau of Mines, 1992, p. 995.
2 J. Roger Loebenstein, "Platinum-Group Metals," from Mineral Commodity Summaries, 1995, pp. 126-127.
3 J. Roger Loebenstein, 1995, Op. Cit.. p. 126.
4 U.S. Environmental Protection Agency, "Platinum-Groups Metals," from 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. Office of Solid Waste, p. 3-159.
5 J. Roger Loebenstein, 1992. Op. Cit. p, 997.
513
-------
EXHIBIT 1
SUMMARY OF PLATINUM-GROUP METALS PROCESSING FACILITIES (CONTINUED)
Facility Name
Eastern Smelting and
Refining Corp.
Engelhard Corp
Gemini Industries
Handy and Harman
Handy and Harman
Hauser & Miller
JM Ney Co
Johnson Matthey
Kinsbursky Brothers
Kennecott Copper
Leach and Garner
Leytess Metal and
Chemical
LG Balfour CO
Martin Metals
McRilley Mark Co.
Multimetco, Inc.
Noranda/Micrometallics
Corp.
Noranda Sampling
PGP Industries, Inc.
Sabin Metals
Location
Lynn, MA
Iselin, NJ
Santa Ana, CA
Fairfield, CT
South Windsor, CT
St. Louis, MO
Bloomfield, CT
West Deptford, NJ
Anaheim, CA
Magma, UT
Attleboro, MA
New York, NY
Attleboro, MA
Los Angeles, CA
CA
Anniston, AL
San Jose, CA
Providence, RI
Santa Fe, CA
Rochester , NY
Type of Operations (source)
Secondary (solutions, sludges, catalysts)
Secondary (spent industrial catalysts, electronic scrap)
Secondary (spent industrial catalysts, petroleum
catalysts)
Secondary
Secondary (filter cake, metallic scrap, spent automotive
catalysts)
Secondary
Secondary
Secondary (filter cake, spent automotive catalysts,
solutions, unrefined ingot)
Secondary (solutions, electronic scrap, spent automotive
catalysts)
Hydrometallurgical precious metals plant recovers
platinum from tankhouse slimes from ore.6
Secondary
Secondary
Secondary
Secondary (electronic scrap, solid scrap)
Secondary
Secondary (spent automotive catalysts)
Secondary (electronic scrap, filter cakes, sludges,
solutions, catalysts, filter media)
Secondary (electronic scrap, solid scrap)
Secondary (spent industrial catalysts, sludges, electronic
scrap)
Secondary (electronic scrap, filter cakes, solid scrap)
6 Kennecott Corporation. Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV
Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
514
-------
EXHIBIT 1
SUMMARY OF PLATINUM-GROUP METALS PROCESSING FACILITIES (CONTINUED)
Facility Name
Sipi Metals
Southwest Smelter &
Refining
Stern Metals
Techamet, Inc.
Technic, Inc.
Texas Instruments
Trifari, Krussman
William Gold Refining
Location
Chicago, IL
Dallas, TX
Attleboro, MA
Houston, TX
Providence, RI
MA
Providence, RI
Buffalo, NY
Type of Operations (source)
Secondary
(electronic scrap)
Secondary
Secondary
Secondary
catalysts)
(spent automotive catalysts, petroleum
Secondary
Secondary
Secondary
Secondary
"Stillwater Mines sends ore to its smelter facility in Columbus, MT.7
After the ores have been smelted, Stillwater Mines ships the platinum-group metal concentrate to Brussels,
Belgium for refining. The concentrates are toll refined and although Stillwater Mines retains ownership of the
metals, the products are generally sold overseas.8
B. Generalized Process Description
1. Discussion of Typical Production Processes
Platinum-group metals can be recovered from a variety of different sources, including electrolytic slimes
from copper refineries or metallic ores. Secondary platinum-group metals can also be recovered from used
equipment, precious metal scrap, petroleum, and spent catalysts (both industrial and automotive). Each source is
associated with a distinct recovery process. In one process the insoluble slimes from copper refining are collected
and processed to recover any residual metal content. Alternatively, the production of platinum-group metals from
ore involves mining, concentrating, smelling, and refining. In the concentrating step, platinum ore is crushed and
treated by froth flotation. The concentrates are dried, roasted (sometimes), and fused in a smelter furnace. This step
results in the production of a platinum-containing sulfide matte. Solvent extraction is used to separate and purify the
six platinum-group metals in the sulfide matte.9 Secondary platinum group metals recovered from scrap and spent
catalysts are refined and used in the fiber glass industry and various catalytic applications.
7 Personal Communication between ICF Incorporated and J, Roger Loebenstein, U.S. Bureau of Mines. October
17, 1994.
8 Ibid.
9 J. Roger Loebenstein, 1992, Op. Cit. pp. 995-996.
515
-------
2. Generalized Process Flow Diagram
There are several methods for recovering and refining platinum-group metals, depending on the source
material used. Exhibit 2 presents the process flow diagrams for the recovery process of the platinum-group metals
from electrolytic slimes. Platinum metals can also be recovered from the ores or from scrap materials. After
recovery and initial processing, the concentrates are sent for refining. Exhibit 3 presents a typical refining process
used to separate each of the six platinum-group metals from a concentrate.
Recovery From Electrolytic Slimes
Often, platinum-group metals are recovered from the slimes that collect in the electrolytic refining cells
used at copper refineries. These slimes are the insoluble material from impure copper anodes that are dissolved as
part of the copper refining process. As shown in Exhibit 2, after the slimes are heated, H2S04 is added to the dried
slimes which then undergo an acid digestion step. Following acid digestion, the slimes are often, but not always,
roasted and then processed by several leaching steps to remove any remaining copper. After the leaching, the
resultant decopperized slimes are melted with a soda-silica flux in a reverberatory furnace. This flux helps in the
formation of a siliceous slag which is removed from the furnace. Air is then blown through the molten metal
followed by the addition of a lime flux. The air oxidizes any remaining lead and the lead oxide forms a slag with the
lime which is then removed from the furnace. The siliceous and lead slags are either recycled or sent to a lead
smelter. Following slag removal, fused soda ash is added to the furnace to form soda slag which is also removed and
sent off-site for tellurium and selenium recovery. The resultant metal is a dore alloy composed of gold, silver, and
platinum-group metal and is processed to recover these metal values,10
Recovery From Metal Ores
Although alluvial deposits are the result of natural concentration processes involving weathering and gravity
separation phenomena, further treatment is required to yield a product suitable for marketing and refining. At
Stillwater, Montana, platinum and palladium are recovered via froth flotation of sulfide minerals. The ore is sent to
a concentrator, followed by froth flotation, and then sent to a smelter operation in Columbus, Montana. The
resulting precious metals matte (solid form) is then sent to MHO metallurgy in Belgium for refining."
An alternative method of recovering platinum-group metals from ore in South Africa involves initial
treatment to reduce the ore to a suitable size via crushing, followed by froth flotation to separate out the platinum-
group metal particles. The flotation concentrates are separated into platinum-bearing minerals and free-metallic
particles by conventional gravity methods. The remainder is further concentrated by smelting, oxygen blowing,
magnetic separation, and pressure leaching.
The froth can be prepared for smelting by thickening, filtering, drying, and pelletizing. The pellets are
smelted in an electric smelter with submerged-arc consumable electrodes. Fluxes and additions are made during
smelting to obtain a matte that contains principally copper-nickel-iron and platinum-group metals. The matte is then
treated by oxygen blowing to produce a high grade matte. The matte is crushed, ground, and magnetically separated.
Any non-magnetic portion is treated by pressure leaching to release copper, nickel, and cobalt. The remaining
solution is recirculated back into the magnetic stream and this mixture is then pressure leached, yielding a final
concentrate. This concentrate along with the mineral material released previously are sent to a refinery for further
10
U.S. Environmental Protection Agency, 1988, Op. Cit.. p, 3-159.
11 Personal Communication between Jocelyn Spielman, ICF Incorporated and J. Roger Loebenstein U.S. Bureau
of Mines, October 17, 1994.
'* "Platinum-Group Metals," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XVIII, 1982, p.
234.
516
-------
EXHIBIT 2
PLATINUM GROUP METAL RECOVERY FROM COPPER REFINING SLIMES
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-158 - 3-163.)
Raw Slimes
Herrcshoff Furnace
T >
Scrubber Mud ^^
A Gas
1 , 5
^^ t-ume „, .
1 Solution Crude Se
II ' 1
To Selenium Plant 1 Leach
^
I Holding
H,O
1 >
Gas Caustic Le
m i IUAU,
1 ^ 1
Dried Slime
f
„.,_ _ S",
igesters 1™— — ^^- Waste
(
?oaster Scrap Copper
i
, J^ Leach Liquor to
Y CuSO. Plant or
,T»nt5 ^ Cement Silver Liberator Cells
^^ H,SO.
I
Caustic ^^_ .
Caustic Te-Pb Mud "" H2O
/ Slimes w W
^ Gases „ r Soda Slag ^^ -^r -
1 Solution Slag
w To Anode^^
* Furnace ^^ _
To Selenium Plant Dorc *
t
v |
tBodes ,.._..
Neutralization Tank
Parting Plant
I Solution I Neutrali
vL vL Mud
To Se Plant To Te Plant
Platinum Group Metals
517
-------
Stillwater Mine sends the platinum-group metal concentrate out of the country for refining after it is
processed at their smeltering facility in Columbus, Montana.13 Other platinum-group metals facilities in the United
States refine secondary platinum-group metals from used equipment, scrap metals, petroleum, and spent catalysts.
The refining process takes advantage of the solubility of platinum and palladium. Each platinum group metal is
removed from the platinum-group metal concentrate in order of its solubility. Exhibit 3 presents the typical order of
removal. In general, platinum and palladium are removed first, followed by rhodium, ruthenium, osmium, and
iridium. Exhibit 3 also presents various compounds that may be produced through further purification of each
individual platinum-group metal,
Platinum and palladium
Most refining procedures are based on the ready solubility of gold, platinum, and palladium in aqua regia
and the ease with which gold can be reduced to the metallic form from the chloride solution by the addition of
ferrous salts or sulfur dioxide. Solvent extraction is used as an alternative method for separating gold at some
refineries.14 In the aqua regia refining process, platinum metal concentrates are treated with aqua regia to dissolve
platinum, palladium, and gold. The other platinum-group metals (ruthenium, osmium, iridium, and osmium) and
silver are insoluble. After the gold is separated from the solution either by reduction or solvent extraction, the
remaining solution is treated with ammonium chloride to precipitate the platinum as ammonium chloroplatinate. The
palladium remains in solution.l5
The filtrate from the platinum-recovery contains palladium chloride and can be treated with ammonia and
hydrochloric acid. The solution is heated to yield a solution of palladium (II) tetrammine dichloride. The addition
of hydrochloric acid causes the formation of palladium dichloride diammine as a precipitate which can easily be
dissolved in cold dilute ammonia. The resultant high-purity salt, when heated, can be converted readily into metal.
Some refineries reduce pure palladium salt to palladium black with formic acid. The palladium black can then be
ignited to form a palladium sponge. The aqueous byproducts of the formic acid are easier to handle than the
corrosive fumes that result from firing the salts.16
The undissolved materials remaining after the aqua regia and any platinum-group metals recovered after the
removal of platinum and palladium from solution are combined with concentrates high in rhodium, ruthenium, and
iridium. Fluxing materials, such as lead carbonate plus carbon, are added, following which the mixture is heated.
The molten charge is poured into a conical mold and solidified. After solidification, the slag is removed and the lead
which contains rhodium, iridium, ruthenium, and silver is melted, granulated, and treated with nitric acid. The lead
and silver are dissolved and removed, leaving an insoluble residue containing the platinum-group metals.17
13- Personal Communication between ICF Incorporated and J. Roger Loebenstein, U.S. Bureau of Mines, October
17, 1994.
" "Platinum-Group Metals," 1982, Op. Cit.. p. 238.
15 Ibid.
16 Ibid.
17 Ibid.
518
-------
EXHIBIT 3
PLATINUM GROUP METAL REFINING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1982, pp. 228 - 239.)
I Aqua Regia
• * — —> — ~ «P— —
Solvent Extraction With Dibutyl Carbital
I
Precipitate,
Impure Gold
Mel
ting
Gold Anodes
Electrolyt
c Refining
Pure Gold,
Sponge
Filtrate
H,PtCl6, H,PdCl4
r
Ammonium Chloride
Precipitate,
Impure Platinum Salt,
(NHJ,PCL
i
Ignition
Impure Platinum
Sponge
Melting and Granulation Aqua Regia, 5
Gold Grain
Filtrate
H,PdCl4
1
Ammonia, Hydrochloric Acid
Precipitate,
Impure Palladium Salt
(Pd(NHJ,Ct)
adium Chloride Ammonia, Hydrochloric A
Impure Sodium
Platinum Chloride,
NaJHCl,.
Precipitate,
Pure Palladium Salt.
(PdCNH,),CU
i
Filtrate,
Traces of Platnum
Metal
cj^ Zinc Reduction
Precipitate.
Recovered - -'
Platinum Metals
Bromate I]
-lydrolysis
519
-------
EXHIBIT 3 (Continued)
520
-------
Rhodium
The residue is then treated with sodium bisulfate and heated to 500° C to convert rhodium into the sulfate.
After sodium hydroxide is added, the resultant crude hydroxide is precipitated out, washed, dissolved in hydrochloric
acid (HC1), neutralized with sodium carbonate and treated with sodium nitrite. These steps yield the stable complex
(NH4)3[Rh(NO2)6]. The contaminating base metals can be precipitated out of solution through hydrolysis, while
leaving rhodium in solution. Rhodium can be precipitated by the addition of ammonium chloride, following which
the ammonium salt is treated with HC1 and the solution is passed through an ion exchange column. Ion exchange
separates ammonium and any base metals from the high-purity rhodium, leaving it in solution. The rhodium is
precipitated as finely divided metal by boiling with formic acid. After washing, the metal is ignited then cooled
under hydrogen.18
Ruthenium
The ruthenium, osmium, and indium residue from the bisulfate fusion is mixed with sodium peroxide and
heated to 500° C, yielding sodium ruthenate and sodium osmate. These compounds are dissolved in water and
treated with chlorine in a distillation apparatus. The resultant ruthenium tetroxide and osmium tetroxide are
absorbed in dilute HC1. After boiling, the chloride solution is mixed with nitric acid to remove osmium. The
mixture is then treated with ammonium chloride to yield ammonium chlororuthenate crystals. The latter are washed
and ignited to yield ruthenium which is treated and cooled in hydrogen to give pure ruthenium powder.19
Osmium
Osmium tetroxide is produced in the same process as ruthenium tetroxide. After the osmium is removed
from the ruthenium solution, the osmium tetroxide is then converted to sodium osmate. The addition of KOH causes
the formation of precipitate potassium osmate. The salt is stored and can be converted to osmium metal.
Iridium
The insoluble indium dioxide is converted with aqua regia to the chloride which is then precipitated with
additional nitric acid and ammonium chloride. This salt is dissolved in a dilute ammonium sulfide solution in which
impurities precipitate as sulfides, whereas the indium remains in solution. Treatment with nitric acid and ammonium
chloride yields pure ammonium chloroiridate which, upon ignition and reduction by hydrogen, yields pure iridium
powder.
3, Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
"Ibid.
19 Ibid.
521
-------
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between froth flotation and smelting for the recovery of platinum group metals from metal ores. EPA identified this
point in the process sequence as where beneficiation ends and mineral processing begins because it is here where a
significant chemical change to the sulfide mineral ore occurs. EPA also determined that all wastes generated during
the recovery of platinum group metals from copper electrolytic slimes are mineral processing wastes. Therefore,
because EPA has determined that all operations following the initial "processing" step in the production sequence are
also considered processing operations, irrespective of whether they involve only techniques odierwise defined as
beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing operation are
considered mineral processing wastes, rather than beneficiation wastes. EPA presents the mineral processing waste
streams generated after the beneficiation/processing line in section C.2, along with associated information on waste
generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Although Exhibits 2 and 3 identify the following wastes as associated with the production of platinum-
group metals, no characterization, generation, or management data are available for these wastes.
Concentration
Tailings and Filtrate. Tailings are generated during the froth filtration and sent to a tailings pond for
disposal.
Wastewater. Wastewater from the thickening process is likely to contain heavy metals.
2. Mineral Processing Wastes
Recovery
Scrubber Off-gases. As shown in Exhibit 2, off gases are generated from the scrubber following roasting.
SO2 Waste, As shown in Exhibit 2, waste sulfur dioxide is produced from acid digestion.
522
-------
Slag. The slag generated during smelting is likely to contain metallic particles and may be crushed and
blended with concentrate for recycling to the electric furnace.20 Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 5 metric tons/yr, 46 metric tons/yr, and 460 metric
tons/yr, respectively. We used best engineering judgment to determine that this waste may be recycled and may
exhibit the characteristic of toxicity (lead and selenium). This waste is classified as a by-product.
Spent Solvents. After dissolving the material to be refined in aqua regia, a series of elements (e.g., gold,
platinum, and palladium) are precipitated from the solution. Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 300 metric tons/yr, 1,700 metric tons/yr, and 3,000
metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit the
characteristics of toxicity (lead and silver) and ignitability.
Spent Acids. Following solvent extraction, the insoluble platinum-group metals (e.g., rhodium, iridium,
osmium, and ruthenium) are separated to yield pure metals. The resultant wastes from these processes would most
likely be spent acids which might contain residual metals.21 Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 300 metric tons/yr, 1,700 metric tons/yr, and 3,000
metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit the
characteristics of toxicity (lead and silver), corrosivity, and reactivity.
D. Non-uniquely Associated Hazardous Wastes
Non-uniquely associated hazardous wastes may be generated at on-site laboratories, and may include used
chemicals and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naphtha), and
acidic tank cleaning wastes,
E. Summary of Comments Received by EPA
New Factual Information
One comment was received to correct information about one facility in Utah, EPA has incorporated this
new information into the document. (COMM 40)
Sector-specific Issues
None.
20 Gregg J. Hodges, et. al., "Stillwater Mining Co.'s precious metals smelter: From pilot to production, Minir
Engineering. July 1991.
21 U.S. Environmental Protection Agency, 1988, Op. Cit. p. 3-162.
523
-------
BIBLIOGRAPHY
Hodges, G., G. Reset, J. Matousek, and P. Marcantoni, "Stillwater Mining Co.'s precious metals smelter: From pilot
to production," Mining Engineering, July 1991.
Loebenstein, J. Roger. "Platinum-Group Metals." From Mineral Commodities Summary. U.S. Bureau of Mines.
1995. pp. 126-127.
Loebenstein, J. Roger. "Platinum-Group Metals." From Minerals Yearbook Volume 1. Metals and Minerals. 1992.
pp. 995-996 .
Loebenstein, J. Roger. "Platinum-Group Metals." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985.
pp. 595-608.
Personal Communication between Jocelyn Spielman, ICF Incorporated and J. Roger Loebenstein, U.S. Bureau of
Mines. October 17, 1994.
"Platinum-Group Metals." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XVIII. 1982. pp.
228-239.
Public Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes, January 25, 1996.
U.S. Environmental Protection Agency. "Platinum-Group Metals." From 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. Office of Solid Waste. 1988. pp. 3-158 - 3-163.
524
-------
PYROBITUMENS, MINERAL WAXES, AND NATURAL ASPHALTS
A. Commodity Summary
Bituminous materials comprise a group of hydrocarbons including pyrobitumens, mineral waxes, and
asphalts, Pyrobitumens are mined predominately in Utah and are used in rubber, paints, varnishes, and insulating
and waterproofing compounds.
Mineral waxes are not present in the United States as a natural substance, and therefore, must be extracted
from lignite or cannel coal. Although coal exists in many parts of the United States, the only known production of
mineral waxes from coal occurs in California. The use of this extraction product known as "Montan Wax," is
limited to paints, wood fillers, floor polish, rubber mixtures, and candles.
In the United States, naturally occurring asphalt (gilsonite) is found in commercial quantities only in eastern
Utah and western Colorado, There are three types of naturally occurring asphalt; native asphalt (bitumen), lake
asphalt, and rock asphalt.' Asphalts have a variety of uses including paving, flooring, roofing, and waterproofing.
American Gilsonite in Bonanza, Utah is the world's largest producer and exporter of gilsonite (natural asphalt). The
only other producer of natural asphalt is Ziegler Chemical and Mineral Corporation, also in Utah.
B. Generalized Process Description
1, Discussion of Typical Production Processes
The production processes associated with the production of pyrobitumens, mineral waxes, and natural
asphalts are limited to a few simple operations, including extraction, grinding, blending, and packaging. Exhibits 1
through 3 present simplified process flow diagrams for the production of pyrobitumens, mineral waxes, and natural
asphalts. The production processes and wastes associated with each mineral commodity are discussed below.
2, Generalized Process Flow Diagram
Pvrobitumens
As shown in Exhibit 1, the production process for pyrobitumens consists of cracking in a still, recondensing,
and grading. Due to the low cost and availability of petroleum refining substitutes, the production of pyrobitumens
appears to be low.
Mineral Waxes
As shown in Exhibit 2, mineral wax processing consists of solvent extraction from lignite or cannel coal.
Cannel coals yield a material that contains 60 to 90 percent light yellow or brown waxy substances. The crude wax
is refined by extracting, typically with a mixture of benzene and methanols. Distilling the solvent leaves a wax too
darkly colored to be used without added refining. Acid mixtures are used to oxidize and remove the dark materials,
leaving a series of bleached waxes.2 The extraction product is known as "Montan Wax," Extraction solvents used in
the production of mineral waxes may be listed in 40 CFR 261 Subpart D.3
1 "Asphalt," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. Ill, 1992, pp. 689-724.
2 "Lignite," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed.. Vol. XV, 1995, p. 316.
3 U.S. Environmental Protection Agency, Technical Background Document, Development of the Cost.
Economic, and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral
Processing Wastes, Office of Solid Waste, 1989, pp. A-9.
525
-------
EXHIBIT 1
PYROBITUMEN PROCESSING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988.)
Pyrobitumens
Cracking
Still
(1) Waste Catalyst
(2) Still Bottoms
Condensation
Pyrobitumen
Products
Grading
Source: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes. 1988.
526
-------
EXHIBIT 2
MINERAL WAX PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988.)
Lignite or
Cannel Coal
Montan Wax
Solvent
Extraction
(1) Spent Solvent
(2) Spent Coal
Source: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes. 1988,
527
-------
Natural Asphalts
American Gilsonite operates a 110 ktpy facility in Bonanza, Utah. Mine development begins with the
boring of shafts. The shafts are equipped with steel inserts that are comprised of four pipes equally spaced around
the perimeter of the shaft. Once a shaft is bored, inserts are lowered into the borehole. As each section is lowered
into the shaft the next section is lined up with it, and the two are welded together at the surface. This procedure is
repeated until the inserts line the shaft from top to bottom. When a mine is worked out the liner assembly is pulled
and reused. Hand-held pneumatic chipping hammers with moilpoint bits are used to break out the ore. Broken ore
flows by gravity to the toe of the sloping face at the floor of the drift. From there it is airlifted to the surface through
a pipe. When air lifted ore reaches the surface it enters a baghouse. The larger pieces drop first, and the rest is
collected in filter bags. All solids are discharged into elevated storage bins and are then transferred by truck to a
processing plant.
American Gilsonite's plant consists of concrete storage silos, truck receiving bins, a vibrating bed dryer,
pulverizing machinery, and packaging equipment. Pneumatic conveying systems and sophisticated dust control
equipment are state-of-the-art and allow for the handling of gilsonite in large quantities. Before entering the
processing plant, gilsonite ore is segregated by grade in receiving bins. From these bins the ore is processed through
a vibrating bed dryer, where excess moisture is removed. It is then passed over a double-deck screen, where it is
classified according to particle size for storage in silos. From the silos, ore is fed to product bins from which it is
either loaded directly as bulk product, fed to a bagging machine, or fed to a pulverizer. Pulverized product is
segregated into product bins from which it can be loaded directly as bulk product or packaged at a second bagging
machine.4 Exhibit 3 contains the natural asphalt production process diagram.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as
4 Harry D. Lewis, "Gilsonite," from Industrial Minerals and Rocks. Society of Mining, Metallurgy, and
Exploration, 1994, pp. 535-541.
528
-------
EXHIBIT 3
NATURAL ASPHALT PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988.)
Asphalt Products
Rock
Asphalt
I
Size
Reduction
I
Grading
i
Blending
Source: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes. 1988.
529
-------
information on ore type(s), the functional importance of each step in the production sequence, and waste generation
points and quantities presented above.
Pyrobitumens
EPA determined that for pyrobitumens, the beneficiation/processing line occurs when the pyrobitumens are
thermally cracked in a still to produce a significantly altered material. Therefore, because EPA has determined that
all operations following the initial "processing" step in the production sequence are also considered processing
operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all solid wastes
arising from any such operation(s) after the initial mineral processing operation are considered mineral processing
wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams generated after
the beneficiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
Mineral Waxes and Natural Asphalts
Based on a review of the processes, there are no mineral processing operations involved in the production
of mineral waxes or natural asphalts.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Pyrobitumens
None identified.
Mineral Waxes
Probable wastes from the production of mineral waxes include spent solvents and spent coal.
Natural Asphalt
None identified.
2. Mineral Processing Wastes
Pyrobitumens
Still bottoms. Although no published information regarding waste generation rate or characteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 2 metric tons/yr, 45,000 metric tons/yr, and 90,000 metric tons/yr, respectively. We used
best engineering judgement to determine that this waste may exhibit the characteristic ignitability.
Waste catalyst. Although no published information regarding waste generation rate or.charaeteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 2 metric tons/yr, 10,000 metric tons/yr, and 20,000 metric tons/yr, respectively. We used
best engineering judgement to determine that this waste may exhibit the characteristic of toxicity for cadmium and
selenium. This waste may be recycled and is classified as a spent material.
Mineral Waxes
None identified.
Natural Asphalt
530
-------
None identified.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
531
-------
BIBLIOGRAPHY
"Asphalt." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. III. 1992. pp. 689-724.
Lewis, Harry. "Gilsonite." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. pp. 535-541.
"Lignite." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. XV. 1995. p. 316.
U.S. Environmental Protection Agency. Technical Background Document. Development of the Cost. Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. Office of Solid Waste. 1989. pp. A-9.
U.S. Environmental Protection Agency. "Bituminous Materials." From 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. 1988. pp. 2-70 - 2-76.
532
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RARE EARTHS
A. Commodity Summary
The rare earth elements are comprised of scandium, yttrium, and 15 lanthanide elements, of which cerium,
lanthanum, and neodymium are the most abundant. While rare earth elements are found in several minerals, almost
all production comes from less than 10 minerals, primarily monazite and bastnasite. Because the scandium industry
is, for the most part, separate and distinct from the yttrium and lanthanide industries it is the subject of a separate
commodity summary (see the chapter on scandium).
The United States is a major producer and consumer of rare earth ores and compounds that are used in
petroleum fluid cracking catalysts, chemical and pollution-control catalysts, metallurgical applications, glass and
ceramics, permanent magnets, phosphors, and electronics.1
In 1993 two domestic mines, Molycorp, Incorporated and RGC (USA) Minerals Incorporated, produced
rare earths. Molycorp, Inc.'s facility in Mountain Pass, CA is the sole producer of rare earth minerals from
bastnasite ore.2 In 1995, Molycorp supplied over 60 percent of U.S.-produced cerium products, with competition
from China, the former states of the U.S.S.R., and India.3 The use of bastnasite ore is preferred in the market over
monzanite ore because of due to lower concentrations of natural radionuclides which results in lowers worker
exposures to low level radiation.4 The Mountain Pass facility is an integrated mining and beneficiation/processing
facility.5 Twenty facilities produce rare earth materials. Exhibit 1 presents the names, locations, and products of the
facilities involved in the production of rare earth materials, however, not all of these facilities engage in primary
mineral processing activities.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Most production of rare earth elements is from the minerals monazite and bastnasite. Processing of these
ores is by sulfuric and hydrochloric acid digestion. The compounds recovered from these processes must be
processed further to produce and recover rare earth metal compounds. Processes include solvent extraction and
reduction.6 Exhibits 2 through 6 present typical process flow diagrams for the production of rare earths.
Bastnasite is produced only by Molycorp at Mountain Pass, California. It is produced as a mineral
concentrate and consumed captively at this facility. Monazite is produced by Associated Minerals at Green Cove
Springs, Florida as a byproduct of beach sand mining for titanium and zircon minerals.7
1 James Hedriek, "Rare Earths," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp.
134-135.
2 Molycorp, Inc., Comment submitted in response to the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
3 Ibid.
4 Ibid.
5 Ibid.
6 Ibid.
7 U.S. Environmental Protection Agency, Technical Background Document. Development of the Cost. Economic
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. Office of Solid Waste, 1989, pp. A-21 - A-22.
533
-------
2. Generalized Process Flow
Mining
At Mountain Pass, Molycorp mines rare earth ore in an open pit approximately 100 meters deep. Blast
holes drilled at 3 to 4 meter spacing are routinely assayed for total rare earth oxides and other elements by
fluorescence methods. Approximately 300 kilotons per year are mined with a stripping ratio of 5:1. The ore is
crushed and blended in stockpiles that contain about 40 kilotons and fed to a mill located less than 100 meters from
the pit.8
EXHIBIT 1
SUMMARY Or RARE EARTHS PROCESSING FACILITIES
Facility Name
Crucible Materials
Delco Remy
Division of General Motors
Hitachi Magnetics
IG Technologies
Molycorp9
Mountain Pass Mine & Mill
Neomet
Nord Resources
Reactive Metals & Alloys Corp.
Research
RGC (USA) Mineral Inc.
Rhone-Poulenc Chemicals Co.
W.R. Grace
Location
Elizabethtown, KY
Anderson, IN
Edmore, MI
Valparaiso, IN
Mountain Pass, CA
Mountain Pass, CA
West Pittsburgh, PA
Jackson, NJ
West Pittsburgh, PA
Phoenix, AZ
Green Cove Springs, FL
Phoenix, AZ
Mineville, NY
Freeport, TX
Chattanooga, TN
Products
Rare earth magnets
Rare earth magnets, neodyrnium-iron-boron
magnet alloys
Rare earth magnets
Rare earth magnets
Bastnasite mine
Uncertain
Neodymium-iron-boron magnet alloys
Uncertain
Mischmetal
Uncertain
Byproduct monazite
Neodymium-iron-boron magnet alloys
Uncertain
Uncertain
Uncertain
8 James Hedrick, "Rare Earths, the Lanthanides, Yttrium, and Scandium," from Minerals Yearbook Volume 1.
Metals and Minerals. U.S. Bureau of Mines, 1992, pp. 1035-1047.
9 Molycorp, Inc., 1996, Op. Cit
534
-------
Molycorp's mine was the leading producer of rare earths in both the United States and the rest of the world in 1992.
In 1993, mine production decreased from the 1992 level of 22,713 tons to 16,465 tons of rare earth oxides,10
Almost all mining of heavy mineral sands from surface placer deposits is done by floating cutterhead or
bucket wheel dredges that concentrate the heavy minerals onboard and discharge the unwanted tailings back into
previously mined areas. An onboard wet mill separates the heavy minerals from the lighter weight fraction through
wet gravity equipment that includes a series of screens, hydroclones, spirals, and cones. Wet mill mixed heavy
mineral concentrate is sent to a dry mill to separate the individual heavy minerals and produce a concentrate. Dry
mill processing includes a combination of scrubbing, drying, screening, electrostatic, electromagnetic, magnetic, and
gravity processes. Gravity methods include the use of jigs, spiral and cone concentrators, and shaking tables. Sizing
and preconcentration commonly is performed at the mine site by trommels, shaking screens, and gravity separation.
Many dredges have such facilities on board or utilize floating preconcentration plants.11 Monazite can be separated
from zircon by electrostatic methods such as electromagnetic or gravity methods. Xenotime is usually separated
from monazite by precise gravity methods. Some deposits may require acid leach treatment and calcining to
eliminate iron oxide or other grain coatings.
Some sand deposits, too difficult to mine by dredging, are mined using dry methods. Ore is stripped with
scrapers, bulldozers, and loaders. Sands recovered by these techniques are crushed, screened, and processed by the
wet mill equipment described above.
Recovery
Monazite Ore Processing
Rare earth metals are recovered as oxides from monazite ore by sulfuric acid digestion (Exhibit 2). The ore
undergoes grinding, spiraling, or other similar operations for the initial coarse purification of the ore. Magnetic
separation removes die magnetic ore constituents which can be processed separately or discarded as waste. The
refined ore is then digested with sulfuric acid at 200-220°C. Rare earth sulfates and thorium sulfates are men
dissolved and removed from the waste monazite solids by filtration. Rare earth elements are then precipitated as
oxalates or sulfates. These precipitates undergo caustic digestion or roasting to form rare earth oxides which are
finally recovered by filtration. The resulting filtrate is discarded as waste.12
Bastnasite Ore Processing
To recover rate earths from bastnasite ore, die ore is crushed, ground, classified, and concentrated to
increase rare earth concentrations.13 These processes, as well as die subsequent beneficiation and mineral processing
steps, are described in the following paragraphs. The final filtration step yields lead and iron filter cake while die
final drying step yields die rare earth concentrates.14
U.S. Bureau of Mines, Rare Earths Annual Report. 1993.
11 Stephen B. Castor, "Rare Earth Minerals," from Industrial Minerals and Rocks. 6di ed., Society for Mining,
Metallurgy, and Exploration, 1994, pp. 827-837.
12 U.S. Environmental Protection Agency, "Rare Earths," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. 3-164 - 3-174.
13 Molycorp, Inc., Comment submitted in response to the Second Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. May 12, 1997,
14 Ibid.
535
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EXHIBIT 2
RECOVERY OF RARE EARTHS FROM MONAZTTE BY THE SULFURIC ACID PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174)
MonaziteOe
H.SCV
Cold Water-
^
+
Magnetic
Separation
*
Grinding
I
Digestion
200-220°C
1 Slurry
Dissolution of
Rare Earths and
Thorium Sulfates
1
Filtration — —
Filtrate
T
Double Sulphate
Precipitation
1
Filtrate
T
Recovery of
Thorium and Minor
Rare Earth Fractions
^^ Magnetic
^^ Fractions
^ Waste Monazite
^" Solids
NaOH and Water
1
Cake ^^ Caustic
Digestion
Slurrry
T
c-i • ^^ Waste
Filtration ^^- _,
^^ Filtrate
*
Rare Earth
Hydroxide Cake
536
-------
EXHIBITS
RECOVERY OF RARE EARTH CHLORIDES FROM BASTNASITE ORE
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing
Wastes, 1988, pp. 3-164 - 3-174., and Molycorp, Inc., Comment on Second
Supplemental Proposed Rule Applying Phase FV Land Disposal Restrictions to Newly
Identified Mineral Processing Wastes, May 12th, 1997.)
Bastnasite Ore
Cerium Solids
Cerium Thickening,
Filtering, Drying,
Purification
I
Crushing, Screening,
and Blending
1
Classification
- Waste Tailings
Flotation
- Waste Tailings
Leaching
(HC1)
60-65% Rare Earth Oxides
Roasting
1200°F
i
85% Rare Earth Oxides
Soluble Lanthanides
Acid Leaching/
Digestion (HC1)
^
Slurry
Rare Earth Concentrates
Fe and Pb Precipitation
I
Filter Cake
Lanthanide Concentrates
to Solvent Extraction
96% Cerium
537
-------
Purification/Concentration
Flotation
Flotation is used at Mountain Pass to make a bastnasite concentrate containing about 60-65 percent rare
earth oxides.15 This concentrate is either used on-site as feed for chemical separation of rare earth elements, leached
to produce a 70 percent rare earth oxide concentrate, or shipped off-site to customers.
Recovery of Concentrate
Recovery of rare earth concentrates from monazite and xenotime is accomplished by digestion in a hot
concentrated base or acid solution. At Rhone-Poulenc Inc. plants, which process most of the world's monazite, rare
earth elements are extracted in a concentrated solution of sodium hydroxide at 140 to 150°C. After cooling,
hydroxides of rare earth elements and thorium are recovered by filtration, and thorium is separated by selective
precipitation or dissolution. At Mountain Pass, bastnasite is roasted at 1200°F to drive off CO2 and leached/digested
with dilute, chilled HC1 to dissolve most of the trivalent rare earth elements.16'17 Specifically, in this "leach" step the
solid lanthanide ore is reacted with HC1 to produce lanthanide chloride. This leaching also produces lead and iron
chloride wastes, which are subsequently reacted with ammonia and sodium hydrogen sulfide, respectively, to form
small volumes of solid iron hydroxide and lead sulfide wastes. In this step, cerium oxide is also leached to produce a
higher concentrate cerium oxide product. In this roasting/leaching sequence, the roasting step converts cerium (III)
fluorocarbonate to cerium (IV) oxide, which then undergoes leaching with HC1 to produce a cerium oxide
concentrate. This second leach step produces a final or intermediate product (low grade cerium concentrate) that
does not undergo further beneficiation or processing.18 The residue, cerium concentrate, is sold as a polishing
abrasive.19'20
The rare earth hydroxide and chloride concentrates recovered from sulfuric acid and hydrochloric acid
leaching/digestion operations must undergo further processing to produce and recover individual rare earth metal
compounds such as fluorides, nitrates, carbonates, oxides, and pure metals, for a variety of applications. Processes
include solvent extraction and reduction.
Rare Earth Separation by Solvent Extraction
To separate individual rare earths in a mixture from each other, an aqueous solution containing rare earth
salts is sent countercurrent to an immiscible organic stream which selectively extracts one rare earth from the others.
Several stages of extractions are needed to separate each rare earth metal. Each organic stream is then scrubbed with
an aqueous stream to transfer the rare earth element into an aqueous phase. Because all of the products are aqueous
solutions, the spent solvents leave the process as wastes.21 Exhibit 4 presents a process flow diagram for solvent
extraction.
15 Ibjd.
16 Molycorp, Inc., 1997, Op. Cit.
17 Molycorp, Inc., 1996, Op. Cit.
18 U.S. Environmental Protection Agency, Lowrance, Sylvia K. to Mark A. Smith, Attorney, Unocal Corporation,
April 7, 1992.
19 Stephen Castor, 1994, Op. Cit.. pp. 827-837.
20 Molycorp, Inc., 1996, Op. Cit.
21 Molycorp, Inc., 1997, Op. Cit.
538
-------
EXHTOIT4
RARE EAKIH SEPARATION BY SOLVENT EXTRACTION
(Adaptedfrom: 1988 Final Draft SumnarylteportrflVIreirfln^^
Rare Earth Nitrate Solution
(La,Pr,N4Sm)
Nitric Add Extraaion
Scrub ^^
Scrubbing
Tri-butyl
| Phosphate
Solution
Solvent (SmNdHNOj) Aqueous Solution (ft, La)
Water pfr-
Waste ^
Solvent ^^
f
Batch
Extraction
t
Concentrate or
Precipitate and
Redissolve
1 Aqueous (Sm, Nd) 1
Solvent p»»
Scrub p»~
Back Extract p*-
Waste Solvent -^
Precipitate
and
Redissolve
|
ExQBcnon
and
Scrubbing
i Solvent (Sm)
Bade
Extraction
1
..
Extraction ^h — S°lvent
p-^^^— and
Scrubbing -^U— Scrub
1 Solvent (ft)
Q^J. -^ Back Extract
Extraction ^^
P^- Waste Solvent
..
Aqueous Sm Aqueous Nd
t
Aqueous La
Aqueous Pr
539
-------
Calcium Reduction
High purity rare earth metals can be produced by the metallothermic reduction of rare earth halides. This
process is used when 99,99 percent purity is required. After converting the rare earths into fluorides, they are
reduced to the metallic state through contact with calcium or barium at high temperatures.22 Exhibit 5 presents a
flow diagram for calcium reduction.
Ten of the rare earths (lanthanum, cerium, praseodymium, neodymium, gadolinium, terbium dysprosium.
holmium, erbium, and lutetium as well as scandium, and yttrium) are produced by calcium reduction. The raw
material form of these metals is the metal fluoride. The individual metal fluoride is placed with calcium metal into a
reduction vessel where a heat-driven reaction produces pure rare earth metal and calcium fluoride. The metals are
further purified by melting in a vacuum to remove impurities. Casting is dependent upon the form in which a buyer
wants the metal. Non-contact cooling water is used to cool both the reduction vessels and the melting and casting
equipment.
Mischmetal
Mischmetal Production
Wet rare earth chlorides or hydrated rare earth compounds must be stripped of their water before
electrolytic reduction can take place in order to prevent decay of the graphite anode during electrolysis. The anode
could be decayed by the reaction of the liberated oxygen in the electrolyte with the carbon anode to form carbon
dioxide. Batch or continuous mode dryers may be used. Both gas heat and electric heat have been used to ran the
dehydration furnaces.23
Dry rare earth chlorides are reduced to mischmetal in electrolytic cells. Batch process electrolysis reduces
the rare earth salts to metal in 8 to 12 hours. Excess slag is removed and may be sold for its rare earth chloride
content. Following reduction, the mischmetal is cast into bars or ingots for future uses.24 Exhibits 6 and 7 present
process flow diagrams for mischmetal production.
Mischmetal Reduction
Mischmetal is an alloy typically composed of cerium, lanthanum, neodymium, praseodymium, other rare
earth metals, and iron. Mischmetal processing reduces the oxide form of the rare earth metals (samarium, europium,
and ytterbium) to an elemental form. In this reaction, the mischmetal acts as a reducing agent and is oxidized to a
mixture of rare earth metal oxides. The process is performed at a low pressure and a temperature below the melting
point so that the metals vaporize or sublime. The pure metal is condensed and collected in a crystalline mass of high
purity. These solids may be crashed into powder or melted and cast if a solid product form is desired.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
22 Ibid.
23 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume X, Office of Water Regulations
and Standards, May 1989, pp. 5376-5384.
24 Ibid.
540
-------
EXHIBITS
CALOIMREDUCTION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
Rare Earth
Fluorides
Calcium
I !
Non-Contact
Cooling
Calcium
Reduction
Reduced Metal
Non-Contact
Cooling
Melting
and
Casting
I
Impurities
Pure Rare Earth
Metal Ingot
Calcium
Fluoride
-------
Page Intentionally Blank
-------
4. Beneftciation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation. >
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In
contrast to beneficiation operations, processing activities often destroy the physical and chemical structure of the
incoming ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that
entered the operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes
are derived from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given
facility within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as
information on ore type(s), the functional importance of each step in the production sequence, and waste generation
points and quantities presented above.
EPA determined that for rare earths and mischmetal, the beneficiation/processing line occurs between ore
preparation and acid digestion when the ore is vigorously attacked with concentrated acids, resulting in the physical
destruction of the ore structure.
After careful analysis of Molycorp's process information, EPA determined in 1991 and 1992, that two
distinct operations occur during what Molycorp classifies as its "second leach step." The Agency believes that those
determinations are still appropriate. Molycorp submitted extensive comments on EPA's conclusions, which
are addressed in the response to comments document in the record.
Because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
-------
Page Intentionally Blank
-------
mineral processing waste streams generated after the benefieiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
C, Process Waste Streams
Rare earth element ores and commodities, as well as byproducts and waste materials from rare earth
processing, are naturally radioactive, due to contained thorium.
1. Extraetion/Beneficiation Wastes
Tailings and magnetic fractions are possible waste streams from the extraction and beneficiation of rare
earths.
2, Mineral Processing Wastes
Off-gases from dehydration from the furnaces are treated by water or alkaline scrubbers to remove
particulates and acid. The treated gases are vented.25 Existing data and engineering judgment indicate that this waste
does not exhibit any characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material
further.
Spent iron hydroxide cake. Existing data and engineering judgment indicate that this waste does not
exhibit any characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent lead and sand filter cinders. This waste contains waste components (e.g., lead) that originate from
the orebody as a result of direct contact with the mineral values (i.e., lanthanides) being processed.
Spent monazite solids. Existing data and engineering judgment indicate that this waste does not exhibit
any characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent offgases from electrolytic reduction. Off-gases from electrolytic reduction include chlorine gas,
carbon monoxide and carbon dioxide gases from the carbon in the graphite anodes, and hydrochloric acid fumes.
These gases are contacted with water to both cool the gases and to absorb particulates and hydrochloric acid vapors.
The partially cleansed gases are then contacted with sodium hydroxide solution, resulting in the formation of sodium
hypochlorite. After a sufficient hypochlorite concentration is attained, the solution may be sold as a byproduct.26
Existing data and engineering judgment indicate that this waste does not exhibit any characteristics of a hazardous
waste. Therefore, the Agency did not evaluate this material further.
Waste filtrate. Existing data and engineering judgment indicate that this waste does not exhibit any
characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material further.
Waste solvent. Although no published information regarding waste generation rate or characteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 2,000 metric tons/yr, 1,000,000 metric tons/yr, and 2,000,000 metric tons/yr, respectively.
We used best engineering judgment to determine that this waste may exhibit the characteristic of ignitability. EPA
does not considers this material to be a waste, because it is fully recycled.
Spent lead filter cake. This waste may be stabilized with a polysilicate material and then reinserted into
the process for extraction of additional cerium. Tailings containing carbonates are used to precipitate iron. The
resulting lead filter cake may exhibit the characteristic of toxicity for lead. Although no published information
regarding waste generation rate or characteristics was found, we used the methodology outlined in Appendix A of
25 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 5376-5446.
26 Ibid.
543
-------
this report to estimate a low, medium, and high annual waste generation rate of 3,300 metric tons/yr, 4,200 metric
tons/yr, and 5,000 metric tons/yr, respectively. EPA believes this material is fully recycled to recover metal values,
and not land stored.
Lead backwash sludge. Existing data and engineering judgment indicate that this waste does not exhibit
characteristics of a hazardous waste. Therefore, the Agency did not evaluate the material further. Further,
Molycorp, Inc. asserted that its Mountain Pass facility no longer produces this waste.
Waste zinc contaminated with mercury. Although no published information regarding waste generation
rate or characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low,
medium, and high annual waste generation rate of 200 metric tons/yr, 45,000 metric tons/yr, and 90,000 metric
tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit the characteristic
of toxicity for mercury. One firm, Molycorp, Inc., asserted that its Mountain Pass facility no longer produces this
waste.
Solvent extraction crud. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 200 metric tons/yr, 45,000 metric tons/yr, and 90,000 metric tons/yr,
respectively. However, this waste is only generated at one facility and one firm, Molycorp, Inc., indicated that its
Mountain Pass facility no longer produces this waste. We used best engineering judgment to determine that this
waste may exhibit the characteristic ignitability. This waste may be recycled and formerly was classified as a spent
material.
Spent surface impoundment liquids are a likely waste stream from rare earth production. Surface
impoundment liquids were generated at a rate of 477,000 metric tons per year in 1991.27 Waste characterization data
are presented in Attachment 1. This waste is not expected to be hazardous.
Spent surface impoundment solids. This waste stream was generated at a rate of 100 metric tons per year
in 1991 and may be toxic for lead.28 This waste is not expected to be hazardous. Waste characterization data are
presented in Attachment 1.
Lantfaanide Production
Spent ammonium nitrate processing solution is a possible waste stream from lanthanide separation. The
1991 waste generation rate for the sector was 14,000 metric tons per year. This waste may exhibit the characteristic
of corrosivity.29 Attachment 1 presents waste characterization data.
Cerium Production
Process wastewater. This waste stream may be toxic for lead as well as contain detectable levels of
ammonium. This wastewater may also be corrosive. The 1991 waste generation rate for the sector was 7,000 metric
tons per year.30 Waste characterization data are presented in Attachment 1. This waste may be recycled and
formerly was classified as a spent material.
Mischmetal Production
27 U.S. Environmental Protection Agency, 1992, Op. Cit.. Vol. I, pp. 1-2 -1-
28 Ibid.
29 Ibid.
30 Ibid.
544
-------
EXfflBIT6
MISCHMETAL REDUCTION PROCESS
(Adapted from 1988 Final Draft Summary Report of Mnerai Industry (Processing Wastes, 1988, pp. 3-164 - 3-174)
Rare Earth
Metal Oxide Metal
Non-Contact
Cooling
Crystalline
Rare Earth
Metal
Mschmetal
Reduction
(Vacuum
Distillation)
Mixed Rare Earth
Oxides
Crushing
and
Packaging
Rare Earth
Metal Product
Spent scrubber liquor from wet air pollution control is generated from mischmetal production.
Although no published information regarding waste generation rate or characteristics was found, we used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
of 100 metric tons/yr, 500,000 metric tons/yr, and 1,000,000 metric tons/yr, respectively. We used best engineering
judgment to determine that this waste may exhibit the characteristic of corrosivity. This water may be recycled or
discharged to wastewater treatment. This waste formerly was classified as a spent material.
545
-------
EXHTOIT7
MISCHMETAL PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, pp. 5376 - 5446.)
To Atmosphere
t
To Atmosphere
Backwash
HiO * ...
, ^ ^ Waste
and — ^ Scrubber — ^ c.
M r->u Stream
INa(JH To Atmosphere
^R ^^
Gas
1 1
Waste
H2O — >- Quench — >* S{ream H2O — >* Scrubber
t t
Gas
H2O
NaOH
^ Waste
Stream
H20 — >-
Wet
Rare Earth > D' Dry Rare Earth Chloride ^
Chloride
^
Dry Rare Earth
t ts
1 Dilute 1
NaOCl
Scrubber ^ FiUci
4
| Gas |
3 \\i t H2°
^ Waste 2
Quench ^Steam
T Gas
^ Mscliiuetal to
Elecliolyuc ^ Casting^orming
Reduction
Cell 1
t *
Slag
Chloride
NaOCl
-------
Wastewater from caustic wet air pollution control. Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 100 metric tons/yr, 500,000 metric tons/yr, and
1,000,000 metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit
the characteristics of toxicity for chromium and lead and corrosivity. Scrubber liquor is recycled and the bleed
stream is discharged to treatment. This waste formerly was classified as a spent material.
Spent electrolytic cell quench water and scrubber water. Waste characterization data are presented in
Attachment 1. This waste is not expected to be hazardous.
Electrolytic cell caustic wet APC sludge. Although no published information regarding waste generation
rate or characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low,
medium, and high annual waste generation rate of 70 metric tons/yr, 700 metric tons/yr, and 7,000 metric tons/yr,
respectively. We used best engineering judgment to determine that this waste may exhibit the characteristic of
corrosivity. This waste is recycled and is classified as a sludge.
Spent sodium hypochlorite filter backwash. The caustic wet air pollution control system following the
water quench or water scrubber is designed to recover chlorine present in the gas stream. Sodium hydroxide is
circulated through the scrubber and the reaction with chlorine forms sodium hypochlorite. When a 12 to 15 percent
sodium hypochlorite concentration is attained, the solution is drawn off and sold for industrial use. This waste is not
expected to be hazardous.
D, Non-uniquely Associated Hazardous Wastes
Ancillary hazardous wastes may be generated at on-site laboratories, and may include used chemicals and
liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, waste
oil (which may or may not be hazardous), and other lubricants. At Molycorp, Inc's facility in Mountain Pass, CA
several wastes are considered to be non-uniquely associated. These include pinion grease (contains 50 percent
aromatic oils, 35 percent petroleum asphalts, and 0-10 percent 1,1,1 triehloroethane) and spilled solvent cleaned
from the chemical plant's floor.
E. Summary of Comments Received by EPA
New Factual Information
Two commenters provided new information on facility specific operations and processes (COMM58,
COMM68). This new information was incorporated into the Agency's sector report.
Sector-specific Issues
Two commenters objected to EPA's determination that mineral processing occurs in the rare earth sector, in
that they believed this was a reversal of a prior determination by the Agency (COMM40, COMM58, COMM68).
One commenter, Molycorp, Inc., responded to both the Supplemental Proposed Rule Applying Phase IV Land
Disposal Restrictions to Newly Identified Mineral Processing Wastes and the Second Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes (COMM68,
COMM40). The concerns of Molycorp, Inc. stem from the Agency determining that mineral processing occurs in
the rare earth sector, rather than it being strictly a beneficiation process, which the commenter believed contradicted
the 1989 Mining Waste Exclusion Rule.
547
-------
BIBLIOGRAPHY
Castor. Stephen B. "Rare Earth Minerals." From Industrial Minerals and Rocks. 6th ed. Society for Mining,
Metallurgy, and Exploration. 1994. pp. 827-837.
Hedrick, James. "Rare Earths." From Mineral Commodity Summaries. U.S. Bureau of Mines. 1995. pp. 134-135.
Hedrick, James. "Rare Earths, the Lanthanides, Yttrium, and Scandium." From Minerals Yearbook Volume 1.
Metals and Minerals. U.S. Bureau of Mines. 1992. pp. 1035-1047.
RTI Survey, W.R. Grace, Chatanooga, TN, 1988, ID# 101824.
RTI Survey 101402. National Survey on Solid Wastes from Mineral Processing Facilities. Rhone-Poulenc,
Freeport, TX. 1989.
U.S. Bureau of Mines. Rare Earths Annual Report. 1993.
U.S. Environmental Protection Agency. Molycorp Waste Interpretation, Briefing for Matthew Straus, March 6,
1992.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol.1. August 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol.1. August 1992. pp. 10-2 - 10-18.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Vol. X. Office of Water Regulations
Standards. May 1989. pp. 5376-5446.
U.S. Environmental Protection Agency. Technical Background Document. Development of the Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral
Processing Wastes. Office of Solid Waste. 1989. pp. A-21 - A-22.
U.S. Environmental Protection Agency. "Rare Earths." From 1988 Final Draft Summary Report of Mineral
Industry Processing Waste. 1988. pp. 3-164 - 3-174.
548
-------
ATTACHMENT 1
549
-------
l/l
l/l
o
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT LIQUIDS - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0.008 0.008 0.008 1/1
0/0
0/0
0/0
0.03 0.03 0.03 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT SOLIDS - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
20000 20000 20000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
20000 20000 20000 1/1
7500 7500 7500 1/1
0/0
2000 2000 2000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
110000 110000 110000 1/1
0/0
33 33 33 1/1
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level in Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
.
-
.
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
U1
Ul
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT AMMONIUM NITRATE PROCESSING SOLUTION - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Suifide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0.046
0.229
0.0025
0,038
0.009
-
0.0025
0.009
0.054
0.005
0.053
0.001
0.005
0.005
0.0001
-
-
0.0025
0.005
-
-
0.001
0.005
0.025
69
-
-
-
1,126
-
0.1
107.13
0,38
10.11
0.01
0.07
0.01
-
0.03
0.06
4.93
0.04
0.05
0.02
56.08
0.02
0.00
-
-
0.01
0.04
-
-
0.02
0.09
0.34
595
-
-
-
11,108
-
7.07
109.17
0.97
20
0.025
0.11
0.009
-
0.095
0,24
9.8
0.085
0,053
0.03
221
0.045
0.0005
-
-
0.016
0.097
-
-
0.046
0.25
0.5
1,494
-
-
-
21,300
-
9.59
111.2
3/3
2/2
4/5
5/5
1/1
0/0
4/5
3/5
2/2
2/3
1/1
4/4
6/6
3/4
2/3
0/0
0/0
1/3
3/5
0/0
0/0
3/4
0/3
0/3
3/3
0/0
0/0
0/0
3/3
0/0
9/9
2/2
EP Toxicity Analysis - PPM
Minimum Average Maximum
.
-
0.002 0.049
0.006 6.99
-
-
0.003 0.013
0.027 0.048
0.0005 0.065
-
-
0.005 0.014
-
-
0.0065 0.06
0.009 0.07
0,004 3.28
0.023 0.05
0.009 0.02
-
.
,
-
.
.
-
-
.
.
.
-
-
0.132
20
-
-
0.03
0.079
0.15
-
-
0.02
-
-
0.094
0.124
9.8
0.095
0.038
-
-
-
-
-
-
-
-
-
-
-
# Detects
0/0
0/0
3/3
3/3
0/0
0/0
3/3
3/3
2/3
0/0
0/0
2/3
0/0
0/0
2/3
3/3
3/3
3/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5,0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
-
-
-
-
-
.
212 1
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
27.9
0.50
0.50
0.50
0.05
-
0.00050
0.00050
0.5
0.5
8.57
0.0005
154
3.68
0.00010
0.50
0.008
0.50
0.50
2.50
0.50
1.98
-
•
152
0.20
-
-
0.034
0.030
0.4
-
35.7
0.50
0.50
0.50
0.05
-
0.039
0.26
0.50
1.08
10.19
2.50
2,117
104
0.00010
0.50
1.25
0.50
0.50
2.50
0.50
8.09
-
-
786
15.10
-
-
1,675
4,740
0.7475
-
43.5
0.50
0.50
0.50
0.05
-
0.054
0.50
0.50
1.65
11.80
8.45
4,080
204
0.00010
0.50
4.00
0.50
0.50
2.50
0.50
14.20
-
-
1,420
30.0
-
-
6,490
9,480
1.1
-
Detects
2/2
0/2
0/2
0/2
0/2
0/0
1/4
1/4
0/2
1/2
2/2
3/4
2/2
2/2
0/2
0/2
2/4
0/2
0/2
0/2
0/2
2/2
0/0
0/0
2/2
2/2
0/0
0/0
4/4
2/2
4/4
0/0
EP Toxicity Analysis -
Minimum Average
23.2
0.50
0.50
0.50
0.05
-
0.05
0.50
0.50
0.50
7.55
0.63
1,020
2.52
0.0001
0.50
0.50
0.50
0.50
2.50
0.50
1.98
-
-
-
-
-
-
-
-
25.6
0.50
0.50
0.85
0.05
0.05
0.50
0.50
.1.56
7.76
5.31
4,955
10.4
0.0001
0.50
0.50
0.50
0.50
2.50
0.50
7.24
PPM
Maximum #
28
0.50
0.50
1.20
0.05
0.05
0.50
0.50
2.62
7.97
10.0
8,890
18.3
0.0001
0.50
0.50
0.50
0.50
2.50
0.50
12.5
-
-
-
-
-
-
-
-
Detects
2/2
0/2
0/2
1/2
0/2
0/0
0/2
0/2
0/2
1/2
2/2
2/2
2/2
2/2
0/2
0/2
0/2
0/2
0/2
0/2
0/2
2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 1
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 4
-
LH
Ul
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Ul
Ul
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT ELECTROLYTIC CELL QUENCH WATER - CERIUM\LANTHANIDES\RARE EARTHS
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0.005
0.006
-
0.001
-
0.001
0.001
-
0.01
-
0.14
-
-
0.0002
-
0.013
0.005
0.001
0.001
-
0.06
0.0003
-
-
-
-
-
-
-
-
-
-
0.0067
0.0177
-
0.0010
-
0.0073
0.0173
-
0.0230
-
0.2733
-
-
0.0008
-
0.0380
0.0110
0.0010
0.0057
-
0.1167
0.0075
-
-
-
-
-
-
-
-
-
-
0.01
0.025
-
0.001
-
0.02
0.033
-
0.033
-
0.4
-
-
0.002
-
0.051
0.023
0.001
0.015
-
0.19
0.022
-
-
-
-
-
-
-
-
-
# Detects
0/0
3/3
3/3
0/0
3/3
0/0
3/3
3/3
0/0
3/3
0/0
3/3
0/0
0/0
3/3
0/0
3/3
3/3
3/3
3/3
0/0
3/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
--
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
RHENIUM
A.
Commodity Summary
The principal source of rhenium is molybdenum concentrates which are derived from porphyry copper
deposits. Rhenium-containing products include ammonium perrhenate, perhennie acid, and metal powder. Rhenium
is used in high-temperature superalloys (such as those used for manufacturing jet engine components) because it
improves the strength properties of nickel alloys at high temperatures (1,000 °C). Rhenium alloys are used in
thermocouples, temperature controls, heating elements, ionization gauges, mass spectrographs, electron tubes and
targets, electrical contacts, metallic coatings, vacuum tubes, crucibles, electromagnets, and semiconductors.
Rhenium is also used in petroleum-reforming catalysts for die production of high octane hydrocarbons for use in
lead-free gasoline. Bimetallic platinum-rhenium catalysts have replaced many of the monometallic catalysts.1
Rhenium is usually traded either as ammonium perrhenate or rhenium metal,2
According to the U.S. Bureau of Mines, ores containing rhenium are mined domestically by eight
companies. Exhibit 1 presents the names and location of mose companies generating molybdenum concentrates that
contain rhenium.
EXHIBIT 1
SUMMARY OF RHENIUM FACILITIES
Facility Name
Chino Mines Co.
Cyprus-Climax
Cyprus-Climax
Kennecott Minerals Co.
Magna Copper Corp.
Magna Copper Co.
Phillips Dodge Corporation
Sheilds Resources Inc. (Continental Pit)
Location
Hurley NM
Sierrita, AZ
Bagdad, AZ
Bingham Canyon, UT
San Manuel, AZ
Miami, AZ
Morenci, AZ
Butte, MT
Type of Operation
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Molybdenum concentrates
Although most of diese companies typically send their concentrates out of the United States to be toll
refined, there is one compnay that recovers and refines rhenium domestically. Cyprus-Climax roasts and recovers
rhenium at their Sierrita facility. Additionally, Cyprus-Climax has a rhenium recovery operation at Fort Madison,
Iowa.3 Rhenium consumption was estimated as 6,000 kilograms in 1994.4
1 Blossom, J. W., "Rhenium," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995,
pp. 136-137.
2 Blossom, J.W., "Rhenium," from Mineral Facts and Problems. 1985, p. 667.
3 Personal communication between Jocelyn Spielman, ICF Incorporated, and J.W. Blossom, U.S. Bureau of
Mine*,. October 17, 1994.
4 Blossom, J. W., 1995, Op. Cit. p. 136.
555
-------
B. Generalized Process Description
1. Discussion of Typical Production Processes
In general, rhenium is recovered from the off-gases produced when molybdenite, a byproduct of the
processing of porphyry copper ores for molybdenum, is roasted. During the roasting process, molybdenite
concentrates are converted to molybdic oxide and rhenium is converted to rhenium heptoxide. The rhenium oxides
are sublimed and carried off with the roaster flue gas, sulfur oxides, and the entrained dust. Once the technical
grade molybdic oxide is separated from the off-gases, it may be further processed to either molybdenum or
ferromolybdenum.5 The off-gases are then processed to recover rhenium as described in detail below. Exhibit 2
provides an overview of the rhenium recovery process and how it is associated with the production of molybdenum,
2. Generalized Process Flow Diagram
As shown in Exhibit 3, the rhenium recovery process can be separated into five main steps:
(1) scrubbing; (2) solvent extraction or ion exchange; (3) precipitation (addition of H2S and HC1) and filtration; (4)
oxidation and evaporation; and (5) reduction.
Scrubbing
The rhenium heptoxide entrained in flue gas is readily soluble in aqueous ammonia solutions and can be
removed by wet scrubbing. Collection efficiencies are on the order of 65% and the unrecovered rhenium remains in
the off-gases that escape into the stack.6
Solvent Extraction or Ion Exchange
The rhenium heptoxide absorbed and dissolved in the scrubber liquor can be recovered at much greater
efficiencies than the rhenium from the flue gas. Recoveries of better than 95% have been attained from liquor with
rhenium concentrations in excess of 300 ppm. The rhenium is removed from the scrubber liquor via either solvent
extraction or selective ion exchange in a solid bed.7
Precipitation and Filtration
After ion exchange treatment (or solvent extraction) rhenium is stripped from the resin (or solvent) and
recovered from the resulting eluviate solution as ammonium perrhenate crystals (NH4ReO4).888 As shown in Exhibit
2, the perrhenate solution is precipitated to ReS2 through the addition of H2S, HC1, and NH4CNS, followed by
filtration. The resulting salt solutions are then sent to further treatment.
5 U.S. Environmental Protection Agency, Development Document for Effluent Limitation Guidelines and
Standards for Nonferrous Metals Manufacturing Point Source Category. Vol. II, Office of Water Regulations
Standards, May 1989, pp. 3363.
6 Ibid., p.3365.
7 Ibid.
8 Ibid.
556
-------
Molybdenum
Sulfide
Concentrate
Molybdenum
Sulfide
Concentrate
EXHIBIT 2
MOLYBDENUM AND RHENIUM PRODUCTION PROCESSES
(Adapted from: Development Document for Effluent Limitation Guidelines and Standards for Nonferrous Metals Manufacturing
Point Source Category, 1989, pp. 3341 - 3483.)
Gas
Wastewatcr
Wastcwatcr
Rhenium Scrubber Solution
Wastcwatcr
i
Gas
h
Roasting
1
L
Leaching
1
r
Technical
Grade
Molybdic Oxide
fe,
^
Wastcwatcr
Pure
Molybdic Oxide
Ammonium Molybdate
Molybdenum
Metal Powder
Leaching,
Dissolving,
Crystallization
Ammonium ^
W
Molybdate
Calcining
Pure
Moiybdic
Oxide
Wastcwatcr
-------
U1
U1
oo
EXHIBIT 3
RECOVERY OF RHENIUM FROM MOLYBDENITE CONCENTRATES
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-175 - 3-178.)
To Stack or
SO2 Capture
(ARC Dust)
Spent
Solutions
H2O2, NH4OH
-------
Reduction
The dry ammonium perrhenate is generally reduced to high purity rhenium metal powder with purified dry
hydrogen in an externally heated furnace. The hydrogen reduction is accomplished in two stages, the first at 300° to
350° C and the second at 700° to 800° C. The metal powder is then sintered into bars by compression at 45 to 50 kg
per mm2, using stearic acid in either stage as a plasticizer. The bars are then rolled to sheet, strip, and foil, or swaged
and drawn into rod and wire. These products are annealed at recrystallization temperature after cold working to
ensure maximum ductility.9
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneficiation/Processing Boundary
Since rhenium is recovered from off-gases from the production of molybdenum, please see the report for
molybdenum presented elsewhere in this background document for a description of where the
beneficiation/processing boundary occurs for this mineral commodity sector.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
None Identified.
2. Mineral Processing Wastes
Exhibits 2 and 3 identify the following wastes associated with the recovery of rhenium.
Roasting and Wet Scrubbing
Slag. Slag is produced during roasting. Existing data and engineering judgment suggest that this material
does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Roaster Dust. Dust removed after the roasting of molybdenum concentrates is sent to further treatment.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
APC Dust/Sludge. After wet scrubbing, unrecovered rhenium remains in the off-gases that are captured in
the stacks. The captured dust and sludge are sent to further treatment. Existing data and engineering judgment
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Spent Barren Scrubber Liquor. Barren scrubber liquor generated during wet scrubbing contains treatable
concentrations of toxic metals, particularly selenium. Although it is discharged as a wastewater stream, the two
plants that report this waste stream achieve zero discharge. Specific practices at these two plants through lime
addition and sedimentation, total reuse in other plant processes, evaporation, and contract hauling.10 Although no
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 0 metric
tons/yr, 100 metric tons/yr, and 200 metric tons/yr, respectively. We used best engineering judgment to determine
9 J.W. Blossom, 1985, Op. Cit. p. 667.
10 U.S. Environmental Protection Agency, 1989. Op. Cit. p. 3430
559
-------
that this waste may be. recycled and may exhibit the characteristic of toxicity for selenium. This waste was formerly
classified as a spent material,
Ion Exchange and Solvent Extraction
Spent Rhenium Raffinate. As shown in Exhibit 3, raffinate results from the solid bed ion exchange and is
sent for neutralization and disposal. This waste stream has a reported waste generation rate of 88 metric tons/yr. We
used best engineering judgment to determine that this waste may exhibit the characteristic of toxicity for lead.
Spent Ion Exchange Solutions, Two facilities reporting this waste stream from ion exchange achieve zero
discharge through treatment, reuse, evaporation ponds, and contract hauling. Although no analytical data are
available for this waste stream, one facility reported that the solution contains treatable concentrations of selenium as
well as high concentrations of molybdenum and iron. When rhenium recovery is achieved using solvent extraction,
the resultant solution may also contain priority organics." Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Precipitation and Filtration
Spent Salt Solutions. The salt solutions that result from filtration are sent to further treatment. Existing
data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
" U.S. Environmental Protection Agency, 1989.;
560
-------
BIBLIOGRAPHY
Blossom, J.W, "Rhenium," Mineral Commodititv Summaries. 1995. pp. 136-137.
Blossom, J.W. "Rhenium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 666-667.
Personal communication between Jocelyn Spielman, ICF Incorporated, and J.W. Blossom, U.S. Bureau of Mines.
October 17, 1994.
U.S. Environmental Protection Agency. Development Document for Effluent Limitation Guidelines and Standards
for Nonferrous Metals Manufacturing Point Source Category. Office of Water Regulations Standards. May
1989. pp. 3341-3483.
U.S. Environmental Protection Agency. "Rhenium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-175 - 3-178.
561
-------
Page Intentionally Blank
562
-------
RUTILE (Synthetic)
A. Commodity Summary
Synthetic rutile (TiO2) is manufactured through the upgrading of ilmenite ore to remove impurities (mostly
iron) and yield a feedstock for production of titanium tetrachloride through the chloride process. The chemical
composition of synthetic rutile is similar to that of natural rutile, but differs in physical form. Synthetic rutile
concentrates are composed of very fine crystals and are porous, whereas natural rutile grains are composed of single
crystals.1
Since 1977, Kerr-McGee Chemical Corporation has produced synthetic rutile at its Mobile, Alabama plant;
it is the only U.S. producer of synthetic rutile today. Because of its purity in comparison with ilmenite, rutile and
synthetic rutile are the preferred feedstocks for production of titanium tetrachloride intended for sponge and metal
production. The development of processes to produce synthetic rutile was necessitated by the small quantity of
economic reserves of natural rutile worldwide,2 Thus, despite the fact that the U.S. has large reserves of ilmenite, the
majority of sponge produced is manufactured from imported rutile and synthetic rutile, primarily from Australia and
Malaysia,3
Because it is relatively free of impurities, less wastes are generated using rutile and synthetic rutile to
produce titanium tetrachloride and titanium dioxide pigment than with ilmenite. The process of converting ilmenite
to synthetic rutile generates 0.7 tons of waste per ton of product, and the chloride process generates about 0.2 tons of
waste per ton of TiO2 product using rutile as a feedstock. In comparison, direct ehlorination of ilmenite generates
approximately 1.2 tons of waste (primarily ferric chloride) per ton of TiO2.4
B. Generalized Process Description
1. Discussion of Typical Production Processes
Several processes using oxidation, reduction, leaching, and/or ehlorination have been developed to remove
iron from low-grade, beach sand ilmenite and produce synthetic rutile having 90 to 97% TiO2 and very low levels of
impurities. These processes can be organized in three categories:
(1) Processes in which the iron in the ilmenite ore is completely reduced to metal and separated either
chemically or physically;
(2) Processes in which the iron is reduced to the ferrous state and chemically leached from the ore; and
(3) Processes in which selective ehlorination is used to remove the iron.5
1 J. Gambogi, Annual Report: Titanium-1992. U.S. Bureau of Mines, December 1993, p. 1.
2 U.S. Environmental Protection Agency, Technical Background Document: Development of the Cost.
Economic, and Small Business Impacts Arising from the Reinterpretarion of the Bevill Exclusion for Mineral
Processing Wastes. Office of Solid Waste, August 1989, p. B-39.
3 J, Gambogi, 1993, Op. Cit. pp. 5, 18.
4 J.*Gambogi, "Rutile," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p. 141.
5
J. Gambogi, 1993, Op. Cit.. p. 3.
563
-------
Kerr-McGee uses the Benelite Cyclic process, in which hydrochloric acid is used to leach iron from reduced
ilmenite. The plant has an annual capacity of almost 91,000 metric tons. The plant recycles most of its waste
streams and reportedly discharges no liquid wastes.6
2. Generalized Process Flow Diagram
Benelite Cyclic Process
In the Benelite Cyclic process (Exhibit 1), developed by the Benelite Corporation of America, raw ilmenite
sand containing 54 to 65% TiO2 is roasted with heavy fuel oil in a rotary kiln at 870° C. The fuel oil functions as a
reducing agent, converting ferric iron (Fe3+) in the ilmenite to the ferrous (Fe2+) state. The fuel oil is burned at the
discharge end of the kiln, and the resulting gases are passed through a cyclone and an incinerator to remove solids
and unreacted hydrocarbons.7
The reduced ilmenite is then batch-digested in rotary-ball digesters with 18-20% HC1 at 140° C. Ferrous
oxide in the ilmenite is converted to soluble ferrous chloride, and the TiO2 portion of the ilmenite is left as a solid.
Spent acid liquor, which contains excess HC1 and ferrous chloride, is sent to an acid regeneration circuit. The TiO2
solids are washed with water and filtered and calcined at 870° C, yielding synthetic rutile with approximately 94%
TiO2. Exhaust gases from the calciner are treated to remove solids and acidic gases before they are released to the
atmosphere.8
In the acid regeneration circuit, the spent acid liquor is sent to a preconcentrator where one-fourth of the
water in the liquor is evaporated. The concentrated liquor is sprayed through atomizers, causing the droplets to dry
out, yielding HC1 gas and ferric oxide powder. The gas is cycloned and then sent to an absorber to remove HC1 for
reuse. The ferric oxide powder is slurried with water to create the waste stream iron oxide slurry.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
High-grade synthetic rutile (98% TiO2) has been generated through batch-scale and continuous rotary kiln
carbothermic metallization of ilmenite, followed by treatments such as catalytic rusting, acidic chloride leaching, and
oxidation-leaching.9
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
6 D. Carr, ed., Industrial Minerals and Rocks. Society for Mining, Metallurgy, and Exploration, Inc., 1994, p.
1085.
7 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. B-40.
8 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. B-40.
9 A. Damodaran, etal.. "On Extraction of High Grade Synthetic Rutile from Indian Ilmenite," The Minerals,
Metals & Materials Society, 1992, p. 1079.
564
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EXHIBIT 1
BENELITE CYCLIC PROCESS FOR SYNTHETIC RUTILE PRODUCTION
(Adapted from: Kerr-McGee Corp., Comments on Notice of Proposed Rulemaking, 1989.)
Illmenite Ore
(54 - 65% TIO2)
Offgases
Off gases
Synthetic Rutile
(94% TiO2)
Offgases
Iron Oxide
Slurry
565
-------
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between screening/cleaning of sand and reduction in a rotary kiln. EPA identified this point in the process sequence
as where beneficiation ends and mineral processing begins because it is here where a significant chemical change to
the ilmenite ore occurs. Therefore, because EPA has determined that all operations following the initial "processing"
step in the production sequence are also considered processing operations, irrespective of whether they involve only
techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial
mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA
presents the mineral processing waste streams generated after the beneficiation/processing line in section C.2, along
with associated information on waste generation rates, characteristics, and management practices for each of these
waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Beach/alluvial sands containing ilmenite are excavated by dragline, front-end loader, or suction dredging;
the sands are spiral concentrated to remove low density tailings. The sands are then dried and separated
electrostatically to remove quartz and other nonconducting minerals, which are processed to produce zircon and
monazite product and wastes consisting of quartz and epidote minerals. Conducting materials are magnetically
separated to sort ilmenite from rutile, followed by screening and cleaning. No wastes from beach sand processing
are expected to exhibit hazardous characteristics.10
2. Mineral Processing Wastes
The Benelite Cyclic process for manufacturing synthetic rutile generates three mineral processing wastes,
as described below.
Air Pollution Control Dust/Sludges
Air pollution control (APC) dust/sludges are generated by the cycloning of off-gases from the roasting step
to remove solids. Solids are also removed from off-gases from the calcining step. Off-gases from the spray roaster
used in the acid regeneration circuit are also cycloned to remove entrained solids, and subsequent gases from the
absorber are scrubbed. APC dust/sludge is believed to be recycled back into the production process (possibly to the
roasting step) and is not regarded as a solid waste." This waste stream has a reported waste generation rate of
10(U.S. Environmental Protection Agency, "Titanium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988. p. 3-219.
11 D. Carr, ed., 1994, Op. Cit.. p. 1085.
566
-------
30,000 rnt/yr. Although no published information regarding characteristics was found, we used best engineering
judgment to determine that this waste may exhibit the characteristic of toxicity (cadmium and chromium).12-0 This
waste stream is fully recycled and is classified as a sludge.
Spent Iron Oxide Slurry
Iron oxide slurry is the primary waste stream generated in the production of synthetic rutile; it is generated
in the acid regeneration circuit. Approximately one-half metric ton of slurry is generated for every metric ton of
synthetic rutile. The disposal method for this waste is unknown.14 This waste stream has a reported waste generation
rate of 45,000 mt/yr. We used best engineering judgment to determine that this waste may be partially recycled and
may exhibit the characteristic of toxicity (cadmium and chromium). This waste is classified as a by-product.
Spent Acid Solution
Spent acid solution is generated in the digestion step. Spent acid liquor, which contains excess HC1 and
ferrous chloride, is sent to an acid regeneration circuit to recover HC1 for recycle back to the digester. This waste
stream is generally recycled back into the process and is not regarded as a solid waste.15 This waste stream has a
reported waste generation rate of 30,000 mt/yr. Although no published information regarding characteristics was
found, we used best engineering judgment to determine that this waste may exhibit the characteristics of toxicity
(cadmium and chromium) and corrosivity. This waste stream is classified as a spent material,
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
12 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. B-39.
13 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set,
Office of Solid Waste, August 1992, p. 1-6.
14 U.S. Environmental Protection Agency, 1989, Op. Cit., p. B-40 - B-41.
15 Ibid.
567
-------
BIBLIOGRAPHY
Carr, D., ed. Industrial Minerals and Rocks. Society for Mining, Metallurgy, and Exploration, Inc. 1994. p. 1085.
Damodaran, A., P. Mohan Das, P. Sai, and G. Surender. "On Extraction of High Grade Synthetic Rutile from Indian
Ilmenite." The Minerals, Metals & Materials Society. 1992. p. 1079.
Gambogi, J. Annual Report: Titanium-1992. U.S. Bureau of Mines. December 1993.
Gambogi, J. "Rutile." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 140-141.
Kerr-McGee Corp. "Comments on Notice of Proposed Rulemaking, U.S. Environmental Protection Agency, April
17,1989." Submitted May 31, 1989.
U.S. Environmental Protection Agency. "Titanium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-217 - 3-227.
U.S. Environmental Protection Agency. Technical Background Document: Development of the Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral
Processing Wastes. Office of Solid Waste. August 1989. pp. B-39 - B-41.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
568
-------
SCANDIUM
A.
Commodity Summary
Although scandium was not mined domestically in 1993. scandium ore was intermittently recovered from
tailings and concentrates as needed. By-product scandium concentrates previously produced in Utah and tailings
previously generated by mining fluorite in Montana were available for processing to recover high purity scandium
oxide. Although four processing companies, two in Colorado, one in Illinois, and ooe in New Jersey, produced
refined scandium products in 1993, no domestic facility recovered scandium from uranium.1 One company in Iowa
had the technology to produce ultra-high purity (99.9999%) scandium oxide. Companies in Arizona, Illinois, and
Iowa possessed capacity to produce ingot and distilled scandium metal products. Exhibit 1 presents the names and
locations of facilities once involved in the production of scandium.
EXHIBIT 1
SUMMARY OF SCANDIUM FACILITIES
Facility Name
Baldwin Metals Processing
Co.
Boulder Scientific Co.
Interpro (subsidiary of
Concord Trading Corp.)
Materials Preparation
Center
Rhone Poulenc, Inc.
Kennecott
Climax Mine
APL Engineered Materials
Sausville Chemical Co.
Location
Phoenix, AZ
Mead, CO
Golden, CO
Ames, I A
Phoenix, AZ
Garfield, UT
Climax, CO
Urbana, IL
Garfield, NJ
Type of Operation
Ingot and distilled scandium metal production.
Refining. Processed scandium concentrates derived from
thortveitite-bearing tailings from the mined-out Crystal
Mountain fluorite mine near Darby, Montana.
Refining. Processed stocks of scandium concentrates
previously generated by the Energy Fuels Nuclear uranium
plant at Bingham Canyon, Utah.
Scandium Oxide and Ingot Production (research organization).
Ingot and distilled scandium metal production.
Scandium is available for refining in the form of a byproduct
generated during processing of uranium at the copper mine.
Scandium is available for refining from the tungsten byproduct
generated during the molybdenum operation.
Refining. Ingot and distilled scandium metal production.
Refining. Processed scandium concentrates to produce
scandium oxide, fluoride, nitrate, chloride, and acetate.
1 Personal communication between Jocelyn Spielman, ICF Incorporated and James B. Hedrick, Scandium
Specialist, U.S. Bureau of Mines, October 20, 1994.
569
-------
Scandium used in the United States is primarily from domestic sources. Some minor amounts of scandium
are recovered by recycling laser crystal rods. The principal uses for scandium are metallurgical research, high-
intensity metal halide lamps, analytical standards, electronics, lasers, and research.2
Scandium is a soft silver metal which has a slightly yellow cast when exposed to air. Scandium readily
reacts with acids and is not easily attacked by water. The metal does not tarnish in air, but at high temperatures (500
to 800 °C) scandium can be oxidized in air. Scandium is extremely electropositive, and therefore, its oxide is basic
and acid soluble. Scandium exhibits a trivalent state in compounds and has no other observed valences. Scandium is
chemically similar to rare earth elements; however, its ion size places it in geochemical equilibria with aluminum,
magnesium, hafnium, and zirconium. Therefore, scandium is rarely found in the earth ores, but has been noted in
minor amounts in gadolinite, xenotime, allanite, davidite, and others.3
B, Generalized Process Description
1. Discussion of Typical Production Processes
Scandium is generally produced by small, bench-scale batch processes. Much initial recovery is from in-
plant streams where solvent extraction is being used to recover other metals such as uranium. These crude materials
are then worked up to high purity oxides and metals. The principal domestic scandium resource is fluorite tailings
from the Crystal Mountain deposit near Darby, Montana. Tailings from the mined-out fluorite operations, which
were generated from 1952 to 1971, contain thortveitite and associated scandium-enriched minerals. Resources are
also contained in the tungsten, molybdenum, and titanium minerals from the Climax molybdenum deposit in
Colorado, and in the kolbeckite (sterrettite), varsite, and crandallite at Fairfield, Utah.4 Scandium is extracted from
thortveitite by several methods.
2. Generalized Process Flow Diagram
Recovery From Thortveitite
As shown in the attached process flow diagrams, scandium can be recovered from thortveitite using several
methods. Each method involves a distinct initial step (i.e., acid digestion, grinding, or chlorination) followed by a
set of common recovery steps, including leaching, precipitation, and filtration.
Acid Digestion, Grinding, and Chlorination. Scandium is extracted from thortveitite by several methods.
The method shown in Exhibit 2 involves digestion of thortveitite with concentrated hydrochloric or sulfurie acid,
yielding a gelatinous silica residue that contains scandium. Another method, shown in Exhibit 3, begins by finely
grinding thortveitite and then combining it with charcoal at 1,800 °C to form scandium carbide. This carbide is then
further decomposed with hydrochloric acid, forming soluble scandium chloride. Exhibit 4 presents a third method
that involves heating thortveitite in the presence of chlorine gas and carbon at 850 °C to form scandium chloride.
2 James B. Hedrick, "Scandium," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995, pp. 148-
149.
3 U.S. Environmental Protection Agency, "Scandium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. Office of Solid Waste, 1988, p. 3-20.
4 James B, Hedrick, 1995, Op. Cit. pp. 148-149.
570
-------
EXHIBIT 2
SCANDIUM FROM THORTVEmTE #1
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-20 - 3-30.)
Thortveitite
Ore
Sulfuric Acid
Ammonium Oxalate
or Tartrate
Concentrated HC1
or
T
Silica Residue
Containing Scandium
Spent Acid
Waste Sulfuric Acid
Waste Solution
Spent Wash Water
571
-------
EXHIBIT 3
SCANDIUM FROM THORTVEITITE #2
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-20 - 3-30.)
Charcoal
Ammonium Oxalate
or Tartrate
I
Thortveitite
Ore ^
Sc
Hydrochloric
Acid ^
Grinding
1800°C
1 .
-andium Carbide
1
Leaching
1
Scandium Chloride
Leaching
^
1
Leaching Solution
Spent Acid
Waste Acid
^ Waste Sulfuric Acid
^- Waste Solution
572
-------
EXHIBIT 4
SCANDIUM FROM THORTVEmTE »
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-20 - 3-30.)
Thortveitite
Ore
Sulfuric Acid
Ammonium Oxalate
or Tartrate
I
Scandium Chloride
Scandium Oxide
Waste Chlorine
Solution
Waste Sulfuric Acid
Waste Solution
+ Filter Wash
573
-------
EXHIBIT 4 (Continued)
SCANDIUM FROM THORTVEITITE #3
Scandium Oxide
Hydrochloric
Acid ~
1
Wash
Scandium Chloride
Ion Exchange
Scandium Metal
Waste Acid
Solvent Extraction
T
Scandium Metal
574
-------
In a fourth method, scandium can also be extracted from thortveitite using hydrofluoric acid in a similar
method. Methods using magnesium or ammonium-hydrogen fluoride have also been used. Regardless of the method
used, these initial recovery steps are followed by leaching, precipitation, filtration, washing, and ignition at 900 °C to
form scandium oxide.5
Leaching, Precipitation, and Filtration. Scandium is obtained by leaching scandium chloride with
sulfuric acid. Scandium is recovered from the leaching residues by adding ammonium oxalate or tartrate to the
solution forming a scandium precipitate. This precipitate is filtered and washed, then decomposed by ignition at 900
"C, forming scandium oxide. The scandium oxide is then dissolved in hydrochloric acid to form scandium chloride.6
Purification. Scandium chloride is purified via distillation. Distillation removes a large quantity of
metallic impurities, including iron, cadmium, magnesium, and chromium, along with carbon and nitrogen. Ion
exchange or solvent extraction is also used for further purification.7
Recovery From Uranium (no longer used)
Alternatively, as shown in Exhibit 5, scandium was also once recovered from a byproduct generated during
the processing of uranium at the copper mines in Garfield, Utah. The stripped solvent from uranium ore solvent
extraction was acidified in stages. First the solvent was treated with hydrofluoric acid and filtered. Next, the
resultant filter cake was treated with hydrochloric acid, followed by digestion and filtration. Oxalic acid was added
to the resultant scandium, iron, and uranium filtrate to form scandium oxalate, which was calcined to yield scandium
oxide. A second treatment with hydrochloric acid followed by extraction and stripping yielded scandium metal.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
In addition to the methods described, the U.S. Bureau of Mines has investigated solvent extraction methods
for recovering scandium from the leach filtrates of sulfated tantalum tailings.8
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In
5 U.S. Environmental Protection Agency, 1988, Op. Cit. p. 3-20.
6 Ibid.
7 Ibid.
8 Michael D. Odekirk and Donna D. Harbuck, "Scandium Solvent Extraction from Liquors Produced by Leaching
Sulfated Tantalum Tailings," EPD Congress, The Minerals, Metals & Materials Society, 1993, pp. 83-97.
575
-------
EXHIBITS
SCANDIUM FROM URANIUM
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-20 - 3-30.)
Stripped Solvent
from Uranium Ore
Solvent Extraction
<0.1 ppmSC
Counter Current
Solvent Extraction
Stage 1
Stage 2
-^- Waste Solvent
Hydrofluoric Acid •
Mixing
Filter
H^- Waste Acid
Hydrochloric Acid •
Filter Cake
10% Scandium
Digester
Thorium, Titanium,
~^- Zirconium, Iron, arid
Silica (ppt)
Oxalic Acid
Digestion Solution
Filter
Scandium, Iron, Uranium Filtrate
Mixing
Scandium Oxalate
Precipitate
Waste Acid
576
-------
Hydrochloric
Acid —
EXHIBIT 5 (Continued)
SCANDIUM FROM URANIUM
Scandium
Oxide
Precipitation
Waste Acid
Scandium Metal
577
-------
contrast to beneficiation operations, processing activities often destroy the physical and chemical structure of the
incoming ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that
entered the operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes
are derived from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line for
scandium recovery from thortveitite occurs between ore preparation and digestion, grinding, or chlorination for
thortveitite processes 1, 2, and 3, respectively. EPA identified these points in the process sequences as where
beneficiation ends and mineral processing begins because it is here where a significant chemical change to the
thortveitite ore occurs. Therefore, because EPA has determined that all operations following the initial "processing"
step in the production sequence are also considered processing operations, irrespective of whether they involve only
techniques otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial
mineral processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA
presents the mineral processing waste streams generated after the beneficiation/processing line in section C.2, along
with associated information on waste generation rates, characteristics, and management practices for each of these
waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
The wastes generated by recovery from uranium may have been radioactive, however, no further
characterization, management, or generation data are available. Those wastes identified in Exhibit 5 include:
Waste Solvent
Waste Hydrofluoric Acid
2. Mineral Processing Wastes
Waste streams are more likely to be associated with the primary products that produced the crude scandium
concentrate. Although it is difficult to predict the amount and nature of wastes resulting directly from scandium
production because of the wide variety of sources that are available as scandium starting materials, the attached
process flow diagrams identify wastes that are generated as a result of scandium production processes.9
For example, using Exhibits 2 through 4 the following wastes result from the production of scandium:
Waste chlorine solution. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent ion exchange resins and backwash. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Spent solvents from solvent extraction. Although no published information regarding waste generation
rate or characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low,
' U.S. Environmental Protection Agency, 1988,;
578
-------
medium, and high annual waste generation rate of 700 metric tons/yr, 3,900 metric tons/yr, and 7,000 metric tons/yr,
respectively. We used best engineering judgment to determine that this waste may be recycled and may exhibit the
characteristic of ignitability. This waste is classified as a spent material.
"Crud" from the bottom of the solvent extraction unit. Existing data and engineering judgment suggest
that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
this material further.
Dusts and spent filters from decomposition. Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Spent acids (e.g., hydrochloric and sulfuric). Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 700 metric tons/yr, 3,900 metric tons/yr, and 7,000
metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit the
characteristic of corrosivity.
Waste solutions/solids from leaching and precipitation. Existing data and engineering judgment suggest
that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
this material further.
Spent wash water. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
As shown in Exhibit 5, the following wastes were generated when scandium was recovered through
extraction from uranium ores. Since the process is no longer used, the Agency did not evaluate these materials
further.
Digester precipitates
Waste Oxalic Acid
Waste Hydrochloric Acid
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Commented Received by EPA
EPA received no comments that address this specific sector.
579
-------
BIBLIOGRAPHY
"Rare Earth Metals." From Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XIX.
pp. 841.
Hedrick, James B. "Scandium." From Mineral Commodity Summaries. U.S. Bureau of Mines. 1995.
pp. 148-149.
Hedrick, James B. "Rare Earths: The Lanthanides, Yttrium, and Scandium." From Mineral Yearbook Volume 1.
Metals and Minerals. U.S. Bureau of Mines. 1992. pp. 1035-1047.
Odekirk, Michael D. and Harbuck, Donna D. "Scandium Solvent Extraction from Liquors Produced by Leaching
Sulfated Tantalum Tailings." Salt Lake City Research Center. U.S. Bureau of Mines. EPD Congress. The
Minerals, Metals & Materials Society. 1993. pp. 83-97.
Personal communication between Jocelyn Spielman, ICF Incorporated and James B. Hedrick, Scandium Specialist,
U.S. Bureau of Mines. October 20, 1994.
U.S. Environmental Protection Agency. "Scandium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-20-3-30.
580
-------
SELENIUM
A.
Commodity Summary
Selenium is found in 75 different mineral species, however, pure selenium does not exist as an ore. For this
reason, primary selenium is recovered from anode slimes generated in the electrolytic refining of copper. One
facility, ASARCO - Amarillo, TX, processes this slime further to recover tellurium. For more information on
tellurium recovery, see the tellurium report. According to the U.S. Bureau of Mines, three copper refineries, Asarco,
Phelps Dodge, and Kennecott, accounted for all of the domestic production of primary selenium. The 1994
production was worth S3 million. End uses of selenium include:
» electronics, 35 percent;
• chemicals and pigments, 20 percent;
* glass manufacturing, 30 percent; and
• other, including agriculture and metallurgy, 15 percent.1
Exhibit 1 lists the names and locations of the facilities involved in the production of selenium.
EXHIBIT 1
SUMMAEY OF SELENIUM PROCESSING FACILITIES
Facility Name
ASARCO
Kennecott (RTZ)
Phelps Dodge
Location
Amarillo, TX
Garfield, UT
El Paso, TX
B.
Generalized Process Description
1, Discussion of Typical Production Processes
Generally, 30-80 percent of the selenium contained in copper anode slimes is recovered by commercial
operations. Several methods of selenium recovery may be used. The two major processes for selenium recovery are
smelting with soda ash and roasting with soda ash. Other methods include roasting with fluxes, during which the
selenium is either volatilized as an oxide and recovered from the flue gas, or is incorporated in a soluble calcine that
is subsequently leached for selenium. In some processes, the selenium is recovered both from the flue gas and from
the calcine. At the process end points, selenium metal is precipitated from solutions of sodium selenite or selenious
acid by sulfur dioxide.2 Exhibits 2 through 4 present process flow diagrams for selenium production.
' Stephen Jasinske, "Selenium," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp.
150-151.
2 Neldon Jenson, "Selenium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp. 705-711.
581
-------
EXHIBIT 2
SODA ROASTING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-187 - 3-193.)
Copper Slime
Containing Selenium
Soda Ash
Water
Acid
SO.
Water
^
w
fc
^
w
^
fc
Copper
Removal
1
Roasting
1
Leaching
1
Neutralization
1
Precipitation
!
Washing
1
Drying
and
Pulverizing
^ Copper
^ Slag
^ Waste Solids
Precipitate to
^ Tellurium
Recovery
^ Wastewater
^ Wastewater
I
Selenium
582
-------
EXHIBIT 3
SODA SMELTING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-187 - 3-193.)
Soda
Ash Silica Air Niter
II II
Copper Slime „ Oxidation
CuiiUiiiing • ^» Removal ^ SnicUiug ^ and
Selenium Volatilization
1 1 1
Sulfuric Acid Copper slag Water " siag
precipitate We.,,.. W
/_, . . f Sulfuric f
toTelemum ^ S(eam ^ Watw
Recovery i i 1
1 1 1 w"'e 1
1
Wastewater
Selenii
Flue
^^ i. i
W1 Pailiculale
Collection
Soda Ash
1 \
1
Solids to
Precious Metal Recovery
^*' Dicing
1
im -^f — Pulverizing
U1
00
U)
-------
EXHIBIT 4
SELENIUM PURIFICATION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-187 - 3-193.)
Crude Selenium
Sodium
Sulfite
Sulfuric
Acid
1
Dissolution
i
Filtration
Precipitation
Distillation
T
Purified Selenium
Waste Filter Cake
Wastewater
1 Waste Impurities
584
-------
2. Generalized Process Flow
Roasting with Soda Ash
As shown in Exhibit 2, decopperized slime is roasted with soda ash to produce sodium selenite and sodium
selenate. The selenium is then leached with water, neutralized to precipitate tellurium, and then sparged with SO, to
precipitate selenium,3
Smelting with Soda Ash
As shown in Exhibit 3, decopperized slime is mixed with soda ash and silica and smelted in a furnace. Slag
containing silica, iron, and several other metal impurities is generated as waste. The molten charge containing
selenium is aerated to oxidize and volatilize the selenium, and the remaining solids are removed for precious metal
recovery. The soda ash is leached with water and filtered to separate unwanted solid impurities, which are discarded
as waste. The selenium-containing filtrate is neutralized to precipitate out tellurium, and is acidified to precipitate
selenium. The selenium containing material formerly classified as sludge is then boiled, washed, dried, and
pulverized to yield the selenium product.4
Selenium Purification
The selenium obtained from either smelting with soda ash or roasting with soda ash is then purified. As
shown in Exhibit 4, the crude selenium is dissolved in sodium sulfite, and the resulting solution is filtered to remove
unwanted solids as waste filter cake. The resulting filtrate is acidified with sulfuric acid to precipitate the selenium.
The selenium precipitate is distilled to drive off impurities, producing a high purity selenium for commercial and
industrial use.
Kennecott Utah Copper Corporation (KUCC)
One company now recovers selenium via a hydrometallurgical process. Liquid from its gold recovery
circuit is treated with SO2 to precipitate crude selenium. The crude selenium is retorted (distilled) in an electric
melting furnace. The offgas from the selenium retort is cooled to collect the selenium. After retorting and
condensation, the pure selenium is crushed, sized, and packaged for shipment.5
High purity selenium is currently produced from crude coked selenium. After wet grinding, pulping, and
decantation washing with hot water to (remove impurities such as arsenic), the high purity circuit feed is leached
with hot sodium sulfite solution. Selenium dissolves to form a compound similar to sodium thiosulfate. After
leaching, the slurry settles and the solution is decanted through a clarifier press to the precipitation tanks. Selenium
is precipitated by acidification of this solution with concentrated H2SO4. The solutions are kept cool during
acidification to obtain red amorphous selenium. After precipitation, the slurry is settled and most of the solution
decanted to waste. Settled slurry is repulped with water and heated with steam. Heating converts the red selenium to
a gray crystalline powder. The slurry is then centrifuged in a perforated bowl centrifuge and the solids washed by
displacement with copious amounts of water.
Centrifuge cake is charged into the first stage of the three stage distillation circuit. Condensed selenium
from these stills is collected in fractionating trays. Samples for spectrographic analysis of 19 elements are taken
through the run. Early fractions are high in tellurium and other high-boiling-point impurities. Impure fractions are
3 Ibid.
4 U.S. Environmental Protection Agency, "Selenium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. 3-187-193.
5 Kenecott Utah Copper Corporation. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
585
-------
rejected to sulfite leaching or redistillation in the first-stage stills. Acceptable fractions from the first-stage stills are
advanced to second-stage distillation in a silicon carbide retort. Condensed selenium from this stage is passed
through a shotter (pelletizer) and quenched with water. Seven fractions are normally made and a sample of each is
analyzed spectrographically for 19 impurity elements. First and last fractions, as well as others showing abnormal
impurity levels, are recycled to an appropriate part of the purification circuit. Acceptable fractions are advanced to
third-stage distillation. Condensed selenium shot from third-stage distillation is again collected in seven fractions,
each of which is analyzed spectrographically. Reject fractions are recycled back to an appropriate part of the circuit.
Acceptable selenium shot from third-stage distillation is made up into lots and blended. Samples from the blended
material are analyzed again spectrographically and chemical analysis is made for halogens, sodium sulfur, and
nonvolatile material Finally, acceptable lots are packaged for sale or stored for doped selenium production.6
3, Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Beneficiation/Processing Boundaries
Since selenium is recovered as a by-product of other metals, all of the wastes generated during selenium
recovery are mineral processing wastes. For a description of where the beneficiation/processing boundary occurs for
this mineral commodity, see the sector report for copper presented elsewhere in this document.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Not applicable.
2. Mineral Processing Wastes
Selenium is recovered from anode slimes generated from the electrolytic refining of copper. Because of
this, all wastes from selenium production generated after the production of the copper anode slimes are mineral
processing wastes. Listed below are possible waste streams from selenium production.
Plant process wastewater (PWW). This waste may exhibit the characteristic of toxicity for lead. In
addition, this waste may also exhibit the characteristic of corrosivity since it is expected to have a pH of 0.8 to 1.9.
The 1991 generation rate for the sector was 66,000 metric tons per year.7 Waste characterization data are presented
in Attachment 1. This waste may be recycled and formerly was classified as a spent material.
Slag. This waste may contain silica, iron, and other metal impurities. Although no published information
regarding waste generation rate or characteristics was found, we used the methodology outlined in Appendix A of
this report to estimate a low, medium, and high annual waste generation rate of 50 metric tons/yr, 500 metric tons/yr,
and 5000 metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit
the characteristic of toxicity for selenium. Slag may be recycled and formerly was classified as a byproduct.
Spent filter cake. Although no published information regarding waste generation rate or characteristics
was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high
annual waste generation rate of 50 metric tons/yr, 500 metric tons/yr, and 5,000 metric tons/yr, respectively. We
used best engineering judgment to determine that this waste may exhibit the characteristic of toxicity for selenium.
This waste may be recycled and formerly was classified as a byproduct.
6 Ibid.
7 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, Vol. I, August, 1992, pp. 1-2 -1-8.
586
-------
Tellurium slime wastes are sent to tellurium product recovery. Although no published information
regarding waste generation rate or characteristics was found, we used the methodology outlined in Appendix A of
this report to estimate a low, medium, and high annual waste generation rate of 50 metric tons/yr, 500 metric tons/yr,
and 5,000 metric tons/yr, respectively. We used best engineering judgment to determine that this waste may exhibit
the characteristic of toxicity for selenium. This waste formerly was classified as a byproduct.
Waste solids. Although no published information regarding waste generation rate or characteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 50 metric tons/yr, 500 metric tons/yr, and 5,000 metric tons/yr, respectively. We used best
engineering judgment to determine that mis waste may exhibit the characteristic of toxicity for selenium.
D. Non-uniquely Associated Wastes
Non-uniquely associated wastes may be generated at on-site laboratories, and may include used chemicals
and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, waste
oil (which may or may not be hazardous), and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
One commenter provided new information about its facility's selenium recovery process (COMM 40). This
new information has been included in the sector report.
Sector-specific Issues
None.
587
-------
BIBLIOGRAPHY
Jasinski, Stephen. "Selenium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
150-151.
Jenson, Neldon. "Selenium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 705-711.
Lansche, Arnold M. "Selenium and Tellurium - A Materials Survey." U.S. Bureau of Mines. Information Circular
8340. 1967. pp. 32-34.
"Selenium and Selenium Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XX.
1982. pp. 575-599.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. Vol. I. August, 1992. pp. 1-2 -1-8.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. Vol. II. August, 1992. pp. 32-2 - 32-6.
U.S. Environmental Protection Agency. "Selenium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-187 - 3-193.
588
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ATTACHMENT 1
589
-------
10
O
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PLANT PROCESS WASTEWATER (ACID PLANT SLOWDOWN) - SELENIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfaie
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
0.50
0,50
0.50
0.50
2.000
-
0.017
0.50
0.50
0.090
1,63
1.42
14.90
1.06
0.00072
23.30
0.10
0.50
0.50
2.50
0,50
0.50
-
-
27,000
40.00
-
-
158
25
0.80
25.20
0.50
0.50
1.45
0.50
0.050
-
0.034
0.50
0.50
0,30
1.63
9.16
14.90
1.06
0.00072
88.43
0.30
2.05
.0.50
2.50
0.50
0.50
-
-
27,400
80.00
-
-
158
20,313
1,35
26.35
0.50
0.50
2.40
0.50
0.050
-
0.050
0.50
0.50
0.50
1.63
16.90
14.90
1.06
0.00072
130
0.50
3.60
0.50
2.50
0.50
0.50
-
-
27,800
120
-
-
158
40,600
1.90
27.50
Detects
0/1
0/1
1/2
0/1
0/1
0/0
1/2
0/1
0/1
1/2
1/1
2/2
1/1
1/1
1/1
3/3
1/2
1/2
0/1
0/1
0/1
0/1
0/0
0/0
2/2
2/2
0/0
0/0
1/1
2/2
2/2
2/2
EP Toxicity Analysis -
Minimum Average
0.32
0.050
0.95
0.050
0.0050
-
0.043
0.11
0.050
0.050
1.50
12.00
14.10
0.98
0.00088
20.90
0.050
0.90
0.050
0.25
0.050
0.21
-
-
-
-
-
-
-
-
0.32
0.050
0.95
0.050
0.0050
-
0.043
0.11
0.050
0.050
1.50
12.00
14.10
0.98
0.00088
20.90
0.050
0.90
0.050
0.25
0.050
0.21
-
-
-
-
-
-
-
-
PPM
Maximum
0.32
0.050
0.95
0.050
0.0050
-
0.043
0.11
0.050
0.050
1.50
12.00
14.10
0.98
0.00088
20.90
0.050
0.90
0.050
0.25
0.050
0.21
-
-
-
-
-
-
-
-
# Detects
1/1
0/1
1/1
0/1
0/1
0/0
1/1
1/1
0/1
0/1
1/1
1/1
1/1
1/1
1/1
1/1
0/1
1/1
0/1
0/1
0/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
.
5.0 1
-
-
0.2 0
-
-
1.0 0
5.0 0
.
.
.
-
-
-
-
-
-
.
-
212 2
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SILICON AND FEEROSILICON
A.
Commodity Summary
Most ferrosilicon is used as an alloying element in the ferrous foundry and steel industries. Aluminum
producers and the chemical industry were the main consumers of silicon metal. Ferrosilicon was produced by six
companies in seven plants in the United States in 1992, and silicon metal was produced by six companies in eight
plants.1 Exhibit 1 lists these facilities and their locations. There are two standard grades of ferrosilicon, with one
grade approximately 50 percent silicon and the other 75 percent silicon by weight.2 The purity of silicon metal
generally ranges from 96 to 99 percent.
EXHIBIT 1
SUMMARY OF FERROSILICON AND SILICON SMELTING AND REFINING FACILITIES (IN 1992)'
Facility Name
American Alloys Inc.
Applied Industrial Minerals Corp.
Dow Corning Corp.
Elkem Metals Co.
Elkem Metals Co.
Globe Metallurgical Inc.
Globe Metallurgical Inc.
Keokuk Ferro-Sil Inc
Silicon Metaltech Inc.
Simetco Inc.
SKW Alloys Inc
SKW Alloys Inc
Location
New Haven, WA
Bridgeport, AL
Springfield, OR
Alloy, WV
Ashtabula, OH
Beverly, OH
Selma, AL
Keokuk, IA
Wenatchee, WA
Montgomery, AL
Calvert City, KY
Niagara Falls, NY
Products
FeSi and Si
FeSi
Si
Si
FeSi
FeSi and Si
Si
FeSi
Si
Si
FeSi
FeSi and Si
1 - Cunningham, L. D., "Silicon." Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992. p. 1191.
1 L.D. Cunningham, "Silicon," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, p.
152.
2 L.D. Cunningham, "Silicon," from Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of
Mines. 1992. p. 1183.
591
-------
B. Generalized Process Description
1. Discussion of Typical Production Processes
In the United States all primary production of ferrosilicon and silicon metal is by the reduction of silica
(SiO2) to silicon (Si) in submerged arc electric furnaces. High purity silicon is made from metallurgical grade
silicon, and is, therefore, secondary processing which is outside the scope of this report.
2. Generalized Process Flow Diagram
Exhibits 2 and 3 are typical production flow diagrams illustrating the production of silicon and ferrosilicon.
As shown in the exhibits, the feed silica is washed, sized, and crushed. The silica is then mixed with a reducing
agent, and either coal, coke, or charcoal. Wood chips are added for porosity. The mixture is fed into the furnace,
and when ferrosilicon is being produced, iron or steel scrap is added.3 The furnace is tapped periodically and the
molten ferrosilicon or silicon metal is drawn out and cast into ingots. The ingots are allowed to cool, then are
crushed to produce the final product.4
High purity silicon used in the electronics industry is made from silicon metal, and is therefore beyond the
scope of this report. However, a brief overview of the production process is included for completeness. Naturally
occurring quartz is converted to metallurgical grade silicon by heating it with coke in an electric furnace. The low
grade silicon is then converted to high grade haiide or halosilane which is then reduced with a high purity reagent.5
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Research is being conducted in Austria on the production of ferrosilicon from lump quartz and charcoal
using a plasma reactor. Other input substitutions also are being investigated, including using sand as a replacement
for quartz, and taconite tailings instead of iron or steel. In addition, the use of plasma reactors in smelting silicon is
being investigated in Austria.6'7
4. Beneflciation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
3 U.S. Environmental Protection Agency, "Silicon and Ferrosilicon," from 1988 Final Draft,Summary Report of
Mineral Industrial Processing Wastes. 1988, pp. 3-194 - 3-195.
4 L.D. Cunningham, 1992, Op. Cit.. p. 1184.
5 "Silicon and Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XX, 1982, p. 836.
6 Goodwill, J, E,, "Plasma Melting and Processing - World Developments," 48th Electric Furnace Conference
Proceedings, New Orleans, LA, December 1 l-14th 1990, p. 280.
7 Goodwill, J. E,, "Developing Plasma Applications for Metal Production in the USA," Ironmaking and
Steelmaking. Vol. XVII, No. 5,1990, pp. 350-354,
592
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EXHIBIT 2
SILICON PRODUCTION
Silica
Coal, Coke, or
ClldlCOdl ^
Wood .
Chips
^
r
Washing,
Sizing, and
Crushing
1
r
Mixing
^
r
Furnace
1
Fu
D
r
me
ust
-------
l/l
UD
EXHIBIT 3
FERROSILICON PRODUCTION
Coal, Coke, or
Charcoal
Wood
Chips
Iron and
Steel -
Silica
W ashing,
Sizing, and
Crushing
Mixing
Furnace
Fume
Dust
Cooling
Crushing
Ferrosilicon
-------
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between ore crushing and charging to the furnace because silica is thermally reduced to silicon or ferrosilicon in the
furnace. Therefore, because EPA has determined that all operations following the initial "processing" step in the
production sequence are also considered processing operations, irrespective of whether they involve only techniques
otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after die initial mineral
processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents
below the mineral processing waste streams generated after the beneficiation/processing line, along with associated
information on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction and Beneficiation Wastes
The following wastes may result from beneficiation activities: gangue, spent wash water, and tailings. No
information on waste characteristics, waste generation, or waste management for these waste streams was available
in the sources listed in the bibliography.
2. Mineral Processing Wastes
Dross. The waste to product ratio for dross is approximately 1:99. Dross from the production of silicon
metal can be used to produce ferrosilicon. Ferrosilicon dross can be used to produce silicomanganese. Dross can
also be sold as an aggregate.8 Dross is recycled and is not believed to be a solid waste.9 Existing data and
engineering judgement suggest that this material does not exhibit any characteristics of hazardous waste. Therefore,
the Agency did not evaluate this material further.
Slag. Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
APC Dust/Sludge. The furnaces are generally equipped with fume collection systems and baghouses to
reduce air pollution by capturing emissions from the furnace.10 Originally, the baghouse dust (microsilica) was
considered of little or no value. However, microsilica is now used as an additive in a number of different products,
8 Personal communication between ICF Incorporated and Joseph Gamboji, U.S. Bureau of Mines, June 28, 1989.
9 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Volume I, Office of Solid Waste, August 1992, pp. 1-4 and 1-6.
10
"Silicon and Ferrosilicon," Op. Cit. p. 3-195.
595
-------
including high-strength concrete.11 Existing data and engineering judgement suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
L.D. Cunningham, 1992, Op. Cit.. p. 1184.
596
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BIBLIOGRAPHY
Alsobrook, A.F, "Silica: Specialty Minerals." From Industrial Minerals and Rocks. 6th ed. Society for Mining,
Metallurgy, and Exploration. 1994. pp. 893-911.
Cunningham, L. D. "Silicon." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 152-153.
Cunningham, L. D. "Silicon." From Minerals Yearbook. Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 1183-1198.
Goodwill, J.E. "Developing Plasma Applications for Metal Production in the USA." Ironmaking and Steelmaking.
Vol. XVII. No. 5. 1990. pp. 350-354.
Goodwill, J. E. "Plasma Melting and Processing - World Developments." 48th Electric Furnace Conference
Proceedings. New Orleans, LA. December ll-14th 1990. pp. 279-281.
Neuharth, C.R. "Ultra-High-Purity Silicon for Infrared Detectors: A Materials Perspective." U.S. Bureau of Mines
Information Circular 923*7. 1989. pp. 1-13.
Personal communication between ICF Incorporated and Joseph Gamboji, U.S. Bureau of Mines, June 28, 1989.
"Silicon and Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XX. 1982, pp. 826-848.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Volume I. Office of Solid Waste. August 1992. p. 1-5.
U.S. Environmental Protection Agency. "Silicon and Ferrosilicon." From 1988 Final Draft Summary Report of
Mineral Industrial Processing Wastes. 1988. pp. 3-194 - 3-198.
597
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Page Intentionally Blank
598
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SODA ASH
A,
Commodity Summary
Six companies in Wyoming and California comprise the United States soda ash industry, which is the
largest in the world. The total estimated value of domestic soda ash produced in 1994 was S650 million. According
the U.S. Bureau of Mines, the six producers had a combined nameplate capacity of 11 million tons per year and
operated at 83% of that capacity in 1994. Soda ash is used in many products:
glass. 49%
soap and detergents, 13%
flue gas desulfurization, 3%
chemicals, 23%
distributors, 5%
pulp and paper, 2%'
Soda ash is the common name for sodium carbonate. This alkali compound is the eleventh largest inorganic
chemical, in terms of production, of all domestic inorganic and organic chemicals, excluding petrochemical
feedstocks. Natural soda ash is produced from trona ore, sodium carbonate-bearing brines, or surface mineralization.
All of the active facilities produce natural soda ash from sodium carbonate-rich brines or from underground mining
of trona ore.2 Synthetic soda ash can be made by one of several chemical reactions that use common raw materials
for feedstocks, such as limestone, salt, and coal. Other technologies produce soda ash as a byproduct.3 Exhibit 1
presents the names and locations of the facilities involved in the production of soda ash.
EXHIBIT 1
SUMMAHY OF SODA ASH PROCESSING FACILITIES
Facility Name
FMC Corporation
General Chemical Partners
North American Chemical Company
Rhone-Poulenc Mine
Tenneeo
TG Soda Ash Mine
Location
Green River, WY
Green River, WY
Argus,CA
Westend, CA
Green River, WY
Green River, WY
Green River, WY
1 Dennis Kostick, "Soda Ash," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp.
156-157.
2 Dennis S. Kostick, "Soda Ash and Sodium Sulfate," from Minerals Yearbook Volume 1. Metals and Minerals,
U.S. Bureau of Mines, 1992, pp. 1237-1250.
3 Dennis Kostick, "Soda Ash," from Industrial Minerals and Rocks. 6th ed.. Society for Mining, Metallurgy, and
Exploration, 1994, pp. 929-955.
599
-------
B. Generalized Process Description
1. Discussion of Typical Production Processes
Soda ash from Wyoming trona is mined, crushed, dried, dissolved, filtered, recrystallized, and redried. In
California, soda ash from sodium carbonate-bearing brines in solution is mined, carbonated, filtered, dried.
decomposed, bleached, and recrystallized to dense soda ash. These processes are described in more detail below.
2. Generalized Process Flow Diagram
All the Wyoming trona mines use room and pillar mining with multiple entry systems. Most use a
combination of one or more types of mining: conventional, continuous, longwall, shortwall, or solution.4 The FMC
Corporation is the only natural soda ash producer that uses longwall mining to augment its mining technology.
Shortwall mining is used exclusively by TG Soda Ash, Inc. Since the late 1980's, most Wyoming soda ash
companies have installed continuous hauling systems to replace shuttle cars. FMC Corporation has been discharging
tailings and spent solutions from solution mining to its tailing ponds since about 1953. Since then, sodium carbonate
decahydrate crystals have been collecting on the bottom of these ponds at a rate of 20 to 30 cm per year. In 1985,
FMC began using a bucket wheel dredge to extract almost 160 kt of crystals annually from the 485 hectare pond.
The crystals are slurried, dewatered, melted, and processed into soda ash in the refinery. Other producers have
similar ponds where sodium carbonate decahydrate has collected since the plants were built. Because of
environmental considerations and the cost of constructing and maintaining tailing ponds, all the producers now inject
waste tailings underground. This will reduce the future buildup of sodium decahydrate in the tailing ponds. In
addition, several of the Wyoming soda ash producers are selling their spent purge liquors that contain dissolved
sodium carbonate in solution to local power utility companies for pH control of process water.5 Trona ore must be
further refined to yield a 99% pure soda ash product.
Sodium sulfate, sodium chloride, potassium chloride, and borax must be physically and chemically removed
from sodium carbonate bearing brines in order to process the sodium carbonate content into refined soda ash. The
Wyoming facilities use one of two processes to refine soda ash from trona ore: (1) the monohydrate process or (2)
the sesquicarbonate process. The two processes are essentially the same, differing only in the sequencing of
procedures. The monohydrate method is the primary process used today to make soda ash. In addition to these two
processes, the North American facilities at Searles Lake produce soda ash via another operation.6
Monohydrate Process
In the monohydrate process, trona is crushed and calcined in rotary gas-fired calciners operating at 150-
300°C. Calcining removes water and carbon dioxide from the ore, and leaves an impure product containing 85%
soda ash and 15% insolubles. The thermal decomposition of trona involves the following reaction:
2Na2CO3 • NaHCO3 • 2H2O (trona) + heat - 3Na2CO3 + CO2 + 5H2O
The calcinate is dissolved with hot water and sent to evaporative, multiple-effect crystallizers or mechanical vapor
recompression crystallizers where sodium carbonate monohydrate crystals precipitate at 40-100°C. This is below the
transition temperature of monohydrate to anhydrous soda ash. The insoluble portion of the ore containing shale and
shortite are collected by clarifiers, filtered, and washed to recover any additional alkali before they are piped as a
slurry to tailing ponds or injected underground. Some companies pass the liquor through activated carbon beds prior
to crystallization to remove trace organics solubilized from the oil shale so that the organics do no interfere with
crystal growth rate. The crystals are sent from the crystallizers to hydroclones and dewatered in centrifuges. The
4 Ibid.
5 Ibid.
6 Ibid.
600
-------
centrifuge cake is conveyed to steam tube dryers where the crystals are dehydrated into anhydrous soda ash at 150°C,
screened, and sent to storage or shipment. The final product made by the monohydrate process is dense soda ash.7
Exhibit 2 presents a process flow diagram for the monohydrate process.
Sesquicarbonate Process
The sesquicarbonate process, the second process used to process Wyoming trona, produces light to
intermediate grades of soda ash crystals. The trona is crushed, dissolved in hot mother liquor, clarified, filtered, and
passed to cooling crystallizers where crystals of sodium sesquicarbonate precipitate. Activated carbon is added to
filters to control the organics that interfere with crystal growth. The sodium sesquicarbonate is hydrocloned,
centrifuged, and calcined using gas or indirect steam heat. Dense soda ash can be made by calcining the sodium
sesquicarbonate at 350°C.8 Exhibit 3 presents a process flow diagram of the sesquicarbonate process.
Searles Lake Process
At the North American Chemical Company facility at Searles Lake, complex brines are first treated with
carbon dioxide gas in carbonation towers to convert the sodium carbonate in solution to sodium bicarbonate, which
will precipitate under these conditions. The sodium bicarbonate is separated from the remainder of the brine by
settling and filtration and is then calcined to convert the product back to soda ash. The decarbonated brine is cooled
to recover borax and Glauber's salt. A second dissolving, precipitating with carbon dioxide, filtering, and calcining
the light soda ash to dense soda ash, results in a refined product of better than 99% sodium carbonate.9 Exhibit 4
presents the Searles Lake process.
Sodium Bicarbonate
Sodium bicarbonate, baking soda, is manufactured by percolating carbon dioxide gas through a carbonation
tower containing a saturated soda ash solution. The sodium bicarbonate precipitate is collected, filtered, centrifuged,
dried, screened, and packaged. Three of the five sodium bicarbonate producers are also soda ash producers.10
Sodium Hydroxide
Sodium hydroxide, or chemical caustic soda, is made from lime and soda ash by the following reaction:
Ca(OH)2 + NajCO3 - CaCo3 + 2NaOH
7 Ibid.
,8 Ibid.
9 U.S. Bureau of Mines, 1992, Op. Cit.. pp. 1237-1250.
10 Dennis Kostick, 1994, Op. Cit. pp. 929-955.
601
-------
EXHIBIT 2
THE MONOHYDRATE PROCESS
(Adapted from: Soda Ash: Mineral Processing Waste Generation Profile.)
Off gases
Product
Dissolution
t
Liquid/Solid
Separation/
Washing
1
r
Make-up
^ Water
Insolubles
to
Disposal
Offgases
Sale
Cooling
Product
Calcining
Centrifical
Separation
Evaporation/
Crystallization
t
s
I
Carbon
Spent Carbon
to
Disposal
Salt Purge
to
Disposal
602
-------
EXHIBIT 3
THE SESQUICARBONATE PROCESS
(Adapted from: Soda Ash: Mineral Processing Waste Generation Profile.)
Crashed
Ore
Product
Make-up
Dissolution
Offgases
t t
n
t
Liquid/Solid
Separation/
Washing
i
r
Water
Insolu
to
Dispo*
Sale
CooEng
Product
Calcining
(2 Stages)
Centrifigatioti
Vacuum
Crystallization
Sa
D
Carbon
Spent Carbon
to
Disposal
Salt Purge
to
Disposal
603
-------
EXHIBIT 4
THE SEARLES LAKE PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-43 - 2-46.)
Brine
Light Soda Ash-4-
Dense Soda Ash
I
Carbonation
Tower
Clarifier
I
Washing
Filtration
Dryer
T
Calciner
Bleaching
Furnace
Dissolution
Reprecipitation
Clarifier
Filtration
Dryer
(1) Clarifier Overflow
•> (2) Filtrate
->• (3) Clarifier Overflow
->• (4) Filtrate
604
-------
The lime is slaked and added to dissolved soda ash to produce chemical caustic soda. Calcium carbonate is
precipitated from the reaction, calcined back to lime, and recycled. FMC uses about half of its caustic soda to
produce captive sodium cyanide for precious metal recovery at its gold operation. ''
Sodium Sesquicarbonate
Sodium sesquicarbonate is a hydrated compound containing soda ash and sodium bicarbonate. Trona ore is
first crushed and dissolved to separate the insoluble impurities. The sodium compounds in solution are then
clarified, filtered, crystallized, centrifuged, calcined, and recovered as long needle-shaped monoclinic crystals of
sodium sesquicarbonate. FMC has a 50 ktpy sodium sesquicarbonate facility that sells mainly to the detergent
industry. 12
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Benefidation/Processing Boundaries
Based on a review of the process, there are no mineral processing operations involved in the production of
soda ash.
C. Process Waste Streams
1. Extraction/Beneflciation Wastes
Extraction and beneficiation wastes include overburden, tailings, and spent dissolution wastes. The trona
ore dissolution wastes are sent to tailings ponds. Waste tailings are injected underground.
Monohydrate Process Waste Streams
Ore insolubles. About 110 to 150 kg per kkg of ore insolubles are generated. These insolubles are
transported to evaporation ponds for disposal.13
Filter aid and carbon absorbent. The waste generation for these wastes ranges from about 0.5 to 2 kg per
kkg of product. Spent carbon absorbent and spent filter aids are sent to on-site evaporation ponds for disposal.14
Scrubber water. Scrubber liquor is recycled to the process for recovery of additional product.15
Partieulates from crushing and calcination are generated. The calciner off gases contain carbon dioxide.
Airborne paniculate emissions from crushing are about 1.5 kg per kkg of product. From calcination, emissions are
about 95 kg per kkg or product. The particulates from crushing and conveying are collected in bags and recycled to
the ore bin which feeds the calciners. Residual emissions from the bag collectors are 0.015 kg per kkg of product.
Particulates from the calciner consist of raw sodium carbonate dust. These particulates are passed through dry
" Ibid.
12 Ibid.
13 Ibid.
14 Ibid.
13 IMd.
605
-------
cyclones and electrostatic precipitators in series. The overall removal efficiency is 99.5%, resulting in residual
particulates of 0.28 kg per kkg of product. Collected particulate is periodically recycled to the calciner.16
At the Tenneco Corporation facility in Green River, WY, tailings generated from the calcining process are
discharged to the tailings tank. The tailings tank also receives fly ash and bottom ash generated from using coal to
fire the calcining kiln and the steam boiler. This waste is treated in a thickening tank by adding anionic and cationic
flocculants to the tailings to increase the solids content from approximately 10 to 50% solids. The waste is then
disposed of in one of two waste management units, (1) the tailings pond, or (2) the mine void. The mine void is
located in an old mine shaft approximately 800 feet below ground. Tailings which will be disposed of in the mine
void are first accumulated in a holding tank adjacent to the mine shaft. The tailings are gravity fed into the mine
when the holding tank fills. Tailing supernatant that accumulates in the mine is collected in a sump and periodically
pumped and disposed of in the tailings pond. Eighty percent of the time thickened tailings are disposed of in the
mine void and the remainder of the time thickened tailings are disposed of directly in the tailings pond.17
Airborne emissions from product drying, cooling, and packaging are generated from the monohydrate
process. These wastes are controlled by the use of baghouses and wet scrubbers, with the recovered materials being
recycled to the process. Emissions from the sodium carbonate drier are generated at about 2 kg per kkg of product.
After wet scrubbing, residual emission is 0.02 kg per kkg of product. Product cooling generates about 0.7 kg of
emissions per kkg of product. After bag dust collection, the residual emission is 0.005 kg per kkg of product.
Product screening, storing, and packaging generates 1.4 kg of emissions per kkg of product. After bag dust
collection, residual emission is 0.005 kg per kkg of product.18
Purge liquor. Purge liquor from calcining is often sold as a sulfur neutralizer or dust suppressant. At the
California facility, purge liquor is produced in the brine operation and is sent back into the lake.
Mother liquor is a possible waste stream from centrifugation. This waste stream is recycled.
Trona ore processing waste is generated from the purification of calcined material.
At the Stauffer Chemical Company facility in Green River, WY, trona ore processing waste is generated at
each of five calcining rakes after dissolution and purification. Waste from trona ore processing is pumped to a tank
and combined with sluice water from a tailings pond so the waste can be pumped to one of the three on-site surface
impoundments designated to receive the waste. The waste sent to the three impoundments contains approximately
10% sodium carbonate. As water evaporates the sodium carbonate dries forming sodium decahydrate.19
At General Chemical in Green River, WY, 1,451,488 metric tons of this waste was generated in 1988. This
waste was characterized by a pH of 11.5. The waste is either sold or sent to an unlined surface impoundment.20
16 Ibid.
17 U.S. Environmental Protection Agency, Mineral Processing Waste Sampling Survey Trip Reports. Tenneco
Corporation, Green River, WY, August 1989.
18 Ibid.
" Ibid.
20 RTI survey for General Chemical Partners, Green River, WY, 1988, ID# 100388.
606
-------
At the Tg Soda Ash facility in Green River, WY, 580 million gallons of this waste were reported in 1988,
This waste reportedly had a pH of 11.5. The waste was sent to a surface impoundment lined with in-situ clay for
solids precipitation and dewatering.21
Sesquicarbonate Process Waste Streams
Trona ore participates are generated from crushing, drying, and calcination. About 1,5 kg per kkg of
trona ore particulates are generated from crushing. About 2 kg per kkg of particulates are generated by drying
operations. Approximately 95 kg per kkg of particulates are produced by calcination. Paniculate emissions from
drying and packaging are controlled by wet scrubbers and dry bag collectors, respectively. Emissions after control
average 0.02 kg per kkg from the driers and 0.02 kg per kkg from the product packaging operations. Solids
recovered from the dry bag collectors are recycled to product storage. Emissions from ore calcination are also
collected and recycled.22
Scrubber water is generated from air pollution control devices. This is recycled to recover additional
product.23
steps.24
Ore residues. About 110 to 150 kg per kkg or ore residues, chiefly shale, are generated in the initial
Spent carbon and filter wastes from carbon absorption and filtration range from 0.5 to 2.0 kg per kkg per
product. Waste filter aids and carbon absorbents are washed to the evaporation ponds for final disposal. Solid
wastes from initial ore leaching are slurried to tailings ponds to settle out suspended materials and then to the final
disposal ponds which serve as evaporation ponds from which there is no discharge.25
Suspended particulate matter is generated by the use of wet scrubbers for air pollution control, resulting
in wastewater containing 2 kg per kkg of suspended particulates.26
Purge liquor from calcining. This waste is often sold as a sulfur neutralizer or dust suppressant.
Mother liquor from centrifugation. This waste stream is often recycled.
Searles Lake Process Waste Streams
Calciner off gases. About 170 kg of water vapor and 415 kg of carbon dioxide per kkg of soda ash are
generated by calcination of the sodium bicarbonate intermediate. These offgases are cooled to recover water for
other on-site uses and for use in product purification. After water removal, the carbon dioxide in recycled to the
initial process calcination step.27
21 RTI Survey for Tg Soda Ash, Green River, WY, 1988, ID# 100206.
22 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals Industry. Volume
III, August 1980, Chapter 13.
23 Ibid.
24 Ibid.
25 Ibid.
26 Ibid.
27
7 Ibid.
607
-------
Particulate emissions from driers. These emissions are controlled by dry collectors, and the recovered
solids are recycled to the process. Residual airborne paniculate emissions are less than 1 kg per kkg of product.28
Spent brine. Spent brine from the initial carbonation and filtration steps contains about 16,000 kg per kkg
of product of unrecovered sodium carbonate and other raw brine constituents. The spent brine contains about 65%
water, 16% sodium chloride, and 19% of other constituents including sodium sulfate, borax, and potassium chloride.
This waste stream is combined with other waterborne waste streams and returned to the brine source.29
Waste mother liquor. This waste stream is generated from product recrystallization and contains
principally unrecovered sodium carbonates, along with smaller amounts of other raw brine constituents such as
sodium sulfate, borax, and potassium chloride. This waste stream is combined with other waterborne waste streams
and returned to the brine source.30
2. Mineral Processing Wastes
None identified.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
28 Ibjd.
29 Ibjd.
30
Ibid.
608
-------
BIBLIOGRAPHY
"Alkali and Chlorine Products," Klrk-Othmer Encyclopedia of Chemical Technology. 4th ed. 1992. Vol. I. pp.
876.
Kostick, Dennis S. "Soda Ash." From Industrial Minerals and Rocks. 6th ed. Society for Mining, Metallurgy, and
Exploration. 1994. pp. 929-955.
Kostick, Dennis. "Soda Ash." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp.
156-157.
Kostick, Dennis, "Soda Ash and Sodium Sulfate." From Minerals Yearbook Volume 1. Metals and Minerals. U.S.
Bureau of Mines. 1992. pp. 1237-1250,
Kostick, Dennis. "Soda Ash." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 741-755.
RTI survey for General Chemical Partners, Green River WY, 1988. ID# 100388.
RTI Survey for Tg Soda Ash, Green River, WY. 1988. ID# 100206.
U.S. Environmental Protection Agency, Mineral Processing Waste Sampling Survey Trip Reports. Termeco
Corporation, Green River, WY. August 1989.
U.S Environmental Protection Agency. "Soda Ash." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 2-43-46.
U.S, Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. III.
August 1980. Chapter 13.
609
-------
Page Intentionally Blank
610
-------
SODIUM SULFATE
A.
Commodity Summary
The domestic natural sodium sulfate industry consists of three producers in California, Texas, and Utah. In
addition, the recovery of sodium sulfate as a byproduct from facilities that manufacture rayon and various chemicals
accounts for nearly 50% of total domestic production. The total value of sodium sulfate sold was estimated at $50
million in 1994. End uses of sodium sulfate are soap and detergents (40%), pulp and paper (25%), textiles (19%),
glass (5%), and other uses (11%).'
In its natural form, sodium sulfate is found in two minerals, mirabilite (Glauber's salt) and thenardite. Its
occurrence is widespread and it is commonly found in mineral waters such as sea water, atmospheric precipitation,
and saline lakes. Essentially all commercial deposits of sodium sulfate resulted from the accumulation and
evaporation of surface and ground water in basins with interior drainage. These basins, or playas, are found in arid
to semlarid regions.2
At the present time, sodium sulfate production is chiefly from brine deposits in Searles Lake, California;
Great Salt Lake, Utah; and in Western Texas, North American Chemical Company processes sodium sulfate from
Searles Lake at Trona, California. Great Salt Lake Minerals and Chemicals Corp., an affiliate of North America
Chemical Co., operates a plant at the north end of the Great Salt Lake, which produces sodium sulfate as a
byproduct. This facility has a sodium sulfate capacity of 22.7 to 32.9 kilotons per year. Ozark-Mahoning Company
operates one plant in Western Texas near Seagraves. Exhibit 1 presents the names and locations of the facilities
involved in the production of sodium sulfate.3
EXHIBIT 1
SUMMARY OF SODIUM SULFATE PROCESSING FACILITIES
Facility Name
Great Salt Lake Minerals and Chemicals Corp.
North American Chemical, Inc.
Ozark-Mahoning Co,
Location
Great Salt Lake, UT
Searles Lake, CA
Western Texas
B, Generalized Process Description
1. Discussion of Typical Production Processes
There are three principle methods used to produce sodium sulfate from brines: (1) the Ozark-Mahoning
process used in Western Texas, (2) the North American Chemical Company process at Searles Lake, and (3) the
process used by the Great Salt Lake Minerals and Chemical Corp. in Utah. Because these three processes are all
1 Dennis Kostick, "Sodium Sulfate," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995,
pp. 158-159.
2 Sid Mcllveen and Robert L. Cheek, Jr., "Sodium Sulfate Resources," from Industrial Minerals and Rocks. 6th
edition. Society for Mining, Metallurgy, and Exploration, 1994, pp. 959-970.
3 Ibid.
611
-------
slightly different, each is described in more detail below. Exhibits 2 and 3 present process flow diagrams for sodium
sulfate production.
2. Generalized Process Flow Diagram
Ozark-Mahoning Co. Process
The Ozark-Mahoning Company, the nation's second largest natural producer, operates a facility in Western
Texas. As shown in Exhibit 2, brines are refrigerated to selectively precipitate Glauber's salt which is subsequently
filtered and washed. Washing produces a saturated solution of Glauber's salt which is converted to the anhydrous
form in mechanical vapor recompression crystallizers. Hydroclones and centrifuges separate the anhydrous crystals
from the saturated solution, which is returned to evaporators. Anhydrous sodium sulfate is then dried in a rotary kiln
and the resultant material is a product of 99.7% purity.4
North American Chemicals. Inc. Process (Searles Lakel
North American Chemicals, Inc. operates two facilities near Searles Lake, CA~the West End plant and the
Argus plant. The West End plant is North America's only source of sodium sulfate. Here, sodium sulfate is
recovered along with soda ash and borax. As shown in Exhibit 3, mixed brines are carbonated with carbon dioxide
to precipitate sodium bicarbonate, which is removed by filtration. The decarbonated brine is cooled three times to
produce two successive batches of borax and one of Glauber's salt. By heating, the sodium bicarbonate is converted
to soda ash and the borax is either crystallized as a hydrate or dehydrated to anhydrous form. The Glauber's salt is
washed, melted, and recrystallized as anhydrous sodium sulfate; 99.3% purity can be obtained.5
Great Salt Lake Minerals and Chemical Corp. Process
Great Salt Lake Minerals and Chemicals Corp. operates a facility on the Great Salt Lake for the production
of potassium sulfate and magnesium chloride, of which sodium sulfate is a byproduct. Brine is pumped from the
Great Salt Lake into solar evaporation ponds where sodium chloride precipitates. Sodium sulfate crystals precipitate
in a fairly pure state when winter weather cools the brine to -1 to 4°C. The crystals are picked up by large
earthmoving machinery and stored outdoors until further processing can take place. The harvested Glauber's salt is
melted and anhydrous sodium sulfate precipitated by the addition of sodium chloride to reduce its solubility through
the common ion effect. The final product is 99.5% pure.6
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None identified.
4. Beneficiation/Processing Boundaries
Based on a review of the process, there are no mineral processing operations involved in the production of
sodium sulfate.
4 Sid Mcllveen and Robert L. Cheek, Jr., 1994, Op. Cit.. pp. 959-970.
5 Ibid.
6 Ibid.
612
-------
EXHIBIT 2
OZARK-MAHONING PROCESS
{Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-47 - 2-51.)
Brine
Sodium Sulfate
Product
Refrigeration
Crystallization
Filtration
Washing
Dehydration
Solid-Liquid
Separation
(1) Waste Brine
(2) Wastewater
613
-------
EXHIBITS
THE SEARLES LAKE PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-47 - 2-51.)
Brine
Light Soda Ash-
Dense Soda Ash -
I
Carbonation
Tower
Clarifier
Washing
Filtration
Dryer
Calciner
Bleaching
Furnace
Dissolution
Reprecipitation
Clarifier
Filtration
Dryer
•>• (1) Clarifier Overflow
• (2) Filtrate
(3) Clarifier Overflow
(4) Filtrate
614
-------
C. Process Waste Streams
Existing data and engineering judgement suggest that the wastes listed below from sodium sulfate
production do not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these
materials further.
1. Extraetion/Beneficiation Wastes
Ozark-Mahoning Process
Waste brine and wastewater are wastes from filtrating and washing Glauber's salt. Literature reports that
these wastes are reinjected into the salt formation.
Searles Lake Process
Clarifier overflow.
Filtrate.
2. Mineral Processing Wastes
None identified.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
615
-------
BIBLIOGRAPHY
Kostick, Dennis. "Sodium Sulfate." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995.
pp. 158-159.
Kostick, Dennis. "Sodium Sulfate." From Minerals Yearbook Volume 1. Metals and Minerals. 1992. pp. 1261-
1268.
Kostick, Dennis. "Soda Ash and Sodium Sulfate." From Mineral Facts and Problems. U.S. Bureau of Mines.
1985. pp. 741-755.
Mcllveen, Sid and Robert L. Cheek, Jr. "Sodium Sulfate Resources." From Industrial Minerals and Rocks. 6th ed.
Society of Mining, Metallurgy, and Exploration. 1994. pp. 959-970.
"Sodium Compounds, Sodium Sulfates." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXI.
1983. pp.251.
U.S. Environmental Protection Agency. "Sodium Sulfate." From 1988 Final Draft Summary Report of Mineral
Industry Processing Waste. 1988. pp. 2-47 - 2-51.
616
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STRONTIUM
A, Commodity Summary
According to the U.S. Bureau of Mines, no strontium minerals have been produced in the United States
since 1959. The United States is however, a major producer of strontium compounds. In 1994, primary strontium
compounds were used in color television picture tube glass (66%), pyrotechnic materials (11%), ferrite ceramic
magnets (13%), and other miscellaneous uses (10%)'. Although consumption demands fluctuate from year to year,
the overall consumption of strontium compounds and metals appears to be increasing.2
In early 1984, Chemical Products Corporation (CPC) in Cartersville, Georgia expanded its capacity by 30%
to meet shortfalls in supply that resulted from the 1984 closure of the FMC Corporation plant in Modesto, California.
CPC is now the sole domestic producer of strontium carbonate and strontium nitrate; CPC sells these products as
raw materials to other industries,3 Strontium metal is produced by CALSTRON near Memphis, Tennessee using an
aluminothermic reaction.
B, Generalized Process Description
1. Discussion of Typical Production Processes
Celestite, the most common strontium mineral, consists primarily of strontium sulfate. The second most
common strontium mineral, strontianite, consists primarily of strontium carbonate.
Reportedly, it is very difficult to concentrate strontium minerals to grades acceptable for producing
chemical compounds. The two most common celestite-to-strontium carbonate conversion processes are the soda ash
process and the calcining process. Strontium metal is produced by (1) the thermal reduction of strontium oxide with
metallic aluminum and (2) the electrolysis of fused strontium chloride and ammonium or potassium chloride.
Of the two strontium production processes, the soda ash metfiod is a simpler process; however, the resulting
product is of a lower grade. The calcining method or black ash method, produces chemical-grade strontium
carbonate (SrCO3) which is at least 98% strontium carbonate; whereas, the soda ash method only produces
technical-grade strontium carbonate >95% pure. Although the soda ash method is a simpler process, the lower grade
product causes it to be the less preferred method of recovery. The black ash method is used by CPC.
2. Generalized Process Flow Diagram
Strontium Carbonate Process
Soda Ash Process
Finely powdered celestite is mixed with soda ash and treated with steam for one to three hours. The
celestite and soda ash react to produce less soluble strontium carbonate and soluble sodium sulfate. The two are
separated by centrifuging. Exhibit 1 presents a process flow diagram for the soda ash process.
1 Joyce Ober, "Strontium," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp. 164-
165.
2 Joyce A. Ober, "Strontium," Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines, 1992,
pp. 1323-1332.
3 Personal communication between ICF Incorporated and Joyce Ober, Bureau of Mines, July 21, 1994.
617
-------
ers
CO
EXHIBIT 1
SIMPLIFIED FLOWCHART OF TWO METHODS FOR STRONTIUM CARBONATE PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-198 - 3-199.)
BLACK ASH
SODA ASH
Na2SO,,
95% SrCO,
Precipitates from Solution
Na2SO4
Precipitates from Solution
-------
Calcining Process (Black Ash Process)
Finely powdered coal is mixed with celestite which produces a "black ash." The mixture is heated to
1,100°C in a rotary kiln, expelling oxygen in the form of carbon dioxide from the insoluble strontium sulfate to form
water-soluble strontium sulfide. The strontium sulfide is dissolved in water and the solution is filtered, and then
either treated with carbon dioxide or soda ash in an agitation tank. Strontium carbonate may then form and
precipitate from the solution. The strontium carbonate precipitate is removed from solution by filtering in vacuum
drum filters, dried, ground, and packaged. The sulfur released in the process is either recovered as elemental sulfur
or as other by-product sulfur compounds. This process is used by the CPC plant in Georgia but is called the "white
ash method" because the sodium sulfide is white in color.4 A process flow diagram is shown in Exhibit 1.
Production of Strontium Chemicals
Strontium nitrate is produced by reacting strontium carbonate with nitric acid. Other strontium chemicals
are produced similarly by reacting strontium carbonate with the acid appropriate for the desired result.
Production of Other Strontium Compounds
Chemical-grade strontium carbonate can be used without further purification to produce most other
strontium compounds. Either chemical-grade or technical-grade (greater than 95% pure) can be used for
transformation to other strontium compounds, and in the conversion processes further purification occurs. For some
processes, higher grades of strontium carbonate are necessary and elimination of contamination by particular
elements is emphasized.
Strontium Metal Production
Strontium metal can be produced in two ways. The more common method is through the thermal reduction
of strontium oxide and aluminum metal, subsequent distillation and condensation of metallic strontium on a cooled
plate. The other method is electrolysis of a fused bath of strontium chloride and ammonium chloride or potassium
chloride.5
Other Processes
Strontium ferrite magnets are usually prepared by mixing strontium carbonate, iron oxide, and crystal
growth inhibitors and presintering at 1,000°C to 1,300°C. Strontium titanate is formed by reacting a mixture of high
purity strontium carbonate and titanium dioxide at 2,000° to 2,200°C for several hours.6
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Technologically, there is very little known about strontium. As technology becomes more sophisticated and
the search for alternate materials is intensified, specific properties of strontium will become better known. Strontium
appears to have applications in the metallurgy of aluminum, silicon, and other light metals, as well as potential use as
a solid electrolyte in fuel cells.7
4 "Strontium—Uses, Supply, and Technology," U.S. Bureau of Mines Information Circular, 1989, p. 6.
5 Ibid.
b'ibid.
7 John E. Ferrell, "Strontium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp.777-782.
619
-------
A new process for the extraction and recovery of strontium from acidic waste streams is being developed.
In this process, SREX (Strontium Extraction), strontium is extracted from acidic solution and is stripped from the
organic phase using either water or dilute HNO3. Prolonged exposure of the process solvent to nitric acid at elevated
temperatures or to radiation from a 60CO source produces essentially no deterioration in its performance.
Experiments show that 99.7% of the strontium initially present in a feed solution can be removed using only three
extraction stages.8
4. Beneficiation/Processing Boundaries
Based on a review of the process, there are no mineral processing operations involved in the production of
strontium.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Black Ash Method
Calciner offgas. Calciner emissions may contain carbon dioxide which may or may not be recycled into
the agitation tank. This offgas may also contain sulfur dioxide and ore particles.9
Dilute sodium sulfide solution
Filter muds
Spent ore
Vacuum drum filtrate
Waste solution
Soda Ash Method
Waste sodium sulfate solutions
2. Mineral Processing Wastes
None identified.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
8 Philip E. Horowitz, Mark L. Dietz, and Dan E. Fisher, "SREX: A New Process for the Extraction and Recovery
of Strontium from Acidic Nuclear Waste Streams," Argonne National Laboratory, 1991, pg. 1.
9 U.S. Environmental Protection Agency, "Strontium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988. pp. 3-198 - 3-203.
620
-------
BIBLIOGRAPHY
Ferrell, John E. "Strontium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 777-782.
Horwitz. E. Philip, Mark L. Dietz, and Dan E. Fisher. "SREX: A New Process for the Extraction and Recovery of
Strontium from Acidic Nuclear Waste Streams." Argonne National Laboratory. 1991. pg. 1.
Ober, Joyce A. "Strontium." From Mineral Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines.
'l992. pp. 1323-1332.
Ober, Joyce. "Strontium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. p. 164-
165.
Personal communication between ICF Incorporated and Joyce Ober, Bureau of Mines. July 21, 1994.
"Strontium—Uses, Supply, and Technology." U.S. Bureau of Mines Information Circular. 1989. p. 6.
U.S. Environmental Protection Agency. "Strontium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp.3-198 - 3-199.
621
-------
Page Intentionally Blank
622
-------
SULFUR
A. Commodity Summary
The United States is the world's foremost producer and consumer of sulfur and sulfuric acid, with
production from Frasch, recovered, and byproduct sources. According to the U.S. Bureau of Mines, sulfur (in all
forms) was produced at 169 operations in 30 states, Puerto Rico, and the U.S. Virgin Islands for a total shipment
value of nearly S500 million in 1994. Texas and Louisiana accounted for nearly 50% of domestic production.
Agricultural chemicals (fertilizers) accounted for 61 % of sulfur demand; organic and inorganic chemicals accounted
for 10%; metal mining accounted for 5%; and petroleum refining accounted for 7%. Other miscellaneous uses,
accounting for 17% of demand, were widespread because many products produced by industry require sulfur in one
form or another during some stage of their manufacture.1
Sulfur is a non-metallic element widely used in industry both as elemental sulfur (brimstone) and as sulfuric
acid. Sulfur production is from three sources: combined sulfur, recovered sulfur, and formed sulfur. Combined
sulfur occurs in natural compounds such as iron pyrite, copper sulfides, and gypsurn. Recovered sulfur is produced
as a byproduct of other processes such as oil refining or air pollution control. Formed sulfur is elemental sulfur cast
or pressed into particular shapes to enhance handling and to suppress dust generation and moisture retention.2
In 1994, recovered elemental sulfur was produced by 59 companies at 150 plants in 26 states, one plant in
Puerto Rico, and one plant in the U.S. Virgin Islands. Byproduct sulfuric acid was produced by 16 facilities in
1994.3 The three companies listed in Exhibit 1 produce the bulk of mined sulfur in the United States. These three
companies accounted for 32% of the U.S. production of sulfur in all forms in 1990. All three companies use the
Frasch process for sulfur mining. Pen/oil produces sulfur from its Culberson mine in western Texas and is currently
engaged in exploration activities in western Texas, the Gulf Coast, and elsewhere. Texasgulf currently operates one
mine in Texas (Boling dome), extracting about 40,000 tpy of sulfur. Freeport currently operates two mines in the
Gulf Coast.4 The names and locations of the smaller facilities are not available.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Sulfur is mined from both surface and underground deposits, and is recovered as a byproduct from a
number of industrial processes. In sulfur mining, three techniques are applied: conventional underground methods,
conventional open pit methods, and the Frasch mining method. About 90% of all sulfur mined is obtained through
Frasch mining.5 Frasch mining and sulfur production from recovered, combined, and formed sulfur are described
below in addition to the production process for sulfuric acid.
1 Joyce Ober, "Sulfur," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp. 166-167.
2 Gregory R. Wessel, "Sulfur Resources," from Industrial Minerals and Rocks. 6th edition, Society for Mining,
Metallurgy, and Exploration, 1994, pp. 1011-1046.
3 Joyce Ober, 1995, Op. Cite., pp. 166-167.
"Gregory R. Wessel, 1994, Op. Cit.. pp. 1011-1046.
5 Ibid.
623
-------
EXHIBIT 1
SUMMARY OF MAJOR PRIMARY SULFUR PROCESSING FACILITIES
Facility Name
Freeport Sulphur Co.
Penzoil Sulphur Co.
Texasgulf Inc.
Location
Caminada, offshore
LA
Culberson, W. TX
Boling, TX
2. Generalized Process Flow
Frasch Mining
The Frasch mining process uses hot water to melt sulfur trapped in salt domes. The sulfur is then pumped
to the surface and is either sold as a liquid or cooled and solidified into a number of forms for market. Exhibit 2
presents a process flow diagram for the Frasch process.
Recovered Elemental Sulfur (Claus Process)
Recovered elemental sulfur is a non-discretionary byproduct of petroleum refining, natural gas processing,
and coking plants. Recovered sulfur is produced primarily to comply with environmental regulations applicable
directly to processing facilities or indirectly by restricting the sulfur content of fuels sold or used. The principal
sources of recovered sulfur are hydrogen sulfide in sour natural gas and organic sulfur compounds in crude oil.
Recovery is mainly in the elemental form, although some is converted directly to sulfuric acid. Sulfur in crude oil is
recovered during the refining process. Organic sulfur compounds in crude oil are removed from the refinery feed
and converted to hydrogen sulfide by a hydrogenation process. The sulfur in natural gas is already in the form of
hydrogen sulfide. Hydrogen sulfide from both sources is converted to elemental sulfur by the Claus process. In this
process, concentrated hydrogen sulfide is fired in a combustion chamber connected to a waste heat boiler. Air is
regulated to the combustion chamber so that part of the hydrogen sulfide is burned to produce sulfur dioxide, water
vapor, and sulfur vapor. The high temperature gases are cooled in a waste heat boiler and sulfur is removed in a
condenser. The efficiency of the process is raised by adding as many as three further stages in which the gases
leaving the sulfur condenser are reheated and passed through catalytic converters and additional condensers. Finally.
the total gas stream is incinerated to convert all remaining sulfur-bearing gases to sulfur dioxide before release to the
atmosphere. The sulfur is collected in liquid form. Exhibit 3 presents a process flow diagram for the Claus process.
Combined Sulfur
Combined sulfur can be recovered during the smelting of nonferrous sulfides. Sulfur dioxide in the smelter
gases is converted to sulfuric acid, liquid sulfur dioxide, or oleum. In the United States, byproduct sulfuric acid from
nonferrous metal smelters and roasters supplied about 11 % of the total domestic production of sulfur in all forms in
1990. Sulfur may also be recovered from sulfur dioxide emissions. Regenerative or throwaway flue-gas
desulfurization methods may be used either to recover sulfur in a useful form or to dispose of it as solid waste. Both
recovery methods may employ wet or dry systems and use a variety of compounds such as limestone, sodium
carbonate, and magnesium oxide to neutralize or collect the sulfur dioxide. End products include gypsum, sulfuric
624
-------
EXHIBIT 2
FRASCH PROCESS
(Adapted from: Multi-Medial Assessment of the Inorganic Chemicals Industry, 1980, Chapter 14.)
Water
Bleed Water
(Contains 600 - 1.000 ppm
Dissolved Sulfides)
9-15 Calcium Carbonate
Fugitive Air Emissions
0-5 Hydrogen Suffide
,000 Sulfur
Product
625
-------
EXHIBITS
GLAUS PROCESS
(Adapted from: Multi-Medial Assessment of the Inorganic Chemicals Industry, 1980, Chapter 14.)
Air
515-529 Oxygen
1,000 Sulfur
Off Gas:
(30 - 60 Unreacted Hydrogen Suffide)
575-595 Water Vapor
Sulfide Containing
Refinery Gas
(1,094 - 1,126 Hydrogen Sulfide)
acid, liquid sulfur dioxide, and elemental sulfur, all of which can be used if a local market exists. If no local markets
exist, large quantities of gypsum or sulfuric acid may have to be neutralized or otherwise disposed.6
Formed Sulfur
Formed sulfur may be made in one of several forms, including: flakes, slates, prills, nuggets, granules,
pastilles, and briquettes. To produce flakes, the sulfur is cooled and solidified on the outside of large rotating drams,
from which it peels off into small flakes. To produce slates, molten sulfur is cast onto a continuous conveyer belt
and is cooled with air or water so that it solidifies into a thin sheet. As the slate reaches the end of die belt, the sheet
breaks into smaller pieces. Sulfur prilling can be accomplished witii air or water. In air prilling, molten sulfur is
sprayed from the top of a tower against an upward flow of air. As it falls, the sulfur breaks into small droplets and
cools into prills. In water prilling, the sulfur is sprayed into tanks containing water, from which the prills are
collected and dried. Minor modifications to prilling techniques are used to produce nuggets. Granulation involves
applying successive coats of sulfur to solid particles of sulfur in a granulator until die particle size reaches the
required diameter. In the Procor GX granulation process, liquid sulfur is sprayed into a rotating drum in which small
seed particles of sulfur are recycled from the end of die process. Pastilles are individual droplets of molten sulfur
that have been dropped on a steel belt and cooled by conduction. The Sandvik Rotoform process uses a patented
Ibid.
626
-------
Rotoformer to distribute the sulfur on the belt. At the end of the belt, the pastilles are scraped off and fall onto a
collecting conveyer,7
Sulfuric Acid
Sulfuric acid is usually produced near consumption sites. To produce sulfuric acid, elemental sulfur or any
number of sulfur-bearing materials are burned. The resulting sulfur dioxide is mixed with additional air or oxygen
and passed through a packed bed of supported vanadium pentoxide catalyst. The sulfur dioxide is converted to
sulfur trioxide. The gases emerging from the catalytic reactor are cooled and absorbed in 98-99% sulfuric acid to
generate 98-99% acid. Plants can be either single or double absorption units. In double absorption units, tail gases
from the initial absorption step are mixed with additional sulfur dioxide, reheated and passed through another
catalytic reactor to form additional sulfur trioxide. This material is cooled and absorbed in a second stream of
sulfuric acid to generate additional 98-99% sulfuric acid. Exhibit 4 presents a process flow diagram for the
production of sulfuric acid,8
The process is modified somewhat if feed materials other than pure sulfur are used. Materials such as spent
sulfuric acid, hydrogen sulfide, and off-gases from smelters are also used for the manufacture of sulfuric acid.9
If spent acid is the feed material, it is thermally decomposed to yield a gas stream containing sulfur dioxide,
small amounts of sulfur trioxide, water vapor, and small amounts of organic materials. The gas stream is cooled or
the sulfuric acid is scrubbed to condense out water and organics, and is then demisted to remove residual water. The
purified sulfur dioxide gas stream is reheated, mixed with additional air or oxygen, and sent to catalytic converters.
The process proceeds from this point as it does with pure sulfur as the feed.10
When smelter or pyrite roasting off-gases containing sulfur dioxide are used as the feed material, the gas
stream is passed through a series of dry filtration devices to remove entrained paniculate matter. The gas is cooled
to remove water vapor before it can be used in the process."
Sulfur from pyrite is produced by roasting the iron sulfide to produce sulfur dioxide gas and iron oxide
solid. The gas is treated to produce either elemental sulfur or sulfiiric acid and the iron oxide is sold as feed for iron
making. There are no wastes from this process.12
3. Identification/Discussion of Novel (or otherwise distinct) Processes
There has been sporadic production of elemental sulfur from volcanic deposits in the western United States,
but the selective mining techniques used would eliminate the generation of wastes.13
7 Ibid.
8 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals Industry. Vol. Ill,
1980, Chapter 14.
9 Ibid.
10 Ibid.
11 Had-
12 Ibid.
13 U.S. Environmental Protection Agency, "Sulfur," from 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988, pp. 2-55 - 2-56.
627
-------
en
INJ
00
EXHIBIT 4
SULFUMC ACID PRODUCTION
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 198Q, Chapter 14)
Wastewater (Condensate)
Containing 20 Sulfuric Acid
and Dissolved Sulfur Dioxide
330-360
Sulfur
487-513
Oxygen
1 Vanadium I'eiitoxide
Tail Gases:
Sulfur Dioxide, 99.2%
Sulfuric Add
Waste
1 Spoil Catalyst
103 Less
Wastewater receded
1,000 Sulfuric Add
Product
-------
4. Beneficiation/Processing Boundaries
Frasch Processing
Based on a review of this process, there are no mineral processing operations involved in the production of
sulfur via the Frasch proces.
Claus Process and Combined Sulfur
Based on EPA's review of these processes, both were determined to start with sulfur recovered from other
operations such as petroleum refining and other mineral smelting operations and as such, are completely outside the
scope of the Mining Waste Exclusion.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Based on existing data and best engineering judgement, none of the wastes listed below from sulfur
production are expected to exhibit characteristics of hazardous waste. Therefore, the Agency did not evaluate these
materials further.
Frasch Process Wastestreams
Wastewater. Wastewater from Frasch mining may contain 600 to 1,000 ppm dissolved sulfides and 14,000
to 60,000 ppm of dissolved chlorides. Bleed water retrieved from the formation is produced in amounts ranging
from 38,000,000 to 1.6 billion liters per day. Well seal water is generated in amounts ranging from 5,000 to 20,000
liters per day and contains up to 60 ppm dissolved sulfides. At anhydrite plants, seal water and water recovered from
the formation are treated and reused. At off-shore salt dome plants, bleed water and seal water are combined and
discharged without further treatment. At on-shore facilities, bleed water, area runoff, seal water, and other
wastewater are combined and sent to aeration lagoons. There, sulfides are oxidized to sulfates and thiosulfates. The
sulfide content of the raw effluent is reduced from the range of 600 to 1,000 ppm to the range of 10 to 40 ppm prior
to discharge.14
Air emissions. Emissions from the mine, generated during sulfur recovery, may contain hydrogen sulfide.
The hydrogen sulfide fugitive emissions may range from 0 to 5 kg per kkg of product.15
Sludge. Calcium carbonate sludge is generated by water pretreatment and ranges from 9 to 15 kg per kkg
of product. The calcium carbonate water treatment sludge is recovered and reused. At anhydrite plants, it is used as
drilling mud.
Filter cake. At salt dome plants, about 3.5 kg per kkg of product of waste filter cakes from sulfur filtration
are generated. At salt dome facilities, filter cakes from sulfur purification are stored for future recovery of additional
product.
Miscellaneous wastes such as residues and spilled sulfur are generated from the Frasch process. After
processing, residues are landfilled.
14 U.S. Environmental Protection Agency, 1980, Op. Cit, Chapter 14.
15 Ibid.
629
-------
2. Mineral Processing Wastes
Based on existing data and best engineering judgement, the wastes listed below from sulfur production and
sulfuric acid production are not primary mineral processing wastes. Therefore, the Agency did not evaluate these
materials further.
Claus Process
Tail gases. An airborne waste from product recovery is generated and contains unconverted hydrogen
sulfide gas ranging from 5,000 to 12,000 ppm, 300 to 500 ppm carbon disulfide, 300 to 5,000 ppm carbon
oxysulfide, and up to 200 ppm sulfur vapor. (The carbon disulfide and carbon oxysulfide are produced by side
reactions of organic compounds present in the feed stream and sulfur dioxide generated in the process.) From 950 to
4,400 cubic meters of tail gases are produced per kkg of sulfur product.16 Tail gases are typically recovered and
processed to recycle sulfur compounds. There are several methods used to recover sulfur compounds from these
gases. The processes are described briefly below.
The SCOT process reconverts sulfur compounds in tail gases to hydrogen sulfide. This stream is scrubbed
from the tail gases with amine solution, the regeneration of which releases a purified hydrogen sulfide which is
recycled to the Claus process. This process recovers over 98% of the sulfur compounds in the tail gases.17
The Beavon and Stretford processes are also used to recover sulfur from tail gases. The Beavon process
catalytically reduces sulfur oxides to hydrogen sulfide and the Stretford process removes the hydrogen sulfide by
absorption in an amine solvent. Regeneration of the solvent releases a purified hydrogen sulfide which is converted
to sulfur. About 98% removal of sulfur compounds from the tail gases is achieved.18
The Citrate process, developed by the Bureau of Mines, and the Wellman Lord process are used to recover
most sulfur compounds from the tail gases as sulfur. These processes involve reduction of the sulfur dioxide present
in the tail gases to sulfur.19
Spent catalysts. Spent catalysts are recycled or landfilled.20
Sulfuric Acid Production
Airborne emissions from double absorption plants range from 0.5 to 3 kg per kkg of sulfur dioxide and
from 0.1 to 0.15 kg per kkg of sulfuric acid mists. The high end of the range represents plants using wet feed
materials. Emissions from single absorption plants are controlled in one of five ways: (1) demisters and wet
scrubbers, (2) scrubbing with aqueous ammonia solutions, (3) the Wellman Lord process, (4) molecular sieves to
absorb sulfur dioxide, and (5) no control.21
16 Ibid.
17 Ibid.
18 Ibid.
19 Ibid.
20 Ibid.
21 Ibid.
630
-------
Wastewater, This wastewater includes wastewater from wet scrubbing, spilled product, and condensates.
This waste contains dissolved sulfur dioxide and sulfuric acid values. This wastewater is usually neutralized and
lagooned to settle suspended solids prior to discharge.22
Spent catalyst. Spent catalyst, generally vanadium pentoxide, are usually landfilled and sometimes
reprocessed.23
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific spector.
22 Ibjd.
23 Ibid.
631
-------
BIBLIOGRAPHY
Ober, Joyce. "Sulfur," Prom Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 166-167.
U.S. Environmental Protection Agency. "Sulfur." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 2-55 -2-56.
U.S. Environmental Protection Agency. Multi-Media Assessment of the Inorganic Chemicals Industry. 1980.
Vol. III. Chapter 14.
Wessel, Gregory R. "Sulfur Resources." From Industrial Minerals and Rocks. 6th ed. Society for Mining,
Metallurgy, and Exploration, 1994. pp. 1011-1046.
632
-------
TANTALUM, COLUMBIUM, AND FERROCOLUMBIUM
A. Commodity Summary
Tantalum is used in the electronics industry, as well as in aerospace and transportation applications.
Columbium (the commonly used synonym for the element niobium) is used as an alloying element in steels and in
superalloys. Tantalum and columbium are often found together in pyrochlore and baripyrochlore, the main
columbium containing minerals, as well as in columbite. These minerals contain relatively small amounts of
tantalum, pyrochlore, and baripyrochlore, having a columbium pentoxide-to-tantalum pentoxide ratio of 200 to 1 or
greater.1 Columbite contains slightly larger amounts (up to eight percent) of tantalum.2 Tantalite is the primary
source of tantalum pentoxide, and contains small amounts of columbium pentoxide. Microlite is another source of
tantalum pentoxide. Tantalum is also recovered from tin slags.3 There has been no significant mining of tantalum or
columbium ores in the United States since 1959. Producers of columbium metal and ferrocolumbium use imported
concentrates, columbium pentoxide, and ferrocolumbium. Tantalum products are made from imported concentrates
and metal, and foreign/domestic scrap.4
Ferrocolumbium is an alloy of iron and columbium. Ferrocolumbium is used principally as an additive to
improve the strength and corrosion resistance of steel used in high strength linepipe, structural members, lightweight
components in cars and trucks, and exhaust manifolds. High purity ferrocolumbium is used in superalloys for
applications such as jet engine components, rocket assemblies, and heat-resisting and combustion equipment.3
Exhibit 1 summarizes the principal producers of tantalum, columbium and ferrocolumbium in the United States in
1992. Only Cabot Corporation and Shieldalloy Metallurgical Corporation use ores as their starting material.6
B. Generalized Process Description
1. Discussion of Typical Production Processes
Tantalum and columbium ores are processed by physically and chemically breaking down the ore to form
columbium and tantalum salts or oxides, and separating the columbium and tantalum salts or oxides from each other.
These salts or oxides may be sold, or further processed to reduce the salts to the respective metals. Ferrocolumbium
is made by smelting the ore with iron, and can be sold as a product or further processed to produce tantalum and
columbium products.7 These processes are described in greater detail below.
1 L.D. Cunningham, "Columbium (Niobium) and Tantalum," Minerals Yearbook Volume 1. Metals and
Minerals. U.S. Bureau of Mines, 1992, pp. 435-436.
2 L.D. Cunningham, "Columbium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 187.
3 L.D. Cunningham, 1992, Op. Cit.. p. 438.
4 L.D. Cunningham, "Columbium" and "Tantalum," Mineral Commodity Summaries, U.S. Bureau of Mines,
January 1995, pp. 48 and 170.
L.D. Cunningham, 1992, Op. Cit, pp. 435-436.
6 Personal Communication between ICF Incorporated and Larry D. Cunningham, U.S. Bureau of Mines,
November 1994.
7 Ibid.
633
-------
EXHIBIT 1
SUMMARY OF TANTALUM, COLUMBIUM, AND FERROCOLUMBIUM PRODUCERS (IN 1992)"
Facility Name
Cabot Corp.
Kennametals. Inc.
Herman C. Stark Inc. (NRC, Inc.)
Reading Alloys, Inc.
Shieldalloy Metallurgical Corp.
Teledyne Wah Chang Albany
Thai Tantalum Inc.
Location
Boyertown, PA
Latrobe, PA
Newtown, MA
Robesonia, PA
Newfield, NJ
Albany, OR
Gernee, IL
Type of Products
Cb and Ta pentoxide/metal, FeCb, Ta
capacitor powder
Cb and Ta carbide
Cb and Ta metal, Ta capacitor powder
FeCb
FeCb
Cb pentoxide/metal, FeCb
Ta metal
" - Cunningham, L.D., "Columbium (niobium) and Tantalum," Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines. 1992.
p.453
b - Personal Communication between ICF Incorporated and Larry D. Cunningham, U.S. Bureau of Mines, November 1994.
2. Generalized Process Flow Diagram
Tantalum and Columbium Production
Exhibit 2 illustrates the processing of tantalum and columbium. There is no domestic mining of columbium
or tantalum, and the ore is imported either directly or as a concentrate. Therefore, domestic processing of
columbium and tantalum may begin after the milling step shown in Exhibit 2. Tantalum and columbium are
extracted from the source materials, imported concentrates, and tin slags, by digestion and liquid-liquid extraction.
(Teledyne Wah Chang Albany does not use this process. In previous years they had operated a chlorination/
hydrolysis process, but now operates an acid digestion process. However, their acid process does not use liquid-
liquid extraction.)8 When tin slags are used for the recovery of tantalum, they are sometimes upgraded in an electric
furnace process (not shown), yielding a synthetic concentrate.9 The slag is smelted with carbon to reduce the iron,
tantalum, and columbium components, which are collected as a high carbon ferroalloy containing columbium- and
tantalum carbides. This ferroalloy is treated with a metal oxide to selectively oxidize carbided components other
than tantalum and columbium. The tantalum and columbium carbides are reoxidized and can be substituted for
tantalum and columbium concentrates.10
8 Personal Communication between ICF incorporated and Chuck Knoll, Teledyne Wah Chang, Albany, OR,
November 1994.
9 L.D. Cunningham, 1992, Op. Cit.. pp. 438-39.
10 "Tantalum and Tantalum Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol.
XXIII, 1983, p. 549.
634
-------
EXHIBIT 2
PRIMARY COLUMBIUM-TANTALUM PROCESS
(Adapted from: U.S. Environmental Protection Agency, 1989, p. 4359.)
Ore
'" MIBK *
^ | H,Oas (Recycle) |
Nh, Ta
I Gangue
y (Waste)
Nb Impurities
1 Fresh MIBK
Extraction
HF »K NH
MIBK i I Deioniied 1 NH, i
T Water
T It * * i
(MIBK)Nh^ ^ ^ (H,0)Nb ^
"
Precipitation
H:O
+
Ta
^
r
Precipitation
Impurities I 'Fresh
(Waste) MIBK ^ r 1
Filtrate ~ "
(Waste)
Filter
r
Filter
^ 1
Calciner
r
Calciner
Nb (Oxide)
^ 1
Nb Reduction
Deionized
W'ater
KF
i
Or
V
F[U" ^^ "»t™le
(or Central ^" ,Waste)
rugation)
Filtrate
(Waste)
— — ^ ^ r
Dryer
Ta (Salt)
y
Ta Reduction
Ta (Oxide)
r
Nb Reduction
Tantalum Meta
I Columbium I Tantalum
W Metal V Metal
cn
ui
ui
-------
The concentrate or slag is digested with aqueous hydrofluoric acid (sometimes in conjunction with sulfurie
acid) to form fluoride salts of the metals. Unreacted concentrate or slag (gangue) is removed by settling and
decantation and is disposed of as a low level radioactive waste. This leaching process also generates an acid mist
that may be controlled by wet scrubbers. The scrubber liquor is a source of wastewater."
These metal-fluoride salts are then extracted with methyl isobutyl ketone (MIBK). The liquid-liquid
extraction procedure first recovers the tantalum salt. Additional hydrofluoric acid is added to change the solubility
of the columbium salt, which is then extracted by MIBK. The raffinate (containing the spent hydrofluoric acid
solution) from this step is considered wastewater. The salts are then recovered from each of the MIBK solutions by
liquid-liquid extraction with deionized water. The raffinate from this second set of extractions is the barren MIBK.
which is recycled. Fugitive air fumes from the solvent extraction process are controlled by wet air pollution control
devices, which generate wastewater.12 The water and tantalum solution from the extractor contains a fluotantalic
acid solution, from which potassium fluotantalate (K-salt, K2TaF7) or tantalum pentoxide (Ta2O5) can be precipitated
through the addition of either potassium fluoride, or ammonia. Potassium chloride (not shown) is used sometimes in
place of potassium fluoride.13 Columbium pentoxide is precipitated from me columbium stream by the addition of
ammonia. A wet scrubber may be used to control fluoride fumes generated during precipitation of either metals'
oxide or salt. The aqueous liquor (filtrate) is discarded. The resulting crystals are washed with water and dried.14
The columbium oxide precipitates are calcined in a kiln; wet scrubbers are used to control gaseous fumes. Tantalum
salts are also dried, but wet scrubbers are not normally used. The water vapor, however, may be condensed,
captured, and discharged.15
Columbium and tantalum salts are reduced to metal by a number of methods, including: sodium reduction,
aluminothermic reduction, carbon reduction, and electrolysis. Sodium reduction (not shown) is a popular method for
producing both columbium and tantalum from their salts. In this process, sodium reduces the columbium or tantalum
to metal. Layers of the columbium or tantalum salt are alternated with layers of sodium in a reaction vessel, then
capped with sodium chloride to prevent oxidation of the reduced metal. The reaction mixture is often ignited
electrically, but once ignited, the exothermic reaction is self-sustaining. Wet scrubbers are often used to control the
gaseous emissions from the reaction vessel. After cooling, the columbium or tantalum metal-containing material is
crushed, and any iron picked up from the reaction vessel is removed magnetically. The remaining metal powder is
further purified by leaching with water, followed by nitric or hydrofluoric acid.16
The aluminothermic reaction (not shown) also may be used on both columbium and tantalum salts. This
method also may be used on certain ferrocolumbium ores that do not require digestion and separation of columbium
and tantalum salts. The salt (or ore) is mixed with aluminum powder. Potassium chlorate is added to provide
additional reaction heat, and magnesium is added to properly ignite die mixture. Columbium and tantalum are
reduced to metal while aluminum is oxidized.17
11 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume VIII, Office of Water
Regulations and Standards, May 1989, p. 4352.
13 L.D. Cunningham, 1992, Op. Cit.. pp. 438-39.
14 U.S. Environmental Protection Agency, 1989, Qf2._Cit,, p. 4352.
15 Ibid., p. 4353.
16 Ibid.
17 Ibid.
636
-------
Carbon reduction (not shown) takes place through a two-step route known as the Balke process and can be
used on both columbium and tantalum salts. Its predominant use, however, is in the reduction of the metal oxides.
The metal oxide is first mixed with fine carbon and heated under vacuum to 1800°C, where a metal carbide and
carbon monoxide are formed. The carbide is then mixed with more oxide and reacts to form the pure metals and
additional carbon monoxide. No known wastewater is generated during this process."
Electrolytic reduction (not shown) of tantalum is sometimes practiced, using fused salt techniques.
Potassium fluotantalate (K-salt), the crystal which was precipitated by potassium fluoride in the separation of salts
step, is electrolyzed to yield pure tantalum metal. The pure tantalum metal is then separated from the cathode by
pulverizing the cathode and subsequent acid leaching, resulting in a metal solution and the cathode material (usually
carbon)."
Electron beam melting is currently the most common method of consolidation, as shown in Exhibit 3.20 A
beam of high voltage, low current electrons is focused onto the crude metal and the top of a retractable tantalum
ingot contained in a water cooled copper cylinder. The beam melts the crude metal, and the falling molten globules
from a pool on top of the ingot. The process is continuous, with the ingot being lowered as the molten metal
solidifies. Most impurities boil out of the pool into the high vacuum environment (required by the electron beam)
and are removed.21 Arc melting, as shown in Exhibit 4, occurs in much the same way as electron beam melting,
except that a low voltage, high current arc of electricity melts the crude metal.22
Simultaneous compaction and direct resistance heating (not shown) is the oldest process and is somewhat
undesirable, as the metal must be processed two or three times to reach sufficient purity. The metal is typically
compacted at about 6,900 atmospheres and heated to 1,400-1,500°C for several hours. It is then rolled and sintered
at 2,300 °C. Several rolling and sintering steps may be required.23
Ferrocolumbium Production
Ferrocolumbium is made from pyroehlore concentrates, usually by an aluminothermic process with an iron-
iron oxide mixture. Exhibit 5 illustrates this process. Pyroehlore, aluminum powder, and iron scrap, and/or iron
oxide are mixed together, frequently with small amounts of lime or fluorspar as fluxing agents, in a batch reactor.
Sometimes sodium chlorate or some other powerful oxidizer is added to provide additional reaction heat. A typical
reactor consists of a refractory lined steel shell, and occasionally a floor consisting of slag from previous reduction
reactions is used. After the reaction has come to completion, the molten ferrocolumbium lies at the bottom of the
reactor and the slag floats on it. Most of the impurities go into the slag and some easily reduced metals go into the
ferrocolumbium. After a period of cooling, the metal is separated from the slag, and is crushed and sized. At some
facilities, an electric furnace is used to provide the heat necessary for the reaction, in place of the aluminothermic.
18 Ibid.
"Ibid.
20 "Tantalum and Tantalum Compounds," 1983, Op. Cit.. p. 552.
21 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 4354.
22 "Tantalum and Tantalum Compounds," 1983, Op. Cit.. p. 551.
23 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 4354.
637
-------
EXHIBIT 3
ELECTRON BEAM MELTING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 552.)
Focused Electron Beam
Vacuum
High Voltage Power Lead
Tantalum
Feedstock
Ingot Puller
638
-------
EXHIBIT 4
VACUUM ARC MELTING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 551.)
n-
Vacuum
Electrode
Drive
0
3 Power Terminal
Tantalum
Ingot
Cooled
Mold •
Vacuum
Seal
Electrode
Holder
, Tantalum
Feedstock
. Molten
Pool
Power
Terminal
639
-------
EXHIBIT 5
FERROCOLUMBIUM PRODUCTION
Pyrochlore (Ore)
Aluminum
Iron Scrap or Oxide
Ferrocolumbium
640
-------
method. In this process, the quantity of aluminum can be substantially reduced and other reducing agents such as
ferrosilicon can be used.24 High purity ferrocolumbium cannot be made directly from pyrochlore because of the high
alkali content. It can, however, be manufactured from columbium pentoxide produced by treating the lower purity
ferrocolumbium made from pyrochlore concentrates."6
3. Identification/Discussion of Novel (or otherwise distinct) Processes
Direct chlorination of tin slag is being investigated as an alternative to digestion and leaching, as a way to
reduce the amount of toxic waste generated.26
4. Extraction/Beneflciation Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
Tantalum/Columbium
EPA determined that for the production of tantalum/columbium, the beneficiation/processing line occurs
between milling and digestion because the physical structure of the ore is destroyed. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams
24 "Niobium and Niobium Compounds," Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol. XV,
1982, pp. 823-824.
25
Cunningham, L.D., 1992, Op. Cit., p. 436.
261. Gaballah, E. Allain, and M. Djona, "Chlorination and Carbochlorination of a Tantalum and Niobium
Pem«>xides Bearing Concentrates," Mineral Processing and Environmental Engineering. Vandoeuvre, France, 1993,
p. 760.
-------
generated after the beneficiation/processing line, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
Ferrocolumbium
EPA determined that for ferrochromium, processing begins with the reaction of iron and the ore in the
furnace because the ore is changed into a more useful form by significant physical and chemical changes in the
furnace. Therefore, because EPA has determined that all operations following the initial "processing" step in the
production sequence are also considered processing operations, irrespective of whether they involve only techniques
otherwise defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral
processing operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents
below the mineral processing waste streams generated after the beneficiation/processing line, along with associated
information on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
The following waste streams have been associated with the processing of tantalum and columbium
concentrates and slags.
1. Extraction and Beneficiation Wastes
Currently, there is no domestic extraction of columbium or tantalum ores.
2. Mineral Processing Wastes
Digestion
Scrubber Overflow. Approximately 19,000 metric tons of scrubber overflow are produced annually in the
United States. Available data do not indicate the waste exhibits hazardous characteristics.27 Therefore, the Agency
did not evaluate this material further.
WWTP Liquid Effluent. Approximately 206,000 metric tons of WWTP Liquid Effluent are produced
annually in the United States.28 Existing data and engineering judgement suggest that this material does not exhibit
any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent Potassium Titanium Chloride. Available data do not indicate the waste exhibits hazardous
characteristics.29 Therefore, the Agency did not evaluate this material further.
27 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Volume 1, Office of Solid Waste, August 1992, p. 1-7.
28 Ibid.
29 Ibid.
642
-------
Spent Raffinate Solids. Approximately 2,000 metric tons of raffinate solids, from the liquid-liquid
extraction procedure are produced annually in the United States.30 This waste may exhibit the hazardous
characteristic of corrosivity.31 The waste is not recycled.
Digester Sludge. Approximately 1,000 metric tons of digester sludge are produced annually in the United
States.32 This waste may exhibit the hazardous characteristic of corrosivity.33 The waste is not recycled.
WWTP Sludge. Existing data and engineering judgement suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Process Wastewater. There are several operations which produce wastewater (see Exhibit 3). Process
wastewater may contain fluoride, copper, lead, zinc, cadmium, 1,2-dichloroethane, chloroform, chromium, selenium,
arsenic, nickel, and ammonia. The pH of the individual waste streams may be high or low depending on the
operations that generated each waste stream. For instance, the pH of the wastewater generated through digestion is
likely to be low, while wastewater resulting from ammonia precipitation is likely to be high.34 Therefore, the pH of
the mixture of these streams will depend on the quantity and pH of each contributing stream. We used best
engineering judgement to determine that this waste stream may be recycled. The waste was formerly classified as a
spent material. Approximately 146,000 metric tons of process wastewater are produced annually in the United
States.35 Attachment 1 contains data on process wastewater.
APC Dust Sludge. Available data do not indicate that APC dust sludge generated by the production of
ferrocolumbium exhibits hazardous characteristics.36 Therefore, the Agency did not evaluate this material further.
Slag. This material is generated by the aluminothermic production of ferxocolumbium. During the
processing sequence, most of the impurities contained in the raw materials report to the slag. However, some of the
easily reduced metals will go into the ferrocolumbium layer.37 Existing data and engineering judgement suggest that
this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
30
Ibid.
31 U.S. Environmental Protection Agency, Technical background Document. Development of Cost. Economic.
and Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989, p. 3-6.
32 Ibid.
33 U.S. Environmental Protection Agency, Op. Cit., August 1989, p. 3-6.
34 U.S. Environmental Protection Agency, "Columbium and Tantalum," 1988 Final Summary Report of Mineral
Industrial Processing Wastes. 1988, pp. 3-84 - 3-85.
35 U.S. EPA, 1992, Op. Cit., p. 1-7.
36 Ibid., p. 1-4.
37 "Niobium and Niobium Compounds," 1982, Op. Cit.. pp. 823-824.
643
-------
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
644
-------
BIBLIOGRAPHY
Brown, R.E., and G.F. Murphy. "Ferroalloys." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. p.
265.
Cunningham, L.D. "Columbium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 185-196.
Cunningham, L,D. "Columbium (niobium)," From Mineral Commodity Summaries. U.S. Bureau of Mines.
January 1995. pp. 48-49.
Cunningham, L.D. "Columbium (niobium) and Tantalum." From Minerals Yearbook. Volume 1. Metals and
Minerals. U.S. Bureau of Mines. 1992. pp. 435-460.
Cunningham, L.D. "Tantalum." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1994. pp.
170-71.
Cunningham, L.D. "Tantalum." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 811-822.
Gaballah, I., E. Allain, and M. Djona. "Chlorination and Carbochlorination of a Tantalum and Niobium Pentoxides
Bearing Concentrates." Mineral Processing and Environmental Engineering. Vandoeuvre, France. 1993.
p. 760.
"Niobium and Niobium Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XV.
1982. pp. 823-827.
Personal Communication between ICF incorporated and Chuck Knoll, Teledyne Wah Chang, Albany, OR.
November 1994.
Personal Communication between ICF Incorporated and Larry D. Cunningham, U.S. Bureau of Mines. November
1994.
Sutill, Keith R. "Greenbushes Lithium Generates A New Source of Income." Engineering and Mining Journal. 188,
No. 11. 1987. pp. 40-43.
"Tantalum and Tantalum Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXIII.
1983. pp. 547-553.
U.S. Environmental Protection Agency. "Columbium and Tantalum." From 1988 Final Draft Summary Report of
Mineral Industrial Processing Wastes. Office of Solid Waste. 1988. pp. 3-80 - 3-87.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Volume VIII. Office of Water
Regulations and Standards. May 1989.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
U.S. Environmental Protection Agency, Technical background Document. Development of Cost. Economic, and
Small Business Impacts Arising from the Reinterpretation of the Bevill Exclusion for Mineral Processing
Wastes. August 1989. p. 3-6.
Weiss, Norman L., Ed. "Columbium and Tantalum." SME Mineral Processing Handbook. Volume II. Society of
Mining Engineers. 1985. p. 27-3.
645
-------
ATTACHMENT 1
646
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - TANTALUM/COLUMBRIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis -
Minimum Average
50000
0.010
0.003
-
0.001
-
0.008
0.006
-
0.200
25000
0.020
-
-
0.000
-
0.500
0.002
0.000
0.000
7800
0.600
0.001
2650
-
10000
-
40000
900
-
3.0
-
50000
6.461
6.256
-
0.126
-
6.392
232.846
-
56.553
25000
255.869
-
-
0.013
-
2.460
13.507
0.040
0.365
7800
331.960
0.006
14037.50
-
45750
-
40000
9450
-
8.4
-
PPM
Maximum #
50000
30.00
45.00
-
0.500
-
40.00
1000
-
300
25000
1000
-
-
0.063
-
10
70
0.070
1.180
7800
1000
0.033
45000
-
1 30000
-
40000
18000
-
12.0
-
Detects
1/1
10/10
13/13
0/0
13/13
0/0
13/13
13/13
0/0
13/13
1/1
13/13
0/0
0/0
13/13
0/0
10/10
10/10
4/4
9/9
1/1
10/10
17/17
4/4
0/0
4/4
0/0
1/1
2/2
0/0
5/5
0/0
EP Toxicity Analysis - PPM
Min. Ayg. Max. # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 2
-
CTI
£>
-J
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
648
-------
TELLURIUM
A. Commodity Summary
According to the U.S. Bureau of Mines, commercial grade tellurium and tellurium dioxide are recovered
from anode slimes at one electrolytic copper refinery in the United States (ASARCO - Amarillo, TX). Selenium is
also recovered from the copper anode slimes during this process (see Selenium sector report). High purity tellurium,
tellurium master alloys, and tellurium compounds are produced by primary and intermediate processors from
commercial-grade metal and tellurium dioxide. Tellurium is used mainly in the production of free-machining steels.
It is also used as a minor additive in copper and lead alloys and malleable cast iron, as an accelerator in rubber
compounding, in thermoelectric applications, and as a semiconductor in thermal-imaging and photoelectric
applications. Tellurium is added to selenium-base photoreceptor alloys to increase the photo speed. In 1994, iron
and steel products remained the largest end use, followed by nonferrous metals, chemicals, and other uses.1 Some
common commercial tellurium products include tellurium dioxide, sodium tellurate, ferrotellurium, and tellurium
diethyldithiocarbamate.2
B, Generalized Process Description
1. Discussion of Typical Production Processes
Nearly all tellurium is obtained as a material formerly labeled as byproduct of the electrolytic refining of
copper. Although copper slimes are valued primarily for gold, silver, and occasionally platinum-group metals,
tellurium is available to the refiner for the added cost of recovery and refining.3 Tellurium is present in copper
refinery slimes in concentrations ranging from a trace to 8 percent and is recovered as precipitated tellurous acid.
Tellurium metal can be produced from the crude tellurous acid by one of three purification methods described below.
Metal tellurides for semiconductors are made by direct melting, after which, the excess tellurium is volatilized under
reduced pressure. The resultant tellurium vapor is then passed over a heated metal in an inert gas carrier and
undergoes a high temperature reduction of oxy compounds with hydrogen or ammonia.1'
2. Generalized Process Flow Diagram
The process flow for the production of tellurium can be separated into two stages. The first stage involves
the removal of copper from the copper slimes (an intermediary product is tellurous acid). The second stage involves
the recovery of tellurium metal and purification of the recovered tellurium. The process flow diagrams for a typical
recovery process are presented in Exhibits 1 through 3. Exhibit 1 shows the steps involved in producing tellurous
acid from copper anode slimes. The process flow diagrams for two methods of recovering tellurium metal from
tellurous acid, acid precipitation and electrolytic purification, are presented in Exhibits 2 and 3, respectively.
1 Stephen M. Jasinski, "Tellurium," from Mineral Commodities Summary. U.S. Bureau of Mines, 1995, pp. 172-
173.
2 "Tellurium," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXII, 1983, p. 663.
3 Neldon L. Jensen, "Tellurium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 825.
"Tellurium," 1983, Op. Cit. p. 663.
649
-------
EXHIBIT 1
TELLURIUM RECOVERY FROM COPPER SLIMES
(Adapted from: 1988 Final Draft Summary Report of Mineral Processing Wastes, 1988, pp. 204 - 210.)
Copper Slime
Containing Tellurium
Soda
Ash
Water
Sulfuric
Acid
Sodium
Hydroxide
Sodium
Sulfide
I
Copper Removal
Copper
Roasting
Slag
Soda Slime
Leaching
Leached Slag
Sodium Tellurite Solution
Neutralization/
Precipitation
Liquid to Selenium
Recovery
Precipitate
Dissolution
Precipitation
T
Solids
Neutralization/
Precipitation
Wastewater
Tellurous Acid Precipitate
650
-------
EXHTOIT2
PURIFICATION OF TELLURIUM BY ACT) PRECIPITATION
(Adapted from: 1988 Final Draft Summary Report of Mineral Indistry Processing Wastes, 1988, pp. 204 - 210.)
Hydrochloric or
Sulfuric Acid
Sulfur
Dioxide
Water
Qude Tellurous Acid Solids
Wastewater
Wastewater
Tellurium Metal
651
-------
EXHIBITS
ELECTROLYTIC PURIFICATION OF TELLURIUM
(Adapted from 1988 Final Draft Summary Report of Mneral Industry Processing Wastes, 1988, pp. 204 - 210.)
Sodium
Hydroxide
Water
Qude Tellurous Acid Solids
Waste Electrolyte
Wastewater
Tellurium Mstal
652
-------
Removal of copper and production of tellurous acid
Since tellurium is recovered from copper refinery slimes, the first step in the recovery process shown in
Exhibit 1 is the removal of copper from the slimes. Copper is generally removed by aeration in dilute sulfuric acid.
oxidative pressure-leaching with dilute sulfuric acid, or digestion with strong acid followed by water-leaching.
During the copper removal, much of the tellurium is dissolved. This tellurium is recovered by cementing
(precipitation of metallic copper), leaching the cement mud with dilute caustic soda, and neutralizing with sulfuric
acid. The precipitate from the neutralization contains tellurium as tellurous acid suitable for recovery.5 Some of the
liquid wastes from this neutralization/precipitation step are sent to selenium recovery.
Copper-free slimes are treated by one of the four following methods: (1) refining with soda ash in a dore or
cupeling furnace; (2) combined oxidation and alkalinization by roasting or baking a slime-soda ash mix; (3) removal
of selenium by roasting and caustic soda leaching; or (4) boiling the slime with caustic soda. The soda slag from the
soda refinement or the roasted product of the oxidation is leached with water to extract sodium tellurite. The
insoluble sodium tellurate in the leached slag is returned to the copper-anode furnace. The liquor obtained from the
selenium removal and the boiling with caustic soda contains lead. In all cases, the solution contains selenium and
impurities. Whatever the method, the liquor is neutralized to pH 6-6.2 with sulfuric acid to precipitate impure
tellurous acid as tellurium mud, which contains lead sulfate, silica, and other impurities. The mud is purified by
redissolving in caustic soda and reprecipitating. Impurities, such as lead are, removed by careful precipitation from
the caustic solution with sodium sulfide. Fractional neutralization of the initial impure caustic solution yields
tellurous acid of a purity acceptable for reduction to the metal.6
Recovery and purification of tellurium
Tellurium is recovered from the precipitated tellurous acid by three methods: (1) direct reduction; (2) acid
precipitation; and (3) electrolytic purification. The electrolytic purification method is the preferred method.7 The
high boiling temperature of tellurium precludes purification by atmospheric distillation, but low pressure distillation
is feasible. Heavy metal impurities (iron, copper, tin, lead, antimony, bismuth) remain in the still residue. Volatile
selenium is a persistent contaminant, and may be as high as 500 ppm in the distilled tellurium.8
Direct Reduction. Some of the drawbacks associated with direct reduction include heavy fuming of
telluride dioxide and the formation of organic decomposition products. The reduction with sulfur is rapid and leaves
a clean melt, but the heavy fumes are problematic.9
Acid Precipitation. As presented in Exhibit 2, purification by acid precipitation first involves dissolving
the crude tellurous acid solids in hydrochloric acid or sulfuric acid. Crude common salt is added to the acidified
solution, and tellurium is precipitated by adding sulfur dioxide. The resultant precipitate undergoes filtration,
washing, drying, and melting. In an alternative method, tellurium is dissolved in a strong nitric acid, hydrolyzed to
white 2TeO2NO3 and precipitated by diluting and boiling, and separating. The resultant precipitate is washed
(redissolving and rehydrolyzing, if desired), dissolved in hydrochloric acid, and reduced with sulfur dioxide. Ultra
high-purity tellurium is prepared by zone refining in a hydrogen or inert-gas atmosphere.10
5 Ibid., p. 662.
6 Ibid.
7 Ibid.
8 Ibid.
9 Ibid.
10 Ibid.
653
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Electrolytic Purification. As shown in Exhibit 3, electrolytic purification involves dissolving crude
tellurous acid solids in caustic soda to yield a solution containing sodium tellurite and free caustic soda. The
solution then undergoes electrolysis in a cell equipped with stainless-steel electrodes. The cathodes are then
removed, washed, dried, and melted.''
As a result of a modernization, KUCC also recovers tellurium. Following decopperization, the autoclave
liquid is processed through a column containing copper to extract copper telluride. The tellurium cementate is then
packaged in drums for sale.12
3. Identification/Discussion of Novel (or otherwise distinct) Processes
None Identified.
4. Beneflciation/Processing Boundary
Since tellurium is recovered from anode slimes from a copper refinery, all wastes generated by this mineral
commodity sector are mineral processing wastes. For a description of the beneficiation/processing boundary for this
sector, please see the report on copper presented elsewhere in this background document.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Not Applicable
2. Mineral Processing Wastes
Recovery from Copper Anode Slimes
Slag. As shown in Exhibit 1, slag is generated from roasting and leaching. Slag from leaching may be
wasted or returned to a copper anode for further processing while the slag from roasting is wasted.13 Although no
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 100 metric
tons/yr, 1,000 metric tons/yr, and 4,500 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may be partially recycled and may exhibit the characteristic of toxicity for selenium. This
waste formerly was classified as a by-product.
Solid waste residues. Solids, likely containing sulfur, are generated from precipitation as impurities and
are discarded as waste.14 Although no published information regarding waste generation rate or characteristics was
found, we used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual
waste generation rate of 100 metric tons/yr, 1,000 metric tons/yr, and 4,500 metric tons/yr, respectively. We used
best engineering judgment to determine that this waste may exhibit the characteristic of toxicity for selenium.
11 Ibid.
12 Kenecott Utah Copper Corporation. Comment submitted in response to the Supplemental Proposed Rule
Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
13 U.S. Environmental Protection Agency, "Tellurium", from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. Office of Solid Waste, 1988, pp. 204 - 210.
14 U.S. Environmental Protection Agency, 1988, Op. Cit. pp. 204 - 210.
654
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Wastewater. There is wastewater associated with the neutralization steps that follow both the addition of
sulfurie acid and the addition of sodium sulfide in Exhibit 1, The liquid resulting from the addition of sulfuric acid is
sent to selenium recovery. Generation rate estimates for this waste stream are included in the estimates for the
wastewater stream from purification of tellurous acid as discussed below.
Purification of Tellurous Acid
The following wastes have been identified as generated during the purification step.
Fumes of Telluride dioxide. Telluride dioxide fumes are generated during the direct reduction step.
Wastewater. One of the waste streams associated with the acid precipitation step of tellurium recovery is
wastewater from washing, with an acidic pH. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low. medium,
and high annual waste generation rate of 100 metric tons/yr, 10,000 metric tons/yr, and 20,000 metric tons/yr,
respectively. We used best engineering judgment to determine that this waste may be recycled and may exhibit the
characteristics of toxicity (selenium) and corrosivity. This waste formerly was classified as a spent material.
Waste Electrolyte. Waste electrolytes are generated during electrolytic purification. Although no
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 100 metric
tons/yr, 1,000 metric tons/yr, and 10,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity (lead and selenium).
D. Non-uniquely Associated Wastes
Non-uniquely associated wastes may be generated at on-site laboratories, and may include used chemicals
and liquid samples. Other hazardous wastes may include spent solvents (e.g., petroleum naphtha), and acidic tank
cleaning wastes, and polychlorinated biphenyls from electrical transformers and capacitors.
E. Summary of Comments Received by EPA
New Factual Information
One commenter indicated that its facility now recovers tellurium (COMM 40). This new information has
been incorporated in the "Recovery and puification of tellurium" section.
Sector-specific Issues
None.
655
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BIBLIOGRAPHY
Jasinski, Stephen M. "Tellurium." From Mineral Commodities Summary. U.S. Bureau of Mines. 1995. pp. 172-
173.
Jensen, Neldon L. "Tellurium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1992.
pp. 823-828
"Tellurium." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXII. 1983. pp. 658-663.
U.S. Environmental Protection Agency, "Tellurium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 204-210.
656
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TIN
A. Commodity Summary
The primary source of tin is the mineral eassiterite, SnO2, which occurs in vein and lode deposits. More
than 80% of the tin ore in the world is found in placer deposits with tin content as low as 0.015%.' Final uses of tin
include cans and containers, electrical components, construction, transportation, and other uses.2
China and Brazil are the world's largest producers of tin, followed by Indonesia and Bolivia. These
countries account for 77% of U.S. tin imports. Tin production in the United States is negligible, with small amounts
of tin concentrates mined from a placer deposit at Cache Creek Gold Mine near Fairbanks, Alaska in 1993.3 The
sole U.S. tin smelter in Texas City, Texas ceased production in 1989.4
B. Generalized Process Description
1. Discussion of Typical Production Processes
Tin concentrate is processed by smelting and refining. Prior to smelting, any impurities in the concentrate
are removed by roasting, leaching with water, and acid leaching. Cassiterite, a carbon reducing agent, and limestone
and silica are smelted to create molten tin, which is cast in slabs. These slabs are then refined either
pyrometallurgically or electrolytically.
2. Generalized Process Flow Diagram
Tin smelting is most commonly conducted in reverberatory furnaces because they offer better process
control and yield cleaner slags. Electric furnaces are sometimes used by smaller smelters for their energy efficiency.5
Blast furnaces, kilns, and horizontal furnaces are used to smelt low-grade tin concentrate.6
As shown in Exhibit 1, smelting is conducted as a batch operation in which a charge of eassiterite (tin
oxide) concentrate, a carbon reducing agent (coke), and fluxes consisting of limestone and silica is smelted for 10 to
12 hours in a two-stage process. In the first stage, carbon monoxide is formed in the furnace and reacts with eassite-
rite (tin oxide concentrate) to produce tin and carbon dioxide. The silica flux reacts with eassiterite under reducing
conditions to yield stannous silicate. Iron, which is also present in the concentrate, reacts with silica to yield ferrous
silicate. In the second stage, the silicates fuse with fluxes to create a liquid slag. Unreacted carbon in the fuel
reduces the stannous silicate to tin and the ferrous silicate to iron.''8 In addition to molten tin and slag, an off-gas is
1 "Tin and Tin Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXIII, 1983, pp. 18,
23.
2 J. Carlin, "Tin," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995, pp. 182-178.
3 Randol Mining Directory 1994/95. p. 189.
4 J. Carlin, 1994, Op. Cit, pp. 182-183.
5 U.S. Bureau of Mines, Mineral Facts and Problems. Bulletin 675, 1985, p. 850.
6 Carr, D., ed., Industrial Minerals and Rocks. Society for Mining, Metallurgy, and Exploration, Inc., 1994. p.
672.
7 U.S. Environmental Protection Agency, 'Tin," from 1988 Final Draft Summary Report to Mineral Industry
Processing Wastes. 1988, pp. 3-214.
8 Carr, D., ed., 1994, Op. Cit.. p. 672.
657
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EXHIBIT 1
TIN SMELTING PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3 - 214.)
Tin Concentrates and Residues
Coke
Limestone
Offgas to Scrubber
Slag
Cell Slimes to Recycle
Waste Acid
Tin Product
658
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also generated and is sent to a caustic scrubber to control sulfur dioxide emissions. Additional wastes include brick
linings from the furnace and spent fabric filters, both of which are recycled.
After smelting, the batch is tapped into a settler; slag overflows the settler and is collected and resmelted,
while the remaining molten tin is cast into slabs (tin anodes) to be refined.9 Crude tin is most commonly refined by
heat treatment (pyrometallurgical) but can also be refined by electrolytic methods.
Heat treatment consists of heating the tin slab slightly above its melting point but below the melting points
of impurities, such as iron and copper. The molten tin is poured into kettles and agitated in a process called boiling.
Remaining impurities collect in a surface layer of dross, which is skimmed and resmelted. The remaining tin, with a
purity greater than 99.8%, is cast in molds.
Electrolytic refining (see Exhibit 1) requires greater capital expenditures for equipment but yields a purer
product. Electrorefining may be conducted in either an acid or alkaline bath.10 The acid bath consists of stannous
sulfate, creosulfonic or phenolsulfonic acids, and free sulfuric acid with beta naphthol and glue to prevent deposits
from forming on the cathodes. Slimes can form on the tin anodes if the anodes have high lead levels; the slimes are
scrubbed off. The alkaline bath consists of potassium or sodium stannite and free alkali. Lead is precipitated as lead
plumbite in slimes that form on the anodes. Pure tin generated in either bath is recast into ingots for sale.11 Waste
slimes and waste acid or alkaline baths are shipped off-site for reprocessing and recycle.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
A research program is being conducted at the Colorado School of Mines for developing a pyrochemical
process using molten salts for recovering reactive metals, including tin, from beneficiated ore. The process takes
place in a hybrid reactor combining electrolytic production of a calcium reductant and in situ utilization of the
reductant to reduce metal compounds, specifically tin oxide. The reactor operates at a temperature less than
1,000°C. The technology is reported to generate little waste.12
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficjation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
9 U.S. Bureau of Mines, 1985, Op. Cit. p. 850.
10 "Tin and Tin Alloys," 1983, Op. Cit. p. 23.
11
U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-214.
12 Mishra, B., D. Olson, and W. Averill, "Applications of Molten Salts in Reactive Metals Processing," presented
at the Conference for Emerging Separation Technologies for Metals and Fuels, Palm Coast, FL, March 13-18, 1993,
sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
659
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EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between acid leaching and smelting. EPA identified this point in the process sequence as where beneficiation ends
and mineral processing begins because it is here where a significant chemical change to the cassiterite occurs.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents the mineral
processing waste streams generated after the beneficiation/processing line in section C.2, along with associated
information on waste generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Waste streams include tailings slurry and process wastewater from mining placer deposits, which are held in
a tailings pond for settling of solids. The remaining water is either discharged to receiving waters through an
NPDES outfall or reused in the mining process.13 Most likely contaminants are arsenic, lead, and zinc. Other
beneficiation wastes generated during roasting and acid leaching include spent waste acids, sludges, and waste
liquids.
2. Mineral Processing Wastes
Smelting operations generate solid, liquid, and gaseous wastes. However, since tin is no longer produced
domestically, these waste streams were not included in our analysis.
Slag
Slag is generated during smelting of tin concentrates through the fusion of ferrous silicate with limestone
flux. Slag is collected when molten tin is tapped into a settler. Slag is believed to be resmelted and is therefore most
likely not disposed as a solid waste. The Newly Identified Mineral Processing Waste Characterization Data Set
(NIMPW Characterization Data Set) indicates that, when operating, the sole U.S. tin smelter generated
approximately 15,000 metric tons of slag annually.14 Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Process Wastewater and Treatment Impoundment Sludge
Process wastewater is generated as blowdown from the scrubbing of off-gases generated during smelting.
Approximately 83,000 metric tons are generated annually by two plants when they are operating;15 in 1984, the
13 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-211.
14 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, August 1992, p. 1-7.
15 Ibid.
660
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Texas City smelter generated 22,000 liters of wastewater per metric ton of tin produced,16 Process waste water is
disposed in impoundments and treated by chemical precipitation and sedimentation; solids settle to create treatment
impoundment sludge.
EP toxicity tests conducted in 1984 on samples of scrubber solids and pond water revealed the wastes to
exhibit the characteristic of EP toxicity for arsenic (15.5 ppm for scrubber solids, 22.9 ppm for scrubber pond
water).'' Sampling results are shown in Attachment 1.
Brick Lining and Fabric Filters
Furnaces used in smelting tin concentrates are lined with brick, which periodically must be replaced. Spent
brick is resmelted for its tin value.
Fabric filters used in baghouses for filtering off-gases are recycled when spent.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Refining, both through heat treatment (pyrometallurgically) and electrolytically, generate solid and liquid
wastes, as described below.
Dross
Dross forms during pyrometallurgical refining when tin slab is heated above its melting point; impurities
such as lead and copper are captured in a layer of dross at the surface of the molten tin. Dross is skimmed and
resmelted. Although no published information regarding waste generation rate or characteristics was found, we used
the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation
rate of 0 metric tons/yr, 100 metric tons/yr, and 200 metric tons/yr, respectively. We used best engineering judgment
to determine that this waste may exhibit the characteristic of toxicity for lead.
Waste Acid and Alkaline Baths
A waste electrolyte stream (waste baths), generated in electrolytic refining, most likely contains high metals
concentrations and may exhibit the corrosivity and EP toxicity characteristics.18 Waste baths are shipped off-site for
reprocessing.19 Although no published information regarding waste generation rate or characteristics was found, we
used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate of 0 metric tons/yr, 100 metric tons/yr, and 200 metric tons/yr, respectively. We used best
engineering judgment to determine that this waste may exhibit the characteristics of toxicity (arsenic, cadmium,
chromium, lead, and mercury) and corrosivity.
Slimes
Slimes, which form on tin anodes during electrolytic refining, may be corrosive and contain high levels of
lead. Slimes are shipped off-site for reprocessing.20 Although no published information regarding waste generation
rate or characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low,
16 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-214.
17 U.S. Environmental Protection Agency, 1992, Op. Cit.. pp. 34-2.
18 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-212.
19 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-215.
20 Ibid.
661
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medium, and high annual waste generation rate of 0 metric tons/yr, 100 metric tons/yr, and 200 metric tons/yr.
respectively. We used best engineering judgment to determine that this waste may exhibit the characteristics of
toxicity (lead) and corrosivity.
D. Non-unlquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
662
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BIBLIOGRAPHY
Carlin, J. "Tin." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1994, pp. 182-183.
Carr, D., ed. Industrial Minerals and Rocks. Society for Mining, Metallurgy, and Exploration, Inc. 1994. p. 672.
Mishra, B., D. Olson, and W. Averill. "Applications of Molten Salts in Reactive Metals Processing." Presented at
the Conference for Emerging Separation Technologies for Metals and Fuels, Palm Coast, FL, March 13-18,
1993. Sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
Randol Mining Directory 1994/95. 1992. p. 189.
"Tin and Tin Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rded. Vol. XXIII. 1983, pp. 18,23.
U.S. Bureau of Mines. Mineral Facts and Problems. Bulletin 675. 1985. p. 850.
U.S. Environmental Protection Agency. "Tin." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-211 - 3-216.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
663
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Page Intentionally Blank
664
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TITANIUM
A. Commodity Summary
Titanium (Ti) metal is known for its high strength-to-weight ratio and corrosion resistance. Titanium metal
is alloyed with aluminum and vanadium, among other metals, for use in aircraft and spacecraft; in 1994, about 70
percent of titanium metal produced was used in jet engines, airframes, and space and missile applications.1
Titanium metal is also employed in the chemical, power generation, marine, ordnance, and medical industries.
Titanium is also used in ceramics, coatings for welding rods, heavy aggregate, and steel furnace flux. The major use
of titanium, however, is as a white pigment for paints, rubber, paper, and plastics.2 Titanium tetrachloride, an
intermediate in TiO, production, is also sold for use in the production of titanium metal.
Ilmenite (FeTiO3) is the most abundant titanium-bearing mineral and is comprised of about 43 percent to 65
percent titanium dioxide (TiO2), A second major mineral form of titanium is rutile, a crystalline, high-temperature
polymorph of TiO2, containing about 95 percent TiO,. Another crystalline form of TiO2, anatase, is not
commercially available at present, but deposits of anatase-bearing ore are being developed in Brazil.3 Titanium
minerals are found in hard rock deposits in New York, Virginia, North Carolina, Arkansas, Wyoming, and
California, and in beach and alluvial sands ("black sands") in the Atlantic and Gulf Coastal Plain geologic provinces
in the southeast and southern U.S." Other sources of titanium include titaniferous slags (70-85 percent TiO2) made
by electric furnace smelting of ilmenite with carbon.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Titanium dioxide pigment is manufactured through either the sulfate, chloride, sulfate-chloride, or chloride-
ilmenite process. The sulfate process, used at two U.S. plants, employs digestion of ilmenite ore or TiO3-rich slag
with sulfuric acid to produce a cake, which is purified and calcined to produce TiO2 pigment. The sulfate process
generates sulfuric acid wastes in as much as two times the product weight, requiring treatment by neutralization
before disposal of the wastes. In the more common chloride process, rutile, synthetic rutile, or high-purity ilmenite is
chlorinated to form titanium tetrachloride, which is then purified to form TiO2 pigment. The sulfate-chloride
process, used by one facility, employs both the sulfate and chloride processes to manufacture TiO, pigment. In the
sulfate phase of the sulfate-chloride process, TiO2 rich slag is digested with sulfuric acid to produce a porous cake,
which is purified and calcined to produce TiO, pigment. In the chloride phase, rutile ore is chlorinated to form
titanium tetrachloride, which is then purified to form TiO2 pigment. A fourth process, the chloride-ilmenite process,
is similar to the chloride process, but a low-purity ilmenite is converted to titanium tetrachloride in a two-stage
chlorination process. This proprietary process is conducted exclusively by Du Pont at its Edgemoor, DE and New
Johnsonville, TN plants and at its DeLisle plant in Pass Christian, MS. Exhibit 1 presents active U.S. titanium
dioxide production facilities and the processes and ores utilized at each.
Titanium sponge, which is cast into ingots for further processing into titanium metal, is produced by
purifying titanium tetrachloride generated by the chloride process. Exhibit 2 presents the active U.S. titanium
sponge and ingot production facilities.
1 J. Gambogi, "Titanium and Titanium Dioxide," from Mineral Commodity Summaries. U.S. Bureau of Mines,
January 1995, p. 180,
2 J. Gambogi, Annual Report: Titanium-1992. U.S. Bureau of Mines, December 1993, p. 1.
3 J. Gambogi, 1993, Op. Cit., p. 1.
4 U.S. Environmental Protection Agency, "Titanium," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988. p. 3-217.
665
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EXHIBIT 1
U.S. TITANIUM DIOXIDE PRODUCTION FACILITIES"
Facility Name
E.I. Du Pont de Nemours & Co., Inc.
(Du Pont)
Du Pont
Du Pont
Du Pont
Kemira, Inc.
Kerr-McGee Chemical Corp.
Kronos, Inc.
SCM Chemicals, Inc.
SCM Chemicals, Inc.
Location
Antioch. CA
Edgemoor, DE
New Johnsonville, TN
Pass Christian, MS
Savannah, GA
Hamilton, MS
Lake Charles, LA
Ashtabula, OH
Baltimore, MD
Process
Chloride
Chloride-Ilmenite
Chloride-Ilmenite
Chloride-Ilmenite
Sulfate-Chloride
Chloride
Chloride
Chloride
Chloride
Sulfate
Ore Type.
Rutile
Ilmenite
Ilmenite
Ilmenite
Slag/Rutile
Synthetic Rutile
Unknown
Rutile
S. African Slag
Rutile
S. African Slag
• J. Gambogi, 1993, Op. Cit.. p. 13.
2. Generalized Process Flow Diagram
Sulfate Process
In the sulfate process, which is presented in Exhibit 3, ilmenite ore or slag with high TiO2 content is
digested with sulfuric acid, forming a porous cake; this cake is further dissolved by dilute acid to form titanyl sulfate
(TiOSO4). Scrap iron is added to the digestion process to ensure that iron impurities remain in the ferrous (Fe2+)
state so that the eventual TiO2 product can be easily washed. The titanyl sulfate solution is then clarified, yielding
what was formerly characterized as a waste sludge, and then concentrated through vacuum evaporation, which
promotes crystallization of copperas (ferrous sulfate heptahydrate, FeSO4-7H2O) to remove iron. (If low-iron, high-
TiO2 slag is used as feed, it is not necessary to crystallize copperas.) Copperas by-product is separated by filtration,
which also removes a second material formerly characterized as a waste sludge. The filtered titanyl sulfate solution
is vacuum-evaporated a second time and hydrolyzed at 90° C to precipitate hydrated titania (TiO(OH)2). The titania
hydrate is then filtered and washed, yielding filtrate waste and wastewater, respectively, before being calcined at
1,000° C to produce TiO2 product.5
Chloride Process
In the chloride process, presented in Exhibit 4, rutile or high-grade ilmenite is converted to titanium
tetrachloride (TiCl4). The conversion takes place in a chlorinator (e.g., fluidized bed reactor) in the presence of
' U.S. Environmental Protection Agency, 1988,
riL, pp. 3-221 - 3-222.
666
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EXHIBIT 2
U.S. TITANIUM SPONGE AND INGOT PRODUCTION FACILITIES"
Facility Name
Howrnet Corp., Titanium Ingot Div,
A, Johnson Metals Corp,
Lawrence Aviation Industries, Inc.
Oregon Metallurgical Corp. (Oremet)
RMICo.
Teledyne Allvac
Teledyne Wan Chang Albany
Titanium Hearth Technologies of America
Titanium Metals Corp. of America (Timet)
Viking Metallurgical Corp.
Wyman-Gordon Co.
Location
Whitehall, MI
Lionville, PA
Port Jefferson, NY
Albany, OR
Niles, OH
Monroe, NC
Albany, OR
Lionville, PA
Henderson, NV
Verdi, NV
Worcester, MA
Product
Ingot
Ingot
Ingot
Sponge & Ingot
Ingot
Ingot
Ingot
Ingot
Sponge & Ingot
Ingot
Ingot
J. Gambogi, 1993, Op. Cit.. p. 11.
chlorine gas at 850° C to 950° C, with petroleum coke added as a reductant. All U.S. producers of TiCL, use fluid-
bed chlorinators; static-bed systems also can be used.6 The volatile metal chlorides, including TiCl4, are collected,
and the non-volatile chlorides and the unreacted solids that remain in the chlorinator are wasted, forming the special
waste stream "chloride process waste solids."7 The gaseous product stream is purified to separate the titanium
tetrachloride from other chlorides. Separation is by fractional condensation, double distillation, and chemical
treatment. Ferric chloride (FeCl3) is removed as an acidic liquid waste stream through fractional condensation.
Additional trace metal chlorides are removed through double distillation. Finally, vanadium oxychloride (VOC13),
which has a boiling point close to that of TiCl4 (136° C), is removed as a low-volume non-special waste by
complexing with mineral oil and reducing with hydrogen sulfide to VOC12, or by complexing with copper (not shown
in Exhibit 4). The purified TiCl4 is then oxidized to TiO, at 985 ° C, driving off chlorine gas, which is recycled to
the chlorinator. Aluminum chloride is added in the oxidation step to promote formation of the rutile crystal, which is
the TiO2 product.8
6 J. Gambogi, 1993, Op. Cit.. p. 3.
7 U.S. Environmental Protection Agency, "Titanium Tetrachloride Production," from Report to Congress on
Special Wastes from Mineral Processing. Vol. II, Office of Solid Waste, July 1990, p. 13-3.
8 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-222.
667
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EXHIBIT 3
SULFATE PROCESS FOR TITANIUM DIOXIDE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-221.)
illmenite Ore or
High TiO2 Slag
12S04 +
Scrap ^•
Iron
Extraction
1 TiOS04
Clarification
1
Sludge
Vacuum Evaporation
and Crystallization
Filtration
FeSO4.7H2O
(Copperas)
Vacuum Evaporation
& Heating 90 ° C
TiO(OH)2
(Titania Hydrate)
Filter
Washing
Filtrate
Waste
Wastewater
Calcining
TiO2 Product
668
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EXHIBIT 4
CHLORIDE PROCESS FOR TITANIUM DIOXIDE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-223.)
I Rutile or High Grade/
Processed Ilmenite
Petroleum Coke ^
Fluid Bed
Chlorinator
Non-reacted Solids
^ to waste
TiCl4 & Other
y Metal Chlorides
Fractional
Condensation
^> FeCl3 to Waste
TiCl4 & Trace
y Impurities
Mineral Oil ^
a,
Double
Distillation
1
Chemical
Treatment
1
Oxidation
at 985 ° C
^_ Trace Metal
Chlorides
*> VOC12
•^ Aluminum Chloride
TiO2 Product
669
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Sulfate-Chloride Process
The sulfate-chloride processes uses both the sulfate and chloride processes. Kemira, located in Savannah,
Georgia, is the only facility known to use this combined process to manufacture TiO2 pigment. In the sulfate
process, TiO2rich slag is digested with sulfuric acid to produce a porous cake, which is purified and calcined to
produce TiO2pigment. In the facility's chloride process, rutile ore is chlorinated to form titanium tetrachloride,
which is then purified to form TiO2 pigment. As part of the sulfate process, the facility transports the weak acid
wastewater from the manufacturing process in above ground pipes to an on-site elementary neutralization unit for
neutralization. The wastewater is discharged via an NPDES-permitted outfall to the Savannah River; the remaining
non-hazardous solids are then sold as a product. Other wastewater generated by Kemira is treated in an in-plant
neutralization system, and pumped through a series of ponds and then discharged to an NPDES-permitted outfall.
Chloride-Ilmenite Process
In the chloride-ilmenite process, presented in Exhibit 5, low-grade ilmenite (approximately 65 percent
TiO2) is converted to TiCl4. The ilmenite ore used in the process contains a much larger amount of iron than the
other ores (i.e., rutile or high-grade ilmenite) used to produce TiCl4. As in the chloride process, the chloride-ilmenite
process takes place in a chlorinator in which the ore is chlorinated in the presence of coke as a reducing agent.
According to Du Pont, however, the process differs from the chloride process in that it is a two-step reaction
sequence referred to as "selective chlorination." Both of these steps occur in the chlorinator. In the first step,
ilmenite ore is reacted with the chlorine gas and coke. Within seconds, the chlorine reacts with the iron oxide in the
ilmenite ore, producing gaseous iron chlorides that are subsequently condensed in a spray condenser to form iron
chloride waste acids, which are either sold as product or disposed as part of the waste stream "titanium tetrachloride
waste acids." This step reportedly yields enriched ilmenite ore consisting of more than 95 percent TiO2 and having
the same basic particle structure as the original ilmenite ore feed.9 In the second (or processing) step of the
simultaneous beneficiation-chlorination process, the beneficiated ore, which remains in the chlorinator, is converted
to gaseous TiCl4 over a period of several hours. The TiCl4 is further refined to remove contaminants, which are
combined with the iron chloride waste stream.10 The process for converting TiCl4 to TiO2 is similar to that used in
the chloride process, as described above.
Titanium Sponge (Kroll Process)
The production of titanium sponge by the Kroll process, as shown in Exhibit 6, requires the same feed
materials as does the chloride process for pigment production, because both require TiCl4. TiCl4 used for sponge
production is made in the same manner as that for pigment production; however, because TiCl4 needed for metal
production must have high purity, more effort is expended to remove impurities, particularly oxygen and carbon
compounds.11 Rutile and rutile substitutes are the only titanium feed materials used for sponge production,12
presumably because they offer a more pure source of titanium than ilmenite.
9 Memorandum from D. Derkics, U.S. Environmental Protection Agency, Office of Solid Waste and Emergency
Response, "Notes of the October 24, 1989 Meeting with Representatives of E.I. DuPont de Nemours & Company,"
submitted to Mining Waste Docket No. F-89-MW2P-FFFFF, 1989, p. 2.
10 Letter from C. Goldstein, Covington & Burling, Washington, D.C., to Randolph L. Hill, U.S. Environmental
Protection Agency, Office of General Counsel, November 16, 1990, p. 2.
11 "Titanium and Titanium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXIII,
1981,p. 114.
12 J. Gambogi, 1993, Op. Cit. p. 4.
670
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CD
"-J
EXHIBIT 5
CHLORIDE-ILMENITE PROCESS SCHEMATIC - DELISLE PLANT
(Adapted from: U.S. EPA National Survey of Solid Wastes from mineral Processing Facilities: Questionnaire # 102013,1989.)
I Ore
TiCL
Ti
-------
EXHIBIT 6
KROLL PROCESS FOR TITANIUM SPONGE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-223.)
HNO3orHCL
Waste
Sponge
Removal
Acid
Leach
Drying
Crushing
Screening
i
•no,
Reduction
Reactor
MgCl2
Electrolysis
Mg
MgCL
Vacuum
Distillation
Sponge
Removal
Sponge in
23kg
Drums
1
672
-------
The Kroll process, based on the use of liquid magnesium as a reductant in an argon or helium atmosphere,
is the major commercial process for producing titanium sponge. (The Hunter process, which relies on sodium as the
reductant, is another sponge production process.) TiCl4 and liquid magnesium are combined in a reduction reactor at
900° C to form molten magnesium chloride (MgCl2), which is tapped from the bottom of the reactor. The MgCl: is
reduced by electrolysis to form magnesium metal (which is recycled to the reactor) and chlorine gas. The product.
called sponge because of its appearance and high porosity, is processed further to remove residual magnesium,
MgClj, and unreacted TiQ4, which can comprise as much as 30% by weight.13 (Prior to purification, the sponge is
crushed to improve purification.) Two methods are commonly used. Nitric acid (HNO3) or hydrochloric acid (HC1)
is used to acid leach the sponge, creating an acidic liquid waste, known as leach liquor, containing the impurities
(primarily MgCl2), while vacuum distillation at 960-1,020° C separates the sponge from a MgCl, stream that can be
recycled to the electrolysis step and used in the reduction reactor.14 Sponge can also be purified using an inert
(argon) gas sweep at 1,000° C.15J6 After drying, crushing, and screening, the sponge is packaged in air-tight 23-kg
drums before further processing into ingots. Sponge also can be crushed to create titanium powder.
Titanium Ingot
Titanium ingots are formed from sponge using two or more successive vacuum-arc melting operations.17
Scrap titanium metal or alloys can be added. Ingots can be milled by conventional methods of forging, hot- and
cold-rolling, and extrusion.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
The U.S. Bureau of Mines has studied new processes to produce titanium alloys, with a focus on
developing a continuous process to produce titanium powder for metallurgical applications. The Bureau also has
researched methods to improve present methods of batch-type reduction, arc melting, and fabrication of titanium
alloys.18
4, Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
13 "Titanium and Titanium Alloys," 1981, Op. Cit., p. 116.
14 U.S. Environmental Protection Agency, 1988, Op. Cit. pp. 3-224 - 3-225.
15 J. Gambogi, 1993, Op. Cit.. p. 4.
16 "Titanium and Titanium Alloys," 1981. Op, Cit.. p. 116.
17 J. Gambogi, 1993, Op. Cit. p. 4.
18 J. Gambogi, 1993, Op. Cit.. p. 8.
673
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ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes,
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
just before the acid digestion step in the sulfate process (identified as the "extraction" step in Exhibit 3). EPA
identified this point in the process sequence as where beneficiation ends and mineral processing begins because this
is where TiO2 in the ore undergoes a significant chemical change through conversion by H2SO4 to TiOSO,. In both
die chloride and chloride-ilmenite processes, die beneficiation/processing line occurs just before die chlorination
step. Similarly, beneficiation ends and mineral processing begins at diis point because TiO2 is chemically converted
to TiO4 through reaction with chlorine. Therefore, because EPA has determined that all operations following the
initial "processing" step in the production sequence are also considered processing operations, irrespective of
whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from any such
operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather than
beneficiation wastes. EPA presents below the mineral processing waste streams generated after the beneficiation/
processing line, along with associated information on waste generation rates, characteristics, and management
practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Hard rock deposits of ilmenite and rutile are mined in open pits; mined ore is crushed, ground, classified,
magnetically separated, and floated to recover ore values. The major wastes from these operations are tailings from
separators and flotation cells and, based on EPA data, these wastes are not expected to exhibit hazardous
characteristics. Beach/alluvial sands containing ilmenite and rutile are excavated by dragline, front-end loader, or
suction dredging; the sands are spiral concentrated to remove low density tailings. The sands are then dried and
separated electrostatically to remove quartz and odier nonconducting minerals, which are processed to produce
zircon and monazite product and wastes consisting of quartz and epidote minerals. Conducting materials are
magnetically separated to sort ilmenite from rutile, followed by screening and cleaning. No wastes from beach sand
processing are expected to exhibit hazardous characteristics.19
2. Mineral Processing Wastes
The sulfate process for producing titanium dioxide yields two mineral processing wastes, waste solids and
waste acids. These wastes are described below.
Sulfate Process Waste Solids
Waste solids are generated at two points in the sulfate process. The first point occurs when titanyl sulfate
(TiOSO4), which is generated by digesting ilmenite or slag with sulfuric acid, is clarified. This material (formerly
characterized as a waste sludge) also is generated when copperas by-product (FeSO4'7H2O) is separated from the
solution containing titanyl sulfate after the solution is concentrated through vacuum evaporation. This waste stream
was removed from the Mining Waste Exclusion because it is generated in volumes less than the high volume
criterion of 45,000 metric tons per facility annually, (Volume data are unavailable for this waste stream due to
19 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-219.
674
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confidential business information [CBI] designation.) The waste did pass the low hazard criterion for special waste
status,20
Sulfate Process Waste Acids
Waste acids are generated when titania hydrate, generated by vacuum-evaporation and hydrolysis of titania
sulfate, is filtered prior to washing. The operator of the Kemira. Inc. facility in Savannah, GA, treats this waste acid
filtrate (which has a field pH of 0.5) with lime in its waste acid neutralization plant and discharges the treated
effluent through an NPDES outfall to the Savannah River.21 We used the methodology outlined in Appendix A of
this report to estimate a low, medium, and high annual waste generation rate of 200 metric tons/yr, 39,000 metric
tons/yr, and 77,000 metric tons/yr, respectively. This waste stream was removed from the Mining Waste Exclusion
because it failed the low hazard criterion for chromium and pH (i.e., it exhibits the characteristics of toxicity and
corrosivity).22 Additional data (Attachment 1) also suggest that this waste stream exhibits the toxicity characteristic
for arsenic, chromium, selenium, and silver.
The chloride process and chloride-ilmenite process for manufacturing TiCl4 each generate two primary
mineral processing wastes, waste acids and waste solids. Waste acids and solids are recovered from the fluid-bed
chlorinator as a slurry and separated; descriptions of the separated acids and solids are provided below. Several
other waste streams are generated in the treatment and disposal of these wastes, including wastewater treatment
effluent and solids, which are commonly discharged to on-site surface impoundments prior to the effluent being
discharged through an NPDES outfall and the solids being disposed in a landfill. In addition, the chloride and
chloride-ilmenite processes generate several other waste streams, including ferric chloride and ferric chloride sludge.
scrubber water and solids, and vanadium oxychloride,
Chloride and Chloride-ilmenite Process Waste Acid and Solids
Waste acids and solids from the chloride and the chloride-ilmenite processes are generated in the
ehlorination step as a combined acids/solids slurry. The combined waste acids and solids are treated by a
solids/liquids separation process, and the resulting chloride process waste solids (a mineral processing special waste)
are landfilled, while the chloride process waste acids are deep-well injected at some plants. Approximately 49,000
metric tons of waste acids and 414,000 metric tons of waste solids are generated annually.23 We used best
engineering judgment to determine that this waste may be partially recycled and may exhibit the characteristics of
toxicity (chromium, selenium, and lead) and corrosivity. This waste was formerly characterized as a spent material.
Data for this waste stream are presented in Attachment 1.
Waste Ferric Chloride and Ferric Chloride Treatment Sludge
Waste ferric chloride is generated in both the chloride and the chloride-ilmenite processes when gaseous
titanium tetrachloride is separated from other chlorides. Ferric chloride is removed as an acidic, liquid waste stream
through fractional condensation and treated with lime and either landfilled or sold as a by-product. Although EPA
found no published information regarding waste generation rate or characteristics, we used the methodology outlined
in Appendix A of this report to estimate a low, medium, and high annual waste generation rate for waste ferric
chloride of 22,000 metric tons/yr, 29,000 metric tons/yr, and 35,000 metric tons/yr, respectively. We used best
engineering judgment to determine that waste ferric chloride may exhibit the characteristic of corrosivity and the
characteristic of toxicity for cadmium, chromium, lead, and silver. This waste is fully recycled and was formerly
20 55 FR 2341-2342.
21ICF Incorporated, Kemira. Inc.: Mineral Processing Waste Sampling Visit — Trip Report. September 1989, p.
3.
22 55 FR 2342.
23 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, August 1992, p. 1-7.
675
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classified as a by-product. Data for this waste stream are presented in Attachment 1. For ferric chloride treatment
sludge, we estimated that the medium annual waste generation rate would be 75 percent of that for waste ferric
chloride, with the high and low rates ±20 percent of the medium rate. Therefore, we estimated a low, medium, and
high annual waste generation rate for ferric chloride treatment sludge of 18,000 metric tons/yr, 22,000 metric tons/yr,
and 26,000 metric tons/yr, respectively. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Two scrubber water waste streams are generated in the chloride process, as described below. Data
describing these waste stream are presented in Attachment 1.
Chlorination Off-gas Scrubber Water
Chlorination off-gas scrubber water is generated by the scrubbing of off-gases created in the condensation
of the reaction gas produced in the Chlorination step. Off-gases are cleaned in water wash towers and then passed
through a caustic tower and a Venturi scrubber. After leaving the scrubber, the gas stream is either released to the
atmosphere, or passed through three additional scrubbers for further cleansing.24 We used the methodology outlined
in Appendix A of this report to estimate a low, medium, and high annual waste generation rate for Chlorination off-
gas scrubber water of 1.2 million metric tons/yr, 1.5 million metric tons/yr, and 1.8 million metric tons/yr,
respectively. (The excessive generation rate for this wastewater [i.e., greater than one million metric tons/yr] is due
to commingling of numerous individual waste streams.) We used best engineering judgment to determine that
chlorination off-gas scrubber water may exhibit the characteristics of corrosivity and toxicity for chromium,
Chlorination Area-Vent Scrubber Water
Chlorination area-vent scrubber water is generated by the scrubbing of cleaned gas from the chlorination
off-gas scrubbers (described above) and ventilation vapors from TiCl4 purification operations. This scrubber system,
like that for chlorination off-gases, consists of a wash water tower and a Venturi scrubber operated in series. After
leaving this scrubber system, the cleaned gases are vented to the atmosphere.25 We used the methodology outlined in
Appendix A of this report to estimate a low, medium, and high annual waste generation rate for chlorination area-
vent scrubber water of 150,000 metric tons/yr, 180,000 metric tons/yr, and 220,000 metric tons/yr, respectively. We
used best engineering judgment to determine that chlorination area-vent scrubber water may exhibit the
characteristics of corrosivity and toxicity for chromium.
Spent Vanadium Oxychloride
Vanadium chloride is removed from the gaseous product stream containing TiCl4 by complexing with
mineral oil and reducing to vanadium oxychloride (VOC12), a low-volume non-special mineral processing waste,
with hydrogen sulfide, or by complexing with copper. Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 100 metric tons/yr, 22,000 metric tons/yr, and
45,000 metric tons/yr, respectively. Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Wastewater Treatment Plant Liquid Effluent
Wastewater treatment plant liquid effluent, a post-mineral processing waste, consists of treated wastewaters
such as contact cooling water and/or liquid wastes from the chlorination step (i.e., waste acids) and the TiCl4
24 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Volume IX: Primary and Secondary
Titanium. Primary Zirconium and Hafnium, EPA 440/1-89-019.9, Office of Water Regulations and Standards, May
1989, p. 4861.
25 Ibid,
676
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purification, oxidation, or finishing steps. Effluent is sent to a surface impoundment for settling of solids before
discharge through an NPDES outfall. Although no published information regarding waste generation rate or
characteristics was found, we used the methodology outlined in Appendix A of this report to estimate a low, medium,
and high annual waste generation rate of 900 metric tons/yr, 140 million metric tons/yr, and 270 million metric
tons/yr, respectively. (The excessive generation rate for this wastewater [i.e., greater than one million metric tons/yr]
is due to commingling of numerous waste streams.) Existing data (Attachment 1) and engineering judgment suggest
that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
this material further.
Wastewater Treatment Plant Sludge/Solids
Wastewater treatment plant sludge/solids, also a post-mineral processing waste, consists of what was
formerly characterized as sludges and solids resulting from the treatment of the wastewaters described above. These
materials are disposed in on- or off-site landfills. Approximately 420,000 metric tons are generated annually.26 We
used best engineering judgment to determine that this waste may exhibit the characteristics of toxicity (chromium).
Data describing this waste stream are presented in Attachment 1.
Spent Surface Impoundment Liquids
Surface impoundment liquids consist of various waste streams, such as chloride process waste acids and
solids in slurry form and wastewater treatment plant effluent. Waste acids managed in surface impoundments are
generally routed to a solids/liquids separation process and then disposed by deep-well injection. Treated effluent is
discharged through NPDES outfalls after solids have settled. This waste stream is considered post-mineral
processing. Although no published information regarding waste generation rate or characteristics was found, we
used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate of 630 metric tons/yr, 3,400 metric tons/yr, and 6,700 metric tons/yr, respectively. We used best
engineering judgment to determine that this waste may be recycled and may exhibit the characteristics of toxicity
(chromium and lead). This waste was formerly characterized as a spent material. Data describing this waste stream
are presented in Attachment 1.
Spent Surface Impoundment Solids
Surface impoundment solids settle out of liquid and slurry waste streams, such as chloride process waste
acids and solids in slurry form and wastewater treatment plant effluent, that are managed in surface impoundments.
Surface impoundment solids may be dredged from the impoundment and moved to on- or off-site solids landfills.
This waste stream is considered post-mineral processing; approximately 36,000 metric tons are generated annually,27
We used best engineering judgment to determine that this waste may exhibit the characteristic of toxicity (chromium
and lead). Data describing this waste stream are presented in Attachment 1.
The Kroll process for manufacturing titanium sponge from TiCl4 generates seven waste streams, one of
which is a mineral processing waste and the others, post-mineral processing wastes.
TiCl4 Purification Effluent
TiCl4 purification effluent, classified as a mineral processing waste, is generated in preparing TiCl4 for the
Kroll process. We used the methodology outlined in Appendix A of this report to estimate a low, medium, and high
annual waste generation rate of 26,000 metric tons/yr, 33,000 metric tons/yr, and 39,000 metric tons/yr, respectively.
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous
waste. Therefore, the Agency did not evaluate this material further.
~6 U.S. Environmental Protection Agency, 1992, Op. Cit. p. 1-7.
27 Ibid.
677
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Reduction Area Scrubber Water
Reduction area scrubber water is generated by the scrubbing of vapors released during magnesium
reduction of TiCl4 in the reduction vessel. The vapors are cleansed in the reduction area scrubber and released to the
atmosphere, while the resulting scrubber water is treated in the facility wastewater treatment plant.28 We used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
for reduction area scrubber water of 870,000 metric tons/yr, 1.1 million metric tons/yr, and 1.3 million metric
tons/yr, respectively. (The excessive generation rate for this wastewater [i.e., greater than one million metric tons/yr]
is due to commingling of numerous waste streams.) Existing data and engineering judgment suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Melt Cell Scrubber Water
If the reduction process is conducted rapidly, excess MgCl2 can be generated and is collected in a melt cell
before it is recovered through electrolysis. The molten MgCl2 generates vapors that are cleaned by wet scrubbers.
which generates melt cell scrubber water containing low concentrations of toxic metals and acidity.29 We used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
for melt cell scrubber water of 230,000 metric tons/yr, 280,000 metric tons/yr, and 340,000 metric tons/yr,
respectively. Existing data and engineering judgment suggest that this material does not exhibit any characteristics
of hazardous waste. Therefore, the Agency did not evaluate this material further.
Chlorine Liquefaction Scrubber Water
Chlorine liquefaction scrubber water is created by the scrubbing of chlorine gas generated in the electrolytic
reduction of MgCl2. The chlorine gas is passed first to bag filters and is then either returned to the reduction process
or liquefied and sold. During liquefaction, air saturated with chlorine escapes and is treated by burning to convert
the chlorine to hydrochloric acid vapor. This vapor is scrubbed with water, creating the scrubber wastewater.30 We
used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate for chlorine liquefaction scrubber water of 1.6 million metric tons/yr, 2 million metric tons/yr, and
2.4 million metric tons/yr, respectively. (The excessive generation rate for this wastewater [i.e., greater than one
million metric tons/yr] is due to commingling of numerous waste streams.) Existing data and engineering judgment
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not
evaluate this material further.
Sodium Reduction Container Reconditioning Wash Water
Sodium reduction container reconditioning wash water is generated in the cleaning the container (retort
vessel) in which TiCl4 is converted to titanium metal through sodium reduction.31 We used the methodology outlined
in Appendix A of this report to estimate a low, medium, and high annual waste generation rate for sodium reduction
container reconditioning wash water of 6,800 metric tons/yr, 8,600 metric tons/yr, and 10,000 metric tons/yr,
respectively. Existing data and engineering judgment suggest that this material does not exhibit any characteristics
of hazardous waste. Therefore, the Agency did not evaluate this material further.
28 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 4862.
29 Ibid.
3"'lbid.
31 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 4863.
678
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Chip Crushing Scrubber Water
Chip crushing scrubber water is generated in the cleaning of dust-laden air released during the crushing of
titanium chips after they are removed from the reduction container.32 We used the methodology outlined in
Appendix A of this report to estimate a low, medium, and high annual waste generation rate for chip crushing
scrubber water of 260,000 metric tons/yr, 320,000 metric tons/yr, and 390,000 metric tons/yr, respectively. Existing
data and engineering judgment suggest that this material does not exhibit any characteristics of hazardous waste.
Therefore, the Agency did not evaluate this material further.
Leach Liquor and Sponge Wash Water
Leach liquor, a post-mineral processing waste, is generated in the acid leaching of titanium sponge to
remove impurities consisting of MgCl, and unreacted TiCl4. At Timet in Henderson, NV, leach liquor is held in a
polyvinyl chloride-lined pond, neutralized with lime in a concrete mixing tank, and concentrated in a series of solar
evaporation ponds. The resulting solution, close to saturation with magnesium chloride, is sold for use as a dust
suppressant on unpaved roads.33 We used the methodology outlined in Appendix A of this report to estimate a low,
medium, and high annual waste generation rate for leach liquor and sponge wash water of 380,000 metric tons/yr,
480,000 metric tons/yr, and 580,000 metric tons/yr, respectively. We used best engineering judgment to determine
that this waste may be partially recycled and may exhibit the characteristics of corrosivity and toxicity (chromium
and lead). This waste is classified as what was formerly characterized as a spent material. After the sponge is acid-
leached, it is rinsed with water, generating sponge wash water, which may also exhibit the corrosivity characteristic.
Data describing these waste streams are presented in Attachment 1.
Waste Non-Contact Cooling Water
Non-contact cooling water generated in the Kroll process is a post-mineral processing waste. We used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
for waste non-contact cooling water of 100 metric tons/yr, 500,000 metric tons/yr, and 1 million metric tons/yr,
respectively. (The excessive generation rate for this wastewater [i.e., greater than one million metric tons/yr] is due
to commingling of numerous waste streams.) Existing data and engineering judgment suggest that this material does
not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Additional Waste Streams
Two additional waste streams are generated in the Kroll process: smut from magnesium recovery, and
spent brine treatment filter cake. Smut is generated in the recovery of magnesium from the magnesium chloride
solution generated in the reduction process. We used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate for smut from magnesium recovery of 100 metric
tons/yr, 22,000 metric tons/yr, and 45,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may be recycled and may exhibit the characteristic of reactivity with water. This waste was
formerly classified as a by-product. Brine treatment filter cake is created in the solar evaporation of leach liquor.
We used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate for spent brine treatment filter cake of 100 metric tons/yr, 22,000 metric tons/yr, and 45,000 metric
tons/yr, respectively. Existing data (Attachment 1) and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Ibid.
33ICF Incorporated, Timet Corporation: Mineral Processing Waste Sampling Visit — Trip Report. August 1989,
p. 3.
679
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Ingot production generates the following post-mineral processing waste streams:
Pickling Liquor and Wash Water
Three ingot plants use acid pickling to remove surface oxides from massive titanium scrap (plate and sheet
metal) before the scrap is blended with titanium sponge and alloying metals. The pickling liquor is comprised of
hydrochloric, hydrofluoric, and nitric acids; spent pickling liquor and wash water form an acidic wastewater stream.3"
We used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate for pickling liquor and wash water of 2,200 metric tons/yr, 2,700 metric tons/yr, and 3,200 metric
tons/yr, respectively. We used best engineering judgment to determine that this waste may be partially recycled and
may exhibit the characteristics of corrosivity and toxicity for cadmium, chromium, and lead. This waste was
formerly characterized as a spent material. Data describing this waste stream are presented in Attachment 1.
Scrap Detergent Wash Water
Titanium scrap chips and millings are washed with a detergent solution before alloying to remove oil and
dirt, creating an oily, caustic wastewater stream.35 We used the methodology outlined in Appendix A of this report
to estimate a low, medium, and high annual waste generation rate for scrap detergent wash water of 360,000 metric
tons/yr, 450,000 metric tons/yr, and 540,000 metric tons/yr, respectively. We used best engineering judgment to
determine that this waste may be partially recycled and may exhibit the characteristic of toxicity for cadmium,
chromium, selenium, and lead; and the characteristic of corrosivity.
Scrap Milling Scrubber Water
Before alloying, titanium scrap chips and millings are also crushed. A dust scrubber cleans dust-laden air
from this operation, generating scrubber water containing oil and grease, suspended solids, and metals.36 We used
the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation
rate for scrap milling scrubber water of 4,000 metric tons/yr, 5,000 metric tons/yr, and 6,000 metric tons/yr,
respectively. We used best engineering judgment to determine that this waste may be partially recycled and may
exhibit the characteristic of toxicity for cadmium, chromium, selenium, and lead.
Casting Crucible Contact Cooling Water and Wash Water
At one ingot plant, water is used to cool the casting equipment, generating a wastewater containing oil and
grease, metals, and solids. This cooling water is treated through lime precipitation and sedimentation. We used the
methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate
for casting crucible contact cooling water of 190,000 metric tons/yr, 240,000 metric tons/yr, and 290,000 metric
tons/yr, respectively. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further. Casting crucibles
are washed following casting, generating oily wastewater, which is treated by oil skimming, lime precipitation, and
sedimentation.37 We used the methodology outlined in Appendix A of this report to estimate a low, medium, and
high annual waste generation rate for casting crucible wash water of 4,000 metric tons/yr, 5,000 metric tons/yr, and
6,000 metric tons/yr, respectively. Existing data and engineering judgment suggest that this material does not exhibit
any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
34 U.S. Environmental Protection Agency, 1989, Op. Cit, pp. 4843,4864,4945.
35 Ibid.
36 Ibid.
37 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 4946.
680
-------
Finishing Scrap
Finishing scrap is generated in the melting or milling operations used to convert titanium sponge into ingots.
Scrap is generally recycled back into the melting or milling operation and is not regarded as a solid waste.38 We
used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate for finishing scrap of 100 metric tons/yr, 22,000 metric tons/yr, and 45,000 metric tons/yr,
respectively. Existing data and engineering judgment suggest that this material does not exhibit any characteristics
of hazardous waste. Therefore, the Agency did not evaluate this material further.
D. Non-uniquely Associated Wastes
Ancillary hazardous wastes may be generated at on-site laboratories, and may include used chemicals and
liquid samples (e.g., hydrofluoric acid at titanium sponge facilities). Other hazardous wastes may include spent
solvents (e.g., petroleum naptha), and acidic tank cleaning wastes. Non-hazardous wastes may include tires from
trucks and large machinery, sanitary sewage, and waste oil and other lubricants.
E. Summary of Comments Received by EPA
Three commenters submitted comments on the titanium sector report.
New Factual Information
One commenter provided new factual information about its titanium dioxide pigment manufacturing facility
in Savannah, GA that uses the sulfate-chloride process (COMM 49). This information has been included in the
sector report.
Sector-specific Issues
Two commenters addressed the extraction/beneficiation boundary. One commenter agreed with the
Agency's conclusion that iron chloride waste acid from the production of titanium tetrachloride by the chloride
ilmenite process is a mineral processing waste not eligible for the Bevill Exemption (COMM 22). Another
commenter disagreed with the Agency's position that chlorination constitutes beneficiation only when it is used in
preparation for a leaching operation that does not produce a final or intermediate product that does not undergo
further beneficiation or processing (COMM 18). This issue is more fully discussed in the Agency's technical
background document on titanium thresholds.
Ibid.
fifil
-------
BIBLIOGRAPHY
Derkics. D. "Notes of the October 24, 1989 Meeting with Representatives of E.I. DuPont de Nemours & Company."
U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response. Memorandum
submitted to Mining Waste Docket No. F-89-MW2P-FFFFF. 1989. 5 pp.
Gambogi, J. Annual Report: Titanium-1992. U.S. Bureau of Mines. December 1993.
Gambogi, J. "Titanium and Titanium Dioxide." From Mineral Commodity Summaries. U.S. Bureau of Mines.
January 1994. pp. 184-185.
Goldstein, C. Letter to Randolph L. Hill, U.S. Environmental Protection Agency, Office of General Counsel, from
C. Goldstein, Covington & Burling, Washington, D.C. November 16, 1990. 7 pp.
ICF Incorporated. Timet Corporation: Mineral Processing Waste Sampling Visit — Trip Report. August 1989.
ICF Incorporated. Kernira. Inc.: Mineral Processing Waste Sampling Visit — Trip Report. September 1989.
Timet Corporation. RCRA Part B Permit Application. August 1983.
"Titanium and Titanium Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXIII. 1981.
pp. 114.
U.S. Environmental Protection Agency. "Titanium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-217 -3-227.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Volume IX: Primary and Secondary
Titanium. Primary Zirconium and Hafnium. EPA 440/1-89-019.9. Office of Water Regulations and
Standards. May 1989.
U.S. Environmental Protection Agency. National Survey of Solid Wastes from Mineral Processing Facilities:
Questionnaire. Questionnaire Number 102013 submitted by E.I. Du Pont de Nemours, Inc., DeLisle Plant,
Pass Christian, MS. December 1989.
U.S. Environmental Protection Agency. "Titanium Tetrachloride Production." From Report to Congress on Special
Wastes from Mineral Processing. Vol.11. Office of Solid Waste. July 1990. pp. 13-1 - 13-31.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
682
-------
ATTACHMENT 1
683
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PICKLE LIQUOR AND WASH WATER FROM INGOT PRODUCTION - TITANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0.027
0.06
-
0.0002
-
0.19
0.21
-
0.54
-
2.6
-
-
0.0002
-
1.3
0.009
0.0014
1.7
-
0.43
0.01
-
-
-
-
'
-
-
-
-
-
0.579
0.3167
-
0.0011
-
0.227
0.26
-
0.94
-
3.17
-
-
0.0011
-
1.83
0.14
0.50
2.83
-
0.53
3333.67
-
-
-
-
-
-
-
-
-
-
0.88
0.62
-
0.002
-
0.28
0.3
-
1.7
-
4
-
-
0.002
-
2.6
0.22
1.2
3.8
-
0.67
10000
-
-
-
-
-
-
-
-
-
# Detects
0/0
3/3
3/3
0/0
3/3
0/0
3/3
3/3
0/0
a/3
070
373
0/0
0/0
3/3
0/0
3/3
3/3
3/3
3/3
0/0
3/3
3/3
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
-• - o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC
Level
-
-
5.0
100.0
-
-
1.0
5.0
-
-
-
5.0
-
-
0.2
-
-
1.0
5.0
-
-
-
-
-
-
-
-
.
-
-
212
-
# Values
In Excess
-
-
0
0
-
-
0
0
-
-
-
0
-
-
0
-
-
0
0
-
-
-
-
-
-
-
-
-
-
-
0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT BRINE TREATMENT FILTER CAKE - TITANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
iron
^ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
40000 40,000 40,000 1/1
0/0
10.1 10.1 10.1 1/1
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
- ' 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
-
5.0 0
100.0 0
.
.
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
en
oo
ui
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - TITANIUM DIOXIDE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0.01 0.01 0.01 1/1
0/0
0/0
1.10 1.10 1.10 1/1
0.01 0.01 0.01 1/1
0/0
0/0
0/0
0/0
0.02 0.02 0.02 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
160,000 160,000 160,000 1/1
70,000 70,000 70,000 1/1
7 7.15 7.3 2/2
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
- • o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
,
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - TITANIUM DIOXIDE
Constituents
Aluminum
Antimony
Arsenic
Jarium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ron
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
3900
-
-
60
-
-
-
203
20
9
0,2
0.005
100000
200
-
-
13.00
-
-
-
553
-
-
-
-
0.2
-
-
6,100
0.60
4.00
#VALUE!
12,543
-
-
60.00
-
-
-
338
20.00
9.00
67,194
74.60
100,000
1,629
-
-
13.00
-
-
-
553
-
-
-
-
0
-
-
108,773
592
6.25
#VALUE!
16,000
-
-
60.00
-
-
-
524
20.00
9.00
97,000
139
100,000
5,200
-
-
13.00
-
-
-
553
-
-
-
-
0
-
-
200,000
2,000
7.00
#VALUE!
Detects
in
0/0
0/0
2/2
0/0
0/0
0/0
9/9
2/2
2/2
10/10
10/10
1/1
7/7
0/0
0/0
2/2
0/0
0/0
0/0
2/2
0/0
0/0
0/0
0/0
1/1
0/0
0/0
13/13
11/11
4/4
2/2
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5,0 0
-
-
.
5.0 0
-
-
0.2 0
-
-
1,0 0
5.0 0
-
-
-
-
.
-
.
-
-
-
-
212 0
-
01
00
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
. SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - TITANIUM DIOXIDE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum
2,822
-
-
43.00
-
-
-
10.00
20.00
-
17,000
8.00
-
730
-
-
6.00
-
-
-
10.00
62.00
-
-
-
-
290
57,369
1,500
98,000
3.9
19.00
11,502
-
-
138
-
-
-
497
20.00
-
51 ,509
113
-
2,200
-
-
60.75
-
-
-
628
62.00
-
-
-
-
290
57,369
26,175
512,000
5.9
318,755
14,395
-
-
169
-
-
-
887
20.00
-
70,000
167
-
3,700
-
-
79.00
-
-
-
893
62.00
-
-
-
-
290
57,369
100,000
800,000
7.0
425,000
# Detects
4/4
0/0
0/0
4/4
0/0
0/0
0/0
6/6
1/1
0/0
5/5
5/5
0/0
5/5
0/0
0/0
4/4
0/0
0/0
0/0
5/5
1/1
0/0
0/0
0/0
0/0
1/1
3/3
4/4
4/4
7/7
4/4
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
1 00.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - LEACH LIQUOR AND SPONGE WASH WATER - TITANIUM AND TITANIUM DIOXIDE
Constituents
Aluminum
Antimony
Arsenic
3arium
3eryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
2.50
0.07
0.10
2.50
0.00
-
0.16
1.20
2.50
2.50
9.42
1.25
5,000
2.50
0.0002
2,50
2.50
0.01
0.03
2.40
2.50
0.54
0.01
"
-
198
-
-
115
50,000
0
1,670
2.50
1.29
1.30
2.50
0.13
-
0.21
1.85
2.50
2.70
9.42
2.03
25,667
2.50
0.0009
2.50
4.75
1.26
1.27
7.45
2.50
1.52
0.01
-
-
198
-
-
43,023
50,000
0.50
1,670
2.50
2.50
2.50
2.50
0.25
-
0.25
2.50
2.50
2.90
9.42
2.80
40,000
2.50
0.0016
2.50
7.00
2.50
2.50
12.50
2.50
2.50
0.01
-
-
198
-
-
80,000
50,000
1
1,670
Detects
1/1
2/2
2/2
1/1
2/2
0/0
2/2
2/2
1/1
2/2
1/1
2/2
3/3
1/1
2/2
1/1
2/2
2/2
2/2
1/2
1/1
2/2
1/1
0/0
0/0
1/1
0/0
0/0
5/5
1/1
2/2
1/1
EP Toxicity Analysis - PPM
Minimum Average Maximum #
0.05
0.50
0.01
0.50
0.025
-
0.025
0.080
0.050
0.50
0.020
0.010
25,700
0.50
0.00010
0.50
0.17
0.010
0.03
0.55
0.50
0.50
-
-
-
-
-
-
-
•
0.28
0.50
0.26
0.72
0.038
-
0.038
0.29
0.28
1.05
3.29
0.13
43,800
3.24
0.00055
0.50
0.34
0.26
0.26
1.53
1.10
0.52
-
-
-
-
-
-
-
-
0.50
0.50
0.50
0.93
0.050
-
0.050
0,50
0.50
1.60
6.55
0.25
61,900
5.98
0.0010
0.50
0.50
0,50
0.50
2.50
1.70
0.54
-
-
-
-
-
-
-
-
Detects
2/2
2/2
2/2
2/2
2/2
0/0
2/2
2/2
2/2
2/2
2/2
2/2
2/2
2/2
2/2
1/1
2/2
2/2
2/2
2/2
2/2
2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 2
-
00
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SRUBBER WATER - TITANIUM (CHLORIDE PROCESS)
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
0.50
0.50
0.50
0.50
0.15
-
0.050
0.50
0.50
0.50
0.50
0.25
5.87
0.50
0.00010
0.50
0.50
0.50
0.50
2.50
1.51
0.50
-
-
15.40
-
-
-
235,000
3,740
0.5
-
0.50
0.50
0.50
0.50
0.15
-
0.050
0.50
0.50
0.50
0.50
0.25
5.87
0.50
0.00010
0.50
0.50
0.50
0.50
2.50
1.51
0.50
-
-
15.40
-
-
-
235,000
3,740
1.2
-
0.50
0.50
0.50
0.50
0.15
-
0.050
0.50
0.50
0.50
0.50
0.25
5.87
0.50
0.00010
0.50
0.50
0.50
0.50
2.50
1.51
0.50
-
-
15.40
-
-
-
235,000
3,740
1.9
-
Detects
0/1
0/1
0/1
0/1
1/1
0/0
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/1
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/1
0/0
0/0
1/1
0/0
0/0
0/0
1/1
1/1
2/2
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum
0.50
0.50
0.50
0.50
0.10
-
0.050
6.45
0.50
0.50
25.70
0.25
6.56
0.50
0.00028
0.50
2.79
0.50
0.50
2.50
1.82
0.50
-
-
-
-
-
-
-
.
0.50
0.50
0.50
0.50
0.10
-
0.050
6.45
0.50
0.50
25.70
0.25
6.56
0.50
0.00028
0.50
2.79
0.50
0.50
2.50
1.82
0.50
-
-
-
-
-
-
-
-
0.50
0.50
0.50
0.50
0.10
-
0.050
6.45
0.50
0.50
25.70
0.25
6.56
0.50
0.00028
0.50
2.79
0.50
0.50
2.50
1.82
0.50
-
-
-
-
-
-
-
-
# Detects
0/1
0/1
0/1
0/1
1/1
0/0
0/1
1/1
0/1
0/1
1/1
0/1
1/1
0/1
1/1
0/1
1/1
0/1
0/1
0/1
1/1
0/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 1
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 2
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTi SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE/SOLIDS - TITANIUM DIOXIDE
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
ran
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
-
-
-
-
-
-
58
-
-
17000
8
9000
730
-
-
6
-
-
-
600
-
-
-
11000
-
-
40000
1500
98000
7.8
-
-
-
-
-
-
-
-
679
-
-
27,000
8.00
9,000
1,865
-
-
6.00
-
-
-
600
-
-
-
1 1 ,000
-
-
40,000
40,750
98,000
9.4
-
-
-
-
-
-
-
-
1,300
-
-
37,000
8.00
9,000
3,000
-
-
6.00
-
-
-
600
-
-
-
1 1 ,000
-
-
40,000
80,000
98,000
11
-
Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
2/2
0/0
0/0
2/2
1/1
1/1
2/2
0/0
0/0
1/1
0/0
0/0
0/0
1/1
0/0
0/0
0/0
1/1
0/0
0/0
1/1
2/2
1/1
2/2
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC f Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
.
-
-
-
-
212 0
-
CTl
ID
Non~detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - FERRIC CHLORIDE - TITANIUM
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
. 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum
930
25
0,083
23
1.8
18
1.5
310
9.9
18
48000
58
970
2200
0.02
8.8
30
0.02
6.2
0.004
320
52
-
-
326
2
-
-
104160
-
930
25
0.083
23
1.8
18
1.5
310
9.9
18
48000
58
970
2200
0.02
8.8
30
0.02
6.2
0,004
320
52
-
-
326
2
-
-
104160
-
930
25
0.083
23
1.8
18
1.5
310
9.9
18
48000
58
970
2200
0.02
8.8
30
0.02
6.2
0.004
320
52
-
-
326
2
-
-
104160
-
f Detects
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
0/0
0/0
1/1
1/1
0/0
0/0
1/1
0/0
TC # Values
Level in Excess
-
-
5.0 0
1 00.0 0
-
-
1.0 1
5.0 1
-
-
-
5,0 1
-
-
0.2 0
-
-
1.0 0
5.0 1
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTE ACIDS - TITANIUM (CHLORIDE PROCESS)
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOO)
Total Constituent Analysis - PPM
vlinimum Average Maximum #
447
1.73
0.0050
0.50
0.05
-
0.11
35.80
0.78
0.050
12.00
0.0025
7.60
46.00
0.00020
0.25
0.61
0.0050
0.0050
0.0050
13.00
27.00
-
-
-
-
-
44.00
76,000
10,000
2.00
40.00
10,612
1.73
0.0050
0.50
0.05
-
0.11
637
0.78
0.050
27,552
38.67
1,916
2,087
0.00020
0.25
0.61
0.0050
0.0050
0.0050
331
27.00
-
-
-
-
-
1,022
124,500
47,000
2.00
40.00
16,000
1.73
0.0050
0.50
0.05
-
0.11
3,300
0.78
0.050
72,000
58.00
4,800
7,900
0.00020
0.25
0.61
0.0050
0.0050
0.0050
1,500
27.00
-
-
-
-
-
2,000
210,000
200,000
2.00
40.00
Detects
4/4
1/1
0/1
0/1
0/1
0/0
1/1
6/6
1/1
0/1
8/8
2/3
3/3
4/4
1/1
0/1
1/1
0/1
0/1
0/1
5/5
1/1
0/0
0/0
0/0
0/0
0/0
2/2
4/4
6/6
1/1
1/1
EP Toxicity Analysis - PPM
Minimum Average Maximum ff Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- • . - - o/o
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
_
.
5.0 0
100.0 0
-
.
1.0 0
5.0 0
.
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
.
-
-
-
-
-
-
.
-
-
212 1
'
CTl
10
UJ
Non~detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
o>
ID
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTE ACIDS - TITANIUM (SULFATE PROCESS)
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
2.50
0.50
0.0050
0.50
0.050
0.025
0,050
2.50
0.50
0,05
9.42
0,0025
223
2.50
0.00010
0.25
0.50
0,0050
0,0050
0,0050
2.50
0.50
-
-
0
-
-
-
2.50
50000
0
20.00
253
1.15
0.88
1.00
0.10
0,025
0.12
21.63
1.28
0.89
1544
0.44
13,195
28.13
0.00048
0.94
1.03
0.88
0.88
5.00
54.63
13.75
-
-
99
-
-
-
30,735
65,450
0.33
845
480
2.50
2.50
2.50
0.25
0.025
0.25
40.00
2.50
2.50
3000
1.25
40,000
51.00
0.0016
2.50
2.50
2.50
2.50
12.50
100
27.00
-
-
198
-
-
-
80,000
80,900
1
1,670
Detects
3/4
1/4
0/4
0/4
0/4
0/1
1/4
3/4
1/4
0/4
4/4
0/4
6/6
3/4
1/4
0/4
1/4
0/4
0/4
1/4
3/4
2/4
0/0
0/0
2/2
0/0
0/0
0/0
6/7
2/2
3/3
2/2
EP Toxicity Analysis - PPM
Minimum Average Maximum
0.05
0.50
0.01
0.05
0.0050
-
0.0050
0.080
0.050
0.050
0.020
0.010
941
0.50
0.00010
0.50
0.17
0.010
0.005
0.55
0.50
0.50
-
-
-
-
-
-
-
-
363
2.25
1.33
1.31
0.15
-
0.12
31.12
1.64
1..79
2,174
0.77
22,685
39.12
0.00028
2.75
1.89
1.21
1.12
9.76
77.55
7.51
-
-
-
-
-
-
-
-
1,030
5.00
5.00
5.00
0.50
-
0.50
83.00
5.00
5.00
5,910
2.50
61,900
111
0.0010
5.00
5.00
5.00
5.00
25.00
225
24.00
-
-
-
-
-
-
-
-
# Detects
2/4
1/4
1/5
2/5
0/4
0/0
1/5
4/5
1/4
1/4
4/4
1/5
4/4
3/4
0/5
0/2
1/3
0/5
0/5
2/4
3/4
2/4
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
-
1.0 0
5.0 3
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 1
5.0 1
-
.
-
-
-
-
-
-
-
.
212 3
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
TUNGSTEN
A, Commodity Summary
More than 20 tungsten-bearing minerals are known, but the principle domestic ores used to produce
ammonium paratungstate (APT) powder and tungsten metal powder are wolframite, ferberite, and scheelite.
Tungsten occurs in association with minerals of copper, tin, bismuth, or molybdenum and can be recovered either as
the primary product or as a coproduct or byproduct.1
Tungsten ores and concentrates are converted into the following intermediate products: APT, tungstic acid,
sodium tungstate, tungsten metal powder, ferrotungsten, and tungsten carbide powder. Most of the APT is reduced
to tungsten metal powder, which then may be processed into tungsten carbide powder or ferrotungsten.2 End uses of
tungsten include metal working, mining, and construction machinery and equipment, 74%; electrical and electronic
machinery and equipment and transportation, 10%; lamps and lighting, 9%; chemicals, 4%; and other, 3%. The total
estimated value of primary tungsten material consumed in 1994 was $180 million.3
Eleven facilities in the United States produce either APT or tungsten metal. Three of the eleven facilities
produce APT, a precursor to tungsten, as an end product. Four additional facilities are captive plants that produce
APT, then tungsten. All seven of these plants appear to engage in beneficiation operations in the production of APT.
They conduct a variety of operations, including milling (e.g., crashing, grinding, washing), physical separation (e.g.,
gravity concentration, magnetic or electrostatic separation, froth flotation), roasting as a pretreatment for leaching
operations, concentration using liquid separation (e.g., soda autoclaving, solvent extraction, ion exchange), and
calcining (i.e., heating to drive off water or carbon dioxide).
In addition, two plants produce tungsten powder and cemented tungsten carbide using proprietary
processes. A Kennametal plant, located in Fallen, Nevada employs a unique process that produces tungsten carbide
directly from ore. A Curtis Tungsten plant located in Upland, California was recently reopened and produces
tungsten concentrate from ore. Little is known about the operations of these two facilities.
The two remaining facilities obtain APT (a "saleable" mineral product) and produce tungsten carbide or
powder. Tungsten is produced from APT by reduction using hydrogen, followed by a second reduction step using
aluminum, potassium, and silicon. The metal is then washed with hydrochloric acid, and cast into ingots. These two
facilities do not perform beneficiation activities, and there is some question as to whether their operations could even
be considered "mineral processing" operations, because they start with a saleable mineral product (see 54 FR
36592).
For the nine plants that conduct beneficiation and processing operations, names, locations, products,
operations, and waste streams generated are presented in Exhibit 1. Two tungsten mines are in operation, Curtis
Tungsten in Upland, California and U.S. Tungsten in Bishop, California. These are also listed in Exhibit 1.
1 Phillip T. Stafford, "Tungsten," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp. 881-891.
2 Ibid.
3 Gerald Smith, "Tungsten," from Mineral Commodity Summaries. January 1995, pp. 182-183.
695
-------
EXHIBIT 1
SUMMARY OF TUNGSTEN FACILITIES
Facility Name
Buffalo Tungsten
Curtis Tungsten, Incorporated
General Electric
OSRAM Sylvania, Inc.
Kennametal
Teledyne Firth Sterling
Teledyne Advance Materials
U.S. Tungsten
Location
Depew, NY
Upland, CA
Euclid, OH
Towanda, PA
Fallen, NV
LaTrobe, PA
La Vergne, TN
Huntsville, AL
Bishop, CA
Products
APT, Tungsten (carbide)
Tungsten (concentrate)
APT, Tungsten (carbide)
APT, Tungsten (carbide)
Tungsten (carbide)
APT
APT, Tungsten (carbide)
APT
B. Generalized Process Description
1. Discussion of Typical Production Processes
Tungsten is found primarily in quartz veins and contact-metatnorphic scheelite deposits. Both underground
and open pit methods are used in mining operations. Tungsten concentration operations, primarily gravity and
flotation methods, usually are conducted at or near the mine. The concentrate is processed chemically to produce
ammonium paratungstate (APT) from which tungsten metal powder is made. The metal is processed further into
products such as tungsten carbide and ferrotungsten.4
2. Generalized Process Flow Diagram
The production of tungsten metal can be divided into four distinct stages - preparation of ores, leaching of
ore concentrates, purification to APT, and reduction of APT to metal. The actual processes used in each stage vary
with the type and purity of raw material used. The production steps are described in greater detail below. Exhibit 2
presents a process flow diagram of tungsten production.
Preparation of Ore Concentrates
Scheelite and wolframite are the major tungsten containing minerals. Ores containing these minerals are
generally very friable and over grinding can cause sliming problems. Therefore, the ores are generally crushed and
ground in stages and waste fines are kept to a minimum. Concentration of tungsten is usually accomplished by froth
flotation, supplemented by leaching, roasting, or magnetic or high tension separation. The tailings from froth
4 Phillip T. Stafford, 1985, Op. Cit.. pp. 881-891.
696
-------
EXHIBIT 2
TUNGSTEN PRODUCTION
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, pp. 2963 - 3037.)
Recovered Wolframite or Scheelite
T
Stage Crushing and Grinding
T
Classification with Screeas, Hydraulic Classifiers. Settlers and Cones
Jigging and Tabling to Separate Minerals from Gangues
Wolframite Concentrate (re, MnJWQ,
Tungsten Oxide Furnace Reduction
Scheelite
1
1
*
Flotation & Gravity
Separation
1
1
Float
V.Wastes ,
Gravity Separation _ j — ^(Tailings
T
Scheelite Concentrate CaWQ,
HQ Leach
/teachings
( Scrubber )
Water,
Filter & Wash
T
Dissolution in Ammonia
697
-------
flotation usually are sent through a reprocessing and scavenger froth flotation circuit to maximize tungsten recovery.
The beneficiation processes vary with the type of ore being mined.5
The concentrate may be retreated by roasting to remove impurities such as sulfur, arsenic, and organic
residues from flotation. These compounds are oxidized and volatilized. After preparation of the concentrate, the
concentrate is processed to APT via either sodium tungstate or tungstic acid.6
Leaching of Ore Concentrates
Scheelite ores of high quality are usually leached with hot hydrochloric acid to remove phosphorus, arsenic,
and sulfur. An insoluble tungstic acid intermediate is formed which is filtered and washed with dilute hydrochloric
acid.7
Lower grade scheelites are sometimes processed by the high pressure soda process. In this process, the
concentrate is ground and digested in an autoclave with sodium carbonate. This produces a sodium tungstate
solution that is filtered to remove calcium carbonate and silica solids and then further processed to APT or CaWO4.
If molybdenum impurities are present, the sodium tungstate solution is reacted with sodium hydrosulfide to
precipitate molybdenum trisulfide. The molybdenum trisulfide solids are removed with a filter and the sodium
tungstate solution is further processed.8
Scheelite or wolframite can be converted to sodium tungstate solution by the alkali roasting
process. In this process, sodium carbonate is mixed with the concentrate and heated. The roasted concentrate is then
leached with hot water. The leachate, which contains sodium tungstate, is separated from the solids by filtration and
sent to other processes for conversion to APT.9
Purification to APT (Precipitation. Crystallization, and Drying)
Tungstic Acid Purification
Purification of tungstic acid is accomplished by a simple process involving digestion and crystallization.
Insoluble tungstic acid is digested with aqueous ammonia to solubilize the tungsten as ammonia tungstate. The
solution is separated from any remaining solids and magnesium oxide is added. Magnesium ammonium phosphates
and arsenate are precipitated. Activated carbon is added to purify the solution. The activated carbon and
precipitates are removed from the solution by filtration. APT is formed by crystallizing it from solution. The APT
crystals are filtered, washed, and dried. Ammonia evolved during the process is usually recovered and recycled.10
5 U.S. Environmental Protection Agency, "Tungsten," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. 3-228 - 3-244.
6 Ibid.
7 Ibid.
8 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Office of Water Regulations Standards,
Vol. VI, 1989, pp. 2963-3037.
9 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-228 - 3-224.
10 Ibid.
698
-------
Sodium Tungstate Purification
Sodium tungstate from the high pressure soda process and from the alkali roasting process is converted to
APT by two processes. The first approach is to precipitate calcium tungstate (synthetic scheelite) from the sodium
tungstate solution by adding calcium chloride. The solution is filtered to yield sodium chloride, and is discharged. •
The calcium tungstate can then be digested with hydrochloric acid. From this point, the purification is the same as
described above for the purification of the tungstic acid intermediate.11
Synthetic scheelite is also prepared from recycled process solutions and cleanup water, such as spent
crystallization liquor and floor wash, that may contain tungsten values. The calcium tungstate is precipitated with
calcium chloride and can be processed as described above. Alternatively, the calcium tungstate may be sent through
solvent extraction instead of digestion with hydrochloric acid,12
The second approach for purifying the sodium tungstate intermediate is a newer solvent extraction method,
the liquid ion exchange system, where the sodium tungstate solution is converted to ammonia tungstate solution. The
sodium tungstate solution is contacted countercurrently with an organic solvent, which removes the tungstate ions
from solution. The organic solvent is washed with water to remove impurities and then recycled. The ammonium
tungstate solution is fed to a crystallizer where APT crystals are formed. The APT crystals are filtered and dried.13
APT Conversion to Oxide (Calcining)
Dried APT is calcined in a rotary furnace heated indirectly to drive off ammonia and produce tungsten
oxides. The type of oxide produced is a function of furnace atmosphere (i.e. N2, H2> etc.) and temperature. Blue,
brown, or yellow tungsten oxides are possible products.14
Tungsten Oxide Reduction to Metal
Tungsten oxides are reduced to metal powder in high temperature furnaces. The reducing agent is typically
hydrogen. Powders of various particle sizes are produced by varying furnace reaction time, temperature gradient,
hydrogen flow, and layer thickness. Tungsten powder to be used in high-purity applications is leached with acids
such as hydrochloric and hydrofluoric acids, rinsed with water, and dried."
Tungsten Carbide Production
Tungsten carbide is formed by reducing APT or tungsten oxides in the presence of carbon. Tungsten ores
may also be reduced and carburized in a single reaction. In this latter process, impurities are leached with
hydrochloric, sulfuric, or hydrofluoric acid from the furnace product to yield tungsten carbide crystals.16
11 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 2963-3037.
12 Ibid.
13IMd.
14 Ibid.
15 Ibid.
16 Ibid.
699
-------
3. Identification/Discussion of Novel (or otherwise distinct) Processes
A recently developed technique processes tungsten carbide from concentrate eliminating the conventional
method of producing APT. The technique involves the formation of tungsten monocarbide from a molten tungstate
halide phase using gas sparging. The process involves treating concentrates with chloride and silicate salts, with the
resulting product being treated with methane gas to produce high purity tungsten carbide powder.17
4. Beneficiation/Processing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, ehlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between APT calcining and tungsten furnace reduction because it is here, in the furnace, where tungsten oxide is
thermally reduced in the presence of hydrogen to form tungsten powder. Therefore, because EPA has determined
that all operations following the initial "processing" step in the production sequence are also considered processing
operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all solid wastes
arising from any such operation(s) after the initial mineral processing operation are considered mineral processing
wastes, rather than beneficiation wastes. EPA presents below the mineral processing waste streams generated after
the beneficiation/processing line, along with associated information on waste generation rates, characteristics, and
management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneflciation Wastes
Mining and Concentrating Ore
Waste fines are generated from handling tungsten ore. The tailings are sent to tailings ponds.18
17 Phillip T. Stafford, 1985, Op. Cjt.. pp. 881-891.
18 U.S. Environmental Protection Agency, 1988, Op.. Cit.. pp. 2963-3037.
700
-------
Wastewater is generated from processing tungsten ore. Wastewater from thickeners and separators are
sent to tailings ponds. Waters from tailings ponds are discharged to surface water.19
Wet scrubber wastewater is a waste stream generated from roasting.
Waste rock and tailings from mining and concentrating, respectively, are generated from extraction and
beneficiation operations associated with tungsten production. Waste management practices for mine waste rock and
mill tailings appear to be fairly typical of those used throughout the mining industry to manage similar wastes.
Waste rock is generally disposed of in piles or dumps, and tailings are usually piped in slurry form to a tailings
(disposal) impoundment.
Leaching or Ore Concentrates
Tungstic acid rinse water is a waste stream from ore concentrate leaching. This wastewater can be
characterized by acidic pH, concentrations of metals including lead and zinc, and suspended solids. Two plants
appear to leach scheelite ores or synthetic calcium tungstate with hydrochloric acid. Treatment at these plants
involves lime and settling to precipitate metals before discharging the rinse water effluent. Treatment sludges
presumably report to RCRA Subtitle D landfills or disposal impoundments (i.e., as non-hazardous solid wastes).20
Attachment 1 presents additional waste characterization data for this waste stream.
Scrubber wastewater is a waste stream generated from wet air pollution control. This wastewater may
have an acidic pH. The scrubber water is usually treated and discharged or recycled.21 One of the two plants that
leaches scheelite ores or synthetic calcium tungstate with hydrochloric acid neutralizes the scrubber water with lime
and precipitates metals from the waste stream prior to discharge. The other plant recycles the entire waste stream for
use as a tungsten acid rinse water. Sludges from the waste treatment are sent to Subtitle D landfills or disposal
impoundments.
Alkali leach wash is generated from digesting wolframite type ores in caustic solutions to produce sodium
tungstate. Four plants use an alkali leach wash. Sodium tungstate is filtered from the digestion-wash liquor, and the
resulting filtrate is evaporated in surface impoundments, recycled, or discharged. From EPA's Development
Document for Effluent Limitations Guidelines and Standards for the Nonferrous Metals Point Source Category.
Volume 3. (1989), two plants reduced waste flow to zero by filtering the insoluble impurities and using a
combination of evaporation and recycling steps. A third plant discharges this and all liquid wastes to a settling pond
for evaporation, and one plant discharged its wastewater after neutralization and chemical oxidation. This waste
stream is characterized by concentrations of metals and suspended solids.22
Leach filter cake residues and impurities may be generated from the leaching step. This waste contains
gangue, with small amounts of tungsten and other trace elements. Other impurities may include molybdenum and
heavy metals—many in hydrous forms. These wastes may be disposed of in a RCRA Subtitle D landfill or disposed
of in surface impoundments.
Molybdenum sulfide precipitation wet air pollution control waste is generated from the leaching of ore
concentrates. This waste stream is expected to be acidic and contain captured particulates.23
"Ibid.
20 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 2963-3037.
21 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 3-228 - 3-244.
22 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 2963-3037.
23 Ibid.
701
-------
Purification to APT
Spent mother liquor evolved during crystallization is a possible waste stream from purification of
intermediate products to APT. This wastewater is either recycled or discarded.24 This waste stream may contain
high levels of ammonia.
Wastewater from drying APT crystals is usually evaporated.25 This waste stream may contain high levels
of ammonia.
Ion exchange raffinate from the liquid ion exchange process is a source of wastewater. This waste stream
is characterized by a low pH and concentrations of toxic metals, suspended solids, and ammonia. This waste stream
also has concentrations of organics such as acenaphthene, napthalene, phenol, and fluorene.26 Of the two plants
using this method, one plant pumps all of its wastes to a settling pond for evaporation, and the second plant treats
this wastewater with a lime and settle process. Treatment sludge disposal may involve disposal into a RCRA Subtitle
D landfill or impoundment.
Ion Exchange Resins may be generated by the two plants using the ion exchange process. These plants
would need to replace ion exchange resins at regular intervals. These resins may contain constituents and exhibit
characteristics similar to those of raffinate, but with higher concentrations of contained metals.
Calcium tungstate precipitate wash is generated from calcium tungstate precipitation. Four plants are
believed to generate this waste from calcium tungstate precipitation. None of the plants are believed to recycle the
wastewater. This waste stream is characterized by a basic pH, concentrations of ammonia, oil, and grease.
Reportedly, in 1983, one plant achieved zero discharge by sending wastewater to an evaporation pond. Other
facilities used lime treatment and settling techniques, coagulated with polymers and lime, or discharged the waste
without treatment.27
APT Conversion to Oxide
Wet scrubber wastewater from calciners is generated during the conversion of APT to tungsten oxides. In
1989, six plants reported this activity. Of the six plants, one plant recycled and reused the wastewater, another
evaporated the water, recovered ammonia, and reused the ammonia and water. Other treatments included direct
discharge, lime and settle scrubber water, ammonia recovery, direct discharge, primary and secondary settling, and
indirect discharge. Treatment sludges may be landfilled or disposed of in surface impoundments. This wastewater is
characterized by concentrations of ammonia and suspended solids and an alkaline pH.28
2. Mineral Processing Wastes
Reduction to Metal
Scrubber wastewater is generated by reducing tungsten oxides to metal powder. This waste stream is
characterized by concentrations of particulates and soluble salts from fluxes used in the reduction furnaces. In
addition, concentrations of ammonia and an alkaline pH may also be characteristic of this wastewater. This waste
24 Ibid.
25 Ibid.
26 Ibid.
27 Ibid.
28 Ibid.
702
-------
may be recycled. Attachment 1 presents additional waste characterization data for this waste stream,29 This waste is
not expected to be hazardous.
Rinse water and spent acid. This wastewater is discharged to wastewater treatment.30 Although no
published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 0 metric
tons/yr. 0 metric tons/yr, and 21,000 metric tons/yr, respectively. We used best engineering judgement to determine
that this waste may exhibit the characteristic of corrosivity prior to treatment. This waste may be recycled and is
classified as a spent material.
Tungsten Carbide Production
Process Wastewater is generated from tungsten carbide production. This wastewater is likely to be very
acidic and contain suspended solids.31 This wastewater may be combined with rinse water, spent acid, and spent
scrubber liquor for treatment. Attachment 1 presents waste characterization data for process wastewater treatment
plant effluent. Although no published information regarding waste generation rate or characteristics was found, we
used the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste
generation rate of 1,800 metric tons/yr, 3,700 metric tons/yr, and 7,300 metric tons/yr, respectively. We used best
engineering judgement to determine that this waste may exhibit the characteristic of corrosivity. This waste may be
recycled and is classified as a spent material.
Water of formation is produced from reducing tungsten oxides to metal in a hydrogen atmosphere. In
some plants, this water may be recondensed in the reduction furnace scrubber system. This wastewater is
characterized by a basic pH and concentrations of ammonia and suspended solids.32 Attachment 1 presents
additional waste characterization data for this waste stream. This waste is not expected to be hazardous.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from tracks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
29 IMd.
30 Ibid.
31 Ibid.
32 Ibid.
703
-------
BIBLIOGRAPHY
Smith, Gerald. "Tungsten." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. pp. 182-
183.
Stafford. Phillip T. "Tungsten." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 881-891.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol. III. August, 1992. pp. 39-1 - 39-2.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and
704
-------
ATTACHMENT 1
705
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SCRUBBER WASTEWATER - TUNGSTEN
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0.1 0.1 0.1 2/2
0.1 0.1 0.1 2/2
0/0
0/0
0/0
0/0
0.04 0.04 0.04 1/1
0/0
0/0
0/0
0.02 0.02 0.02 1/1
0/0
0/0
0.0002 0.0003 0.0004 2/2
0/0
0.005 0.005 0.005 1/1
0.01 0.01 0.01 2/2
0.02 0.02 0.02 2/2
0.1 0.1 0.1 2/2
0/0
0.06 0.06 0.06 2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
- '
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - TUNGSTIC ACID RINSE WATER - TUNGSTEN
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
iron
_ead
Magnesium
Vlanganese
Vlercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
0.1
0.13
-
0.03
-
0.03
0.1
-
0.2
-
0.2
-
-
0.0005
-
0.05
0.01
0.02
0.1
-
0.6
0.001
-
-
-
-
-
-
-
-
-
-
0.1
3.665
-
0.03
-
0.115
1.05
-
2.6
-
10.1
-
-
0.0008
-
0.525
0.01
0.155
0.4
-
1.3
0.00975
-
-
-
- '
-
-
-
-
-
-
0.1
7.2
-
0.03
-
0.2
2
-
5
-
20
-
-
0.0011
-
1
0.01
0.29
0.7
-
2
0.02
-
-
-
-
-
-
-
-
-
Detects
0/0
1/1
2/2
0/0
1/1
0/0
2/2
2/2
0/0
2/2
0/0
2/2
0/0
0/0
2/2
0/0
2/2
1/1
2/2
2/2
0/0
2/2
4/4
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxiciry Analysis - PPM
Minimum Average Maximum # Detects
0/0
. - 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- . 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
o
oo
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - TREATMENT PLANT EFFLUENT - TUNGSTEN
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum
-
0,002
0,018
-
0.002
0.02
0.024
-
0.01
0,1
0.0002
0.05
0.016
0.03
0.005
-
0.05
0.001
-
-
-
-
-
„
-
0.116
0.118
-
0.009
0.044
0.087
-
0.047
0.140
0.001
0.110
0.234
0.030
0.150
-
0.191
0.157
-
-
-
-
-
-
-
0.8
0.446
-
0.01
0.08
0.22
-
0.148
0.242
0,003
0.202
1
0.03
0.9
-
0.6
0.6
-
-
-
-
-
_
# Detects
0/0
7/7
9/9
0/0
7/7
0/0
10/10
7/7
0/0
10/10
0/0
10/10
0/0
0/0
9/9
0/0
10/10
8/8
1/1
9/9
0/0
10/10
14/14
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
.
5.0 0
100.0 0
-
1.0 0
5.0 0
-
-
5.0 0
0.2 0
1.0 0
5.0 0
.
-
.
-
-
-
-
.
-
212 0
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WATER OF FORMATION - TUNGSTEN
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Orcjanies (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
-
0.01
0.02
-
0,005
-
0.02
0.02
-
0,25
-
0.05
-
-
0.0002
-
0.05
0,01
0,01
0.01
-
0.14
-
-
-
-
-
-
-
-
-
-
-
0,01
0.02
-
0.005
-
0.02
0.02
-
0.25
-
0.05
-
-
0.0002
-
0.05
0.01
0.01
0.01
-
0.14
-
-
-
-
-
-
-
-
-
-
-
0.01
0.02
-
0.005
-
0.02
0.02
-
0,25
• -
0.05
-
-
0.0002
-
0.05
0.01
0.01
0.01
-
0.14
-
-
-
-
-
-
-
-
-
-
Detects
0/0
1/1
1/1
0/0
1/1
0/0
1/1
1/1
0/0
1/1
0/0
1/1
0/0
0/0
1/1
0/0
1/1
1/1
1/1
1/1
0/0
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum f Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC t Values
Level In Excess
.
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
.
-
-
-
-
.
.
-
-
-
212 0
-
o
UD
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Page Intentionally Blank
-------
URANIUM
A. Commodity Summary
Uranium is present in the earth's crust at approximately 2 ppm. Acidic rocks with a high silicate content,
such as granite, have a uranium content that is above average, whereas the uranium contents of basic rocks such as
basalts are lower than the average. However, 90 percent of the world's known uranium resources are contained in
conglomerates and in sandstone.1
From 1980 to 1993, die domestic production of uranium declined from almost 44 million pounds U3O8 to
about 3 million pounds (1,361 metric tons/yr),2 A total of 17 uranium mines were operational in 1992; five
conventional mines (both underground and open pit), four in situ, and eight reported as "other" (heap leach, mine
water, mill tailings, or low-grade stock piles). Extraction/beneficiation operations produce yellowcake (precipitate
containing uraniferous compounds), which is typically shipped to a uranium hexafluoride converter for processing.3'4
The number of mineral processing facilities is currently unknown. Uranium was also produced to a limited extent as
a byproduct of phosphoric acid production at four sites. The primary demand for uranium is by commercial power
generating facilities for use in fuel rods.5
Regulatory Status
Uranium mill tailings are by-product materials from uranium mining (i.e., waste acids from solvent
extraction, barren lixiviants, slimes from solvent extraction and waste solvents generated in the beneficiation process
during the extraction of uranium ore) and therefore, are excluded from the treatment standards being promulgated
today for TC metal wastes. 40 CFR 26I.4(a)(4) states that source, special nuclear or by-product material as defined
by the Atomic Energy Act of 1954 as amended, 42 U.S.C. 2100 et seq, are not solid wastes and thus, subject to this
rule. However, all other wastes not excluded under 40 CFR 261.4, including radioactive mixed wastes, which satisfy
the definition of radioactive waste at 10 CFR Part 61, and also contain waste that is either a listed hazardous waste,
or mat exhibits any of the hazardous characteristics identified in Subpart C of 40 CFR Part 261, are subject to this
rulemaking (assuming the waste is otherwise subject to this rule).
B. Generalized Process Description
1, Discussion of Typical Production Processes
Uranium ore is recovered using either conventional milling or solution mining (in situ leaching),
Beneficiation of conventionally mined ores involves crushing and grinding the extracted ores followed by placement
in a leaching circuit. In situ operations use a leach solution to dissolve desirable uraniferous minerals from in-place
deposits. Uranium in either case is removed from pregnant leach liquor and concentrated using solvent extraction or
ion exchange and precipitated to form yellowcake. Yellowcake is then processed to produce uranium hexafluoride
1 "Uranium and Uranium Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXIII,
1983, p. 504.
2 Department of Energy, Decommissioning of U.S. Uranium Production Facilities. February 1995, p. vii.
3 Kennecott Corporation. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
4 Rio Algom Mining Corp. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
5 U.S. Environmental Protection Agency, "Uranium," from Technical Resource Document. Extraction and
Beneficiation of Ores and Minerals. Vol. 5, January 1995, pp. 3-5.
711
-------
(UF6), which is enriched and further refined to produce the fuel rods used in nuclear reactors.6 Stockpiles of low
grade ore removed from mines may be processed by heap leaching. It can also be economically feasible to separate
the uranium as a by-product from the crude black acid (30 percent phosphoric acid) obtained from the leaching of
phosphate for fertilizers.
2. Generalized Process Flow Diagram
Conventional Milling
Uranium ore is recovered by either open pit (for ore deposits close to the surface of the earth) or
underground mining. The ore is blended, crushed, and ground. Ore high in vanadium is sometimes roasted with
sodium chloride or soda ash prior to grinding in order to convert insoluble heavy metal vanadates (complex
vanadium) into more soluble vanadate, which is then extracted with water. Two basic methods are employed to
extract uranium from ore: acid leaching with sulfuric acid or alkaline leaching with a hot solution of sodium
carbonate and sodium bicarbonate.7 Exhibits 1 and 2 show process flow diagrams for two different leaching
processes.8'9 A process flow diagram for an alkaline leach mill is shown in Exhibit 3. Most mills use acid leaching,
which provides a higher uranium-removal efficiency. Alkaline leaching is used in the treatment of uranium ores
when the lime content results in excessive acid consumption (alkaline leaching is preferred if acid consumption
exceeds 68 kg/ton of ore treated).10'11 Leaching involves bringing a solvent (lixiviant) in contact with the crushed ore
slurry. Uranyl ions are then dissolved by the lixiviant. The pregnant lixiviant is separated from the residual solids
(tails); typically the solids are washed with fresh lixiviant until the desired level of recovery is attained. The
pregnant leach solution then enters a solvent extraction or ion exchange circuit.12
Solution Mining (In Situ Leaching)
In situ leaching, the most commonly employed solution mining technique, involves injecting a barren
solution and lixiviant into the permeable ore zone. The solution penetrates the pores in the ore, leaching out the
uranium and other metals.13 The pregnant solution is then pumped up through production wells, passed through sand
filters to remove any large particles, and transferred to ion exchange units. Ultimately, the uraniferous compounds
are stripped from the ion exchange resins and precipitated to form yellowcake.14 After the uranium is removed, the
barren solutions are reconditioned and recycled. A typical in situ leach process is shown in Exhibit 4.
6 U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 13-16.
7 Werthman, P., and K. Bainbridge, "An Investigation of Uranium Mill Wastewater Treatability," Proceedings of
the 35th Purdue Industrial Waste Conference, 1980, p. 248.
8 Kennecott Corporation. Op. Cit.
9 Rio Algom Mining Corp. Op. Cit.
10 "Uranium and Uranium Compounds," 1983, Op. Cit.. pp. 516-517.
11 "Uranium," in SME Mineral Processing Handbook. Vol. 2, 1985, p. 24-3.
12 U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 18,21.
13 Department of Energy, February 1995, Op Cit.. p. 30.
14 U.S. Environmental Protection Agency, January 1995, Op. Cit.. p. 27.
712
-------
EXHIBIT 1
PROCESS FLOW CHART FOR ACID-LEACH PROCESS 1
(Adapted from: Assessment of Environmental Aspects of Uranium Mining and Milling, U.S. EPA, 1976, p. 36.)
Organic Vapors
Mine Water
Fugitive
Dust
Hot
Water
H2S04 -
NaClO3-
Flocculant
Seepage
Ore Storage
1
1
Crusher
„. 1
Fine
Ore w
Pnri Mill
|
T
Leach Tanks
1
1
T
CCD Tanks
1
T
T T
Pond
Particulat
Emission
^
Bleed
^
e
s
0
"o
C/3
c
a
d
bo
a
OH
^,
A
T
_ . ^^
Pregnant
Pregnant A
Raffinate StriP ^ T
T
^ Yellowcake
3 Precipitation (NH4)2SO4
1
1
Bleed . . .
1
i
T
H2O ^- Centrifuge
1
1
T
^- Particulates ar
Dryer .,
^- Yellowcake
Barren
Organic
-------
EXHIBIT 2
ACID LEACH PROCESS FLOW CHART FOR ACID-LEACH PROCESS 2
(Adapted from: Assessment of Environmental Aspects of Uranium Mining and Milling, U.S. EPA, 1976, p. 38.)
Jaw
Crusher
To Solvent
Extraction
Unit
Treated
Mine
Water
H,S04
MnO,
Water •
Seepage
\
Secondary
Cone Crusher
1
Rod Mil!
1
Ball Mill
1
Leaching
Tanks
1 4_
T
Sand-Slime
Separation
Sands
Tailings
RIP Circuit
Countercurrent
I
^ Particulate
Emissions
i
Iron Powder
Steam
Slimes
^*
I
^ aweco
Screen
Slimes '
VVdtei
NH3 — ^
Bleed
H20— ^
Pregnant
Strip
Yellowcake
Precipitation
Thickener
Barren
Organic
(NH4)2S04
Centrifuge
Dryer
Particulars and Vapors
Yellowcake
Pond
-------
EXHIBIT 3
ALKALINE LEACH PROCESS FLOW CHART FOR AN UNDERGROUND MINE
(Adapted from: Assessment of Environmental Aspects of Uranium Mining and Milling, U.S. EPA, 1976, p. 41.)
Undereround ^
Mine
1 ,
i
X '
w Fugitive
,,. ... Dust
Mine Water
Water
Steam
Soda Ash
Air
Separan
Reclaim
Wash
Water
Seepage
Ore Storage
|
Crusher
Fine 1
Ore *
Grinding
1
Paehuea-
Autoclave
Leaching
T
Filtration
Circuit
i
i
I
i
I
i ^ Paniculate
' Emissions
i
s
I
c
ta
e
so
ft*
^h^
Filter
1 1
Vapors y
Carbonation
1 4_
f
Mill Solution
Storage
- ^»-
Residue
- —
Yellowcake
Precipitation
I
Thickener
l^^ 1
f
Centrifuge
T
Dryer
1 1
1 1
Particulates Yello
and Vapors
1 Residue
^_^
Tailings
Pond
•NH3
-------
01
EXHIBIT 4
URANIUM Iff SITU LEACH PROCESS
(Adapted from: DOE, Decommissioning of U.S. Uranium Production Facilities, 1995, p. 31.)
\
NaOH
Precipitation
Loaded Resin
Ion Exchange
Resin
\
Columns
\
^P>
Stripped Resin
To Evaporation
... ^ Pond
— ..te
Production Well
o
Elution
Columns
Mixer
T
CO,
Clay/Shale
I Uranium Ore Zone
NaCl
NaHCO,
Oxidant
To Evaporation
Pond
Filtering and
Drying
Injection Well
Overburden
Clay/Shale
-------
Solvent Extraction
Solvent extraction is typically employed by conventional milling operations. The pregnant leach solution is
mixed in tanks with the solvent. Normally, the solvents are organic compounds that can combine with either solute
cations or solute anions. The uraniferous ions preferentially move from the aqueous pregnant leach solution into the
organic solvent as the two are mixed and agitated. After the uraniferous compounds have been extracted, the barren
lixiviant (raffinate) is typically sent to the CCD tanks.I5'16 After the solute exchange has taken place, the pregnant
solvent extraction liquor is stripped using various agents such as nitrates, chlorides, sulfates, carbonates, and acids.
The pregnant stripping liquor is then pumped to the precipitation step while the stripped organic solvent is recycled
to the beginning of the solvent extraction circuit.
Ion Exchange
Ion exchange operations, used by most if not all in situ operations and some mills, make use of organic
compounds to perform solute concentration. Generally, fixed organic resins contained within a column are used to
remove uraniferous compounds from the leach solution by ion exchange. As thepregnant leach solution passes
through the ion exchange resins, the uraniferous compounds bind to the resins. The barren leach solution is recycled
back to the leaching circuit. After adsorption, the uraniferous compounds attached to the resins are released (eluted)
by passing a concentrated chloride salt solution through the loaded resins. The pregnant elute liquor can then be
directed to the precipitation circuit. The liquor may be acidified slightly to prevent the premature precipitation of
uraniferous compounds.17
Yellowcake Production
Concentrated uraniferous ions from solvent extraction or ion exchange units are precipitated out of solution
to produce yellowcake. Uranium is usually precipitated from acid solutions by neutralization with ammonia or
magnesia.18 Hydrogen peroxide may also be added to an acid pregnant stripping liquor or pregnant elution liquor to
precipitate uranium peroxide. All forms of the uraniferous precipitate are known as yellowcake.
Alkaline pregnant stripping liquors or pregnant elution liquors typically contain uranyl carbonates. Prior to
the precipitation of the uranyl ions, the carbonate ions are destroyed by adding hydrochloric acid. The carbonates
are converted to carbon dioxide, which is vented off. The acidified solution is neutralized with an alkali or treated
with hydrogen peroxide to precipitate the uraniferous compounds. The yellowcake is separated from the
precipitation solution by filtration. Thickeners may be used in conjunction with filtration units. The filtered
yellowcake is then dried and/or calcined and packaged for shipping. The supernatant generated from the
precipitation and dewatering circuits can be recycled to the respective solvent extraction or ion exchange stripping
solutions.19
13 Kennecott Corporation. Op. Cit.
16 Rio Algom Mining Corp. Op. Cit.
17 U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 22-23.
18 "Uranium and Uranium Compounds," 1983, Op. Cit, p. 522.
19
U.S. Environmental Protection Agency, January 1995, Op. Cit.. p. 23.
717
-------
EXHIBIT 5
PRODUCTION OF URANIUM DIOXIDE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 523.)
Yellowcake
Dissolution in Nitric Acid
Waste Nitric
Acid
Extraction With Tributyl
Phosphate (TBP)
Back-Extraction with HNO3
or Deionized Water
Waste Nitric
Acid
Evaporation
Dehydration and Denitration
UCh
Reduction with Hydrogen
UO,
718
-------
Conversion and Purification Processes
Production of UF4. The crude product from the refineries is purified to a degree that is usable in nuclear
applications. The purified material is converted to uranium dioxide (UO2) as shown in Exhibit 5, UO2 is then
converted to uranium tetrafluoride (UF4) based on the following reaction:
UO2(s) + 4HF(g) —> UF4(s) + 2H20(g)
The process used to convert UO2 to UF4 is shown in Exhibit 6. Uranium tetrafluoride is then converted to either
uranium metal or uranium hexafluoride (UF6), the basic compound for isotope separation,
Production of UF6. Uranium hexafluoride is prepared by direct fluorination of UF4 with elemental fluorine in a
fluorination tower based on the following reaction:
UF4(s) + F2(g) -> UF6(g)
Solid UF4 is fed through suitable locks into the top of the fluorination tower. Filtered and preheated fluorine is
introduced into the side of the tower, Unreacted UF4 is collected in a hopper at the bottom. This material is
periodically removed and recycled.
Production of Uranium Metal. Uranium metal is produced by reduction of UF4 by the Ames process as shown in
Exhibit 7, The reduction process is carried out in a bomb, A charge consisting of anhydrous UF4 powder and
magnesium chips is placed into the bomb. The charge is covered with MgF2 powder, and the bomb is closed with a
screwed-on flange cover. The charge is ignited spontaneously by heating, and the reduction of the UF4 proceeds at a
temperature of 700 °C.20
Uranium-235 Enrichment
Most nuclear reactors built for the generation of electric power are based on uranium fuel enriched in 2j5U.
Normally for such reactors, 235U is enriched from a concentration of 0.7 percent to approximately 2-3 percent. The
processes used to produce enriched uranium include the gaseous-diffusion process, centrifugal isotope separation,
and electromagnetic separation.
3. Identification/Discussion of Novel (or otherwise distinct) Process
An improved Eluex process for uranium extraction was developed in 1957 and later improved by the U.S.
Bureau of Mines.21'22 In this process, a stage of uranium solvent extraction is coupled with each stage of resin elution
rather than the elution and solvent extraction operations being conducted separately. The improved system reduces
the number of stages, retention time, and resin inventory to about one-fourth or one-fifth that of other circuits.
20 "Uranium and Uranium Compounds," 1983, Op. Cit.. pp. 523-528.
21 Kennecott Corporation, Op. Cit.
22 Rio Algom Mining Corp. Op. Cit.
719
-------
NJ
O
EXHIBIT 6
FLOW SHEET FOE UF4 PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 527.)
Vent
CaF2 to Sewer -*^
Solution
f^
Steam Condensate
Noncondcnsables + HF
^
Anhydrous HF
70% HF
70% HF
?
Storage
Tank
Scale 1 m- 1
-^
Tank
Car
Storage
Tank
f ^
Tank
Car
J Scale
Steam Condcnsate
SOURCE: "Uranium and Uranium Compounds," Kirk-Othmcr Encyclopedia of Chemical Technology. 3rd cd., Vol. XXIII, 1983, p. 527.
-------
EXHK .7
THE AMES PROCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 530.)
Mg in UF4 in
Drums Drums
Source: "Uranium and Uranium Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXIII, 1983, p. 530.
-------
A flotation technique also has been developed to extract uranium from seawater. Uranium is present in
seawater in concentrations of 2.9 to 3.3 micrograms per liter. Sea water is the lowest grade but the most abundant
source of uranium. However, it is unlikely that this source of uranium would be considered unless ore reserves
become depleted.
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed, Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between yellowcake production and the conversion/purification processes. EPA identified this point in the process
sequence as where beneficiation ends and mineral processing begins because it is here where yellowcake (uranium
oxide) is chemically oxidized to uranium dioxide. Therefore, because EPA has determined that all operations
following the initial "processing" step in the production sequence are also considered processing operations,
irrespective of whether they involve only techniques otherwise defined as beneficiation, all solid wastes arising from
any such operation(s) after the initial mineral processing operation are considered mineral processing wastes, rather
than beneficiation wastes. EPA presents the mineral processing waste streams generated after the
beneficiation/processing line in section C.2, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
C, Process Waste Streams
1. Extraction/Beneficiation Wastes
Wastes and materials generated by uranium mining operations include waste rock, tailings, spent
extraction/leaching solutions, particulate emissions, organic vapors, and refuse.23
Waste rock and overburden are deposited in waste rock piles or dumps. During the late 1970s, the largest
open pit uranium mines produced an average of 40 million metric tons of overburden annually. Underground mines
produced an average of 2,000 metric tons per year of waste rock during the same time period. Limited data indicate
23 U.S. Environmental Protection Agency, Assessment of Environmental Aspects of Uranium Mining and Milling.
December 1976, pp. 36-43.
722
-------
that waste rock contained higher levels of arsenic, selenium, and vanadium than background levels. Constituents of
concern for waste rock and ore piles include low concentrations of radionuclides as well as sulfur-bearing minerals
that, under certain conditions, may generate acid and, thus, leach metals.24
Most wastes generated by conventional mills are disposed of in tailings impoundments. These wastes,
disposed of in the form of a slurry, include tailings (reground and pulped waste rock from the leaching process),
gangue (including dissolved base metals), spent beneficiation solutions, and process water bearing carbonate
complexes (alkaline leaching), sulfuric acid (acid leaching), sodium, manganese, and iron. Two acid- and alkaline-
leach mills were reported to generate approximately 7,400 and 3,200 to 10,900 m3/day of tailings, respectively. The
tailing pond seepage from the acid-leach mill had a mean pH of 1.7 and contained high concentrations of dissolved
solids (31,780 ppm), radium-226 (127 ppm), and dissolved metals (including lead, nickel, chromium, arsenic, and
selenium). The tailing pond decant from the alkaline-leach mill contained high concentrations of arsenic (4-5 ppm),
selenium (17 - 20 ppm), vanadium (24 - 27 ppm), uranium (55 - 960 ppm), and radium-226 (30 - 667 ppm).25 The
generation rate for tailing pond seepage was estimated to be 1,800 m3/day at the facility mentioned above. We used
the methodology outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation
rate of 17,000 mt/yr, 3,833,500 mt/yr, and 7,650,000 mt/yr, respectively for the tailing pond seepage.
In situ bleed solutions and lixiviant leaching solutions constitute the major wastes directed to lined
evaporation ponds. These solutions consist of barren lixiviant and usually have high levels of radium; other
contaminants (metals, salts) are limited to what may have been solubilized by the lixiviant. Barium chloride is added
to the ponds, which in the presence of radium, forms a barium-radium-sulfate precipitate. This precipitate forms the
majority of sludges in the evaporation ponds. These sludges, which may contain metals, sulfates, chlorides, and
amines, are either disposed of at an NRC-licensed disposal facility or deposited in the tailings impoundment. In
certain locations, where climatic conditions limit the use of evaporation, treated bleed solutions are land applied.26
Reverse osmosis brines, generated during the in situ leaching process, typically contain high concentrations
of salts (total dissolved solids) and may have radionuclide (including naturally occurring radionuclides)
concentrations that exceed NPDES discharge limits. These wastes, along with laboratory wastes and other wastes,
are typically injected into Class I deep disposal wells permitted under the Underground Injection Control (UIC)
program. These deep disposal wells are used as an alternative source of disposal at operations that usually do not
operate a tailings impoundment.27'28
Ion exchange resins are occasionally replaced. Spent resins from in situ operations are disposed of at an
NRC-licensed disposal facility. Conventional mills typically dispose of the spent resins in the tailings
impoundments. The contribution of spent resins to the volume of a tailings impoundment is minimal compared to
the volumes of tailings.29 No information regarding the types of contaminants present in spent ion exchange resins
was found.
Waste solutions are generated during acid/alkaline leaching, solvent extraction, stripping, and precipitation.
Stripping solution could contain nitrates, chlorides, sulfates, hydroxides or acids. Constituents that could accumulate
24
U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 30-37.
Werthman P., and K. Bainbridge, 1980, Op. Cit.. pp. 249-250.
26 Kennecott Corporation. Op. Cit.
Kennecott Corporation. Op. Cit.
25
27
28 Uranium Resources, Inc. Comment submitted in response to the Supplemental Proposed Rule Applying Phase
IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
29 U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 30-37.
723
-------
in the precipitation circuit are primarily anions - sulfates, chlorides, and possibly carbonates. Spent acids from
leaching and wash waters from the washing of leached ore solids are generated at an approximate rate of 1 ,000
gallons per ton of ore processed and are discharged to the tailings ponds. In addition to radionuclides, solvent
extraction solutions include phosphoric acids, amines, and ammonium salts. Process water from alkaline leaching is
generated at a rate of 250 gallons per ton of ore processed and is discharged to the tailings pond.30 The supernatant
generated from precipitation and dewatering circuits can be recycled to the respective solvent extraction or ion
exchange stripping solutions.
Solvent extraction generates by-products (as defined in Section 1 le(2) of the Atomic Energy Act),
including waste acids, barren lixiviant, slimes, and waste solvents. These materials are not considered solid wastes
and are excluded from RCRA regulation at 40 CFR 261.4(a)(4).31'32'33 Although no published information regarding
generation rates for these materials was found, we used the methodology outlined in Appendix A of this report to
estimate low, medium, and high annual generation rates (see Exhibit 8).
2. Mineral Processing Wastes
Although no published information regarding waste generation rates or characteristics was found, we used
the methodology outlined in Appendix A of this report to estimate low, medium, and high annual waste generation
rates (see Exhibit 9).
10 CFR Part 61 provides the Nuclear Regulatory Commission with complete authority to regulate
radioactive waste defined as by-product material at a land disposal facility. The following wastes, therefore, may not
be subject to RCRA if they are not mixed hazardous wastes. It is unclear at this time if all wastes generated at in-situ
uranium mines are NRC by-product wastes. RCRA clearly has jurisdiction over mixed hazardous and radioactive
wastes.
Production of UO,
Waste Nitric Acid from the Production of UO2. Waste nitric acid is produced during dissolution of
yellowcake in nitric acid and during back-extraction. We used best engineering judgment to determine that
this waste may be partially recycled and may exhibit the characteristic of corrosivity. This waste was
formerly classified as a spent material.
Production
Waste Calcium Fluoride. Waste calcium fluoride, which typically contains elevated concentrations of
radionuclides resulting from yellowcake production, is regulated by the Nuclear Regulatory Commission.34
Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Vaporizer Condensate. We used best engineering judgment to determine that this waste may exhibit the
characteristic of corrosivity.
30 Clark, D., Op. Cit. pp. 50 - 51.
31 Kennecott Corporation. Op. Cit.
32 Rio Algom Corp. Op. Cit.
33 Uranium Resources, Inc. Op. Cit.
34
Rio Algom Corp. Op. Cit.
724
-------
Superheater Condensate. We used best engineering judgment to determine that this waste may exhibit the
characteristic of corrosivity,
EXHIBIT 8
Estimated By-Product Generation Rates
By-Product Material35
Waste Acids from Solvent Extraction
Barren Lixiviant
Slimes from Solvent Extraction
Waste Solvents
Generation Rate (metric tons/yr)
Low
1,700
0
1,700
0
Medium
9,350
1,700
9,350
0
High
17,000
17,000
17,000
i.7nn
EXHIBIT 9
Estimated Waste Generation Rates
Waste
Stream
Waste Nitric Acid from Production of UO,36
Vaporizer Condensate
Superheater Condensate
Slag
Uranium Chips from Ingot Production
Waste Generation Rate (metric tons/yr)
Low
1,700
1,700
1,700
0
1,700
Medium
2,550
9,350
9,350
8,500
2,550
High
3,400
17,000
17,000
17,000
3,400
Ames Process
Slag. We used best engineering judgment to determine that this waste may exhibit the characteristic of
ignitability. This waste is fully recycled and was formerly classified as a by-product.
Uranium Chips from Ingot Production. We used best engineering judgment to determine that this waste
may be recycled and may exhibit the characteristic of ignitability. This waste was formerly classified as a
by-product.
35 These materials, generated during uranium beneficiation from the solvent extraction process are not considered
solid wastes and are excluded from RCRA regulation at 40 CFR part 261.4(a)(4).
36
This waste is not considered by the Agency as a mineral processing waste, but a related waste.
725
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D. Non-uniquely Associated Wastes.
No non-uniquely associated waste streams have been identified in the uranium sector. However, standard
ancillary hazardous wastes may include vehicular emissions including particulates, sulfur oxides, carbon monoxide,
and hydrocarbons. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
some waste oil and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
Three commenters provided new information and clarifications of existing information related to the
uranium sector that the Agency has included in this report. (COMM40, COMM66, COMM72)
Sector-specific Issues
One commenter raised an specific issue relating to the use of the term solvent extraction in conventional
uranium milling operations. The commenter stated that the operation does not use halogenated hydrocarbons or
degreasers, but instead uses mostly kerosene with isodecanol and tertiary amine. The commenter suggested that a
better term for solvent extraction would be liquid ton exchange. EPA rejects this argument because the term "solvent
extraction" does not imply use of halogenated solvents. (COMM40)
726
-------
BIBLIOGRAPHY
Clark, D., State-of-the-Art: Uranium Mining. Milling, and Refining Industry. Prepared for EPA, Office of Water
Resources Research, Washington D.C,
Department of Energy, Decommissioning of U.S. Uranium Production Facilities. February 1995.
"Uranium and Uranium Compounds," Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol. XXIII,
1983, pp. 502-543.
"Uranium," in SME Mineral Processing Handbook. Vol. 2, 1985, p. 24-3.
U.S. Environmental Protection Agency, Assessment of Environmental Aspects of Uranium Mining and Milling,
December 1976.
U.S. Environmental Protection Agency, "Uranium," from Technical Resource Document, Extraction and
Beneficiation of Ores and Minerals. Vol. 5, January 1995.
Werthman, P., and K. Bainbridge, "An investigation of Uranium Mill Wastewater TreatabiJity," Proceedings of the
35th Purdue Industrial Waste Conference, 1980.
727
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Page Intentionally Blank
728
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VANADIUM
A. Commodity Summary
According to the U.S. Bureau of Mines, the domestic vanadium industry consists of twelve firms, of which
only six are active.1 Exhibit 1 presents the names and locations of the facilities involved in the production of
vanadium. Raw materials include Idaho ferrophosphorus slag, petroleum residues, spent catalysts, utility ash, and
vanadium bearing iron slag. Some vanadium is recovered from solution mining, however, that is only marginally
economically feasible. Estimated domestic consumption of vanadium in 1994 was 4,100 metric tons.2
EXHIBIT 1
SUMMARY OF VANADIUM PROCESSING FACILITIES
1 Facility Name
Akzo Chemical Company
AMAX Metals Recovery Corp
Bear Metallurgical Corp.
Cotter Corp.
Gulf Chemical & Metallurgical Corp.
Kerr-McGee Chemical Corp
Reading Alloys
Shieldalloy Metallurgical Corp
Stratcor
Teledyne Wah Chang
Umetco Minerals
Stratcor
Location
Weston, MI
Braithwaite, LA
Butler, PA
Canon City, CO
Freeport, TX
Soda Springs, ID
Robesonia, PA
Cambridge, OH
Niagara Falls, NY
Albany, OR
Blanding, UT
Hot Springs, AR
Type of Operations
Vanadium catalysts
Vanadium Pentoxide
Ferrovanadium
Vanadium pentoxide from uranium
byproducts (inactive)
Vanadium pentoxide
Vanadium pentoxide
Aluminum-vanadium master alloy
Ferrovanadium, ammonium
metavanadate, and aluminum-vanadium
Ferrovanadium, aluminum-vanadium
alloy, and Nitrovan (inactive)
Vanadium metal and vanadium-
zirconium alloy
Vanadium pentoxide from uranium
byproducts (inactive)
Vanadium pentoxide
Vanadium is principally used as an alloying element in iron and steel, with the steel industry accounting for
more than 80% of the world's consumption of vanadium. Vanadium is added to the steel making process as a
ferrovanadium alloy. This alloy is produced commercially by the reduction of vanadium pentoxide or vanadium
1 Henry E. Hillard, "Vanadium," from Minerals Yearbook Volume 1. Metals and Minerals, U.S. Bureau of
Mines, 1992, p. 1463.
2 Henry E, Hillard, "Vanadium," from Mineral Commodities Summary. U.S. Bureau of Mines, 1995, p. 184.
729
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bearing-slag with aluminum, carbon, or ferrosilieon,3 The addition of vanadium in amounts as small as 0.1 % to an
ordinary carbon steel can significantly improve both its toughness and its ductility. Such high-strength, low-alloy
(HSLA) steels are attractive for highrise buildings, bridges, pipelines, and automobiles because of the weight savings
obtained,4 Vanadium is also used in the production of titanium alloys for the aerospace industry and as the catalyst
for the production of maleic anhydride and sulfuric acid.5
B. Generalized Process Description
1. Discussion of Typical Production Processes
Vanadium is usually produced as the byproduct or eoproduct of another element, such as iron, uranium,
molybdenum, or phosphorus. In the United States, vanadium is recovered: (I) as a principal mine product, (2) as a
eoproduct from camotite ores, and (3) from ferrous slag as a byproduct in the production of elemental phosphorus.
Increasingly, it is also being recovered by secondary processing of petroleum refinery residues, fly ash, and spent
catalysts.* Exhibit 2 presents an overview of the processes used to recover vanadium from various raw materials.
As Exhibit 2 illustrates, the vanadium product from the primary process is sent either to an acid leach or a
salt roast process. The recovered vanadium product, usually sodium hexavanadate, is further processed to produce
vanadium pentoxide. The vanadium pentoxide can then be reduced further to produce vanadium metal either by the
aluminothermic, calcium, or carbon reduction processes. Each of these processes for preparing ferrovanadium is
described in more detail below.
Vanadium was also once extracted and recovered as a eoproduct with uranium from carnotite by direct
leaching of the ore with sulfuric acid. Alternatively, the uranium ore source was also roasted, followed by
concurrent leaching with dilute sulfuric acid. In some cases, die first leach was with a sodium carbonate solution.
The vanadium and uranium could then be separated from the pregnant liquor by liquid-liquid extraction techniques.7
Due to market factors and die price of uranium, vanadium is not currently recovered from uranium.8
2. Generalized Process Flow Diagram
Vanadium can be recovered both from the primary processing of ores and from secondary processing of
spent catalysts. In both cases, the production of vanadium can be separated into three general stages. Each of these
stages is described below and outlined in the accompanying flow diagrams. The first stage involves die production
of an oxide concentrate. The second stage involves the production of vanadium pentoxide either by fusion or
dissolution. Production of vanadium metal or ingot is the third stage in the operation.
3 Ibid., pp. 1449-1450.
4 Peter H. Kuck, "Vanadium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 895.
5 Ibid.
6 Henry E. Hillard, 1992, Op. Cit.. pp. 1447-1466.
7 Ibid., p. 1449.
8 Personal communication between Jocelyn Spielman, ICF Incorporated and Henry E. Hillard, Vanadium
Specialist, U.S. Bureau of Mines, October 20, 1994.
730
-------
SOURCE
EXHIBIT 2
GENERALIZED FLOWSHEET FOR PROCESSING VANADEFEROUS RAW MATERIALS
(Adapted from: Mineral Facts and Problems, 1905, pp. W5 • 914.)
VANADIUM PRODUCT VANADIUM RECOVERY VANADIUM PRODUCT REDUCTION
FROM PRIMARY PROCESS PROCESS RECOVERED PROCESS
VANADIUM
ADDITIVES
731
-------
EXHIBIT 3
SODIUM HEXAVANDATE PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
Vanadium-bearing
Material
Sodium Salt
Water
Sulfuric Acid
Wash Water
Solid Residues
Filtrate
Sodium hexavandate
732
-------
EXHIBIT 4
VANADIUM PENTOXIDE PRODUCTS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
OPTION 1
OPTION 2
Sodium Hexavandate
Vanadium Pentoxide
Sodium Hexavandate
I
Sodium
Solution
Ammonium
Dissolution
1
PH
Adjustment
I
Precipitation
1
Filtration
I
Calcination
^ Precipitate
*"~ (Impurities)
Vanadium Pentoxide
733
-------
EXHIBIT S
CALCIUM REDUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 198S, pp. 3-245 - 3-253.)
Vanadium Pentoxide
Metallic Vanadium
734
-------
EXHIBIT 6
ALUMINOTHERMIC REDUCTION OF VANADIUM PENTOXIDE
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
Vanadium Pcntoxide
Aluminum
Vanadium Ingot
735
-------
Exhibit 3 presents the process for preparing sodium hexavanadate. Exhibit 4 presents two alternative
processes producing vanadium pentoxide. Exhibits 5 and 6 present two alternative processes for reducing the
vanadium pentoxide to metal.
Production of Sodium Hexavanadate
Recovery From Ore. Regardless of the source of the ore, the first stage in the ore processing is the
production of an oxide concentrate. As shown in Exhibit 3, the ore is crushed, ground, screened, and mixed with a
sodium salt, e.g., NaCI or Na2CO3. This mixture is then roasted at about 850 °C to convert the oxides to water-
soluble sodium metavanadate. The solid mixture is then leached with water to dissolve the metavanadate and the
sodium chloride. The resulting slurry is filtered and the insoluble iron oxide and phosphate are sent to disposal.
Sodium hexavanadate (red cake) or sodium decavanadate is precipitated out by the addition of sulfuric acid and
recovered by filtration.9
If the recovery of vanadium is associated with the recovery of molybdenum, the initial step in the vanadium
recovery process is the removal of phosphorous by precipitation as insoluble magnesium phosphates. Aluminum, if
it is present in solution, is removed as the hydroxide by acidification followed by filtration. Vanadium is then
precipitated as ammonium metavanadate with excess NH4C1, and is separated from the liquid phase by filtration.
Molybdenum does not precipitate and the molybdenum-rich filtrate is routed to the molybdenum recovery process.
When the source for the vanadium recovery is molybdenum, the ammonium metavanadate produced by the NH4C1
precipitation is calcined and fused to produce vanadium pentoxide.10
Recovery From Spent Catalysts, Secondary processing of spent catalysts has become a major source of
vanadium, either using an oxidation catalyst from the production of sulfuric acid or maleic anhydride or a
hydroprocessing catalyst from petroleum refining. Vanadium is recovered by roasting, followed by milling,
leaching, and filtration to separate the solids from the solution containing vanadium. The solutions then go through
various precipitation steps before the precipitation of vanadium as ammonium metavanadate, which is then
decomposed and fused to form vanadium pentoxide or used directly to make other vanadium chemicals."
Production of Vanadium Pentoxide
Exhibit 4 presents two of the methods for producing vanadium pentoxide from sodium hexavanadate: (1)
fusion and (2) dissolution.
Fusion. The red cake or sodium hexavanadate can be further processed and fused at 700° C to yield a dense
black product which is sold as technical-grade vanadium pentoxide, as shown in Exhibit 5. This product contains a
minimum of 86 weight-percent pentoxide and a maximum of 8 weight-percent sodium oxide.'2
Dissolution. Alternatively, the red cake may be further purified by dissolving it in an aqueous solution of
sodium carbonate. Aluminum, iron, and silicate impurities precipitate from solution upon pH adjustment.
9 Ibid.
10 U.S. Environmental Protection Agency, Development Document for Effluent-Limitations Guidelines and
Standards for Nonferrous Metals Manufacturing Point Source Category. Vol. VI, Office of Water Regulations
Standards, May 1989, p. 3512.
" Ibid.
12 Henry E. Hillard, 1992, Op. Cit.. p. 1449.
736
-------
Ammonium metavanadate is then precipitated by the addition of ammonium chloride. The precipitate is calcined to
give a vanadium pentoxide product of greater than 99.8% purity.13
Production of Metallic Vanadium or Vanadium Ingot
Exhibits 5 and 6 present two alternative methods for reducing vanadium pentoxide to metallic vanadium.
Exhibit 5 shows the calcium reduction process and Exhibit 6 outlines the steps for aluminothermic reduction.
Vanadium pentoxide can also be reduced using either the thermit reaction (a variation on the aluminothermic
reduction) or by solid-state carbon reduction.
Calcium Reduction. Calcium reduction involves combining vanadium pentoxide with calcium, adding
iodine as a flux, and heating the mixture in a vacuum to form metallic vanadium. l
-------
* Recovery of vanadium from titaniferous slags by sulphiding."
• Recovery of vanadium from process residues.20
» Extraction of vanadium from industrial waste.21
• Recovery of pure vanadium oxide from Bayer sludge.22
4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from benefieiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, benefieiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Benefieiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in benefieiation.
Mineral processing operations, in contrast, generally follow benefieiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to benefieiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, benefieiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are benefieiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above in this section.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between the production of sodium hexavandate and the production of vanadium pentoxide and metallic vanadium.
EPA identified this point in the process sequence as where benefieiation ends and mineral processing begins because
it is here where a significant chemical change to the sodium hexavandate occurs. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as benefieiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than benefieiation wastes. EPA presents the mineral processing waste streams generated
19 G. J. Njau, B. Pei, and T. Rosenqvist, "Recovery of Reactive Metals (Manganese, Chromium, Vanadium) From
Titaniferous Slags by Sulfiding," Scandinavian Journal Of Metallurgy. 20, No. 2,1991, pp. 149-156.
20 C. R. Edwards, "The Recovery of Metal Values From Process Residues," JQM. 43, No. 6, June 1991, pp. 32-
33.
21 Y. K. Mukherjee and C. K. Gupta, "Extraction of Vanadium From an Industrial Waste," High Temperature
Materials and Processes. 11, Nos. 1-4, January 1993, pp.189-206.
22 Y. K. Mukherjee, S.P. Chakraborty, A.C. Bidaye, and C. K. Gupta, "Recovery of Pure Vanadium Oxide From
Bayer Sludge," Minerals Engineering. 3, Nos. 3-4, 1990, pp.345-353.
738
-------
after the beneficiation/processing line in section C.2, along with associated information on waste generation rates,
characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraetion/Beneficiation Wastes
Described below are those wastes identified as generated from primary mineral processing. Wastes
associated with the secondary processing and recovery from spent catalysts include ammonia emissions from
leaching, wastewater from solvent extraction, wastewater from filtration, and waste alumina.
From Sodium Hexavandate Production.
The following wastes are generated during the production of sodium hexavandate from ore.
Solid residues. Some of the wastes generated during sodium hexavanadate production include solid
residues from leaching and filtrates from filtration.23
Roaster Off gases
Spent Solvent
Spent Filtrate
2. Mineral Processing Wastes
Production of Vanadium Pentoxide.
Wet Scrubber Wastewater. At the facility that recovers vanadium from molybdenum, off gases from the
calcine furnace are controlled with a dry baghouse which recovers the dust particulates. In series with the baghouse
is a wet scrubber employing a dilute hydrochloric acid solution as the scrubbing medium. The scrubber liquor is
routed to the ammonia recovery and reuse system.24 The wastewater generated from scrubbing the emissions from
calcination contains sodium chloride and suspended ferrophosphorus particulates. In 1980, these wastes were
generated containing 30 kg of sodium chloride per kkg of product and up to 2 kg of ferrophosphorus particulates per
kkg of vanadium product. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Spent Precipitate, If the vanadium pentoxide is produced using dissolution, impurities are removed during
pH adjustment. Existing data and engineering judgment suggest that this material does not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Solid Waste. Solid wastes generated as a result of calcination include insoluble ferrophosphorus oxidation
products such as ferric oxide and ferric phosphate. In 1980, these wastes were reported to contain from 7,830 to
8,700 kg of ferric oxide per kkg of vanadium pentoxide product and from 14,670 to 16,300 kg of ferric phosphate
per kkg of vanadium pentoxide product. The waste were water slurried and sent to disposal areas. These solid
wastes are generally limestone treated to neutralize acidic material before the wastes are sent to evaporation ponds.
In 1980, the wastewaters generated by slurrying the solid wastes contained from 22,500 to 25,000 kg of iron oxides
23 U.S. Environmental Protection Agency, "Vanadium," from 1988 Final Draft Summary Report Mineral Industry
Processing Wastes, Office of Solid Waste, 1988, pp. 3-245 - 3-253.
24 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 3513,
739
-------
and iron phosphates per kkg of product,21 Existing data and engineering judgment suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Filtrate and Process Wastewaters, Wastewater resulting from the filtration in Option 2 on Exhibit 5,
contains sodium chloride and sodium sulfate. In 1980, these wastewaters contained from 1,750 to 2,000 kg of
sodium chloride per kkg of product and 933 kg of sodium sulfate per kkg of product. Other process wastewater from
the final vanadium pentoxide recovery steps contained 729 kg of ammonium sulfate per kkg of vanadium pentoxide
product.26 Existing data and engineering judgment suggest that this material does not exhibit any characteristics of
hazardous waste. Therefore, the Agency did not evaluate this material further.
Alloying and Metal Finishing
Slag. Wastes generated from the production of metallic vanadium include slag from calcium and
aluminothermic reduction.27 No further generation or management data are available. Existing data and engineering
judgment suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
25 Versar, Inc., "Vanadium Derivatives," from Assessment of the Inorganic Chemical Industry, Vol. IV, 1980, p.
32-7.
26 Ibid.
27 U.S. Environmental Protection Agency, 1988, Op. Cit. pp. 3-245 - 3-253.
740
-------
BIBLIOGRAPHY
Bartels, James and Theodore H. Gurr, "Phosphate Rock." From Industrial Minerals and Rocks. 6th ed. 1994. pp.
761-762.
Edwards, C R. "The Recovery of Metal Values From Process Residues." JOM. 43. No. 6. June 1991. pp. 32-33.
Hillard, Henry E. "Vanadium." From Minerals Yearbook Volume 1. Metals and Minerals. U.S. Bureau of Mines.
1992. pp. 1447-1466.
Hillard, Henry E. "Vanadium." From Mineral Commodity Summaries. U.S. Bureau of Mines. 1995. pp. 184-185.
Kuck, Peter H. "Vanadium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985. pp. 895-914,
Mukherjee, Y. K. and Gupta C. K. "Extraction of Vanadium From an Industrial Waste." High Temperature
Materials and Processes. 11. Nos. 1-4. January 1993. pp.189-206.
Mukherjee, Y. K., Chakraborty, S.P., Bidaye, A.C., and Gupta C. K. "Recovery of Pure Vanadium Oxide From
Bayer Sludge." Minerals Engineering. 3. Nos. 3-4. 1990. pp.345-353.
Njau, G J., Pei, B, and Rosenqvist T. "Recovery of Reactive Metals (Manganese, Chromium, Vanadium) From
Titaniferous Slags by Sulfiding." Scandinavian Journal Of Metallurgy, 20, No. 2. 1991. pp. 149-156.
Personal communication between Jocelyn Spielman, ICF and Henry Hillard, Vanadium Specialist, U.S. Bureau of
Mines, October 20,1994.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for Nonferrous Metals Manufacturing Point Source Category. Vol. VI. Office of Water Regulations
Standards. May 1989. p. 3512.
U.S. Environmental Protection Agency. "Vanadium." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. Office of Solid Waste. 1988. pp. 3-245-3-253.
741
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Page Intentionally Blank
742
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ZINC
•A.
Commodity Summary
The primary source of zinc is the mineral sphalerite (ZnS), which is the source of about 90 percent of zinc
produced today; zinc can also be recovered from six additional minerals, including hemimorphite, smithsonite,
zincite, hydrozincite, willemite, and franklinite.' The primary uses of zinc are as a protective coating for steel
(galvanizing), as alloys in die casting, as an alloying metal with copper to make brass and bronze, and in chemical
compounds (e.g., zinc oxide) in rubber and paintsre
Canada and Australia were the world's largest producers of zinc in 1994, accounting for 31 percent of mine
production, followed by China, Peru, the United States, and Mexico.3 Canada, Australia, and the U.S. also possess
39 percent of the world's zinc reserves. In the U.S., mines in Alaska, Missouri, New York, and Tennessee produced
more than 90 percent of the nation's total mine output in 1994 of 560,000 metric tons; the four largest U.S. mines (in
order of output) in 1992 and their operators and locations were the following:
Mine Name
Red Dog
Elmwood-Gordonsville
Greens Creek
Balmat
Operator
Cominco Alaska, Inc.
Jersey Miniere Zinc Co.
Greens Creek Mining Co.
Zinc Corp. of America (ZCA)
Location
Northwest Arctic, AK
Smith, TN
Admiralty Island, AK
St. Lawrence, NY
All of these mines produce zinc ore. In addition, several mines in the U.S. produce lead-zinc ore or lead ore with
secondary zinc values, which can be beneficiated to remove zinc for processing. The larger of these mines include
the West Fork and Fletcher mines in Reynolds, MO; the Buick mine in Iron, MO; and die Lucky Friday mine in
Shoshone, ID.4
Four primary zinc smelters (three using the electrolytic process, the fourth using the electrothermic or
pyrometallurgical process) produced 240,000 metric tons of slab zinc in 1994.5 These plants and dieir location and
process type include the following:
1 "Zinc and Zinc Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XXIII, 1983, p. 808.
2 U.S. Bureau of Mines, Mineral Facts and Problems. Bulletin 675, 1985, p. 923.
3 U.S. Bureau of Mines, "Zinc," from Mineral Commodity Summaries. January 1995, p. 191.
4 Jolly, J., "Zinc," in Minerals Yearbook Volume 1. Metals and Minerals 1992. U.S. Bureau of Mines, 1992, p.
1477.
5 U.S. Bureau of Mines, 1995, Op. Cit., p. 190.
743
-------
Facility Name
Big River Zinc Corp,
Jersey Miniere Zinc Co.
Zinc Corp. of America*
Zinc Corp. of America
Location
Sauget, IL
Clarksville, TN
Bartlesville, OK
Monaca, PA
Process
electrolytic
electrolytic
electrolytic
pyrometallurgical
' This facility is no longer operating.
Zinc oxide was produced from zinc metal and scrap by eight companies in 1992. All of these companies
produced French-process zinc oxide, except for one company, Eagle Zinc Co., of Hillsboro, IL, which produced
American-process zinc oxide (both processes are described below).7 Total U.S. production of zinc oxide in 1992
was approximately 105,000 metric tons.
In addition, the U.S. also imported 25,000 metric tons of zinc ore and concentrate and 800,000 metric tons
of slab zinc, scrap, and compounds in 1994,8
B. Generalized Process Description
1. Discussion of Typical Production Processes
Zinc minerals are usually associated with other metals minerals, the most common associations in ores
being zinc-lead, lead-zinc, zinc-copper, copper-zinc, or zinc-silver. Zinc also occurs alone in ores. Due to low zinc
content, zinc-bearing ores must be concentrated before processing. Beneficiation, which usually occurs at the mine,
consists of crushing, grinding, and flotation to produce concentrates of 50-60 percent zinc.9
Zinc is processed through either of two primary processing methods, electrolytic or pyrometallurgical.
However, before use of either method, zinc concentrate is roasted to remove the sulfur from the concentrate and
produce impure zinc oxide, referred to as roasted concentrate or calcine. In electrolytic zinc processing, calcine is
digested with sulfuric acid to form a zinc sulfate solution, from which zinc is deposited through electrolytic refining.
In pyrometallurgical processing, calcine is sintered and smelted in batch horizontal retorts, externally-heated
continuous vertical retorts, or electrothermic furnaces. The sole pyrometallurgical operation in the U.S., Zinc Corp.
of America's Monaca smelter, uses an electrothermic furnace. In addition, zinc is smelted in blast furnaces through
the Imperial Smelting Furnace (ISF) process, which is capable of recovering both zinc and lead from mixed zinc-lead
concentrates. The process is used at 12 plants worldwide and accounts for 12 percent of world capacity. There are
no ISF-process plants in the U.S.10
Zinc oxide is manufactured by either the French or American processes. In the French process, which is
used at ZCA's Monaca smelter, high-grade zinc metal is smelted in horizontal retorts to produce zinc metal vapor.
6 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
7 Jolly, J., 1992, Op, ...Cit.. p. 1472.
8 U.S. Bureau of Mines, 1995, Op. Cit. p. 190.
* "Zinc and Zinc Alloys," 1983, Op;Cit.. pp. 809, 812.
10 U.S. Bureau of Mines, 1985, Op. Cit.. pp. 927-928.
744
-------
which is burned in a combustion chamber. In the American process, zinc oxide is manufactured by oxidizing zinc
vapor in burners; the resulting gases and fume are cooled, and zinc oxide is recovered in baghouses."
2. Generalized Process Flow Diagram
Detailed descriptions of Zinc Corp, of America's Bartlesville, OK (electrolytic) and Monaca, PA
(pyrometallurgical) facilities are presented below. These descriptions are based on sampling trips to the facilities in
1989 in support of EPA rulemaking activities. Although the ZCA facility is no longer operating, the information
presented below still may be applicable to the two remaining operational facilities.
Electrolytic Process
The ZCA electrolytic zinc refinery in Bartlesville, Oklahoma produced several zinc products and associated
by-products from zinc ore concentrates. Zinc products included zinc metal, roofing granules, and zinc sulfate
solution. By-products included cadmium metal, sulfuric acid, lead/silver residue, copper residue, nickel/cobalt
residue, lead scrap, and aluminum scrap. ZCA used zinc sulfide concentrates containing 50-55 percent zinc as the
principal feed for its Bartlesville plant.
Production of zinc products from ore concentrates at this facility involved roasting, leaching (digestion),
purification, and electrowinning. Roasting took place at the Zinc Ore Roaster (ZOR), and the remaining three
processes occurred at tihe Zinc Refinery (ZRF), as shown in the process flow diagram in Exhibit 1. Both the ZOR
and the ZRF are located at the Bartlesville plant.
Zinc ore concentrates were first slurried with water and then roasted, reacting with air to produce a crude
zinc oxide calcine and off-gas from the roaster containing 7-10 percent sulfur dioxide. Calcine dusts were recovered
from the off-gas by two cyclone separators and added to the calcine. The off-gas was humidified and passed through
a wet electrostatic precipitator in a hot tower to remove remaining solids from the sulfur dioxide gas so that it could
be used as feed to produce sulfuric acid in the Zinc Acid Plant (ZAP). Two-thirds of the resulting liquid stream from
the precipitator, known as acid plant blowdown, was pumped directly to the facility's wastewater treatment plant, and
the remaining third was recycled to the hot tower. Total acid plant blowdown flow was approximately 50 gallons per
minute. Process wastewater generated by the ZOR consisted of non-contact cooling water used to cool the calcine as
it exited the roaster and slurry water that leaked from a pump that directed the slurried ore concentrates to the
roaster. These waters were collected in a clay-lined sump outside die roaster and were pumped to the wastewater
treatment plant. A process wastewater stream generated at the ZAP, consisting of cooling tower blowdown, was
pumped directly to the treatment plant.
The leaching (digestion) process dissolved the zinc in the calcine, creating a zinc sulfate solution from
which the zinc could be removed through electrowinning. By mixing die calcine from the roaster with 150-170 g/L
sulfuric acid in a step called neutral leaching, about 90 percent of the zinc in the calcine dissolved. The insoluble
zinc calcine was separated from the leaching solution in a settling tank. Neutral leach zinc sulfate solution was sent
to a purification system, and the solids containing the insoluble zinc were pumped to a residue treatment circuit,
where additional sulfuric acid was added to the solids in a series of three hot acid leach tanks to dissolve another 6-7
percent of the zinc from die calcine. Remaining solids in the resulting slurry were separated in a second settling tank
and filtered into a cake that was dried and sold for its lead and silver content (20 percent lead and up to 70 ounces of
silver per ton).
When the calcine was leached with sulfuric acid in the hot acid leach tanks, iron in the calcine dissolved
along with the zinc. Because this solution still contained recoverable zinc, ZCA recycled the solution to the original
"Zinc and Zinc Alloys," 1983, Op. Cit.. pp. 855.
745
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EXHIBIT 1
ELECTROLYTIC ZINC PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 479.)
H2SO4
t
t
Preleach
Plant
Preleach f
Wastewater to
Treatment
1 »,
^*
, to-
Underflow
Solids to
Copper or "^
Lead Refinery
Solids to
Cadmium -^
Plant
Zinc Oxide
Water— ^
• Zinc
w Concentrate
Storage
t
Roaster
t
Classifier
& Ball Mill
t
Digestion
t
Thickeners
& Filters
t
Zinc
Solution
Purification
t
Electrolysis
t
Cathode
Melting
Furnace
t
Casting
^ Gaseous Emissions
to Acid Plant
*4 Calcine Dust
Zinc Solution
-««^ from Cadmium
^ Plant
Electrolyte Bleed
_ I Wash Water to
, , , Treatment
Acid
Zinc
Dust
^(Zooling Tower
Slowdown
Slag Y Other Shapes
Blocks
746
-------
neutral leach step described above. However, if the dissolved iron in the solution is not removed, it will prevent the
eventual recovery of zinc metal. To remove iron from the solution, ZCA utilized the goethite process.12 Zinc sulfide
concentrates were added to the hot acid leach solution to reduce the dissolved iron to its ferrous or divalent state.
Zinc calcine was added to neutralize remnant sulfuric acid from the hot acid leach step. Zinc oxide and air were then
added to the solution to oxidize the iron from its divalent to trivalent state and precipitate goethite, a hydrated iron
oxide, in a slurry. The slurry settled in a tank; the clarified solution containing recoverable zinc was recycled to the
neutral leach step, and the iron oxide slurry (goethite) solids were washed and filtered.
Goethite removed from the filter contained 30-40 percent iron, but a 1989 study found that recovery of the
iron was not economical.13 Moist goethite cake was stored in an uncovered, unlined waste pile onsite that dates from
1978, when the electrolytic process began at the facility. Runoff from the pile flowed to a clay-lined sump pond and
dien to the wastewater treatment plant.
In the purification step, trace impurities from the zinc oxide calcine that dissolved in the leaching steps were
removed from the neutral leach solution. Like iron, these impurities must be removed so that zinc can be converted
to metal. Zinc dust was added to the solution to chemically replace copper and cadmium, which precipitate out of
solution as a sludge. Cadmium metal and copper residue were recovered for sale. Zinc dust was again added, along
with antimony as a catalyst, to replace nickel and cobalt, which also were recovered for sale. These residues were
stockpiled along with others, such as sump and tank cleanings, on an unlined pad until they were sold or recycled.
Runoff from the pad collected in a sump and was pumped to a large surface impoundment and eventually to the
wastewater treatment plant.
Purified, zinc-rich solution was cooled in evaporative cooling towers and stored in tanks before the zinc was
electrowon from the solution at the cell house. The cell house consisted of 128 electrolytic cells, each with 45 lead
anodes and 44 aluminum cathodes. When electric current passes through the zinc sulfate solution, which serves as
an electrolyte, positive zinc ions deposit on the negatively-charged aluminum cathodes. Half of the cathodes were
removed from their cells each day so that the metallic zinc layer could be scraped off each cathode and so that zinc
could continue to be removed from solution with the other cathodes. Spent solution containing dilute sulfuric acid
was recycled to the neutral leach step of the leaching process. Because of heat build-up in the cells, the zinc sulfate
solution has continuously passed through cooling towers. Non-contact cooling water along with boiler blowdown,
condensate, and brushing water used to wash cathodes made up a process wastewater stream from the ZRF. This
stream flowed through a feeder ditch to a clay-lined sump pond, then to a large, clay-lined surface impoundment, and
was finally pumped to the wastewater treatment plant.
Zinc removed from cathodes was melted in a furnace and cast into 55-pound, 600-pound, or 2,400-pound
ingots. Some zincwa s converted to dust used in the purification system. Zinc fume collected in the furnace
baghouse was recycled. ZCA also converted scrap zinc from its plant and purchased scrap into usable zinc at its
Zinc Secondaries Plant (ZSP), a process that is outside the scope of primary mineral processing and, thus, not
described further.
Most process wastewaters at ZCA were made up of small streams from the roasting, purification,
electrowinning, and zinc secondaries processes. Acid plant blowdown was generated when sulfur dioxide off-gas
from the ZOR passed through a wet electrostatic precipitator in the hot tower to remove solids. Process wastewater
from the ZSP consisted primarily of water from Venturi scrubbers used to collect dusts from rotary drying of calcine.
Process wastewater from the ZRF consisted primarily of brushing water used to wash the aluminum cathodes that
served as a depositional surface for zinc ions during electrowinning. The ZAP, which converted sulfur dioxide gas
generated in the ZOR to commercial-grade sulfuric acid, generated process wastewater consisting of non-contact
cooling tower blowdown. Smaller streams of boiler blowdown, non-contact cooling water from cooling towers, and
condensate also made up the wastewater flow.
12
Additional methods to precipitate iron include the hematite and jarosite processes.
13As of July 1989, ZCA was studying a pilot system to recover iron from goethite: the status of this project is
unknown.
747
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Process wastewater and plant runoff that collected in the two large, clay-lined surface impoundments were
pumped to the wastewater treatment plant. Following a two-stage neutralization process and clarification, sludge
was recycled to the roaster and treated water was pumped to two synthetically-lined holding ponds before it was
injected in a Class I industrial well.
Pyrometallurgical Process
The primary mineral processing operations at the Monaca facility produce a variety of zinc and other
products from ore concentrate (primarily from a New York State mine) and, to a lesser extent, secondary materials
(e.g., cast off material from galvanizing operations). Zinc products include zinc metal, zinc sulfate solution, zinc
dust, and zinc oxide. Other products produced by the facility including sulfuric acid, lead sulfate, cadmium sponge,
ferro-silicate, and processed slag. Due to variations in market conditions, some of these materials, especially ferro-
silicate and slag, may be stored on-site for several years prior to sale,
Ore concentrate is first dried in an ore dryer and then roasted, as shown in the process flow diagram in
Exhibit 2. Off-gas from the ore dryer is scrubbed prior to discharge to the atmosphere and off-gases from roasting
are cleaned prior to being used as the feedstock for sulfuric acid production. Ore dryer scrubber water and acid plant
blowdown (from roaster gas cleaning operations) are mixed in a concrete basin (the "Cottrell pond") where the pH is
raised to prevent corrosion of plant piping prior to being returned to the scrubber or being used as feed in the
sintering process.
The sintering process, which follows roasting, agglomerates the oxidized ore concentrate in preparation for
furnactng. Dust removed from sintering off-gases in baghouses is returned to the sintering operation or used as a
feed to the zinc sulfate circuit.14 The zinc sulfate circuit consists of a series of steps in which the baghouse dust is
first slurried with water and soda ash. The solids (metal carbonates) are then removed from this slurry in a clarifier,
the overflow from which goes to the facility's wastewater treatment plant. Underflow from the clarifier is
centrifuged; liquid removed by the centrifuge is pumped to a concrete basin and then returned to the clarifier and the
solids are leached with sulfuric acid, which solubilizes zinc and cadmium sulfates. Solids are separated using a filter
press and sold for lead recovery. Zinc dust is added to the remaining sulfate solution to precipitate cadmium sponge,
which is sold to a cadmium metal producer, leaving a zinc sulfate solution, which also is sold as a product.
Sinter and coke are charged to an electrothermal furnace in which zinc gas is generated and subsequently
condensed on molten zinc. Uncondensed zinc is removed from the off-gases by a wet scrubber. Water from the wet
scrubber is sent to two concrete basins and then a series of three lined impoundments. About half of the water is then
returned to the scrubber while the other half is sent to the wastewater treatment plant. Blue powder, a mixture of
primarily zinc oxides and elemental zinc, settles out of the scrubber water in both the concrete basins and the
impoundments. Blue powder is removed from the concrete basins on a weekly basis and placed in adjacent concrete
basins to dry prior to being returned to the ore dryer or used to raise the pH of the combined acid plant blowdown
and ore dryer scrubber water. Blue powder is removed from the impoundments along with the impoundment liners
every two or three years, and both the powder and the liners are charged to the furnace.
Zinc from the furnace is made into a variety of final products including furnace grade and high purity zinc
metal, zinc dust, and zinc oxide. Furnace residues are processed to recover coke, which is returned to the furnace as
fines generated by the processing operations, to separate the ferrous and non-ferrous fractions. The ferrosilicates are
stockpiled on site and sold to the iron and steel industry when market conditions permit. The non-ferrous slag is
graded into four sizes and sold or used as a drainage material in the facility's fly ash landfill.
14 Feed to the zinc sulfate circuit also consists of zinc carbonate that was generated before the zinc sulfate circuit
became operational and that is stockpiled on site.
748
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EXHIBIT 2
PYROMETALLURGICAL ZINC PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 480.)
Zinc Concentrates
Gaseous Emissions
to Acid Plant
Recycle Dust
Slab Zinc
Special High
Grade
Zinc Oxide
French
Process
Moisture Calcine Coke
Coal, Clay and Binder
Stack
Slab Zinc
Lower Grades
Zinc Oxide
American
Process
Plant Use
Ferrosilicon
High Zinc Concentrate
Recycled
Reclaimed Coke
Recycled
Lead-Silver
Concentrate to
Lead Plant
749
-------
Wastewaters, which include plant runoff as well as process wastewater from the blue powder impoundments
and the zinc sulfate circuit, go to a lined equalization basin and then to a two-stage neutralization process, followed
by clarification prior to discharge to the Ohio River through an NPDES-permitted outfall. Solids removed from the
clarifier are filtered and then returned to the sintering operation.
3. Identification/Discussion of Novel (or otherwise distinct) Processes
In addition to the Imperial Smelting Furnace process, which is identified above, several other novel
processes for zinc recovery are being (or have been) investigated or utilized.
A research program is being conducted at the Colorado School of Mines for developing a pyrochemical
process using molten salts for recovering reactive metals, including zinc, from beneficiated ore. The process takes
place in a hybrid reactor combining electrolytic production of a calcium reductant and in situ utilization of the
reductant to reduce metal compounds. The reactor operates at a temperature of less than 1,000°C. The technology
reportedly generates little waste.15
Two companies in Canada (Cominco and Kidd Creek) utilize pressure leaching to digest zinc ore
concentrates, eliminating both the roasting step and the need for a sulfuric acid plant in the electrolytic process. Zinc
concentrate is reacted with oxygen and electrolyte recovered from the electrowinning step in a pressure autoclave.
Zinc dissolves and forms zinc sulfate, which is sent to the electrowinning step. Sulfur in the zinc concentrate is
converted to elemental sulfur as part of the residue and is extracted or wasted with the residue. The process
reportedly has lower capital costs than a traditional electrolytic plant.1*
Sulfate roasting of copper-zinc-sulfide concentrate has been examined on a laboratory and pilot-plant scale
in open-hearth and fluidized bed furnaces. The resulting calcine was leached with mild sulfuric acid; zinc and iron
were co-extracted from the leach solution with D2-EPHA (a solvent extractant), and copper sulfate was crystallized
from the purified solution. Recoveries of 95 percent and 99 percent were achieved for zinc and copper,
respectively.17
A solvent extraction process for treating waste streams from electrowinning was developed using acid-base
couple extractants composed of amines and organic acids. Approximately 95 percent of both zinc (as zinc sulfate)
and sulfuric acid in the bleed stream was recovered at concentrations high enough for direct recycle to the process.18
AMAX created a process to recover zinc and other metals from RCRA-hazardous zinc leach residue
through brine leaching. The process involves leaching the residue with a CaCl2 brine solution at pH 2 for one hour at
90°C. Silver, lead, copper, cadmium, zinc, and iron were extracted at percentages of 95, 80, 50, 50, 30, and less
than 0.5 percent, respectively. Zinc was recovered through sulfide precipitation. The remaining residue passed the
EP toxicity test.19
15 Mishra, B., D. Olson, and W. Averill, "Applications of Molten Salts in Reactive Metals Processing," presented
at the Conference for Emerging Separation Technologies for Metals and Fuels, Palm Coast, FL, March 13-18, 1993,
sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
16 U.S. Bureau of Mines, 1985, Op. Cit., p. 927
17 Ferron, C. and J. De Cuyper, "The Recovery of Copper and Zinc from a Sulphide Concentrate Using Sulfate
Roasting, Acid Leaching and Solution Purification," International Journal of Mineral Processing. 35, No. 3-4,
August 1992, pp. 225-238.
18 Eyal, A., et. al. 1990, Op. Cit.. pp. 209-222.
19 Beckstead, L., etal. 1993, Op. Cit.. pp. 862-875.
750
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4. Beneficiation/Processing Boundary
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
prior to the initial roasting step in both the electrolytic and the pyrometallurgical processes. EPA identified this
point in the process sequence as where beneficiation ends and mineral processing begins because it is here, where, as
a result of a chemical reaction, sulfur is removed from the zinc sulfate feedstock. Therefore, because EPA has
determined that all operations following the initial "processing" step in the production sequence are also considered
processing operations, irrespective of whether they involve only techniques otherwise defined as beneficiation, all
solid wastes arising from any such operation(s) after the initial mineral processing operation are considered mineral
processing wastes, rather than beneficiation wastes. EPA presents the mineral processing waste streams generated
downstream of the beneficiation/processing line in section C.2, along with associated information on waste
generation rates, characteristics, and management practices for each of these waste streams.
C. Process Waste Streams
1. Extraction/Beneflciation Wastes
Wastes generated by lead-zinc mining operations include materials such as waste rock, tailings, and refuse.
Many of these materials may be disposed of either on-site or off-site, while others may be used or recycled during
the active life of the operation. Waste constituents may include base metals, sulfides, or other elements found in the
ore, and any additives used in beneficiation operations. The primary waste generated by mineral extraction in
underground mines is mine development rock, which is typically used in on-site construction for road building or
other purposes. Surface mines usually generate large volumes of overburden and waste rock that are generally
disposed of in waste rock dumps.
After the removal of values in the flotation process, the flotation system discharges tailings composed of
liquids and solids. Between 1A and Vi of the tailings generated are made up of solids, mostly gangue material and
small quantities of unrecovered lead-zinc minerals. The liquid component of the flotation waste is usually water and
dissolved solids, along with any remaining reagents not consumed in the flotation process. These reagents may
include cyanide, which is used as a sphalerite depressant during galena flotation. Most operations send these wastes
to tailings ponds where solids settle out of the suspension. The liquid component either is recycled back to the mill
or discharged if it meets water quality standards. The characteristics of tailings from the flotation process vary
751
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greatly, depending on the ore, reagents, and processes used. Lead, zinc, chromium, iron, and sulfate were all found
in the wastewater of the selected facilities.20
In general, most wastes from beneficiation of lead-zinc ores are disposed of in tailings impoundments from
which water is likely to be reclaimed during the mine's life. In addition, other materials typically not considered
wastes, such as mine water, may be managed on-site during the active life of the facility and may ultimately become
wastes. The chemical composition of mine water generated at mines varies from site to site and is dependent on the
geochemistry of the ore body and the surrounding area. Mine water may also contain small quantities of oil and
grease from extraction machinery and nitrates (NO3) from blasting activities. EPA21 and the Bureau of Mines22
reported concentration ranges in mine waters of 0.1-1.9 mg/L for lead, 0.12-0.46 mg/L for zinc, 0.02-0.36 mg/L for
chromium, 295-1,825 mg/L for sulfate, and pH of 7.9-8.8. After the mine is closed and pumping stops, the potential
exists for mines to fill with water. Water exposed to sulfur-bearing minerals in an oxidizing environment, such as
open pits or underground workings, may become acidified.
In addition to wastes generated as part of beneficiation, facilities also store and use a variety of chemicals
required by the mine and mill operations. A list of chemicals used at lead-zinc mines, compiled from data collected
by the National Institute for Occupational Safety and Health (NIOSH), is provided below.23
Acetylene Propane Copper Solution
Calcium Oxide Sodium Cyanide Kerosene
Hexone Sulfur Dioxide Methane, Chlorodifuoro-
Hydrogen Chloride Sulfuric Acid Sodium Aerofloat
Methyl Chloroform Diesel Fuel No. 1 Sulfuric Acid Copper (2+) Salt
Methyl Isobutyl Carbinol Diesel Fuel No. 2 Zinc Solution
Nitric Acid Chromic Acid, Disodium Salt Zinc Sulfate
2. Mineral Processing Wastes
Electrolytic refining operations generate two mineral processing wastes: goethite and leach cake residues,
and saleable residues. These are described below. Wastes formerly generated by the closed ZCA refinery in
Bartlesville, OK have been removed from the input data set to the Regulatory Impact Analysis. The waste stream
descriptions below also have been modified to reflect the fact that wastes from the ZCA facility are no longer being
generated.
Spent Goethite and Leach Cake Residues
Goethite is generated to remove iron from the zinc sulfate solution generated by leaching calcine with
sulfuric acid. Approximately 15,000 metric tons of goethite are generated annually in the U.S.24 Site-specific
information on management practices for goethite were available for only one facility, ZCA's Bartlesville, OK
20 Coppa, L., Waste Disposal Activities and Practices in the United States: Copper. Lead. Zinc. Gold, and Silver.
U.S. Bureau of Mines, Division of Minerals Availability Open File Report, November, 1984, Washington, DC.
21 U.S. Environmental Protection Agency, Report To Congress: Wastes From the Extraction and Beneficiation of
Metallic Ores. Phosphate Rock. Asbestos. Overburden from Uranium Mining and Oil Shale. EPA/530/SW-85-033,
Office of Solid Waste, December, 1985, Washington, DC.
22 Coppa, L., 1984, Op. Cit..
23 National Institute for Occupational Safety and Health, 1990.
24 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste, August 1992, pp. 1-8.
752
-------
refinery. Moist goethite cake was stored in an uncovered, unlined waste pile on-site that dated from 1978, when the
electrolytic process began at the facility. Runoff from the pile flowed to a clay-lined sump pond and then to the
facility's wastewater treatment plant. We used best engineering judgment to determine that spent goethite and leach
cake residues may exhibit the characteristic of toxicity for arsenic, cadmium, chromium, lead, mercury, selenium,
and silver. This waste stream is fully recycled and formerly was classified as a by-product. Data for this waste
stream are presented in Attachment 1.
Saleable Residues
Approximately 10,000 metric tons of various saleable residues are recovered annually in the purification of
the neutral leach zinc sulfate solution.25 These include a lead- and silver-bearing filter cake; a copper and cadmium
sludge, which is created by adding zinc dust to the solution; and a nickel and cobalt residue, also created by adding
zinc dust along with antimony as a catalyst. These residues are stockpiled along with others, such as sump and tank
cleanings, on an unlined pad until they are sold or recycled. Runoff from the pad collects in a sump and is pumped
to a large surface impoundment and eventually to the wastewater treatment plant. Because these residues are
recycled, they are not believed to be solid wastes. JMZ uses its wastewater treatment sludges to produce a
commercial product, synthetic gypsum.26 No chemical characterization data are available at present for these
residues.
Oxide retorting, considered a secondary mineral process because it uses primary zinc metal as a feedstock,
generates clinker as a secondary mineral processing waste. We used best engineering judgment to determine that this
clinker may exhibit the characteristic of toxicity for cadmium.27
Production of primary zinc metal at both electrolytic and pyrometallurgical zinc processing plants generate
several waste streams common to both processes, as described below.
Process Wastewater
Process wastewater is generated at all three of the operating zinc processing plants. Again using ZCA's
formerly active electrolytic refinery in Bartlesville, OK as an example, process wastewaters consisted of small
streams from the roasting, purification, electrowinning, and zinc secondary processes, as described above. Process
wastewater and plant runoff collected in two large, clay-lined surface impoundments and were pumped to the
wastewater treatment plant for neutralization. At ZCA's Monaca, PA smelter, wastewaters include plant runoff as
well as process wastewater from the blue powder impoundments and the zinc sulfate circuit. These wastewaters
collect in a lined equalization basin and are treated in a two-stage neutralization process. Approximately ^.6 million
metric tons of process wastewater are generated annually at the four U.S. primary zinc facilities.28 (The excessive
generation rate for this wastewater [i.e., greater than one million metric tons/yr] is due to commingling of numerous
individual waste streams.) We used best engineering judgment to determine that process wastewater may be
recycled and may exhibit the characteristic of toxicity for arsenic, cadmium, chromium, lead, selenium, and silver; it
may also exhibit the corrosivity characteristic. This waste formerly was classified as a spent material. Data for this
waste stream are presented in Attachment 1.
25 Ibid.
16 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25, 1996.
27 U.S. Environmental Protection Agency, 1992, Op. Cit. pp. 1-8.
28 Ibid.
753
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Acid Plant Blowdown
Acid plant blowdown is generated when sulfur dioxide off-gas from the roasting operations passes through
a wet electrostatic precipitator to remove solids. At ZCA's Bartlesville plant, two-thirds of the acid plant blowdown
was pumped directly to the facility's wastewater treatment plant, and the remaining third was recycled to the hot
tower. At the Monaca facility, acid plant blowdown is discharged to a concrete basin where the pH is raised to
prevent corrosion of plant piping prior to being returned to the scrubber or being used as feed in the sintering
process. Approximately 98,000 metric tons of acid plant blowdown are generated annually at the three U.S. primary
zinc facilities.29 We used best engineering judgment to determine that acid plant blowdown may exhibit the
characteristic of toxicity for arsenic, cadmium, chromium, selenium, and silver; it may also exhibit the corrosivity
characteristic. Data for this waste stream are presented in Attachment 1. We used best engineering judgment to
determine that this waste may also exhibit the characteristic of toxicity for lead and mercury. Although this waste
stream is listed as hazardous, it is no longer generated and accordingly, EPA has revoked its listing as a hazardous
waste. Therefore, this waste stream was not included in our analysis.
Spent Cloths, Bags, and Filters
Cloths, bags, and filters are utilized in operations at each of the three zinc facilities and may become
contaminated with potentially hazardous constituents. Approximately 150 metric tons of these waste materials are
generated annually,30 We used best engineering judgment to determine that spent cloths, bags, and filters may
exhibit the characteristic of toxicity for cadmium, lead, mercury, selenium, and silver. This waste stream is recycled
and formerly was classified as a spent material.
TCA Tower Blowdown
Approximately 250 metric tons of TCA tower blowdown are generated annually. We used best engineering
judgment to determine that TCA tower blowdown may exhibit the characteristic of toxicity for cadmium, lead,
mercury, and selenium; it may also exhibit the corrosivity characteristic.
Spent Synthetic Gypsum
Synthetic gypsum is generated during the treatment of bleed electrolyte from the electrowinning circuit.
Approximately 16,000 metric tons are generated annually.31 The management practice for this mineral processing
waste is unknown, but the gypsum is most likely stockpiled on-site. We used best engineering judgment to
determine* that spent synthetic gypsum may exhibit the characteristic of toxicity for arsenic, cadmium, and lead. Data
for this waste stream are presented in Attachment 1.
Wastewater Treatment Plant Liquid Effluent
Wastewater treatment plant liquid effluent results from the treatment of process wastewaters, including acid
plant blowdown, and plant runoff. Approximately 2.6 million metric tons of effluent are generated annually by the
three operating U.S. plants.32 Effluent generated at ZCA's Bartlesville plant was discharged to a Class I industrial
injection well on site, while effluent from the Monaca smelter is discharged through an NPDES-permitted outfall to
the Ohio River. We used best engineering judgment to determine that wastewater treatment plant liquid effluent may
be partially recycled and may exhibit the characteristic of toxicity for cadmium. This waste stream was formerly
classified as a spent material. Data for this wastestream are presented in Attachment 1.
'29 Ibid.
30 Ibid.
31 Ibid.
32 Ibid.
754
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Wastewater Treatment Plant Sludge
Wastewater treatment plant sludge also results from the treatment of process waste waters, acid plant
blowdown, and plant runoff. Approximately 34,000 metric tons of sludge are generated annually by the three
operating U.S. plants.33 At ZCA's Monaca plant and JMZ's Clarksville plant, these solids are recycled to the zinc ore
roaster for recovery of metal values. We used best engineering judgment to determine that wastewater treatment
plant sludge may exhibit the characteristic of toxicity for cadmium. Data for this waste stream are presented in
Attachment 1.
Spent Surface Impoundment Liquids
Surface impoundment liquid consists of process wastewaters, acid plant blowdown, and plant runoff, the
majority of which is sent on to the wastewater treatment plant. Approximately 1.9 million metric tons of liquids are
generated annually by the three operating plants.34 (The high generation rate for this wastewater is due to
commingling of numerous individual waste streams.) We used best engineering judgment to determine that spent
surface impoundment liquids may exhibit the characteristics of corrosivity and toxicity (cadmium). This waste
stream may be partially recycled and was formerly classified as a spent material. Data for this waste stream are
presented in Attachment 1.
Spent Surface Impoundment Solids
Surface impoundment solids primarily consist of solids that settle out of sludges from treatment of process
water and/or acid plant blowdown. These materials, previously discharged to surface impoundments, are now
managed in tanks and containers.35 Approximately 750 metric tons of solids are generated annually by the three
operating plants.36 We used best engineering judgment to determine that these solids may exhibit the characteristic
of toxicity for arsenic, cadmium, lead, mercury, selenium, and silver. Data for this waste stream are presented in
Attachment 1.
Smelting of zinc ore concentrate generates four mineral processing wastes: zinc-rich slag, zinc-lean slag,
ferrosilicon, and refractory brick.
Zinc-rich Slag
Zinc-rich slag results from the distillation of purified zinc vapor in the electrothermic furnace.
Approximately 157,000 metric tons are generated annually at the Monaca facility.37 EP leach test concentrations of
all eight inorganic constituents with EP toxicity regulatory levels are available for one sample of zinc slag from the
Monaca facility. Of these constituents, only lead was found to exceed the EP toxicity regulatory level, by a factor of
12. The zinc slag sample that failed the EP toxic level was also analyzed using the SPLP leach test, and the lead
concentration measured using the SPLP leach test was three orders of magnitude below the EP toxic level.38
33 Ibid.
34 Ibid.
35 National Mining Association. Comment submitted in response to the Supplemental Proposed Rule Applying
Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes. January 25,1996.
36 U.S. Environmental Protection Agency, 1992, Op. Cit.. pp. 1-8.
37 Ibid.
38 U.S. Environmental Protection Agency, "Primary Zinc Processing," from Report to Congress on Special
Wastes from Mineral Processing. Vol. II, Office of Solid Waste, July 1990, p. 14-3.
755
-------
However, zinc-rich slag Is considered to be a RCRA special waste because of the volume generated; consequently, it
is exempt under the Bevill Exclusion from regulation as a hazardous waste. The slag is treated to recover coke and
zinc fines, which are recycled to the process, and zinc-lean slag and ferrosilicon,
Zinc-lean Slag
Zinc-lean slag, or processed slag, is stored in slag waste piles, disposed in a flyash landfill, or sold for such
uses as road gravel or construction aggregate. Approximately 17,000 metric tons are generated annually at the
Monaca facility.39 We used best engineering judgment to determine that zinc-lean slag may be recycled and may
exhibit the characteristic of toxicity for lead. This waste was formerly classified as a by-product. Data for this waste
stream are presented in Attachment 1.
Waste Ferrosilicon
Ferrosilicon is accumulated in a stockpile until it can be sold. Approximately 17,000 metric tons are
generated annually at the Monaca facility.40 We used best engineering judgment to determine that waste ferrosilicon
may be recycled and may exhibit the characteristic of toxicity for lead. This waste was formerly classified as a by-
product. Data for this waste stream are presented in Attachment 1.
Discarded Refractory Brick
Refractory brick is used to line the furnaces in which primary zinc smelting occurs. As furnaces are
periodically relined, spent brick is removed from the furnaces and disposed, most likely in a landfill on-site.
Approximately 1,000 metric tons of refractory brick are removed from furnaces annually.41 We used best
engineering judgment to determine that refractory brick may exhibit the characteristic of toxicity for arsenic,
cadmium, chromium, and lead.
D. Non-uniquely Associated Wastes
There are no non-uniquely associated wastes in this specific sector. However, typical ancillary hazardous
and non-hazardous wastes may be generated at on-site laboratories, and may include used chemicals and liquid
samples. Other hazardous wastes may include spent solvents (e.g., petroleum naptha), and acidic tank cleaning
wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and waste oil
and other lubricants.
E. Summary of Comments Received by EPA
New Factual Information
One commenter provided new factual information about management of wastewater treatment plant sludge
and spent surface impoundment solids (COMM 58). This commenter also indicated that one smelter, Zinc
Corporation of America's electrolytic smelter in Bartlesville, OK is no longer operating. This information has been
included in the sector report, and estimated waste streams have been reduced appropriately.
Sector-specific Issues
None.
39 U.S. Environmental Protection Agency, 1992, Op. Cit. p. I-
40 Ibid.
41 U.S. Environmental Protection Agency, 1992, Op. Cit., p. I-
756
-------
BIBLIOGRAPHY
Beckstead, L. and E. Chou. "Brine Leaching of Zinc Lead Residue." Presented at the EPD Congress, 1993,
Sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA. pp. 861-875.
Coppa, L. Waste Disposal Activities and Practices in the United States: Copper. Lead. Zinc. Gold, and Silver. U.S.
Bureau of Mines, Division of Minerals Availability Open File Report. November, 1984. Washington, DC.
Eyal, A., A. Baniel, K. Hajdu, and J. Mizrahi. "New Process for Recovery of Zinc Sulfate and Sulfuric Acid from
Zinc Electrowinning Bleed Solutions." Solvent Extraction and Ion Exchange. 8, No. 2. 1990. pp. 209-
222.
Perron, C. and J. De Cuyper, "The Recovery of Copper and Zinc from a Sulphide Concentrate Using Sulfate
Roasting, Acid Leaching and Solution Purification." International Journal of Mineral Processing. 35, No.
3-4. August 1992. pp. 225-238.
Jolly, J. "Zinc." In Minerals Yearbook Volume 1. Metals and Minerals 1992. U.S. Bureau of Mines. 1992. pp.
1467-1485.
Mishra, B., D, Olson, and W. Averill. "Applications of Molten Salts in Reactive Metals Processing." Presented at
the Conference for Emerging Separation Technologies for Metals and Fuels, Palm Coast, FL, March 13-18,
1993. Sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
U.S. Bureau of Mines. Mineral Facts and Problems. Bulletin 675. 1985. p. 923,
U.S. Bureau of Mines. "Zinc." From Mineral Commodity Summaries. January 1994. pp. 194-195.
U.S. Environmental Protection Agency. Report To.Congress: Wastes From the Extraction and Beneficiation of
Metallic Ores, Phosphate Rock. Asbestos. Overburden from Uranium Mining and Oil Shale. EPA/530/SW-
85-033. Office of Solid Waste. December, 1985. Washington, DC.
U.S. Environmental Protection Agency. "Zinc." From 1988 Final Draft Summary Report of Mineral Industry
Processing Wastes. 1988. pp. 3-217 - 3-227.
U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Volume IV: Primary Zinc. Primary
Lead. Secondary Lead, and Primary Antimony. EPA 440/1-89-019.9, Office of Water Regulations and
Standards, May 1989, pp. 479-480.
U.S. Environmental Protection Agency. "Primary Zinc Processing." From Report to Congress on Special Wastes
from Mineral Processing. Vol.11. Office of Solid Waste. July 1990. pp. 14-1 - 14-25.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data Set.
Office of Solid Waste. August 1992.
"Zinc and Zinc Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XXIII. 1983. pp. 807-
851.
757
-------
Page Intentionally Blank
758
-------
ATTACHMENT 1
759
-------
Page Intentionally Blank
760
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - GOETHITE AND LEACH CAKE RESIDUES (ELECTROLYTIC) - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
3eryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
3,130
100
953
25.00
2.50
-
128
25.00
25.00
3,400
150,000
2,530
1,470
860
0.050
25.00
25.00
25.00
0.94
125
25.00
38,900
-
35,000
33,600
-
-
-
25.60
610,000
-
890
3,130
175
1,977
25.00
2.50
-
926
37.50
113
1 1 ,456
273,500
1 1 ,606
1,470
860
0.050
25.00
62.50
25.00
12.08
125
25.00
110,780
-
35,000
36,800
-
-
-
1,013
610,000
-
890
3,130
249
3,000
25.00
2.50
-
2,600
50.00
200
24,000
400,000
20,000
1,470
860
0.050
25.00
100
25.00
25.00
125
25.00
150,000
-
35,000
40,000
-
-
-
2,000
610,000
•
890
Detects
1/1
2/2
2/2
0/1
0/1
0/0
5/5
1/2
1/2
5/5
4/4
5/5
1/1
1/1
0/1
0/1
1/2
0/1
2/3
0/1
0/1
5/5
0/0
1/1
2/2
0/0
0/0
0/0
2/2
1/1
0/0
1/1
EP Toxicity Analysis -
Minimum Average
5.00
5.00
0.014
0.50
0.50
-
6.68
0.001
5.00
3.62
0.050
1.43
70.90
0.27
0.0001
5.00
5.00
0.0010
0.015
25.00
5.00
334
-
-
2,278
0.30
-
-
2.20
-
5.00
5.00
2.51
2.75
0.50
7.82
2.50
5.00
14.26
2.53
1.97
70.90
15.99
0.00345
5.00
5.00
2.50
2.51
25.00
5.00
737
2,278
0.30
2.20
PPM
Maximum
5.00
5.00
5.00
5.00
0.50
-
8.96
5.00
5.00
24.90
5.00
2.50
70.90
31.70
0.0068
5.00
5.00
5.00
5.00
25.00
5.00
1,140
2,278
0.30
-
-
2.20
-
# Detects
0/1
0/1
1/2
1/2
0/1
0/0
2/2
0/2
0/1
2/2
0/2
1/2
1/1
2/2
1/2
0/1
0/1
0/2
0/2
0/1
0/1
2/2
0/0
0/0
1/1
1/1
0/0
0/0
1/1
0/0
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
-
1.0 2
5.0 1
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 1
5.0 1
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
en
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
0.050
0.050
0.0020
0.050
0.005
-
0.0030
0.0010
0.050
0.025
0.030
0.00050
3.02
0.025
0.00010
0.050
0.030
0.0025
0.0015
0.024
0.005
3.00
0.0050
4.60
155
0.30
-
1,300
1.00
4.40
1.00
4.00
15.28
0.30
0.52
0.20
0.02
-
93.09
0.16
1.21
19.83
373
29.84
914
311
0.038
0.22
2.48
8,333
0.12
0.92
0.12
5,872
0.0050
4.60
7,902
18.67
-
1,300
1,277
12,905
5.64
8.25
123
0.93
2.54
0.50
0.05
-
555
0.50
6.60
205
3,500
300
7,160
2,500
0.348
0.50
10.50
100,000
0.50
3.59
0.50
60,000
0.0050
4.60
60,500
56.00
-
1,300
10,000
99,500
10.50
19.80
Detects
7/10
2/11
4/11
3/11
2/10
0/0
17/17
4/11
3/10
7/11
12/13
9/12
13/13
9/11
8/11
2/8
4/11
2/12
1/11
3/11
1/11
25/25
0/1
1/1
14/14
6/6
0/0
1/1
16/16
13/13
24/24
9/9
EP Toxicity Analysis -
Minimum Average
0.050
0.050
0.020
0.050
0.005
-
0.023
0.0050
0.050
0.050
0.050
0.025
2.81
0.050
0.00010
0.050
0.050
0.0025
0.0015
0.25
0.050
0.37
-
-
-
-
-
-
-
-
18.27
1.53
1.59
1.25
0.14
123
1.13
2.19
37.61
174
1.27
288
108
0.0020
1.52
2.93
1.13
1.13
7.03
1.41
7,919
PPM
Maximum
133
10,00
10.00
10.00
1.00
-
589
10.00
10.00
289
737
5.00
2,110
722
0.014
10.00
12.70
10.00
10.00
50.00
10.00
40,500
-
-
-
-
-
-
-
-
# Detects
3/8
2/8
2/10
2/10
0/8
0/0
10/10
1/10
1/8
4/8
3/8
6/10
8/8
6/8
4/10
2/8
1/8
0/10
0/10
0/8
0/8
8/8
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
-
1.0 6
5.0 1
-
. .
-
5.0 1
-
-
0.2 0
-
-
1.0 1
5.0 1
.
-
-
-
-
-
-
-
-
-
-
212 4
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - ACID PLANT SLOWDOWN - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
2.67
0.48
0.99
0.21
0.050
-
3.71
0.049
0.50
1.95
87.10
4.11
9.42
1.37
0.26
0.50
0.50
2.00
0.50
0.0090
0.0010
180
0.085
330
1,860
11.00
-
-
1.00
5,490
0.50
3.30
19.99
0.49
1.11
0.40
1,475
-
155
0.35
0.50
12.63
107
13.64
11.21
4.12
23,246
0.50
0.67
7.87
0.66
1.67
0.33
2,992
0.085
330
12,340
1,317
-
-
1,343
14,395
1.67
3.71
37.30
0.50
1.20
0.50
4,400
-
840
0.50
0.50
29.00
127
23.80
13.00
6.87
162,400
0.50
1.00
16.60
0.98
2.50
0.50
13,200
0.085
330
43,193
1 1 ,400
-
-
5,100
23,300
3.40
4.00
Detects
2/2
1/3
3/3
1/3
1/3
0/0
6/6
1/3
0/2
3/3
2/2
3/3
2/2
2/2
7/7
0/2
1/3
3/3
1/3
1/3
1/3
13/13
1/1
1/1
6/6
12/12
0/0
0/0
11/11
2/2
8/8
3/3
EP Toxicity Analysis -
Minimum Average
5.00
0.50
1.10
0.14
0.050
-
0.83
0.03
0.50
0.17
2.39
1.87
8.52
0.10
0.0064
0.50
0.50
0.055
0.015
2.50
0.50
21.30
-
_
7,330
23.00
-
-
547
20.20
2.75
2.12
1.45
0.28
8.58
1.81
2.75
1.89
53.90
2.54
10.41
2.20
0.079
2.75
2.75
1.69
1.53
13.75
2.75
588
7,330
23.00
547
PPM
Maximum
35.40
5.00
5.00
5.00
0.50
-
19.00
5.00
5.00
5.00
79.70
3.70
12.30
5.00
0.13
5.00
5.00
5.00
5.00
25.00
5.00
1,570
-
-
7,330
23.00
-
-
547
-
# Detects
1/2
0/2
3/4
1/4
0/2
0/0
4/4
2/4
0/2
1/3
3/3
3/4
2/2
2/3
4/4
0/2
0/2
2/4
1/4
0/2
0/2
3/3
0/0
0/0
1/1
1/1
0/0
0/0
1/1
0/0
TC # Values
Level In Excess
-
-
5.0 1
100.0 0
-
-
1.0 2
5.0 1
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 2
5.0 1
-
-
-
-
-
-
-
-
-
-
-
212 6
-
-J
01
uu
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SYNTHETIC GYPSUM - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
1,954 2,945 3,935 2/2
0/0
0/0
0/0
665 779 893 2/2
0/0
0/0
0/0
0/0
290 296 302 2/2
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
5.01 5.08 5.15 2/2
0/0
EP Toxicity Analysis -
Minimum Average
-
0.0030
0.80
-
0.52
0.0010
-
0.51
0.15
2.36
-
0.57
0.0029
-
-
0.0010
0.015
-
'
10.70
-
-
1,160
0.40
-
-
0.15
-
-
0.0040
2.25
-
-
5.81
0.0010
-
0.51
0.23
3.00
-
23.24
0.016
0.0010
0.018
-
-
417
-
-
1,795
0.45
-
-
1.43
-
PPM
Maximum
-
-
0.0050
3.70
-
-
11.10
0.0010
-
0.51
0.30
3.63
-
45.90
0.029
-
-
0.0010
0.020
-
-
824
-
-
2,430
0.50
-
-
2.70
-
# Detects
0/0
0/0
1/2
2/2
0/0
0/0
2/2
0/2
0/0
2/2
2/2
2/2
0/0
2/2
2/2
0/0
0/0
0/2
0/2
0/0
0/0
2/2
0/0
0/0
2/2
2/2
0/0
0/0
1/2
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 1
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT LIQUID EFFLUENT - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
1.00 12,101 24,200 2/2
0/0
3,100 3,100 3,100 1/1
1,300 1,300 1,300 1/1
17,200 17,200 17,200 1/1
6,100 6,100 6,100 1/1
50.00 5,225 10,400 2/2
0/0
0/0
0/0
410 410 410 1/1
0/0
58.29 58.29 58.29 1/1
0/0
0/0
20.00 150,673 450,000 3/3
0/0
0/0
545,000 545,000 545,000 1/1
0/0
0/0
0/0
0/0
0/0
4.88 6.73 8.80 3/3
0/0
EP Toxicity Analysis -
Minimum Average
-
-
0.027
0.50
-
-
0.070
0.012
-
0.030
53.90
1.00
-
49.50
0.000050
-
-
0.0030
0.020
-
-
1,320
-
-
1,340
18.50
-
-
102
-
0.039
3.25
0.125
0.019
0.030
53.90
1.82
49.50
0.0012
0.102
0.045
1,320
1,340
18.50
102
PPM
Maximum #
0.050
6.00
-
0.180
0.025
0.030
53.90
2.64
-
49.50
0.0023
-
-
0.20
0.070
-
-
1,320
-
-
1,340
18.50
-
-
102
-
Detects
0/0
0/0
1/2
1/2
0/0
0/0
2/2
1/2
0/0
0/1
1/1
2/2
0/0
1/1
1/2
0/0
0/0
2/2
1/2
0/0
0/0
1/1
0/0
0/0
1/1
1/1
0/0
0/0
1/1
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
CTl
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
01
01
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum #
23.80
0,60
0,46
0.30
0.042
-
44.40
1.20
3.30
8.20
407
55.50
1,980
189
4.10
0.25
4.50
5,60
0.55
2.40
0.13
2,000
0.51
3,120
545,000
173
-
-
-
430,000
8.80
-
1,887
24.10
57.23
33.65
0.87
-
11,415
17.65
1,171
1,159
12,736
4,862
6,740
4,465
12.20
1.40
256
113
43.25
25.70
1.34
249,250
0.51
3,120
545,000
173
-
-
-
430,000
9.38
-
3,750
47.60
114
67.00
1.70
-
24,200
34.10
3,100
2,170
20,600
8,430
10,400
8,740
20.30
2.55
410
220
70.90
49.00
2.55
526,000
0.51
3,120
545,000
173
-
-
-
430,000
9.96
-
Detects
2/2
1/2
1/2
2/2
1/2
0/0
3/3
2/2
3/3
3/3
3/3
3/3
3/3
2/2
2/2
1/2
3/3
2/2
3/3
0/2
1/2
4/4
0/1
1/1
1/1
1/1
0/0
0/0
0/0
1/1
2/2
0/0
EP Toxicity Analysis -
Minimum Average
0.13
0.00080
0.0055
0.11
0.0050
-
0.19
0.0015
0.82
0.020
13.83
0.42
74.70
31.68
0.00010
0.0088
1.21
0.0015
0.0051
0.57
0.0036
571
0.0050
143
-
-
-
-
-
-
2.40
0.035
0.063
0.31
0.0055
-
0.88
0.049
1.50
0.68
25.06
" 1.85
267
50.09
0.0075
0.012
1.40
0.018
0.017
0.58
0.009
1,540
0.0050
143
-
-
-
-
-
-
PPM
Maximum
4.67
0.070
0.12
0.48
0.0059
-
2.13
0.099
2.18
1,35
36.30
4.56
460
68.50
0.022
0.015
1.58
0.044
0.024
0.58
0.015
2,510
0.0050
143
-
-
-
'
-
-
# Detects
2/2
0/2
0/2
3/3
1/2
0/0
3/3
2/3
2/2
1/2
2/2
3/3
2/2
' 2/2
1/3
1/2
2/2
1/3
3/3
2/2
1/2
2/2
0/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 1
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
.
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RT! SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - ZINC
Constituents
Aluminum
Antimony
Arsenic
3arium
Beryllium
3oron
Cadmium
Chromium
Cobalt
Copper
ron
_ead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organ ics (TOO)
Total Constituent Analysis - PPM
Minimum Average Maximum #
990
-
214
-
-
-
0.00
-
-
3358
200
0.70
800
22.90
0.00
-
257
11.00
185
-
-
0.80
-
-
0
0.00
-
-
0
41.00
z
-
990
-
214
-
-
-
2,834
-
-
3,358
7,905
38,075
14,580
162
4.92
-
257
11.00
185
-
-
132,673
-
-
10,955
216
-
-
990
41.20
6.02
-
990
-
214
-
-
-
40,000
-
-
3,358
19,420
200,000
53,000
302
23.80
-
257
11.00
185
-
-
800,000
-
-
35,000
2,300
-
-
2,800
41.40
10
-
Detects
1/1
0/0
1/1
0/0
0/0
0/0
16/16
0/0
0/0
1/1
4/4
6/6
4/4
2/2
4/4
0/0
1/1
1/1
1/1
0/0
0/0
22/22
0/0
0/0
3/3
12/12
0/0
0/0
8/8
2/2
23/23
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
.
-
-
5.0 0
-
-
0.2 0
-
.
1.0 0
5.0 0
-
-
.
-
.
.
-
-
-
-
,
212 3
-
CTl
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Ol
00
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
1.00 1.00 1.00 1/1
0/0
0/0
0/0
0/0
- 0/0
50.00 50.00 50.00 1/1
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
20.00 20.00 20.00 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
6.50 6.50 6.50 1/1
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
- 0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
. -
-
-
-
-
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - ZINC - LEAN SLAG (SMELTING) - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
pH*
Organics (TOC)
Total Constituent Analysis - PPM
Minimum Average Maximum #
8,120
33.50
5.00
129
0.50
-
0.50
22.70
5.00
650
7,240
1,720
1,100
1,670
0.050
10.60
86.10
5.00
5.00
25.00
10.50
6,710
-
-
943
-
-
100,000
24.80
-
-
2,940
24,060
33.50
5.00
129
0.50
-
0.50
22.70
5.00
650
73,620
2,860
1,100
1,670
0.050
10.60
86.10
5.00
5.00
25.00
10.50
58,355
-
-
943
•
-
100,000
24.80
-
-
2,940
40,000
33.50
5.00
129
0.50
-
0.50
22.70
5.00
650
140,000
4,000
1,100
1,670
0.050
10.60
86.10
5.00
5.00
25.00
10.50
110,000
-
-
943
-
-
100,000
24.80
-
-
2,940
Detects
2/2
1/1
0/1
1/1
0/1
0/0
0/1
1/1
0/1
1/1
2/2
2/2
1/1
1/1
0/1
1/1
1/1
0/1
0/1
0/1
1/1
2/2
0/0
0/0
1/1
0/0
0/0
1/1
1/1
0/0
0/0
1/1
EP Toxicity Analysis -
Minimum Average
1.45
0.50
0.50
0.50
0.050
-
0.050
0.50
0.50
0.50
27.20
59.40
8.16
25.60
0.00010
0.50
4.82
0.50
0.50
2.50
0.50
325
-
-
-
-
-
-
-
-
1.45
0.50
0.50
0.50
0.050
0.050
0.50
0.50
0.50
27.20
59.40
8.16
25.60
0.00010
0.50
4.82
0.50
0.50
2.50
0.50
325
PPM
Maximum #
1.45
0.50
0.50
0.50
0.050
0.050
0.50
0.50
0.50
27.20
59.40
8.16
25.60
0.00010
0.50
4.82
0.50
0.50
2.50
0.50
325
-
-
-
-
-
-
-
-
Detects
1/1
0/1
0/1
0/1
0/1
0/0
0/1
0/1
0/1
0/1
1/1
1/1
1/1
1/1
0/1
0/1
0/1
0/1
0/1
0/1
0/1
1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5.0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 1
-
-
0.2 0
-
-
1.0 0
5.0 0
-
-
-
-
-
-
-
-
-
-
-
212 0
-
01
ID
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
•-J
o
SUMMARY OF EPA/ORD, 3007, AND RT1 SAMPLING DATA - FERROSILICON (SMELTING) - ZINC
Constituents
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Sulfide
Sulfate
Fluoride
Phosphate
Silica
Chloride
TSS
PH*
Organics (TOG)
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
40,000 40,000 40,000 1/1
,0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
300,000 300,000 300,000 1/1
5,000 5,000 5,000 1/1
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
40,000 40,000 40,000 1/1
0/0
0/0
0/0
0/0
0/0
120,000 120,000 120,000 1/1
0/0
0/0
0/0
0/0
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
0/0
TC # Values
Level In Excess
-
-
5,0 0
100.0 0
-
-
1.0 0
5.0 0
-
-
-
5.0 0
-
-
0.2 0
-
-
1.0 0
5.0 0
.
-
-
-
-
-
.
-
-
-
-
212 0
-
Non-detects were assumed to be present at 1/2 the detection limit, TCLP data are currently unavailable; therefore, only EP data are presented.
-------
ZIRCONIUM AND HAFNIUM
A.
Commodity Summary
Zirconium and hafnium occur most commonly in nature as the mineral zircon and less commonly as
baddeleyite. Zircon is used both for its properties as a mineral and as an ore of zirconium and hafnium. Zircon is a
byproduct from the mining and processing of heavy mineral sands for rutile and ilmenite. Zirconium and hafnium
occur together in ores at ratios of about 50:1.'
Zircon sand is produced at two mines in Florida. Zirconium metal is extracted from imported zircon sand
by two domestic producers, one in Oregon and the other in Utah. Exhibit 1 presents the names and locations of
facilities associated with the production of zirconium/hafnium.
EXHIBIT 1
SUMMARY OF ZIRCONIUM/HAFNIUM MINING AND PROCESSING FACILITIES
Facility Name
Du Pont
RGC
Teledyne
Western Zirconium
Location
Trail Ridge, FL
NE Florida
Albany, OR
Ogden, UT
Operations/Products
Mining, extraction
Mining, extraction
Metals, and alloys
Metals, and alloys
The two metals can remain unseparated for all uses except nuclear applications. Because of the extremely
opposite absorption characteristics for thermal neutrons in nuclear reactor cores, the zirconium-cladded fuel rods
must be hafnium free. The strong-absorbing hafnium, if present, would decrease the relative transparency of the
zirconium cladding, and the reactor's efficiency. For this reason, hafnium is used in reactor control rods to regulate
the fission process via neutron absorption. Hafnium is also used as an additive in superalloys, as refractory and
cutting tool coatings, and in oxide and nitride forms. Nuclear fuel rod cladding accounts for most of zirconium's use.
Zircon refractories and foundry sands are used primarily in the production of finished metal and glass products.2
B. Generalized Process Description
1. Discussion of Typical Processes
Zircon is mined from a shoreline deposit in Green Cove Springs, FL and from the Trail Ridge deposit in
north central Florida. Sand ores are mined with dredges, bulldozers, and elevating scrapers. The production
processes used at primary zirconium and hafnium manufacturing plants depend largely on the raw material used. Six
basic operations may be performed: (1) sand chlorination, (2) separation, (3) calcining, (4) pure ehlorination, (5)
reduction, and (6) purification. Plants that produce zirconium and hafnium from zircon sand use all six of these
process steps. Plants which produce zirconium from zirconium dioxide practice reduction and purification only.
1 Thomas E. Gamer, "Zirconium and Hafnium Minerals," from Industrial Minerals and Rocks, 6th ed., Society for
Mining, Metallurgy, and Exploration, 1994, pp. 1159-1164.
2 Ibid.
771
-------
Exhibit 2 presents a process flow diagram for primary zirconium and hafnium production. These processes are
described in further detail below.3
2. Generalized Process Flow Diagram
Sand Chlorination
After drying, concentrated zircon sand is mixed with coke, ground, and fed continuously to the top of a
fluidized bed chlorinator. The basic sand chlorination reaction is as follows:
ZrSiO4 + 2C + 4C12 - ZrCl4 + SiCl4 + 2CO2
Crude zirconium tetrachloride and silicon tetrachloride are condensed from the off-gases. ("Crude zirconium
tetrachloride" is a mixture of zirconium tetrachloride and hafnium tetrachloride.) The crude zirconium tetrachloride
is then hydrolyzed with water and the resulting solution is filtered to remove suspended solids. The reaction is as
follows4:
ZrCl4 + H20 - ZrOCl2 +2HC1
Separation
Iron is removed from the zirconium-hafnium solution from the feed makeup step by extraction. The iron
free zirconium and hafnium solution is passed through a series of liquid-liquid extractions, stripping, and scrubbing
steps to separate zirconium from hafnium. Liquid-liquid extraction, using methyl isobutyl ketone (containing
thiocyanate) as a solvent, separates zirconium from hafnium by preferentially extracting hafnium into the solvent
phase. The zirconium ions are "complexed" with the ammonium thiocyanate and the hafnium is preferentially
extracted by the MIBK. The solvent, MIBK, and the complexing agent, ammonium thiocyanate, are recovered by
steam stripping and recycled to the process.5 (According to a facility representative from Teledyne Wah Chang in
Albany, Oregon, there is no ammonium thiocyanate bleed stream.6)
Hafnium is stripped from the solvent to the aqueous phase by acidification and the recovered solvent is
recycled, after treatment, within the separation operations. The hafnium solution is reacted with ammonium
hydroxide to precipitate hafnium hydroxide. The precipitate is recovered by filtration and the residual wastewater
discharged to treatment. After drying, the hafnium hydroxide is either stored or calcined to produce hafnium
dioxide.7
Zirconium is recovered from the aqueous zirconium stream through chemical treatment and further
extraction with methyl isobutyl ketone. Zirconium is precipitated and filtered as zirconium sulfate. The filter cake
3 U.S. Environmental Protection Agency, Development Document for Effluent Limitations Guidelines and
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. IX, Office of Water Regulations
and Standards, May 1989, pp. 5081-5106.
4 Ibid.
5 J.H. Schemel, ASTM Manual on Zirconium and Hafnium. American Society for Testing and Materials, 1977,
pp. 58-59.
6 Personal communication between ICE Incorporated and Chuck Knoll, Manager of Environmental Affairs,
Teledyne Wah Chang, Albany, Oregon, October 24, 1994.
7 U.S. Environmental Protection Agency, 1989, Op. Cit., pp. 5081-5106.
772
-------
EXHIBIT 2
PRIMARY ZIRCONIUM AND HAFNIUM PRODUCTION
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, pp. 5081 - 5106.)
^ AutiQsphere
773
-------
EXHIBIT 2 (CONTINUED)
Atmosphere
Atmosphere
t
Calcining
Caustic ^"
Scrubber
i i
Atmosphere
Calcining
Scrubbers
1 'Rcc
Caustic,
\
fr Pure
Scrubbers W
cle to
1 i Separations
Hf
Calcination
Zr ZrO
Cajc nation
CI2, Coke
1
Mg
1
1 ^ HfPure HfC14^
Chlori
lation
* ZrPure ZrC14
^ Chlon
1
nation *
I
Mg
H2O »
Magnesium
Recovery ^
Scrubbers
J k
Atmosphere
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Scrubbers
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^ Redu
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h
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Zr
Distillation ^. ^
and Crushing
r
Reduction
20 ^ Off-gas
Scrubber
^ Recycle In
^ Separations
Atmosphere
-------
2 z _
N N
t
o
i
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a
&
^3
'J
t/;
t
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775
-------
can be either sent to calcining or repulped with ammonium hydroxide. Ammonium hydroxide is added to convert the
zirconium sulfate to zirconium hydroxide and to remove trace metals from the zirconium product. The precipitate is
filtered to remove water and sent to the calcining furnace for further processing.8
Calcining
From this point on in the process, zirconium and hafnium are processed separately but identically. The
hafnium and zirconium filter cakes are calcined to produce hafnium oxide and zirconium oxide, respectively.
Scrubber water from calciner emission control operations is recycled to the separation process to recover zirconium'
and hafnium.9
Pure Chlorination
Pure chlorination is essentially the same process as sand chlorination. The pure zirconium or hafnium oxide
is mixed with fine coke and reacted with chlorine to produce the tetrachloride gas. The pure zirconium or hafnium
tetrachloride is then recovered in condensers.10
Reduction
The zirconium tetrachloride and hafnium tetrachloride are reduced to their respective metals in a batch
process using magnesium in a reduction furnace. The tetrachloride is added to magnesium in a retort furnace where
it is converted to zirconium or hafnium metal and magnesium chloride. Off-gases from the furnace pass through a
water scrubber before being released. The scrubber blowdown is recycled to the separation process to recover
zirconium and hafnium."
Zirconium oxide is mixed with magnesium metal powder and placed in a steel cylinder. The cylinder is
then place in a furnace and retorted. Once initiated, die reaction becomes self-sustaining. Zirconium metal sponge
and magnesium oxide are produced.'2
Zirconium oxide can also be used to produce zirconium-nickel alloys. The process is similar to the
magnesium reduction operation except that calcium hydride is used as the reducing agent in the furnace and nickel is
added directly to the mixture of zirconium oxide and calcium.13
Purification
When zirconium or hafnium metal is produced by magnesium reduction of the tetrachloride, a crude metal
regulus with magnesium chloride is formed in the furnace. The magnesium chloride is separated from the zirconium
or hafnium regulus to produce zirconium or hafnium sponge.14
8 Ibid.
9 Ibid.
10 Ibid.
11 Ibid.
12 Ibid.
13 Ibid.
14 Ibid.
776
-------
A different purification process is used when zirconium metal or zirconium-nickel- alloys are produced by
magnesium reduction of zirconium oxide. The zirconium sponge is removed from the reduction cylinder and
pulverized. The impurities are leached out with acid, and the purified metal is rinsed with water. The product is
then dried and sold as metal or alloy powder.15
3. Identification/Discussion of Novel (or otherwise distinct) Processes
A less complicated method may be found to separate hafnium from zirconium and to refine the hafnium. A
new process is being developed where zirconium and hafnium are separated by fractional distillation of the
zirconium tetrachloride. Such a process would eliminate the liquid-liquid extraction and associated precipitation,
calcination, and rechlorination steps currently used.16
4. Beneficiation/Proeessing Boundaries
EPA established the criteria for determining which wastes arising from the various mineral production
sectors come from mineral processing operations and which are from beneficiation activities in the September 1989
final rule (see 54 Fed. Reg. 36592, 36616 codified at 261.4(b)(7)). In essence, beneficiation operations typically
serve to separate and concentrate the mineral values from waste material, remove impurities, or prepare the ore for
further refinement. Beneficiation activities generally do not change the mineral values themselves other than by
reducing (e.g., crushing or grinding), or enlarging (e.g., pelletizing or briquetting) particle size to facilitate
processing. A chemical change in the mineral value does not typically occur in beneficiation.
Mineral processing operations, in contrast, generally follow beneficiation and serve to change the
concentrated mineral value into a more useful chemical form. This is often done by using heat (e.g., smelting) or
chemical reactions (e.g., acid digestion, chlorination) to change the chemical composition of the mineral. In contrast
to beneficiation operations, processing activities often destroy the physical and chemical structure of the incoming
ore or mineral feedstock such that the materials leaving the operation do not closely resemble those that entered the
operation. Typically, beneficiation wastes are earthen in character, whereas mineral processing wastes are derived
from melting or chemical changes.
EPA approached the problem of determining which operations are beneficiation and which (if any) are
processing in a step-wise fashion, beginning with relatively straightforward questions and proceeding into more
detailed examination of unit operations, as necessary. To locate the beneficiation/processing "line" at a given facility
within this mineral commodity sector, EPA reviewed the detailed process flow diagram(s), as well as information on
ore type(s), the functional importance of each step in the production sequence, and waste generation points and
quantities presented above.
EPA determined that for this specific mineral commodity sector, the beneficiation/processing line occurs
between ore preparation and sand chlorination because it is where a significant change to the metal occurs.
Therefore, because EPA has determined that all operations following the initial "processing" step in the production
sequence are also considered processing operations, irrespective of whether they involve only techniques otherwise
defined as beneficiation, all solid wastes arising from any such operation(s) after the initial mineral processing
operation are considered mineral processing wastes, rather than beneficiation wastes. EPA presents below the
mineral processing waste streams generated after the beneficiation/processing line, along with associated information
on waste generation rates, characteristics, and management practices for each of these waste streams.
15 Ibid.
16 Timothy Adams, "Zirconium and Hafnium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985,
pp. 941-956.
777
-------
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Sand Drying Wet Air Pollution Control (APC)
Wastewater.
Monazite inclusions within the zircon grains and/or ionic substitution of uranium, thorium, radium, and/or
actinium for the zirconium and/or hafnium within the mineral lattice result in some radioactive contamination.'7
2. Mineral Processing Wastes
Sand Chlorination
Existing data and engineering judgement suggest that the wastes listed below from sand chlorination do not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
Silicon tetrachloride purification wet APC wastewater. Silicon tetrachloride purification requires wet
air pollution control. That process practices 96 percent recycle of the scrubberwater before discharging it. The
existing treatment for this wastewater consists of chemical precipitation and sedimentation. This waste is discharged
at a rate of 7,498 1/kkg of zirconium dioxide and hafnium dioxide produced.18
Sand chlorination off-gas wet APC wastewater. After zircon ore is chlorinated, crude zirconium-
tetrachloride and silicon tetrachloride are separated and recovered from the off-gases using a series of condensers.
Wet air pollution control equipment is used to remove residual chlorine gas and particulates from the condenser off-
gases. While one plant has achieved zero discharge of this wastewater stream using evaporation ponds, other plants
discharge this stream after dechlorination, chemical precipitation, and sedimentation. Extensive recycle of scrubber
liquor is practiced. This waste is generated at a rate of 16,540 to 43,470 1/kkg of zirconium dioxide and hafnium
dioxide produced.19
Sand chlorination area-vent APC wastewater. Ventilation vapors from the sand chlorination area are
routed to wet air pollution control equipment before being released to the atmosphere. At one plant, which reports a
separate waste stream for area-vent scrubbers, the wastewater generated is discharged after dechlorination, chemical
precipitation, and sedimentation. That plant reported recycling 96 percent of this wastewater. This waste is
discharged at a rate of 8,5241/kkg of zirconium dioxide and hafnium dioxide produced.20
Feed makeup wet APC wastewater. This wastewater is characterized by treatable concentrations of
suspended solids, zirconium, cyanide, and a low pH. Feed makeup steps are intended to remove suspended solids
from crude zirconium-hafnium tetrachloride. This process uses wet scrubbing systems to control emissions. A high
rate of recycle and reuse (92 to 100 percent) of the feed makeup scrubber liquor is achieved prior to discharge.
17 Joseph M. Gambogi, "Zirconium and Hafnium," from Minerals Yearbook Volume 1. Metals and Minerals.
U.S. Bureau of Mines, 1992, pp. 1487-1494.
18 U.S. Environmental Protection Agency, 1989, Op.Cit., pp. 5081-5106.
19 Ibid.
20 Ibid.
778
-------
Chemical precipitation and sedimentation is practiced for this waste stream. This waste is discharged at a rate of
5683 1/kkg of hafnium dioxide and zirconium dioxide produced.21
Separation
Existing data and engineering judgement indicate that the wastes listed below from separation do not exhibit
characteristics of hazardous wastes. Therefore, the Agency did not evaluate these materials further.
Hafnium filtrate wastewater. Separated hafnium is precipitated from solution and filtered before being
sent to the calcining furnace. The filtrate can be reused in the separation process to recover its zirconium content or
disposed of in evaporation ponds.22
Zirconium filtrate wastewater. Separated zirconium is precipitated from solution and filtered before
being sent to the calcining furnace. This wastestream is not recycled or reused. When this wastewater is discharged,
it is treated by ammonia steam stripping, chemical precipitation, and sedimentation. This waste is generated at a rate
of 37,640 to 39,9001/kkg of zirconium dioxide and hafnium dioxide produced.23
Iron extraction (methyl isobutyl ketone) steam stripper bottoms. MIBK is recovered from the iron
extraction wastewater stream using a steam stripper, from which the bottoms are discharged. When this stream is
discharged, it is treated by ammonia steam, stripping, chemical precipitation, and sedimentation.24
Ammonium thiocyanate bleed stream. Ammonium thiocyanate is recycled to the process. As stated
before, according to a facility representative from Teledyne Wah Chang in Albany, Oregon, there is no ammonium
thiocyanate bleed stream.
Calcination
Existing data and engineering judgement suggest that the wastes listed below from calcination do not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
Caustic wet APC wastewater. Wet air pollution control systems are used to clean the off-gases from the
calcining furnaces. A high rate, 90 percent, of recycle or reuse of the discharge from die water scrubbers in die
separations process is achieved. When the blowdown from this operation is discharged it is treated by
dechlorination, chemical precipitation, and sedimentation. This waste is discharged at a rate of 1,539 to 8,997 1/kkg
of hafnium dioxide and zirconium dioxide produced.25
Filter cake/sludge. Zirconium and hafnium filter cakes are calcined to produce zirconium oxide and
hafnium oxide, respectively.
Furnace residue.
21 Ibid.
22 IMd.
23 Ibid.
24 Ibid.
25 Ibid.
779
-------
Pure Chlorination
Wet APC wastewater. Pure chlorination is similar to sand chlorination except that the chlorination of
zirconium oxide and hafnium oxide is carried out in separate reactors at lower temperatures. The scrubbers used for
reactor off-gasses and area ventilation vapors discharge a wastewater stream. This stream may be recycled and the
blowdown is treated by dechlorination, chemical precipitation, and sedimentation before being discharged. It
contains zirconium and chlorine as well as suspended solids. This waste is discharged at a rate of 38.317 1/kkg of
zirconium and hafnium produced.26 Existing data and engineering judgement suggest that this material does not
exhibit any characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material further.
Reduction
Reduction area-vent wet air pollution control wastewater. The plants that reduce zirconium and
hafnium tetrachloride to metal use scrubbers for area ventilation vapors. The scrubber liquor is recycled before it is
discharged after treatment by chemical precipitation and sedimentation. This waste is discharged at a rate of 3,686
1/kkg of zirconium and hafnium produced.27 Existing data and engineering judgement suggest that this material does
not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further.
Purification
Leaching rinse water from zirconium or hafnium metal production. After leaching with acid to remove
impurities, the zirconium and hafnium metals are rinsed with water, dried, and packaged for sale. Treatment for this
stream may consist of pH adjustment before discharge.28 Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 200 metric tons/yr, 1,000,000 metric tons/yr, and
2,000,000 metric tons/yr, respectively. We used best engineering judgement to determine that this waste may exhibit
the characteristic of corrosiyity prior to treatment. This waste is classified as a spent material.
Leaching rinse water from zirconium and hafnium alloy production. After leaching with acid to
remove impurities, the zirconium and hafnium alloys are rinsed with water, dried, and packaged for sale.29 Although
no published information regarding waste generation rate or characteristics was found, we used the methodology
outlined in Appendix A of this report to estimate a low, medium, and high annual waste generation rate of 34,000
metric tons/yr, 42,000 metric tons/yr, and 51,000 metric tons/yr, respectively. We used best engineering judgement
to determine that this waste may exhibit the characteristic of corrosivity prior to treatment. This waste is classified as
a spent material.
Spent acid leachate from zirconium and hafnium metal production. When zirconium and hafnium
metals are purified by leaching, the resulting leachate is not reused or recycled. Existing treatment for this
wastewater stream may consist of pH adjustment before discharge.30 Although no published information regarding
waste generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 0 metric tons/yr, 0 metric tons/yr, and 1,600,000
metric tons/yr, respectively. We used best engineering judgement to determine that this waste may exhibit the
characteristic of corrosivity.
26 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 5081-5106.
27 Ibid.
28 Ibid.
29 Ibid.
30
Ibid.
780
-------
Spent acid leachate from zirconium and hafnium alloy production. When zirconium and hafnium
alloys are purified by leaching, the resulting leachate is not reused or recycled. Existing treatment for this
wastewater stream may consist of pH adjustment before discharge.31 Although no published information regarding
waste generation rate or characteristics was found, we used the methodology outlined in Appendix A of this report to
estimate a low, medium, and high annual waste generation rate of 0 metric tons/yr, 0 metric tons/yr, and 850,000
metric tons/yr, respectively. We used best engineering judgement to determine that this waste may exhibit the
characteristic of corrosivity.
Existing data and engineering judgement suggest that the purification wastes listed below do not exhibit any
characteristics of hazardous wastes. Therefore, the Agency did not evaluate these materials further.
Zirconium chip crushing wet APC wastewater. The zirconium sponge formed by reduction is removed
from the reduction container and crushed. Scrubbers, installed for air pollution control in the crushing operation,
generate a wastewater. Zero discharge of this wastewater is achieved by 100 percent recycle of the scrubber liquor.32
Magnesium recovery off-gas wet APC wastewater. Scrubbers, installed for air pollution control in the
magnesium recovery area, discharge a wastewater which is characterized by treatable concentrations of magnesium
and solids. The scrubber liquor may be recycled prior to treatment which consists of chemical precipitation and
sedimentation followed by discharge. This waste is discharged at a rate of 20,733 1/kkg of zirconium and hafnium
produced.33
Magnesium recovery area vent wet APC wastewater. Ventilation air from the magnesium recovery area
passes through a wet scrubber prior to being released to the atmosphere. The scrubber liquor is recycled prior to
discharge and treatment consists of chemical precipitation and sedimentation. This waste is discharged at a rate of
11,518 1/kkg of zirconium and hafnium produced,34
D. Non-uniquely Associated Wastes
Non-uniquely associated and ancillary hazardous wastes may be generated at on-site laboratories, and may
include used chemicals and liquid samples. Other hazardous wastes may include spent solvents, and acidic tank
cleaning wastes. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil and other lubricants.
E. Summary of Comments Received by EPA
EPA received no comments that address this specific sector.
31 Ibid.
32 Ibid.
33 Ibid.
34 Ibid.
781
-------
BIBLIOGRAPHY
Adams, Timothy. "Zirconium and Hafoium." From Mineral Facts and Problems. U.S. Bureau of Mines. 1985.
pp. 941-956.
Gambogi, Joseph. "Hafnium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January
1995. pp. 74-75.
Gambogi, Joseph. "Zirconium." From Mineral Commodity Summaries. U.S. Bureau of Mines. January
1995. pp. 192-193.
Gambogi, Joseph. "Zirconium and Hafnium." From Minerals Yearbook Volume 1. Metals and Minerals.
U.S. Bureau of Mines. 1992. pp. 1487-1494.
Garnar, Thomas E. "Zirconium and Hafnium Minerals." From Industrial Minerals and Rocks. 6th ed. Society for
Mining, Metallurgy, and Exploration. 1994. pp. 1159-1164.
"Hafnium and Hafnium Compounds." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XII. 1980.
pp. 67-79.
Personal communication between ICF Incorporated and Chuck Knoll, Manager of Environmental Affairs, Teledyne
Wah Chang, Albany, Oregon, October 24, 1994.
Schemel, J.H. ASTM Manual on Zirconium and Hafnium. American Society for Testing and Materials. 1977.
pp. 58-59.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol. III. August 1992. pp. 42-1 - 42-3.
U.S. Environmental Protection Agency. Development Document for Effluent Limitations Guidelines and Standards
for the Nonferrous Metals Manufacturing Point Source Category. Vol. IX. Office of Water Regulations and
Standards. May 1989. pp. 5081-5106.
782
-------
IV. SUMMARY OF FINDINGS
After careful review, EPA has determined that 48 mineral commodity sectors generated a total of 553 waste
streams that could be classified as either extraction/beneficiation or mineral processing wastes (Exhibit 4-1). Based
on further analysis, the Agency identified 358 waste streams out of the total that could be designated as mineral
processing wastes from 40 mineral commodity sectors.
Exhibit 4-2 presents the 358 mineral processing wastes by commodity sector. Of these 358 waste streams,
EPA has sufficient information (based on either analytical test data or engineering judgment) to determine that 133
waste streams are potential RCRA hazardous wastes because they may exhibit one or more of the RCRA hazardous
characteristics (toxicity, ignitability, corrosivity, or reactivity) and, thus, would be subject to the Land Disposal
Restrictions. The hazardous waste streams and their characteristics are listed in Exhibit 4-3. The mineral processing
commodity sectors that generate these wastes are shown in Exhibit 4-4. This exhibit also summarizes the total
number of hazardous waste streams by sector and the estimated total volume of hazardous wastes generated annually.
At this time, EPA does not have sufficient information to determine if the following eight sectors also
generate wastes that could be classified as mineral processing wastes: Bromine, Gemstones, Iodine, Lithium,
Lithium Carbonate, Soda Ash, Sodium Sulfate, and Strontium.
783
-------
EXHIBIT 4-1
SUMMARY OF EXTRACTION/BENEFICIATION AND MINERAL PROCESSING WASTE STREAMS
BY COMMODITY
Commodity
Alumina and Aluminum
Antimony
Beryllium
Waste Stream
Water softener sludge
Anode prep waste
APC dust/sludge
Baghouse bags and spent plant filters
Bauxite residue
Cast house dust
Cryolite recovery residue
Wastewater
Discarded Dross
Flue Dust
Electrolysis waste
Evaporator salt wastes
Miscellaneous wastewater
Pisolites
Scrap furnace brick
Skims
Sludge
Spent cleaning residue
Spent potliners
Sweepings
Treatment Plant Effluent
Waste alumina
Gangue
Wastewater
APC Dust/Sludge
Autoclave Filtrate
Spent Barren Solution
Gangue (Filter Cake)
Leach Residue
Refining Dross
Slag and Furnace Residue
Sludge from Treating Process Waste Water
Stripped Anolyte Solids
Waste Solids
Gangue
Tailings
Wastewater
Nature of Operation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/B eneficiation
784
-------
EXHIBIT 4-1 (Continued)
Commodity
Beryllium (continued)
Bismuth
Boron
Waste Stream
Acid Conversion Stream
Bertrandite thickener slurry
Beryl thickener slurry
Spent Raffinate
Sump Water
Spent Barren filtrate streams
Beryllium hydroxide supernatant
Chip Treatment Wastewater
Dross discard
Filtration discard
Leaching discard
Neutralization discard
Pebble Plant Area Vent Scrubber Water
Precipitation discard
Process wastewater
Melting Emissions
Scrubber Liquor
Separation slurry
Waste Solids
Alloy residues
Spent Caustic Soda
Electrolytic Slimes
Excess chlorine
Lead and Zinc chlorides
Metal Chloride Residues
Slag
Spent Electrolyte
Spent Material
Spent soda solution
Waste acid solutions
Waste Acids
Wastewater
Crud
Gangue
Spent Solvents
Particulate Emissions
Waste Brine
Wastewater
Spent Sodium Sulfate
Waste liquor
Underflow Mud
Nature of Operation
Extraction/Beneficiation
Extraction/Benefidation
Extraction/Beneficiation
Extraction/Beneftciation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing •
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
785
-------
EXHIBIT 4-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Bromine
Slimes
Waste Brine
Water Vapor
Extraction/Benefieialion
Extraction/Benefidation
Extiaction/Beneficiation
Cadmium
Waste Tailings
Caustic washwater
Copper and Lead SuJfate Filter Cakes
Copper Removal Filter Cake
Iron containing impurities
Spent Leach solution
Lead Sulfate waste
Post-leach Filter Cakes
Spent Purification solution
Scrubber wastewater
Spent electrolyte
Zinc Precipitates
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Calcium Metal
Off-gases
Overburden
Calcium Aluminate wastes
Dust with Quicklime
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Cesium/Rubidium
Alkali Alurns
Calciner Residues
Cesium Chlorosonnate
Non-Pollueite Mineral Waste
Precipitated Aluminum
Precipitated Barium Sulfate
Spent Chlorine solution
Spent Ion-exchange solution
Spent Metal
Spent Ore
Spent Solvent
Waste Gangue
Chemical Residues
Digester waste
Electrolvtic Slimes
Pyrolytic Residue
Slag
Extraction/Benefidation
Exrraction/Beneficiation
Exiraction/Benefieiaiion
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Chromium, Ferrochrome, and
Ferrochromiurn-Silicon
Gangue and tailings
Dust or Sludge from ferrochrornium production
Dust or Sludge from ferrochromium-silicon production
Treated Roast/Leach Residues
Slag and Residues
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Coal Gas
Baghouse Coal Dust
Extraction/Beneficiation
786
-------
EXHIBIT 4-1 (Continued)
Commodity
! Waste Stream
Nature of Operation
Coal Pile Runoff
Fines
Gangue
API Oil/Water Separator Sludge
API Water
Cooling Tower Slowdown
Dissolved Air Flotation (DAF) Sludge
Flue Dust Residues
Liquid Waste Incinerator Slowdown
Liquid Waste Incinerator Pond Sludge
Multiple Effects Evaporator Concentrate
Multiple Effects Evaporator Pond Sludge
Sludge and Filter Cake
Spent Methanol Catalyst
Stretford Solution Purge Stream
Surface Impoundment Solids
Vacuum Filter Sludge
Zeolite Softening PWW
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Copper
Crud
Spent Kerosene
Raffmate
Process Wastewaters from Cooling and Refining
Slime
Slimes or "Muds"
Tailings
Spent Ore
Acid plant blowdown
Acid plant thickener sludge
APC dusts/sludges
Spent bleed electrolyte
Chamber solids/scrubber sludge
Waste contact cooling water
Discarded furnace brick
Process wastewaters
Scrubber blowdown
Spent black sulfuric acid sludge
Surface impoundment waste liquids
Tankhouse slimes
WWTP liquid effluent
WWTP sludge
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Elemental Phosphorous
Calcining offgas solids
Fugitive Dust
Extraction/Beneficiation
Extraction/Beneficiation
787
-------
EXHIBIT 4-1 (Continued)
Commodity
Fluorspar and Hydrofluoric Acid
Gem Stones
Germanium
Waste Stream
Condenser phossy water discard
Cooling water
Furnace building washdown
Dust
Waste ferrophospnorus
Furnace offgas solids
Furnace scrubber blowdown
Precipitator slurry scrubber water
Precipitator slurry
NOSAP slurry
Sludge
Spent furnace brick
Surface impoundment waste liquids
Surface impoundment waste solids
Waste Andersen Filter Media
WWTP liquid effluent
WWTP Sludge/Solids
Gangue
Lead and Zinc sulfides
Spent flotation reagents
Tailings
APC Dusts
Off-spec fiuosilicic acid
Sludges
Overburden
Spent chemical agents
Spent polishing media
Waste minerals
Waste Acid Wash and Rinse Water
Chlorinate Wet Air Pollution Control Sludge
Germanium oxides fumes
Hydrolysis Filtrate
Leach Residues
Roaster off-gases
Spent Acid/Leachate
Waste Still Liquor
Wastewater
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Exrraction/Beneficiation
Extraction/Beneficiation
Extraetion/Benef.ciation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Extraetion/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
788
-------
EXHIBIT 4-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Gold and Silver
Black sand
Filter cake
Mercury bearing solution
Mine water
Carbon, carbon fines, and acid wash solution
Spent leaching solution
Spent ore
Spent stripping solution
Sulfur dioxide
Tailings
Waste rock, clay and sand from amalgamation
Waste rock
Waste sulruric acid
Waste steel wool
Zinc cyanide solution
Spent Furnace Dust
Refining wastes
Retort cooling water
Slag
Wastewater treatment sludge
Wastewater
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Iodine
Filtrate waste
Sludge
Sulfur compounds
Waste acid
Waste bleed liquor
Waste brine
Extraction/Beneficiation
Extraction/Beneficialion
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Iron and Steel
Tailings
Wastewater and Waste Solids
Wastewater
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Lead
Concentration Wastes
Mine water
Waste Rock
Acid Plant Slowdown
Acid Plant Sludge
Baghouse Dust
Baghouse Incinerator Ash
Cooling Tower Blowdown
Waste Nickel Matte
Process Wastewater
Slurried APC Dust
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Lead (continued)
Solid Residues
Mineral Processing
789
-------
EXHIBIT 4-1 (Continued)
Commodity
Lightweight
Aggregate
Lithium and
Lithium Carbonate
Magnesium and Magnesia
from Brines
Manganese, Manganese
Dioxide, Ferrornanganese
and Silicomanganese
Waste Stream
Solids in Plant Washdown
Spent Furnace Brick
Stockpiled Miscellaneous Plant Waste
Surface Impoundment Waste Liquids
Surface Impoundment Waste Solids
SVG Backwash
WWTP Liquid Effluent
WWTP Sludges/Solids
Overburden
Waste Rock
Raw fines form primary crushing operations
Sludge from rock washing
APC control scrubber water and solids
APC Dust/Sludge
Surface impoundment waste liquids
WWTP liquid effluent
Acid roaster gases
Flotation Tailings
Gangue
Magnesium/Calcium Sludge
Roaster Off-gases
Salt solutions
Wastewater from Wet Scrubber
Calcium sludge
Off gases
Spent seawater
Tailings
APC Dust/Sludge
Calcincr offgases
Calcium sludge
Casthouse Dust
Casting plant slag
Cathode Scrubber Liquor
Slag
Smut
Spent Brines
Flotation tailings
Gangue
Spent Flotation Reagents
Wastewater
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Benefkiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiadon
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Benefidation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Exrraction/Beneficiation
Extraction/Benef.ciation
Extraction/Beneficiation
Extraction/Beneficiation
790
-------
EXHIBIT 4-1 (Continued)
Commodity
Manganese. Manganese
Dioxide. Ferromanganese
and Silicomanganese (continued)
Mercury
Molybdenum,
Ferrotnolybdenurn. and
Ammonium Molybdate
Phosphoric Acid
Platinum Group
Metals
Waste Stream
APC Dust/Sludge
APC Water
Iron Sulfide Sludge
Ore Residues
Slag
Spent Graphite Anode
Spent Process Liquor
Waste Electrolyte
Wastewater (CMD)
Wastewater (HMD)
Wastewater Treatment Solids
Gangue
Flotation tailings
Spent flotation reagents
Wastewater
Dust
Mercury Quench Water
Furnace Residues
Flotation tailings
Gangue
Spent Rotation Reagents
Wastewater
APC Dust/Sludge
Flue Dust/Gases
Liquid Residues
H2 Reduction Furnace Scrubber Water
Molybdic Oxide Refining Wastes
Refining Wastes
Roaster Gas Blowdown Solids
Slag
Solid Residues
Treatment Solids
Waste Scale
Filtrate
Tailings
Wastewater
Slag
Scrubber offgases
SO2 waste
Spent Acids
Spent Solvents
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing -
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
791
-------
EXHIBIT 4-1 (Continued)
Commodity
Pyrobitumcns,
Mineral Waxes,
and Natural Asphalts
Rare Earths
Rhenium
Scandium
Waste Stream
Spent coal
Spent solvents
Still bottoms
Waste catalysts
Magnetic fractions
Tailings
Spent ammonium nitrate processing solution
Electrolytic cell caustic wet APC waste
Spent Electrolytic cell quench water and scrubber water
Spent iron hydroxide cake
Spent lead filter cake
Lead backwash sludge
Monazite solids
Process wastewater
Spent scrubber liquor
Off-gases from dehydration
Spent off-gases from electrolytic reduction
Spent sodium hypochlorite filter backwash
Solvent extraction crud
Spent surface impoundment solids
Spent surface impoundment liquids
Waste filtrate
Waste solvent
Wastewater from caustic wet APC
Waste zinc contaminated with mercury
APC Dust/Sludge
Spent Barren Scrubber Liquor
Spent Rhenium Raffmate
Roaster Dust
Spent Ion Exchange/SX Solutions
Spent Salt Solutions
Slag
Crud from the bottom of the solvent extraction unit
Dusts and spent filters from decomposition
Spent acids
Spent ion exchange resins and backwash
Spent solvents from solvent extraction
Spent wash water
Waste chlorine solution
Waste solutions/solids from leaching and precipitation
Nature of Operation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
792
-------
EXHIBIT 4-1 (Continued)
Commodity
Selenium
Silicon and
Ferrosilicon
Soda Ash
Sodium Sulfate
Strontium
Waste Stream
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste Solids
Gangue
Spent Wash Water
Tailings
APC Dust Sludge
Dross discard
Slag
Airborne emissions
Calciner offgases
Filter aid and carbon absorbent
Mother liquor
Ore insolubles
Ore residues
Overburden
Paniculate emissions from driers
Particulates
Purge liquor
Scrubber water
Spent brine
Spent carbon and filter wastes
Spent dissolution wastes
Suspended paniculate matter
Tailings
Trona ore particulates
Trona ore processing waste
Waste mother liquor
Waste Brine
Clarifier overflow filtrate
Wastewater
Calciner offgas
Dilute sodium sulfide solution
Filter muds
Spent Ore
Vacuum drum filtrate
Waste sodium sulfate solution
Waste solution
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneftciation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extxaction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
793
-------
EXHIBIT 4-1 (Continued)
Commodity
Sulfur
Synthetic Rutile
Tantalum, Columbium
and Ferrocolumbium
Tellurium
Tin
Waste Stream
Air emissions
Filter cake
Frasch process residues
Sludge
Spilled sulfur
Wastewater
Airborne emissions from sulfuric acid production
Spent catalysts (Claus process)
Spent vanadium pentoxide catalysts from sulfuric acid production
Tail gases
Wastewater from wet-scrubbing, spilled product and condensates
APC Dust/Sludges
Spent ton Oxide Slurry
Spent Acid Solution
APC Dust Sludge
Digester Sludge
Spent Potassium Titanium Chloride
Process Wastewater
Spent Raffinate Solids
Scrubber Overflow
Slag
WWTP Liquid Effluent
WWTP Sludge
Slag
Fumes of telluride dioxide
Solid waste residues
Waste Electrolyte
Wastewater
Process Wastewater
Tailings Slurry
Brick Lining and Fabric Filters
Dross
Process Wastewater and Treatment Sludge
Slag
Slimes
Waste Acid and Alkaline baths
Nature of Operation
Extraction/Beneiiciation
Extraction/Beneficiation
Exrraction/Ber.eficiation
Extraction/Beneficiation
Extraction/Ber.eficiaiion
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiatior,
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
794
-------
EXHIBIT 4-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Titanium and
Titanium Dioxide
Flotation Cells
Tailings
Spent Brine Treatment Filter Cake
FeCl Treatment Sludge .
Waste Ferric Chloride
Finishing Scrap
Leach Liquor and Sponge Wash Water
Waste Non-Contact Cooling Water
Pickling Liquor and Wash Water
Scrap Detergent Wash Water
Scrap Milling Scrubber Water
Reduction Area Scrubber Water
Chlorination Off gas Scrubber Water
Chlorination Area - Vent Scrubber Water
Melt Cell Scrubber Water
Chlorine Liquefaction Scrubber Water
Chip Crushing Scrubber Water
Casting Crucible Contact Cooling Water
Smut from Mg Recovery
Spent Surface Impoundment Liquids
Spent Surface Impoundment Solids
TiC14 Purification Effluent
Spent Vanadium Oxychloride
Sodium Reduction Container Reconditioning Wash Water
Casting Crucible Wash Water
Waste Acids (Chloride process)
Waste Solids (Chloride process)
Waste Acids (Sulfate process)
Waste Solids (Sulfate process)
WWTP Liquid Effluent
WWTP Sludge/Solids
Extraction/Beneficiation
Exrraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Tungsten
Alkali leach wash
Calcium tungstate precipitate wash
Ion exchange raffmate
Ion exchange resins
Leach filter cake residues and impurities
Molybdenum sulfide precipitation wet air pollution control waste
Scrubber wastewater
Spent mother liquor
Tungstic acid rinse water
Waste fines
Extraction/Benefieiation
Extraction/Beneficiation
Extraction/Benefieiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Benefieiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Tungsten (continued)
Waste rock and tailings
Extraction/Benefieiation
795
-------
EXHIBIT 4-1 (Continued)
Commodity
Waste Stream
I Nature of Operation
Wastewater
Wet scrubber wastewater
Spent Add and Rinse water
Scrubber wastewater
Process wastewater treatment plant effluent
Water of formation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Uranium
Waste Rock
Tailings
Organic vapors
Refuse
Spent Extraction/Leaching Solutions
Particulate Emissions
Miscellaneous Sludges
Spent Ion Exchange Resins
Tailing Pond Seepage
Waste Acids from Solvent Extraction
Barren Lixiviant
Slimes from Solvent Extraction
Waste Solvents
Waste Nitric Acid from Production of UO,
Vaporizer Condensate
Superheater Condensate
Slag
Uranium Chips from Ingot Production
Waste Calcium Fluoride
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Vanadium
Roaster Off-gases
Solid residues
Spent Filtrate
Spent Solvent
Filtrate and Process Wastewaters
Solid Waste
Spent Precipitate
Slag
Wet scrubber wastewater
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Zinc
Refuse
Tailings
Waste rock
Acid Plant Slowdown
Spent Cloths, Bags, and Filters
Waste Ferrosilicon
Extraction/Beneficiation
Extraction/Beneficiation
Exrraction/Beneficiadon
Mineral Processing
Mineral Processing
Mineral Processing
Zinc (continued)
Spent Goethite and Leach Cake Residues
Saleable residues
Mineral Processing
Mineral Processing
796
-------
EXHIBIT 4-1 (Continued)
Commodity
Zirconium and
Hafnium
Waste Stream
Process Wastewater
Discarded Refractory Brick
Spent Surface Impoundment Liquid
Spent Surface Impoundment Solids
Spent Synthetic Gypsum
TCA Tower Slowdown (ZCA Bartlesville, OK - Electrolytic Plant)
Wastewater Treatment Plant Liquid Effluent
Wastewater Treatment Plant Sludge
Zinc-lean Slag
Monazite
Wastewater
Spent Acid leachate from zirconium alloy production
Spent Acid leachate from zirconium metal production
Ammonium Thiocyanate Bleed Stream
Reduction area-vent wet APC wastewater
Caustic wet APC wastewater
Feed makeup wet APC wastewater
Filter cake/sludge
Furnace residue
Hafnium filtrate wastewater
Iron extraction stream stripper bottoms
Leaching rinse water from zirconium alloy production
Leaching rinse water from zirconium metal production
Magnesium recovery area vent wet APC wastewater
Magnesium recovery off-gas wet APC wastewater
Sand Chlorination Off-Gas Wet APC wastewater
Sand Chlorination Area Vent Wet APC wastewater
Silicon Tetrachloride Purification Wet APC wastewater
Wet APC wastewater
Zirconium chip crushing wet APC wastewater
Zirconium filtrate wastewater
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Extraction/Beneficiation
Extraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
797
-------
EXHIBIT 4-2
SUMMARY OF MINERAL PROCESSING WASTE STREAMS BY COMMODITY
Commodity
Alumina and Aluminum
Antimony
Beryllium
Waste Stream | Nature of Operation
Anode prep waste
APC dust/sludge
Baghouse bags and spent plant filters
Bauxite residue
Cast house dust
Cryolite recovery residue
Wastewater
Discarded Dross
Flue Dust
Electrolysis waste
Evaporator salt wastes
Miscellaneous wastcwater
Pisolites
Scrap furnace brick
Skims
Sludge
Spent cleaning residue
Spent potliners
Sweepings
Treatment Plant Effluent
Waste alumina
Oangue
Wastewater
APC Dust/Sludge
Autoclave Filtrate
Spent Barren Solution
Gangue (Filter Cake)
Leach Residue
Refining Dross
Slag and Furnace Residue
Sludge from Treating Process Waste Water
Stripped Anoiyte Solids
Waste Solids
Spent Barren filtrate streams
Beryllium hydroxide supernatant
Chip Treatment Wastewater
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
798
-------
EXHIBIT 4-2 (Continued)
Commodity
Beryllium (continued)
Bismuth
Cadmium
Calcium Metal
Cesium/Rubidium
Cerium/Rubidium (continued)
Waste Stream | Nature of Operation
Dross discard
Filtration discard
Leaching discard
Neutralization discard
Pebble Plant Area Vent Scrubber Water
Precipitation discard
Process wastewater
Melting Emissions
Scrubber Liquor
Separation slurry
Waste Solids
Alloy residues
Spent Caustic Soda
Electrolytic Slimes
Excess chlorine
Lead and Zinc chlorides
Metal Chloride Residues
Slag
Spent Electrolyte
Spent Material
Spent soda solution
Waste acid solutions
Waste Acids
Wastewater
Caustic washwater
Copper and Lead Sulfate Filter Cakes
Copper Removal Filter Cake
Iron containing impurities
Spent Leach solution
Lead Sulfate waste
Post-leach Filter Cakes
Spent Purification solution
Scrubber wastewater
Spent electrolyte
Zinc Precipitates
Calcium Aluminate wastes
Dust with Quicklime
Chemical Residues
Digester waste
Electrolytic Slimes
Pyrolytic Residue
Slag
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
799
-------
EXHIBIT 4-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Chromium, Ferrochrome, and Ferrochromium-Silicon
Gangue and tailings
Dust or Sludge from ferrochromium production
Dust or Sludge from ferrochromium-silicon production
Treated Roast/Leach Residues
Slag and Residues
Exrraction/Beneficiation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Coal Gas
API Oil/Water Separator Sludge
API Water
Cooling Tower Slowdown
Dissolved Air Flotation (DAF) Sludge
Flue Dust Residues
Liquid Waste Incinerator Slowdown
Liquid Waste Incinerator Pond Sludge
Multiple Effects Evaporator Concentrate
Multiple Effects Evaporator Pond Sludge
Sludge and Filter Cake
Spent Methanol Catalyst
Stretford Solution Purge Stream
Surface Impoundment Solids
Vacuum Filter Sludge
Zeolite Softening PWW
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Copper
Acid plant blowdown
Acid plant thickener sludge
APC dusts/sludges
Spent bleed electrolyte
Chamber solids/scrubber sludge
Waste contact cooling water
Discarded furnace brick
Process wastewaters
Scrubber blowdown
Spent black sulfuric acid sludge
Surface impoundment waste liquids
Tankhouse slimes
WWTP liquid effluent
WWTP sludge
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Elemental Phosphorous
Condenser phossy water discard
Cooling water
Furnace building washdown
Dust
Waste ferrophosphorus
Furnace offgas solids
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Elemental Phosphorous (continued)
Furnace scrubber blowdown
Precipitator slurry scrubber water
Mineral Processing
Mineral Processing
800
-------
EXHIBIT 4-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Predpitator slurry
NOSAP slurry
Sludge
Spent furnace brick
Surface impoundment waste liquids
Surface impoundment waste solids
Waste Andersen Filter Media
WWTP liquid effluent
WWTP Sludge/Solids
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Fluorspar and Hydrofluoric Acid
APC Dusts
Off-spec fluosilicic acid
Sludges
Mineral Processing
Mineral Processing
Mineral Processing
Germanium
Waste Acid Wash and Rinse Water
Chlorinator Wet Air Pollution Control Sludge
Germanium oxides fumes
Hydrolysis Filtrate
Leach Residues
Roaster off-gases
Spent Acid/Leachate
Waste Still Liquor
Waste-water
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Gold and Silver
Spent Furnace Dust
Refining wastes
Retort cooling water
Slag
Wastewater treatment sludge
Wastewater
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Iron and Steel
Wastewater
Mineral Processing
Lead
Acid Plant Blowdown
Acid Plant Sludge
Baghouse Dust
Baghouse Incinerator Ash
Cooling Tower Blowdown
Waste Nickel Matte
Process Wastewater
Slurried APC Dust
Solid Residues
Solids in Plant Washdown
Spent Furnace Brick
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Lead (continued)
Stockpiled Miscellaneous Plant Waste
Surface Impoundment Waste Liquids
Surface Impoundment Waste Solids
Mineral Processing
Mineral Processing
Mineral Processing
801
-------
EXHIBIT 4-2 (Continued)
Commodity
Lightweight
Aggregate
Magnesium and Magnesia
from Brines
Manganese, Manganese
Dioxide, Ferrornanganese
and Siliconianganese
Manganese, Manganese
Dioxide, Ferrornanganese
and Silicontanganese (continued)
Mercury
Molybdenum.
Ferromolybdenum, and
Ammonium Molybdate
Molybdenum,
Ferromolybdenum, and
Ammonium Molybdate
Waste Stream
SVG Backwash
WWTP Liquid Effluent
WWTP Sludges/Solids
APC control scrubber water and solids
APC Dust/Sludge
Surface impoundment waste liquids
WWTP liquid effluent
APC Dust/Sludge
Calciner offgases
Calcium sludge
Casthouse Dust
Casting plant slag
Cathode Scrubber Liquor
Slag
Smut
Spent Brines
APC Dust/Sludge
APC Water
Iron Sulfide Sludge
Ore Residues
Slag
Spent Graphite Anode
Spent Process Liquor
Waste Electrolyte
Wastewater (CMD)
Wastewater (EMD)
Wastewater Treatment Solids
Dust
Mercury Quench Water
Furnace Residues
APC Dust/Sludge
Flue Dust/Gases
Liquid Residues
H2 Reduction Furnace Scrubber Water
Molybdic Oxide Refining Wastes
Refining Wastes
Roaster Gas Blowdown Solids
Slag
Solid Residues
Treaftnent Solids
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
802
-------
EXHIBIT 4-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Phosphoric Acid
Waste Scale
Mineral Processing
Platinum Group
Metals
Slag
Mineral Processing
Scrubber offgases
Mineral Processing
SO2 waste
Mineral Processing
Spent Acids
Mineral Processing
Spent Solvents
Mineral Processing
Pyrobitumens.
Mineral Waxes,
and Natural Asphalts
Still bottoms
Mineral Processing
Waste catalysts
Mineral Processing
Rare Earths
Spent ammonium nitrate processing solution
Mineral Processing
Electrolytic cell caustic wet APC waste
Mineral Processing
Spent Electrolytic cell quench water and scrubber water
Mineral Processing
Spent iron hydroxide cake
Spent lead filter cake
Lead backwash sludge
Monazite solids
Process wastewater
Spent scrubber liquor
Off-gases from dehydration
Spent off-gases from electrolytic reduction
Spent sodium hypoehlorite filter backwash
Solvent extraction crud
Spent surface impoundment solids
Spent surface impoundment liquids
Waste filtrate
Waste solvent
Wastewater from caustic wet APC
Waste zinc contaminated with mercury
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Rhenium
APC Dust/Sludge
Spent Barren Scrubber Liquor
Spent Rhenium Raffinate
Roaster Dust
Spent Ion Exchange/SX Solutions
Spent Salt Solutions
Slag
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Scandium
Crud from the bottom of the solvent extraction unit
Dusts and spent filters from decomposition
Spent acids
Mineral Processing
Mineral Processing
Mineral Processing
Scandium (continued)
Spent ion exchange resins and backwash
Spent solvents from solvent extraction
Spent wash water
Mineral Processing
Mineral Processing
Mineral Processing
803
-------
EXHIBIT 4-2 (Continued)
Commodity
Selenium
Silicon and
Ferrosilicon
Sulfur
Synthetic Rutile
Tantalum. Columbian!
and Ferrocolumbium
Tellurium
Tin
Tin (continued)
Titanium and
Titanium Dioxide
Waste Stream
Waste chlorine solution
Waste solutions/solids from leaching and precipitation
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste Solids
APC Dust Sludge
Dross discard
Slag
Airborne emissions from sulfuric acid production
Spent catalysts (Claus process)
Spent vanadium pentoxide catalysts from sulfuric acid
production
Tail gases
Wastewater from wet-scrubbing, spilled product and
condensates
APC Dust/Sludges
Spent Iron Oxide Slurry
Spent Acid Solution
APC Dust Sludge
Digester Sludge
Spent Potassium Titanium Chloride
Process Wastewater
Spent Raffmaie Solids
Scrubber Overflow
Slag
WWTP Liquid Effluent
WWTP Sludge
Slag
Fumes of telluride dioxide
Solid waste residues
Waste Electrolyte
Wastewater
Brick Lining and Fabric Filters
Dross
Process Wastewater and Treatment Sludge
Slag
Slimes
Waste Acid and Alkaline baths
Spent Brine Treatment Filter Cake
FeCl Treatment Sludge
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
804
-------
EXHIBIT 4-2 (Continued)
Commodity
Tungsten
Uranium
Waste Stream
Waste Ferric Chloride
Finishing Scrap
Leach Liquor and Sponge Wash Water
Waste Non-Contact Cooling Water
Pickling Liquor and Wash Water
Scrap Detergent Wash Water
Scrap Milling Scrubber Water
Reduction Area Scrubber Water
Chlorination Off gas Scrubber Water
Chlorination Area - Vent Scrubber Water
Melt Cell Scrubber Water
Chlorine Liquefaction Scrubber Water
Chip Crushing Scrubber Water
Casting Crucible Contact Cooling Water
Smut from Mg Recovery
Spent Surface Impoundment Liquids
Spent Surface impoundment Solids
TiC14 Purification Effluent
Spent Vanadium Oxychloride
Sodium Reduction Container Reconditioning Wash Water
Casting Crucible Wash Water
Waste Acids (Chloride process)
Waste Solids (Chloride process)
Waste Acids (Sulfate process)
Waste Solids (Sulfate process)
WWTP Liquid Effluent
WWTP Sludge/Solids
Spent Acid and Rinse water
Scrubber wastewater
Process wastewater treatment plant effluent
Water of formation
Waste Nitric Acid from Production of UO,
Vaporizer Condensate
Superheater Condensate
Slag
Uranium Chips from Ingot Production
Waste Calcium Fluoride
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
805
-------
EXHIBIT 4-2 (Continued)
Commodity | Waste Stream
Vanadium
Zinc
Zirconium and
Hafnium
Filtrate and Process Wastewaters
Solid Waste
Spent Precipitate
Slag
Wet scrubber wastewater
Acid Plant Slowdown
Spent Cloths, Bags, and Filters
Waste Ferrosilicon
Spent Goethite and Leach Cake Residues
Saleable residues
Process Wastewater
Discarded Refractory Brick
Spent Surface Impoundment Liquid
Spent Surface Impoundment Solids
Spent Synthetic Gypsum
TCA Tower Slowdown (ZCA Bartlesville, OK -
Electrolytic Plant)
Wastewater Treatment Plant Liquid Effluent
Wastewater Treatment Plant Sludge
Zinc-lean Slag
Spent Acid leachate from zirconium alloy production
Spent Acid leachate from zirconium metal production
Ammonium Thiocyanate Bleed Stream
Reduction area-vent wet APC wastewater
Caustic wet APC wastewater
Feed makeup wet APC wastewater
Filter cake/sludge
Furnace residue
Hafnium filtrate wastewater
Iron extraction stream stripper bottoms
Leaching rinse water from zirconium alloy production
Leaching rinse water from zirconium metal production
Magnesium recovery area vent wet APC wastewater
Magnesium recovery off-gas wet APC wastewater
Sand Chlorination Off-Gas Wet APC wastewater
Sand Chlorination Area Vent Wet APC wastewater
Silicon Tetrachloride Purification Wet APC wastewater
Wet APC wastewater
Zirconium chip crushing wet APC wastewater
7irconinm filtrate wasrewater
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral. Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
806
-------
EXHIBIT 4-3
LISTING OF HAZARDOUS MINERAL PROCESSING WASTES BY COMMODITY SECTOR
Commodity
Alumina and Aluminum
Metallurgical grade alumina is extracted from bauxite
by the Bayer process and aluminum is obtained from
this purified ore by electrolysis via the Hall-Heroult
process. The Bayer process consists of the following
ive steps: (1) ore preparation, (2) bauxite digestion,
'3) clarification, (4) aluminum hydroxide precipitation,
and (5) calcination to anhydrous alumina. In the
Hall-Heroult process, aluminum is produced through
the electrolysis of alumina dissolved in a molten
cryolite-based bath, with molten aluminum being
deposited on a carbon cathode.
Antimony
Primary antimony is usually produced as a by-
Droduct or co-product of mining, smelting, and
refining of other antimony-containing ores such as
tetrahedrite or lead ore. Antimony can be produced
using either pyrometallurgical processes or a
lydrometallurgical process. For the
pyrometallurgical processes, the method of recovery
depends on the antimony content of the sulfide ore,
and will consist of either volatilization, smelting In a
blast furnace, liquation, or iron precipitation.
Antimony also can be recovered hydrometallurgicaliy
by leaching and electrowinning.
Beryllium
Bertrandite and beryl ores are treated using two
separate processes to produce beryllium sulfate,
BeSO4: a counter-current extraction process and the
Kjellgren-Sawyer process. The intermediates from
the two ore extraction processes are combined and
fed to another extraction process. This extraction
process removes impurities solubilized during the
processing of the bertrandite and beryl ores and
converts the beryllium sulphate to beryllium
hydroxide, Be(OH)2. The beryllium hydroxide is
further converted to beryllium fluoride, BeF,, which is
then cataiytically reduced to form metallic beryllium,
Waste Stream
Cast house dust
Electrolysis waste
Autoclave filtrate
Stripped anolyte solids
Slag and furnace residue
Chip treatment
wastewater
Spent barren filtrate
Filtration discard
Reported
Generation
dOOOmt/yr)
19
58
NA
0,19
21
NA
55
NA
Est./Reported
Generation
(1000mt/yr)
Mln
19
58
0,32
0.19
21
0.2
55
0.2
Avg.
19
58
27
0.19
21
100
55
45
Max
19
58
54
0.19
21
2000
55
90
Number
of
Facilities
with
Process
23
23
6
2
6
2
1
2
TC Metals
As
Y?
Y?
Ba
Cd
Y
Y?
Cr
Y?
Pb
Y?
Y?
Y?
Y?
Hf|
Y
Y?
Se
Y
Afl
Other Hazardous
Characteristics
Corr
N?
N?
Y?
N?
N?
N?
N?
N?
Ifjnlt
N?
N?
N?
N?
N?
N?
N?
N?
Hctv
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 4-3 (Continued)
00
00
Commodity
Bismuth
Bismuth is recovered mainly during the smelting of
copper and lead ores. Bismuth-containing dust from
copper smelting operations Is transferred to lead
smelting operations for recovery. At lead smelting
operations bismuth is recovered either by the
Betterton-Kroll process or the Belts Electrolytic
process. In the Betterton-Kroll process, magnesium
and calcium are mixed with molten lead to form a
dross that contains bismuth. The dross is treated
with chlorine or lead chloride and oxidized by using
air or caustic soda to remove impurities. In the Betts
Electrolytic process, lead bullion is electrolyzed. The
resulting impurities, including bismuth, are smelted,
reduced and refined.
Cadmium
Cadmium is obtained as a byproduct of zinc metal
production. Cadmium metal is obtained from zinc
(umes or precipitates via a hydrometallurgical or a
pyrometallurgical process. The hydrometallurgical
process consists of the following steps: (1 )
precipitates leached with sulfuric acid, (2) cadmium
precipitated with a zinc dust addition, (3) precipitate
filtered and pressed into filter cake, (4) impurities
removed from filter cake to produce sponge, (5)
sponge dissolved with sulfuric acid, (6) electrolysis of
solution, and (7) cadmium metal melted and cast.
The pyrometallurgical process consists of the
following steps: (1) cadmium fumes converted to
water- or acid-soluble form, (2) leached solution
purified, (3) galvanic precipitation or electrolysis, and
(4) metal briquetted or cast.
Calcium
Calcium metal is produced by the Aluminothermic
method. In the Aluminothermic method, calcium
oxide, obtained by quarrying and calcining calcium
limestone, is blended with finely divided aluminum
and reduced under a high temperature vacuum. The
process produces 99% pure calcium metal which
can be further purified through distillation.
Waste Stream
Alloy residues
Spent caustic soda
Electrolytic slimes
Lead and zinc chlorides
Metal chloride residues
Slag
Spent electrolyte
Spent soda solution
Waste acid solutions
Waste acids
Caustic washwater
Copper and lead sulfate
filter cakes
Copper removal filter
cake
Iron containing impurities
Spent leach solution
Lead sulfate waste
Post-leach filter cake
Spent purification solution
Scrubber wastewater
Spent electrolyte
Zinc precipitates
Dust with quicklime
Reported
Generation
dOOOmtfyrt
NA
NA
NA
NA
3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.04
EstJReported
Generation
(1000mt/yr)
Win
0.1
0.1
0
0.1
3
0.1
0.1
0.1
0.1
0
0.19
0.19
0.19
0.19
0.19
0,19
0.19
0.19
0.19
0.19
0.19
0.04
Avg.
3
6.1
0.02
3
3
1
6.1
6.1
6.1
0.1
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9
0.04
Max
6
12
0.2
6
3
10
12
12
12
0.2
19
19
19
19
19
19
19
19
19
19
19
0,04
Number
of
with
Process
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
1
TC Metals
As
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Cr
Pb
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Y?
HCJ
Se
Afl
Other Hazardous
Characteristics
Corr
N?
N?
N?
N?
N?
N?
N?
Y?
Y?
Y?
Y?
N?
N?
N?
Y?
N?
N?
Y?
Y?
Y?
N?
Y?
ignlt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 4-3 (Continued)
Commodity
Chromium and Ferrochromium
Chromite ore is prepared for processing using
several methods, depending on the ore source and
[he end use requirements, although many of these
oeneficiation operations may not be conducted in the
United States. Either ferrochromium or sodium
chromate is initially produced, and may be sold or
further processed to manufacture other chromium
compounds, as well as chromium metal.
Ferrochromium is made by smelting chromite ore in
an electric arc furnace with flux materials and
carbonaceous redcutant.
Coal Gas
Coal is crushed and gasified in the presence of
steam and oxygen, producing carbon dioxide and
carbon monoxide, which further react to produce
carbon oxides, methane and hydrogen. The product
gas is separated from the flue gas, and is processed
and purified to saleable methane.
Copper
Copper is recovered from ores using either-
pyrometallurgical or hydrometallurgical processes
In both cases, the copper-bearing ore is crushed,
ground, and concentrated (except in dump leaching).
Pyrometallurgical processing can take as many as
refining, and electrorefining. Hydrometallurgical
processing involves leaching, followed by either
precipitation or solvent extraction and electrowinning
Waste Stream
ESP dust
GCT sludge
Multiple effects
evaporator concentrate
Acid plant blowdown
APC dusts/sludges
Waste contact cooling
water
Tankhouse slimes
Spent bleed electrolyte
Spent furnace brick
Process wastewaters
WWTP sludge
Generation
(1000mt/yr)
3
NA
NA
5300
NA
13
4
310
3
4900
6
Est./Reported
Generation
(lOOOmt/yr)
Min
3
0.03
0
5300
1
13
4
310
3
4900
6
Avg.
3
0.3
0
5300
220
13
4
310
3
4900
6
Max
3
3
65
5300
450
13
4
310
3
4900
6
Number
of
Facilities
with
Process
1
1
1
10
10
10
10
10
10
10
10
TC Metals
As
Y
Y
Y?
Y'
Y?
Y
Y
Ba
Cd
Y
Y
Y
Y?
Cr
Y
Y?
Y
Y
Y?
Pb
Y
Y?
Y
Y
Y?
HH
Y
Y
Se
Y
Y
Y
Y?
Y
Y?
Ag
Y
Y?
Y
Other Hazardous
Characteristics
Corr
N?
N?
N?
Y
N?
N'
N?
Y
N?
Y
N?
Ignlt
N?
N?
N?
N?
N?
N'
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N'
N?
N?
N?
N?
N?
00
o
-------
EXHIBIT 4-3 (Continued)
00
o
Commodity
Elemental Phosphorus
Phosphate rock or sintered/agglomerated fines are
charged into an electric arc furnace with coke and
silica. This yields calcium silicate slag and
ferrophosphorus, which are tapped. Dusts are
removed from the furnace offgases and phosphorus
is removed from the dusts by condensation.
Fluorspar and Hydrofluoric Acid
Raw fluorspar ore is crushed, ground, and
concentrated. Acid grade fluorspar {a pure form of
concentrate) is mixed with sulfuric acid in a heated
retort kiln, reacting to produce hydrogen fluoride gas
and fluorogypsum. The gas is cooled, scrubbed, and
condensed, and sold as either hydrofluoric acid
solution or anhydrous hydrogen fluoride,
Germanium
Germanium is recovered as a by-product of other
metals, mostly copper, zinc, and lead. Germanium-
bearing residues from zinc-ore processing facilities,
a main source of germanium metal, are roasted and
sintered. The sintering fumes, containing oxidized
germanium, are leached with sulfuric acid to form a
solution. Germanium is precipitated from the
solution by adding zinc dust. Following precipitation,
the germanium concentrates are refined by adding
hydrochloric acid or chlorine gas to produce
germanium tetrachloride, which is hydrolyzed to
produce solid germanium dioxide. The final step
involves reducing germanium dioxide with hydrogen
to produce germanium metal.
Waste Stream
Andersen Filter Media
Precipitator slurry
NOSAP slurry
Phossy Water
Furnace scrubber
blowdown
Furnace Building
Washdown
Off-spec fluosilicic acid
Waste acid wash and
rinse water
Chlorinator wet air
pollution control sludge
Hydrolysis filtrate
Leach residues
Spent acid/leachate
Waste still liquor
Reported
Generation
dOOOmWyr)
0.46
160
160
670
410
700
NA
NA
NA
NA
0.01
NA
NA
Est./Reported
Generation
(lOOOmfvr)
MIn
0.46
160
160
670
410
700
0
0.4
0.01
0.01
0.01
0.4
0.01
Avg,
0.46
160
160
670
410
700
15
2,2
0.21
0.21
0.01
2.2
0.21
Max
0.46
160
160
670
410
700
44
4
0.4
0.4
0.01
4
0.4
Number
of
Facilities
with
Process
• 2
2
2
2
2
2
3
4
4
4
3
4
4 .
TC Metals
As
Y?
Y?
Y?
Y?
Y?
Ba
Cd
Y
Y?
Y?
Y
Y
Y?
Y?
Y?
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y?
H|
Se
Y?
Y?
Y?
Y?
Afl
Y?
Y?
Y?
Y?
Other Hazardous
Characteristics
Corr
N?
N?
N?
N?
Y
N?
Y?
Y?
N?
N?
N?
Y?
N?
Ignlt
N?
Y
N?
Y
N?
N?
N?
N?
N?
N?
N?
N?
Y?
Hctv
N?
Y
Y
Y
N?
N?
N?
N?
N?
N?
N?
N?
N?
-------
EXHIBIT 4-3 (Continued)
Commodity
Gold and Silver
Gold and Silver may be recovered from either ore or
the refining of base metals. Extracted ore is crushed
or ground and then subjected to oxidation by
roasting, autoclaving, bio-oxidation, or chlorination,
and then cyanide leaching (heap, vat, or agitation).
The metals are recovered by activated carbon
loading or the Merrill Crowe process. Activated
carbon loading involves bringing precious metal
leach solutions into contact with activated carbon by
the carbon-in-column, carbon-in-pulp, or carbon-in-
leach process. Gold and silver are then separated
3y acid leaching or electrolysis. The Merrill Crowe
Drocess consistes of filtering and deaerating the
each solution and then precipitating the precious
metals with zinc powder. The solids are filtered out,
melted and cast into bars. The recovery of precious
metals from lead refinery slimes is a normal part of
the operation called "desilverizing." Lead from
previous stages of refining is brought into contact
with a zinc bath which absorbs the precious metals.
Base metals are removed and the dore is sent to
refining.
Lead
Lead ores are crushed, ground, and concentrated.
Pelletized concentrates are then fed to a sinter unit
with other materials (e.g., smelter byproducts, coke).
The sintered material is then introduced into a blast
furnace along with coke and fluxes. The resulting
bullion is drossed to remove lead and other metal
oxides. The lead bullion may also be decopperized
before being sent to the refining stages. Refining
operations generally consist of several steps,
including (in sequence) softening, desilverizing,
dezincing, bismuth removal and final refining.
During final refining, lead bullion is mixed with
various fluxes and reagents to remove remaining
impurities.
Waste Stream
Slag
Spent furnace dust
Acid plant sludge
Baghouse incinerator ash
Slurried ARC Dust
Solid residues
Spent furnace brick
Stockpiled miscellaneous
plant waste
WWTP solids/sludges
WWTP liquid effluent
Reported
Generation
(1000mt/yr)
NA
NA
14
NA
7
0.4
1
NA
380
2600
Est./Reported
Generation
(1000mt/yr)
Win
0.1
0.1
14
0.3
7
0.4
1
0.3
380
2600
Avg.
360
360
14
3
7
0.4
1
67
380
2600
Max
720
720
14
30
7
0.4
1
130
380
2600
Number
of
Facilities
with
Process
16
16
3
3
3
3
3
3
3
3
TC Metals
As
Ba
Cd
Y
Y
Y
Y?
Cr
Pb
Y
Y
Y?
Y
Y
Y?
Y?
HH
Se
Atj
Y?
Y?
Other Hazardous
Characteristics
Corr
N?
Y?
Y?
N?
N?
N?
N?
N?
Y
Y?
Ignlt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
CO
-------
EXHIBIT 4-3 (Continued)
NJ
Commodity
Magnesium and Magnesia from Brines
Magnesium is recovered through two processes:
(1) electrolytic and (2) thermal, in electrolytic
production with hydrous feed, magnesium hydroxide
is precipitated from seawater and settled out. The
underflow is dewatered, washed, reslurried with
wash water, and neutralized with HCL and H2SO4.
The brine is filtered, purified, dried, and fed into the
electrolytic cells. Alternatively, surface brine is
pumped to solar evaporation ponds, where it is dried,
concentrated, and purified. The resulting powder is
melted, fed into the electrolytic cells, and then
casted. The two thermal production processes for
magnesium are the carbothermic process and the
silicothermic process. In the carbothermic process,
magnesium oxide is reduced with carbon to produce
magnesium in the vapor phase, which is recovered
by shock cooling. In the silicothermic process, silica
is reacted with carbon to give silicon metal which is
subsequently used to produce magnesium.
Magnesia is produced by calcining magnesite or
magnesium hydroxide or by the thermal
decomposition of magnesium chloride, magnesium
sulfate, magnesium sulfite, nesquehonite, or the
basic carbonate.
Mercury
Mercury currently is recovered only from gold ores.
Sulfide-bearing gold ore is roasted, and the mercury
is recovered from the exhaust gas. Oxide-based
Qold or© is crushsd dnd mixsd with Wtitor snd ssnt
to a classifier, followed by a concentrator. The
concentrate is sent to an agitator, where it is leached
with cyanide. The slurry is filtered and the filtrate is
sent to electrowinning, where the gold and mercury
are deposited onto stainless steel woo! cathodes.
The cathodes are sent to a retort, where the mercury
vaporizes with other impurities. The vapor is
condensed to recover the mercury which is then
purified.
Waste Stream
Cast house dust
Smut
Dust
Quench water
Furnace residue
RanArtarl
rfeponecf
Generation
dOOOmf/yr)
NA
26
0.007
NA
0,077
Est./Reported
Generation
(1000mt/yr)
Win
0.076
26
0.007
63
0.077
Avg,
0,76
26
0.007
77
0.077
Max
7.6
26
0.007
420
0.077
Number
of
Ce»**!HtlAB
raciiities
with
Process
1
2
7
7
7
TC Metals
As
Ba
Y?
Y
Cd
Cr
Pb
Y?
Ha
Y?
Y?
Y?
Se
Aa
Other Hazardous
Characteristics
Corr
N?
N?
N?
N?
N?
ignlt
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
-------
EXHIBIT 4-3 (Continued)
Commodity
Molybdenum, Ferromolybdenum, and Ammonium
Molybdate
Production of molybdenum and molybdenum
Droducts, including ammonium molybdate, begins
with roasting. Technical grade molybdic oxide is
made by roasting concentrated ore. Pure molybdic
oxide is produced from technical grade molybdic
oxide either by sublimation and condensing, or by
leaching. Ammonium molybdate is formed by
reacting technical grade oxide with ammonium
hydroxide and crystallizing out the pure molybdate.
Molybdenum powder is formed using hydrogen to
reduce ammonium molybdate or pure molybdic
oxide. Ferromolybdenum is typically produced by
reaction of technical grade molybdic oxide and iron
oxide with a conventional metallothermic process
using silicon and/or aluminum as the reductant.
Platinum Group Metals
Platinum-group metals can be recovered from a
variety of different sources, including electrolytic
slimes from copper refineries and metal ores. The
production of platinum-group metals from ore
involves mining, concentrating, smelting, and
refining. In the concentrating step, platinum ore is
crushed and treated by froth flotation. The
concentrates are dried, roasted, and fused in a
smelter furnace, which results in the formation of
platinum-containing sulfide matte. Solvent extraction
is used to separate and purify the six platinum-group
metals in the sulfide matte.
Waste Stream
Flue dust/gases
Liquid residues
Slag
Spent acids
Spent solvents
Reported
Generation
(1000mt/yr)
NA
1
NA
NA
NA
Est./Reported
Generation
(1000mt/yr)
Mln
1.1
1
0.0046
0.3
0.3
Avg.
250
1
0.046
1.7
1.7
Max
500
1
0.46
3
3
Number
of
Facilities
with
Process
11
2
3
3
3
TC Metals
As
Y?
Ba
Cd
Y?
Cr
Pb
Y?
Y?
Y?
Y?
Y?
Ht|
Se
Y?
Y?
Aa
Y?
Y?
Other Hazardous
Characteristics
Corr
N?
N?
N?
Y?
N?
Ignlt
N?
N?
N?
N?
Y?
Rctv
N?
N?
N?
N?
N?
00
UJ
-------
EXHIBIT 4-3 (Continued)
00
Commodity
Rare Earths
Rare earth elements are produced from monazite
and bastnasite ores by sulfuric and hydrochloric acid
digestion. Processing of rare earths involves
fractional crystallization and precipitation followed by
solvent extraction to separate individual rare earth
elements from one another. Ion exchange or
calcium reduction produces highly pure rare earths in
small quantities. Electrolytic reduction of rare earth
chlorides followed by crushing produces a complex
alloy of rare earth metals commonly known as
mischmetal.
Rhenium
In general, rhenium is recovered from the off-gases
produced when molybdenite, a byproduct of the
processing of porphyry copper ores for molybdenum,
is roasted. During the roasting process, molybdenite
concentrates are converted to molybdic oxide and
rhenium oxides are sublimed and carried off with the
roaster flue gas. Rhenium is then recovered from
the off-gases by the following five steps: (1 )
scrubbing; (2) solvent extraction or ion exchange; (3)
precipitation (addition of H2S and HCI) and filtration;
(4) oxidation and evaporation; and (5) reduction.
Scandium
Scandium is generally produced by small bench-
scale batch processes. The principal domestic
scandium resource is fluorite tailings containing
thortveitite and associated scandium-enriched
minerals. Scandium can be recovered from
thortveitite using several methods. Each method
involves a distinct initial step (i.e., acid digestion,
grinding, or chlorination) followed by a set of
common recovery steps, including leaching,
precipitation, filtration, washing, and ignition at
900 C to form scandium oxide.
Waste Stream
Spent ammonium nitrate
processing solution
Electrolytic cell caustic
wet ARC sludge
Process wastewater
Spent scrubber liquor
Solvent extraction crud
Spent lead filter cake
Waste solvent
Wastewater from caustic
wet APC
Spent barren scrubber
liquor
Spent rhenium raffinate
Spent acids
Spent solvents from
solvent extraction
Generation
(1000mt/yr)
14
NA
7
NA
NA
NA
NA
NA
NA
88
NA
NA
Est ./Reported
Generation
(1000mt/yr)
Min
14
0.07
7
0.1
0.1
0.17
0.1
0.1
0
88
0.7
0.7
Avg.
14
0.7
7
500
2.3
0.21
50
500
0.1
88
3.9
3.9
Max
14
7
7
1000
4.5
0.25
100
1000
0.2
88
7
7
Number
of
with
Process
1
1
1
1
1
1
1
1
2
2
7
7
TC Metals
As
Ba
Cd
Cr
Y?
Pb
Y
Y?
Y?
Y?
Hq
Se
Y?
Aq
Other Hazardous
Characteristics
Corr
Y
Y?
Y?
Y?
N?
N?
N?
Y?
N?
N?
Y?
N?
Ignit
N9
N?
N?
N?
Y?
N?
Y?
N?
N
N?
N?
Y?
Rctv
N9
N?
N?
N?
N?
N?
N?
N?
N
N?
N?
N?
-------
EXHIBIT 4-3 (Continued)
Commodity
Selenium
The two principle processes for selenium recovery
are smelting with soda ash and roasting with soda
ash. Other methods include roasting with fluxes,
during which the selenium is either volatilized as an
oxide and recovered from the flue gas, or is
incorporated in a soluble calcine that is subsequently
leached for selenium. In some processes, the
selenium is recovered both from the flue gas and
rom the calcine. To purify the crude selenium, it is
dissolved in sodium sulfite and filtered to remove
unwanted solids. The resulting filtrate is acidified
with sulfuric acid to precipitate selenium. The
selenium precipitate is distilled to drive off impurities.
Synthetic Rutile
Synthetic rutile is manufactured through the
upgrading of ilmenite ore to remove impurities
(mostly iron) and yield a feedstock for production of
titanium tetrachloride through the chloride process.
The various processes developed can be organized
in three categories: (1 ) processes in which the iron
in the ilmenite ore is completely reduced to metal
and separated either chemically or physically;
(2) processes in which iron is reduced to the ferrous
state and chemically leached from the ore; and
(3) processes in which selective chiorination is used
to remove the iron. In addition, a process called the
Benelite Cyclic process uses hydrochloric acid to
leach iron from reduced ilmenite.
Tantalum, Columbium, and Ferrocolumbium
Tantalum and columbium ores are processed by
physically and chemically breaking down the ore to
form columbium and tantalum salts or oxides, and
separating the columbium and tantalum salts or
oxides from one another. These salts or oxides may
be sold, or further processed to reduce the salts to
the respective metals. Ferrocolumbium is made by
smelting the ore with iron, and can be sold as a
product or further processed to produce tantalum
and columbium products.
Waste Stream
Spent filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste solids
Spent iron oxide slurry
ARC dust/sludges
Spent acid solution
Digester sludge
Process wastewater
Spent raffinate solids
Reported
Generation
dOOOmtfyr)
NA
66
NA
NA
NA
45
30
30
1
150
2
Est./Reported
Generation
(lOOOmtfyr)
Win
0,05
66
0.05
0.05
0.05
45
30
30
1
150
2
Avg,
0.5
66
0.5
0.5
0.5
45
30
30
1
150
2
Max
5
66
5
5
5
45
30
30
1
150
2
Number
of
racllltles
with
Process
3
2
3
3
3
1
1
1
2
2
2
TC Metals
As
Y?
Ba
Cd
Y?
Y?
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Pb
Y
Y?
HH
Se
Y?
Y?
Y?
Y?
Y?
*3
Other Hazardous
Characteristics
Corr
N?
Y
N?
N
N?
N?
N?
Y?
Y?
Y
Y?
ignlt
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N?
N?
N?
N?
N?
N?
N?
N?
N?
•N?
N?
CO
—h
Ul
-------
EXHIBIT 4-3 (Continued)
oo
Ol
Commodity
Tellurium
The process flow for the production of tellurium can
be separated into two stages. The first stage
involves the removal of copper from the copper
slimes. The second stage involves the recovery of
tellurium metal and purification of the recovered
tellurium. Copper is generally removed from slimes
by aeration in dilute sulfuric acid, oxidative pressure-
leaching with sulfuric acid, or digestion with strong
acid. Tellurous acid (in the form of precipitates) is
then recovered by cementing, leaching the cement
mud, and neutralizing with sulfuric acid. Tellurium is
recovered from the precipitated tellurous acid by the
following three methods: (1) direct reduction; (2) acid
precipitation; and (3) electrolytic purification.
Titanium and Titanium Dioxide
Titanium ores are utilized in the production of four
major titanium-based products: titanium dioxide
(TiO2) pigment, titanium tetrachloride (TiCI4), titanium
sponge, and titanium ingot/metal. The primary
titanium ores for manufacture of these products are
ilmenite and rutile. TiO2 pigment is manufactured
through either the sulfate, chloride, or chloride-
ilmenite process. The sulfate process employs
digestion of ilmenite ore or TiO2-rich slag with sulfuric
acid to produce a cake, which is purified and
calcined to produce TiO2 pigment. In the chloride
process, rutile, synthetic rutile, or high-purity ilmenite
is chlorinated to form TiCI,,, which is purified to form
TiO2 pigment. In the chloride-ilmenite process, a
low-purity ilmenite is converted to TiCI,, in a two-stage
chlorination process. Titanium sponge is produced
by purifying TiCI,, generated by the chloride or
chloride-ilmenite process. Titanium sponge is cast
into ingots for further processing into titanium metal.
Waste Stream
Slag
Solid waste residues
Waste electrolyte
Wastewater
Pickle liquor and wash
water
Scrap milling scrubber
water
Smut from Mg recovery
Leach liquor and sponge
wash water
Spent surface
impoundment liquids
Spent surface
impoundments solids
Waste acids (Sulfate
process)
Waste acids (Chloride
process)
WWTP sludge/solids
Reported
Generation
(1000mt/yr)
NA
NA
NA
NA
NA
NA
NA
NA
NA
36
NA
49
420
Est./Reported
Generation
(lOOOmt/yr)
Min
0.2
0.2
0.2
0.2
2.2
4
0.1
380
0.63
36
0.2
49
420
Avg.
2
2
2
20
2.7
5
22
480
3.4
36
39
49
420
Max
9
9
20
40
3.2
6
45
580
6.7
36
77
49
420
Number
of
Facilities
with
Process
2
2
2
2
3
1
2
2
7
7
2
7
7
TC Metals
As
Y
Ba
Cd
Y?
Y?
Cr
Y?
Y?
Y?
Y?
Y?
Y
Y?
Y?
Pb
Y?
Y?
Y?
Y?
Y?
Y?
Y?
Hcj
Se
Y?
Y?
Y?
Y?
Y?
Y
Y?
Ac]
Y
Other Hazardous
Characteristics
Corr
N?
N?
N?
Y?
Y?
N?
N?
Y
N?
N?
Y
Y
N
tgnit
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N
N
N
Rctv
N?
N?
N?
N?
N?
N?
Y
N?
N?
N?
N
N
N
-------
EXHIBIT 4-3 (Continued)
Commodity
Tungsten
Tungsten production consists of four distinct stages:
1) ore preparation, (2) leaching, (3) purification to
APT, and (4) reducing APT to metal. Ore
^reparation involves gravity and flotation methods.
Concentration is usually accomplished by froth
flotation, supplemented by leaching, roasting, or
magnetic or high tension separation. The
concentrate is then processed to APT via either
sodium tungstate or tungstic acid (which was
digested with aqueous ammonia) to solubilize the
tungsten as ammonia tungstate. Further purification
and processing yields APT. APT is converted to
tungsten oxide by calcining in a rotary furnace.
Tungsten oxides are reduced to metal powder in
high temperature furnaces. Tungsten carbide is
formed by reducing APT or tungsten oxides in the
presence of carbon.
Uranium
Uranium ore is recovered using either conventional
milling or solution mining (in situ leaching).
Beneficiation of conventionally mined ores involves
crushing and grinding the extracted ores followed by
a leaching circuit. In situ operations use a leach
solution to dissolve desirable uraniferous minerals
from deposits in-place. Uranium in either case is
removed from pregnant leach liquor and
concentrated using solvent extraction or ion
exchange and precipitated to form yellowcake.
Yellowcake is then processed to produce uranium
fluoride (UF6), which is then enriched and further
refined to produce the fuel rods used in nuclear
reactors.
Waste Stream
Spent acid and rinse
water
Process wastewater
Waste nitric acid from
UO2 production
Vaporizer condensate
Superheater condensate
Slag
Uranium chips from ingot
production
Reported
Generation
(1000mt/yr)
NA
NA
NA
NA
NA
NA
NA
Est./Reported
Genern"'::!!
(10uOmt/yr)
Min
0
2.2
1.7
1.7
1.7
0
1.7
Avg.
0
4.4
2.5
9.3
9.3
8.5
2.5
Max
21
9
3.4
17
17
17
3.4
Number
of
Facilities
with
Process
6
6
17
17
17
17
17
TC Metals
As
Ba
Cd
Cr
Pb
Hfl
Se
Afl
Other Hazardous
Characteristics
Corr
Y?
Y?
Y?
Y?
Y?
N?
N?
Ignlt
N?
N?
N?
N?
N?
Y?
Y?
Rctv
N?
N?
N?
N?
N?
N?
N?
CO
-------
EXHIBIT 4-3 (Continued)
oo
00
Commodity
Zinc
Zinc-bearing ores are crushed and undergo flotation
to produce concentrates of 50 to 60% zinc. Zinc is
then processed through either of two primary
processing methods: electrolytic or
pyrometallurgical. Electrolytic processing involves
digestion with sulfuric acid and electrolytic refining.
In pyrometallurgical processing, calcine is sintered
and smelted in batch horizontal retorts, externally-
heated continuous vertical retorts, or electrothermic
furnaces. In addition, zinc is smelted in blast
furnaces through the Imperial Smelting Furnace
process, which is capable of recovering both zinc
and lead from mixed zinc-lead concentrates.
Zirconium and Hafnium
The production processes used at primary zirconium
and hafnium manufacturing plants depend largely on
the raw material used. Six basic operations may be
performed: (1) sand chlorination, (2) separation, (3)
calcining, (4) pure chlorination, (5) reduction, and (6)
purification. Plants that produce zirconium and
hafnium from zircon sand use all six of these process
steps. Plants which produce zirconium from
zirconium dioxide employ reduction and purification
steps only.
Waste Stream
Acid plant blowdown
Waste ferrosilicon
Process waste water
Discarded refractory brick
Spent cloths, bags, and
filters
Spent goethite and leach
cake residues
Spent surface
impoundment liquids
WWTP Solids
Spent synthetic gypsum
TCA tower blowdown
Wastewater treatment
plant liquid effluent
Spent acid leachate from
Zr alloy prod.
Spent acid leachate from
Zr metal prod.
Leaching rinse water from
Zr alloy prod.
Leaching rinse water from
Zr metal prod.
Reported
Generation
(1000mt/yr)
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
NA
NA
NA
NA
Eat/Reported
Generation
(1000mt/yr)
Min
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
0
0
34
0.2
Avg.
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
0
0
42
1000
Max
130
17
5000
1
0.15
15
1900
0.75
16
0.25
2600
850
1600
51
2000
Number
of
Facilities
with
Process
1
1
3
1
3
3
3
3
3
1
3
2
2
2
2
TC Metals
As
Y
Y
Y?
Y
Y?
Y?
Ba
Cd
Y
Y
Y?
Y?
Y
Y?
Y?
Y
Y?
Y?
Cr
Y
Y
Y?
Y
Pb
Y?
Y?
Y
Y?
Y?
Y?
Y?
Y?
Y?
Hfj
Y?
Y?
Y?
Y?
Y?
Se
Y
Y
Y?
Y
Y?
Y?
AH
Y
Y
Y?
Y
Y?
Other Hazardous
Characteristics
Corr
Y
N?
Y
N?
N?
N?
Y
N?
N?
Y?
N?
Y?
Y?
Y?
Y?
Ignlt
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
Rctv
N
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
N?
II Corr., Ignit., and Rctv. refer to the RCRA hazardous characteristics of corrosivity, ignitability, and reactivity.
-------
EXHIBIT 4-4
IDENTIFICATION or HAZARDOUS MINERAL PROCESSING WASTE STREAMS
LIKELY SUBJECT TO THE LDRs
Mineral Processing Commodity Sectors
Alumina and Aluminum
Antimony
Beryllium
Bismuth
Cadmium
Calcium Metal
Chromium and Ferrochromium
Coal Gas
Copper
Elemental Phosphorus
Fluorspar and Hydrofluoric Acid
Germanium
Gold and Silver
Lead
Magnesium and Magnesia from Brines
Mercury
Molybdenum, Ferromolybdenurn, and
Ammonium Motvbdate
Platinum Group Metals
Rare Earths
Rhenium
Scandium
Selenium
Synthetic Rutile
Tantalum, Columbiurn, and Ferrocolumbium
Tellurium
Titanium and Titanium Dioxide
Tungsten
Uranium
Zinc
Number of
Waste
Streams I/
2
3
3
10
11
1
2
1
8
6
1
6
2
8
2
3
2
3
8
2
2
5
3
3
4
9
2
5
11
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
77
22
55
3.7
2.1
0.040
3.0
0
10,500
2,100
0
0.84
0.2
3,000
26
63
2.1
0.45
21
88
1.4
66
100
150
0.80
890
2.2
6.8
9,800
77
48
200
35
21
0.040
3.3
0
10,800
2,100
15
5.0
720
3,080
27
77
250
3.5
1,050
88
7.8
68
100
150
26
1,050
4.4
32
9,800
77
75
2,100
73
210
0.040
6.0
65
11.000
2.100
45
9.2
1400
3.200
34
420
500
6.5
2,100
88
14
86
100
150
78
1.250
30
58
9.800
819
-------
EXHIBIT 4-4 (Continued)
Mineral Processing Commodity Sectors
Zirconium and Hafnium
TOTAL:
Number of
Waste
Streams \l
4
133
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
34
27,016
1.000
30.838
4.500
39.575
I/ In calculating the total number of waste streams per mineral sector, EPA included both non-wastewaters and wastewater mineral processing
wastes and assumed that each of the hazardous mineral processing waste streams were generated in all three waste generation scenarios (low.
medium, and high).
820
-------
APPENDICES
821
-------
Page Intentionally Blank
822
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX A
Detailed Explanations of
Methodology Used to
Estimate Annual Waste Generation
Rates For Individual Waste Streams
823
-------
Page Intentionally Blank
824
-------
Introduction
Due to the paucity of data for several of the mineral commodity sectors and waste streams, we developed a
step-wise method for mineral processing waste volume estimation. We developed an "expected value" estimate for
each waste generation rate using draft industry profiles, supporting information, process flow diagrams, and
professional judgment. From the "expected value" estimate, we developed upper and lower bound estimates, which
reflect the degree of uncertainty in our data and understanding of a particular sector, process, and/or waste in
question. For example, we obtained average or typical commodity production rates from published sources (e.g.,
BOM Mineral Commodity Summaries) and determined input material quantities or concentration ratios from
published market specifications. In parallel with this activity, we reviewed process flow diagrams for information on
flow rates, waste-to-product ratios, or material quantities. We then calculated any additional waste generation rates
and subtracted out known material flows, leaving a defined material flow, which we allocated among waste streams
using professional judgment. Finally, we assigned a high, medium, and low volume estimate for each waste stream.
A key element in developing waste generation rates was the fact that by definition, average facility level
generation rates of solids and sludges are less that 45,000 metric tons/year, and generation rates of wastewaters are
less than 1,000,000 metric tons/year. Using this fact, in the absence of any supporting information, high values for
solids and sludges were set at the highest waste generation rate found in the sector in question or 45,000 metric
tons/year/facility, whichever is lower.
Precise methodology for determining waste generation rates varied depending on the quantity and quality of
available information. The waste streams for which we had no published annual generation rate were divided into
five groups and a methodology for each group was assigned.
1. Actual generation rates for the waste in question from one or more facilities were available.
We extrapolated from the available data to the sector on the basis of waste-to-product ratios to
develop the expected value, and used a value of +/- 20% of the expected value to define the upper
and lower bounds.
2. A typical waste-to-product ratio for the waste in question was available. We multiplied the
waste-to-product ratio by sector production (actual or estimated) to yield a sector wide waste
generation expected value, and used one-half and twice this value for the lower and upper bounds,
respectively.
3. No data on the waste in question were available , but generation rates for other generally
comparable wastes in the sector were. We used the maximum and minimum waste generation
rates as the upper and lower bounds, respectively, and defined the expected value as the midpoint
between the two ends of the range. Adjustments were made using professional judgment if
unreasonable estimates resulted from this approach.
4. No data were available for any analogous waste streams in the sector, or information for the
sector generally was very limited. We drew from information on other sectors using analogous
waste types and adjusting for differences in production rates/material throughput. We used upper
and lower bound estimates of one order of magnitude above and below the expected value derived
using this approach. Results were modified using professional judgment if the results seemed
unreasonable.
5. All we knew (or suspected) was the name of the waste. We used the high value threshold
(45,000 metric tons/year/facility or 1,000,000 metric tons/year/facility) as the maximum value, 0 or
100 metric tons per year as the minimum, and the midpoint as the expected value.
Detailed explanations of the methodology used for each waste generation rate estimate follow.
1997 UPDATE
825
-------
Several of the waste generation rate estimates detailed below have been revised since December 1995 (the
date of initial publication of this appendix) due to comments received on the January 25, 1996 Supplemental
Proposed Rule_Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes and
the May 12, 1997 Second Supplemental Proposed Rule Applying Phase IV Land Disposal Restrictions to Newly
Identified Mineral Processing Wastes, as well as other new information received by the Agency. Changes to waste
generation rate estimates are summarized in Exhibit A-l.
EXHIBIT A-l
CHANGES TO WASTE GENERATION RATE ESTIMATES SINCE DECEMBER 1995
Sector — Waste Stream
Antimony — Autoclave Filtrate
Beryllium — Chip Treatment
'Wastewater
Beryllium — Filtration Discard
Chromium and Ferrochromium —
GCT Sludge
Elemental Phosphorous — Furnace
Scrubber Slowdown
Lead — Stockpiled Miscellaneous
Plant Waste
Molybdenum, Ferromolybdenum,
and Ammonium Molybdate — Flue
Dust/Gases
Rare Earths — Solvent Extraction
Crud
Tellurium - Slag
Tellurium — Solid Waste Residues
1995 Generation Rate Estimate
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
(mifrr)
64,000
32,000
380
1,000,000
50,000
100
45,000
23,000
100
Not Included
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
270,000
0
0
180,000
90,200
400
540,000
270,000
1,200
90,000
45,000
200
4,500
1,000
100
4,500
1,000
100
Current
Generation Rate
Estimate (itrt/yr)
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
54,000
27,000
320
2,000,000
100,000
200
90,000
45,000
200
3,000
300
30
410,000
410,000
410,000
130,000
67.000
300
500,000
250,000
1,100
4,500
2,300
100
9,000
2,000
200
9,000
2,000
200
EXHIBIT A-l (continued)
826
-------
Sector - Waste Stream
Tellurium — Waste Electrolyte
Tellurium — Wastewater
Tungsten — Process Wastewater
1995 Generation Rate Estimate
High:
Medium:
Low:
High:
Medium:
Low:
High:
Medium:
Low:
(rat/jr)
10,000
1,000
100
20,000
10,000
100
7,300
3,700
1,800
Current Generation Rate
Estimate
-------
ANTIMONY
Autoclave Filtrate:
BERYLLIUM
Filtration Discard:
BISMUTH
Alloy Residues:
Spent Caustic Soda:
High: 64,000 mt/yr (32,000 * 2)
Medium: 32,000 mt/yr ((64,000 + 380)72)
Low: 3 80 mt/yr (190* 2)
A high of twice the highest waste generation rate in the sector was selected since this is a
liquid waste stream. Similarly, the low was set equal to twice the lowest waste generation
rate in the sector.
The waste stream may be corrosive (Table A, Text) and contains arsenic, cadmium, lead,
and mercury at concentrations that may exceed TC levels.
Chip Treatment
Wastewater:
High:
Medium:
Low:
1 ,000,000 mt/yr
50,000 mt/yr
100 mt/yr
There was no information on the generation rates of this waste.
This waste may contain chromium above TC concentrations.
High: 45,000 mt/yr
Medium: 23,000 mt/yr
Low: 100 mt/yr
There was no information on the generation rates of this waste.
This waste may contain lead above TC concentrations.
High: 6,000 mt/yr (3,000 * 2 * 1 facility)
Medium: 3,000 mt/yr
Low: 100 mt/yr
Comparing with the metal chlorides residue waste stream shown in Table (avg. waste
generation rate = 3,000 mt/yr). Lower and upper bounds of 100 mt/yr and twice the
medium value were used instead of an order of magnitude above and below the expected
value since production rates are low (1,450 mt/yr).
Waste stream may contain lead since the process uses lead as the starting material.
High: 12,000 mt/yr (6,000*2 * 1 facility)
Medium: 6,100 mt/yr ((12,000 + 100)/2)
Low: 100 mt/yr (100* 1 facility)
No information about the waste stream was available. A high of 12,000 mt/yr was
selected since low production rates (1,450 mt/yr) in the sector are expected to yield low
waste generation rates. The low value was estimated as 100 mt/yr.
Common sense suggests that if large volumes of chemicals were being wasted, the process
would not be economical. If large amounts of waste containing chemicals was being
generated, the chemicals would probably be recovered.
828
-------
Electrolytic Slimes:
Waste stream may contain lead since the process uses lead as the starting material.
High: 200 mt/yr (100 * 2 * 1 facility)
Medium: 20 rnt/yr
Low: 0 (i.e., waste stream is reprocessed)
A low of zero was selected since the slimes are likely to be reprocessed (Text, Section
C.2).
Lead & Zinc
Chlorides:
Total consumption in 1993 was only 1,450 mt. This was compared to the electrolytic
waste stream (waste/product = .014) in the aluminum sector (1450 * .014 = 20 mt/yr).
Upper bound of one order of magnitude above the estimate was selected to account for
any differences in the waste streams.
Waste stream may contain lead since the process uses lead as the starting material.
High: 6,000 mt/yr (3,000 * 2 * 1 facility)
Medium: 3,000 mt/yr
Low: 100 mt/yr
Comparing with the metal chlorides residue waste stream shown in Table (avg. waste
generation rate = 3,000 mt/yr). Lower and upper bounds of 100 mt/yr and twice the
medium value were used instead of an order of magnitude above and below the expected
value since production rates are low (1,450 mt/yr).
Waste stream contains lead.
Slag:
Spent Electrolyte:
High:
Medium:
Low:
10,000 mt/yr
1,000 mt/yr
100 mt/yr
Comparing with the Slag waste stream in the antimony sector (waste/product =
32,000/44,600 = 0.717), the medium value was calculated as (1,450 * 0.717 = 1,040).
Upper and lower bound estimates of one order of magnitude above and below the
expected value were used.
Waste stream contains lead.
High: 12,000 mt/yr (3.000 mt/yr * 4)
Medium: 6,100 mt/yr ((12,000 + 100)/2)
Low: 100 mt/yr (100 * 1 facility)
Low production rates in the sector indicate that the waste generation rates will be low,
therefore, a high value of four times the highest waste generation rate in the sector was
selected.
Spent Soda Solution:
Common sense suggests that if large volumes of chemicals were being wasted, the process
would not be economical. If large amounts of waste containing chemicals was being
generated, the chemicals would probably be recovered.
Waste stream may contain lead since the process uses lead as the starting material.
High: 12,000 mt/yr (3,000 mt/yr * 4)
Medium: 6,100 mt/yr ((12,000+ 100)/2)
Low: 100 mt/yr (100 * 1 facility)
829
-------
Waste Acid
Solutions;
Waste Acids:
See previous comments.
Waste stream may be corrosive (engineering judgment) and may contain lead since the
process uses lead as the starting material.
High: 12,000 mt/yr
Medium: 6,100 mt/yr ((12,000 + 100)/2)
Low: 100 mt/yr (100 * 1 facility)
See previous comments.
Waste stream may be corrosive (engineering judgment). No further information which
may classify the waste stream as hazardous was found.
High: 200 mt/yr (100 * 2 * 1 facility)
Medium: 100 mt/yr
Low: 0
Text, Section C.2. Waste acids are neutralized and discharged with water. Therefore, a
low of 0 was selected.
BORON
Waste Liquor:
CADMIUM
Caustic Washwater:
Copper and Lead
Sulfate Filter Cakes:
Copper Removal
Filter Cake:
Waste stream may be corrosive (engineering judgment). No further information which
may classify the waste stream as hazardous was found.
High: 300,000 (100,000 * 3 Facilities)
Medium: 150,000 mt/yr ((300,000 + 300)/2)
Low: 300 mt/yr (100 * 3 Facilities)
Since some waste liquor may be recycled (text), the high waste generation rate was set at
100,000 mt/yr.
This waste is expected to exhibit the characteristic of toxicity for arsenic.
Methodology for estimating waste generation rates for the waste streams listed
below is provided at the end of the sector.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or be corrosive.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or lead.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
830
-------
Iron Containing
Impurities:
Lead Sulfate Waste:
Post-Leach Filter
Cake:
Spent Purification
Solution:
This waste may be toxic for cadmium.
High:
Medium:
Low:
19,000 mt/yr
l,900mt/yr
190 mt/yr
This waste may be toxic for cadmium.
Spent Leach
Solutions:
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
Scrubber Wastewater:
Spent Electrolyte:
This waste may be toxic for arsenic, cadmium, and/or lead and/or may be
corrosive.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or lead.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium.
High;
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or be corrosive.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or be corrosive.
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium and/or be corrosive.
Zinc Precipitates:
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium.
According to RTC II (Report to Congress on Solid Wastes from Selected Metallic Ore
Processing Operations; Technical Memorandum for the Zinc Sector, 1988), saleable
831
-------
metallic residues from both electrolytic and pyrometallurgical production of zinc amounts
to .127 ton/ton product. This document also cites a production capacity for the sector of
400,000 metric tons, 83% of which is utilized. This amounts to a production rate of
332,000 metric tons per year of zinc. Using the above waste-to-product ratio, 42,164
metric tons of saleable metallic residues are generated per year. These metallic residues
are used for cadmium recovery as well as the recovery of other heavy metals. Therefore,
given an input of 42,164 metric tons and assuming a process efficiency of 50%, 21,082
metric tons of cadmium waste are generated annually. Assuming each of the 11 wastes
from cadmium production is generated equally, a medium annual waste generation rate
for each cadmium waste is 1,900 metric tons. The high estimate is one order of
magnitude above the medium estimate and the low estimate is one order of magnitude
below the medium estimate.
COAL GASIFICATION
MEE Concentrate:
High:
Medium:
Low:
65,000 mt/yr
Omt/yr
0 mt/yr
This waste is most likely entirely recycled. Therefore, both the minimum and medium
value of MEE Concentrate were estimated to be 0. The maximum generation rate was set
at 64,600 mt/yr, based on a ratio of Cooling tower blowdown/MEE Concentrate of 500
gpm/50 gpm, and a cooling tower blowdown generation rate of 646,000 mt/yr.
This waste may contain arsenic and selenium above TC concentrations.
COPPER
Scrubber Blowdown:
High:
Medium:
Low:
4,900,000 mt/yr
490,000 mt/yr
49,000 mt/yr
This waste is similar to acid plant blowdown, but will be generated at a lower volume.
Therefore, we assumed the medium value to be 10 percent of the acid plant blowdown.
The minimum and maximum values are one order of magnitude below and above this
rate, respectively.
This waste may contain arsenic, cadmium, mercury, and selenium above TC
concentrations.
APC Dust/Sludge:
High:
Medium:
Low:
450,000 mt/yr
220,000 mt/yr
1,000 mt/yr
There was no information available for this waste stream so the minimum, medium, and
maximum values were set at 100; 22,000; and 45,000 mt/y, respectively. These rates
apply to 10 facilities so the sector wide generation rates were calculated to be the above
values.
832
-------
ELEMENTAL PHOSPHORUS
Furnace Scrubber
Slowdown:
High:
Medium:
Low:
270,000 mt/yr
Omt/yr
0 mt/yr
The Newly Identified Waste Characterization Data Set Reports that 680,000 mt/yr of
Furnace Scrubber Slowdown was generated in 1989. This generation rate corresponds to
5 facilities. Today, there are only 2 facilities producing elemental phosphorous furnace
scrubber blowdown. The 680,000 mt/yr value was readjusted as follows:
(680,000)/5 = 136,000
136,000 * 2 = 270,000 mt/yr
This waste stream may be treated prior to discharge, therefore, a generation rate of 0
mt/yr was selected for the low and medium estimates,
This waste may is corrosive and toxic for cadmium.
Slag Quenchwater:
High:
Medium:
Low:
1,000,000 mt/yr
Omt/yr
Omt/yr
Default rate is 1,000,000 mt/yr per facility. Since the generation rate is not expected to be
nearly this high, half the default value was selected. Since there are two facilities, a
maximum of 1,000,000 mt/yr was selected. Low and medium estimates were set at 0
mt/yr, since this waste may be treated prior to discharge.
This waste stream is toxic for cadmium and lead.
FLUORSPAR AND HYDROFLUORIC ACID
Off-Spec Fluosilicic
Acid:
High:
Medium:
Low:
44,000 mt/yr
15,000 mt/yr
0 mt/yr
To estimate the maximum quantity of this waste, we assumed the entire three percent of
impurity in acid grade fluorspar was silicon, and that this was the only source of silicon.
Therefore, at Allied Signal three percent of 209,839 short tons fluorspar would be 6,295
short tons. If all of this silicon reacted to form fluosilicic acid (H2SiF6), approximately
32,297 short tons (29,299 metric tons) could be formed at one plant. However, the waste
is off-spec fluosilicic acid, so we assumed that 50 percent could be sold, and there are
three facilities in the sector. So the maximum value for industry is 43,950 mt/yr. We
assumed the medium value to be one-third of the maximum, representing only one percent
silicon in the acid grade fluorspar. Finally, since it is possible to sell this waste as a
product, the minimum generation rate was assumed to be 0 mt/yr.
This waste may exhibit the hazardous characteristic of corrosivity.
833
-------
GERMANIUM
Waste Acid Wash
& Rinse Water:
Chlorinator Wet
APC Sludge:
Hydrolysis Filtrate:
Spent Acid/Leachate:
High: 4,000 mt/yr (1,000 * 4 facilities)
Medium: 2,200 mt/yr ((4,000 + 400)/2)
Low: 400 mt/yr (100 * 4 facilities)
A high rate of 1,000 was selected which is three orders of magnitude below the average
facility generation rate (1,000,000 mt/yr) since the annual consumption rate is only 25
metric tons/yr. The low estimate was set at 3 00 mt/yr.
Since Hydrofluoric Acid is very expensive and the water is being used for rinsing only.
the volume of waste produced is expected to be low. Also, the total consumption rate in
1993 was 25,000 kg (25 mt) (text). Assuming that all of this was produced domestically,
low waste generation rates are expected.
We used engineering judgment to determine that this waste stream may be corrosive and
toxic (arsenic, cadmium, chromium, lead, selenium, and silver).
High: 400 mt/yr (100 * 4 facilities)
Medium: 210 mt/yr ((400 + 10)/2)
Low: 10 mt/yr
A high rate of 100 was selected based on the low consumption rates (25 mt/yr). The low
was set equal to the highest known production rate in the sector.
Since the wet APC system is primarily being used to control fumes, and concentrated
germanium is being used in the process (as compared to germanium with lot of
impurities), the sludge generated is expected to be low to medium in volume.
We used engineering judgment to determine that this waste stream may be toxic (arsenic,
cadmium, chromium, lead, selenium, and silver).
High: 400 mt/yr (100 * 4 facilities)
Medium: 210 mt/yr ((400 + 10)/2)
Low: 10 mt/yr
A high rate of 100 was selected based on the low consumption rates (25 mt/yr). The low
was set equal to the highest known production rate (10 mt/yr) in the sector.
We used engineering judgment to determine that this waste stream may be toxic (arsenic,
cadmium, chromium, lead, selenium, and lead).
High: 4,000 mt/yr (1,000 * 4 facilities)
Medium: 2,200 mt/yr ((4,000 + 400)72)
Low: 400 mt/yr (100* 4 facilities)
A high rate of 1,000 was selected which is three orders of magnitude below the average
facility generation rate (1,000,000 mt/yr) since the annual consumption rate is only 25
tons/yr. The low estimate was set at 100 mt/yr.
Waste stream may be corrosive and toxic (arsenic and lead).
834
-------
Waste Still Liquor:
High: 400 mt/yr (100 * 4 facilities)
Medium: 210 mt/yr ((400 + 10)/2)
Low: 10 mt/yr
A high rate of 100 was selected based on the low consumption rates (25 mt/yr). The low
was set equal to the highest known production rate in the sector.
Waste stream may be ignitable (engineering judgment) and toxic (arsenic, cadmium,
chromium, lead, selenium, and silver).
GOLD AND SILVER
Spent Furnace Dusts,
Refining Wastes,
Slag, and Wastewater
Treatment Sludge:
High:
Medium:
Low:
720,000 mt/yr
360,000 mt/yr
100 mt/yr
Wastewater:
By definition, average facility-level generation rates of solids and sludges are less than
45,000 metric tons. Therefore, due to lack of more precise information, this was used as a
high-end in order to estimate waste generation rates for spent furnace dusts, refining
wastes, slag, and wastewater treatment sludge from gold and silver production. There are
16 known gold and silver smelters and refineries. Therefore a high-end estimate of
720,000 metric tons, a low-end estimate of 100 metric tons, and a medium estimate of
360,000 metric tons (the midpoint between the high and low estimates) were set for the
wastes.
Each of these wastes may be toxic for silver.
High:
Medium:
Low:
1,700,000 mt/yr
870,000 mt/yr
440,000 mt/yr
According to the Effluent Guidelines, 1989, wastewater generated from the production of
gold and silver is made up of wastewater from electrolyte preparation wet air pollution
control, smelter wet air pollution control, silver chloride reduction spent solution, and
electrolytic cells wet air pollution control. These are generated at the following waste-to-
product ratios:
* Electrolyte preparation wet APC: .05 L/troy ounce silver in electrolyte
* Smelter wet APC: 6.73 L/troy ounce gold and silver smelted
4 Silver chloride reduction spent solution: .4 L/troy ounce silver reduced
* Electrolytic cells wet APC: 19 L/troy ounce gold refined electrolytically
Gold and silver production rates of 2.10 million troy ounces and 59.3 million troy ounces,
respectively, were used. These yield wastewater generation rates of 3,517; 791,912;
28,136; and 47,328 metric tons. Therefore^ the medium estimate of total waste generation
for wastewater is the sum of these four, 870,893 metric tons. One-half and twice the
medium value were assigned as lower and upper bounds, respectively.
This waste may be toxic for arsenic, cadmium, chromium, lead, and/or silver.
835
-------
LEAD
Baghouse Incinerator High: 30,000 mt/yr
Ash: Medium: 3,000 mt/yr
Low: 300 mt/yr
A low generation rate of 100 mt/yr was selected. A high generation rate of 10,000 mt/yr
was selected since the waste generation rates are not expected to be as high as 45,000
mt/yr, A medium value one order of magnitude above the low generation rate was
estimated.
The waste may be TC toxic for cadmium and lead.
Stockpiled High: 180,000 mt/yr
Miscellaneous Medium: 90,200 mt/yr
Plant Waste: Low: 400 mt/yr
High and low generation rates of 45,000 and 100 mt/yr,respectively were selected since
no other information about the waste stream was available. The medium rate was
calculated as the average of the high and low generation rates.
The waste may be TC toxic for cadmium and lead.
MAGNESIUM AND MAGNESIA FROM BRINES
Casmouse Dust: High: 7,600 mt/yr
Medium: 760 mt/yr
Low: 76 mt/yr
Casthouse dust is analogous to aluminum production casthouse dust. Aluminum
production casthouse dust is generated at a medium rate of 19,000 metric tons per year.
Therefore, since the annual production rate for magnesium is about 25 times less than that
of aluminum, a medium waste generation rate of 760 metric tons was assigned to
casthouse dust. Upper and lower bound estimates of one order of magnitude above and
below the medium value were assigned.
This waste may be toxic for barium.
MOLYBDENUM, FERROMOLYBDENUM, AND AMMONIUM MOLYBDATE
Flue Dust/Gases:
High:
Medium:
Low:
540,000 mt/yr
270,000 mt/yr
1,200 mt/yr
There was no information on the generation rates of this waste, but 12 facilities produce
it. Therefore, we multiplied default values by 12 to estimate the minimum, medium and
maximum generation rates.
This waste may contain lead above TC concentrations.
836
-------
PLATINUM GROUP METALS
Slag:
High:
Medium:
Low:
460 mt/yr
46 mt/yr
4.6 mt/yr
Spent Acids:
Spent Solvents:
Comparing with the slag waste stream in the antimony sector (waste/product =
32,000/44,600 = 0.717), the medium value was calculated as (65 * 0.717) 46 mt/yr.
Upper and lower bound estimates of one order of magnitude above and below the
expected value were used.
The waste stream may contain selenium and lead since these two TC metals are being
produced in the process.
High: 3,000 mt/yr (1,000 * 3 facilities)
Medium: 1,700 mt/yr ((3,000 + 300)/2)
Low: 300 mt/yr (100 * 3 facilities)
A high rate of 1,000 mt/yr was selected which is three orders of magnitude below the
highest possible average facility generation rate (1,000,000 mt/yr) since the production is
only 65 mt/yr. The low estimate was set at 100 mt/yr.
The waste stream may be corrosive (engineering judgment). The waste stream may
contain silver and lead, since these two TC metals are being produced in the process.
High: 3,000 mt/yr (1,000 * 3 facilities)
Medium: 1,700 mt/yr (3,000 + 300/2)
Low: 300 mt/yr (100 * 3 facilities)
See the previous comment.
The waste stream may be ignitable. The waste stream may contain silver and lead, since
these two TC metals are being produced in the process.
PYROBITUMENS, MINERAL WAXES, AND NATURAL ASPHALT
Still Bottoms:
Waste Catalysts:
Methodology for estimating waste generation rates for the waste streams listed
below is provided at the end of the sector.
High: 90,000 mt/yr (45,000 mt/yr * 2 facilities)
Medium: 45,000 mt/yr
Low: 2 mt/yr
This waste may be ignitable.
High: 20,000 mt/yr (10,000 mt/yr * 2 facilities)
Medium: 10,000 mt/yr
Low: 2 mt/yr
This waste may be toxic for cadmium and/or selenium.
No information was available on waste generation rates from the production of
pyrobitumens, mineral waxes, and natural asphalts. There are only two facilities that
produce bituminous materials. Therefore, since the production must be less than 45,000
metric tons per facility, the waste generation rate for still bottoms was set as follows:
837
-------
RARE EARTHS
Electrolytic Cell
Caustic Wet APC:
high, 90,000; medium, 45,000; and low, 2 metric tons. Waste catalysts are assumed to be
generated in lower volumes because they are usually recycled. Therefore, a high value
was set at 10,000 metric tons per facility. This yields waste catalyst generation rates of
high, 20,000; medium, 10,000; and low, 2 metric tons.
The methodology for estimating waste generation rates for the waste streams
listed below is provided after the estimates.
High:
Medium:
Low:
7,0 00 mt/yr
700 mt/yr
70 mt/yr
This waste may be corrosive.
The Development Document for Effluent Limitations Guidelines, 1989, gives waste-to-
product ratios for spent electrolytic cell quench water and scrubber water and spent
sodium hypochlorite filter backwash from mischmetal production. Spent electrolytic cell
quench water and scrubber water is produced at a rate of 9,390 to 12,683 L/kkg
mischmetal produced. Spent sodium hypochlorite filter backwash is produced at a rate of
362 L/kkg mischmetal produced.
Since mischmetal is produced by only one company, Reactive Metals and Alloys
Corporation in West Pittsburgh, Pennsylvania, information on production of mischmetal
is CBI. For this reason an approximation must be made. The following facts guided the
estimation:
* Mischmetal is produced from rare earth chlorides which are produced from
bastnasite ore.
* Annual production of mischmetal will not exceed annual production of rare earth
chlorides since mischmetal is a specialty product.
4 Production of rare earth chlorides will not exceed production of bastnasite ore
since rare earth chlorides come from bastnasite ore.
* Substituting production of bastnasite ore for production of mischmetal will yield
conservative estimates of waste generation rates.
The 1994 Minerals Yearbook gives a production rate for bastnasite concentrates of
20,787 metric tons of rare earth oxide (REO) content. Mischmetal is made from rare
earth chlorides which are made from bastnasite ore. According to the 1992 Minerals
Yearbook, three grades of bastnasite ore are produced in the United States: (1) unleached
concentrate, 60% REO, (2) acid-leached concentrate, 70% REO, and (3) calcined
concentrate, 85% REO. These grades specifications were used to establish the total
volume of bastnasite ore. The following relationship was used in the calculation.
Ore production in metric tons of REO = %REO in ore
Total Ore Production 100
This calculation yields the following bastnasite ore production rates:
* Calcined: 24,000 metric tons bastnasite ore
* Acid-leached: 30,000 metric tons bastnasite ore
* Unleached: 35,000 metric tons bastnasite ore
838
-------
Solvent Extraction
Crud:
Spent Lead
Filter Cake:
Spent Scrubber
Liquor:
Waste Solvent:
Wastewater from
Caustic Wet APC:
Waste Zinc
Contaminated with
Mercury:
Assuming all three grades are produced equally, dividing the above values by three gives
the annual production of each of the three grades of bastnasite ore (calcined, 8,152 metric
tons; acid-leached, 9,899 metric tons; and 11,548 metric tons). Totalling these three
values provides the total production of bastnasite ore, 29,599 metric tons. Substituting
this value for mischmetal in the waste-to-product ratios yields a high-end generation rate.
The medium and low-end estimates are one and two orders of magnitude below this
value, respectively.
The methodology for estimating waste generation rates for the waste streams
listed below is provided at the end of the sector.
High:
Medium:
Low:
90,000 mt/yr
45,000 mt/yr
200 mt/yr
The default value of 45,000 mt/yr was reduced by a factor of 10 since the generation rate
is not expected to be that high.
This waste may be ignitable.
High:
Medium:
Low:
5,000 mt/yr
4,200 mt/yr
3,300 mt/yr
This waste may be toxic for lead.
High: 1,000,000 mt/yr (1,000,000*1 facility)
Medium: 500,000 mt/yr
Low: 100 mt/yr (100*1 facility)
This waste may be corrosive.
High: 2,000,000 mt/yr
Medium: 1,000,000 mt/yr
Low: 200 mt/yr (100* 14 facilities)
This waste may be ignitable
The default value of 1,000,000 mt/yr was reduced by a factor of 10 since waste solvents
are presumed to be generated in smaller quantities than other wastes.
High: 1,000,000 mt/yr (1,000,000* 1 facility)
Medium: 500,000 mt/yr
Low: 100 mt/yr (100* 1 facility)
This waste may be corrosive and/or toxic for chromium and/or lead.
High: 90,000 mt/yr (45,000* 14 facilities)
Medium: 45,000 mt/yr
Low: 200 mt/yr (100* 14 facilities)
The default value of 45,000 was reduced by a factor of 10 since the rate is not expected to
be that high.
839
-------
RHENIUM
Spent Barren
Scrubber
Liquor:
High: 200 mt/yr (100 * 2 facilities)
Medium: 100 mt/yr ((200 + 0)/2)
Low: 0
Text indicates that plants achieve zero discharge through reuse and treatment. Therefore.
a low of zero and a high of 100 mt/yr were selected.
The waste stream contains selenium.
SCANDIUM
Spent Acids:
Spent Solvents from
Solvent Extraction:
SELENIUM
Spent Filter Cake:
Waste Solids:
High: 7,000 mt/yr (1,000 * 7 facilities)
Medium: 3,900 mt/yr ((7,000 + 700)/2)
Low: 700 mt/yr (100* 7 facilities)
A high rate of 1,000 was selected which is three orders of magnitude lower than
1,000,000 mt/yr. Based on the very low production rates (0.5 tons/yr), the waste
generation rate is not expected to be as high as 1,000,000 mt/yr. A low of 100 mt/yr was
selected.
The waste stream may be corrosive (engineering judgment).
High: 7,000 mt/yr (1,000 * 7 facilities)
Medium: 3,900 mt/yr ((7,000 + 700)/2)
Low: 700 mt/yr (100 * 7 facilities)
A high rate of 1,000 was selected which is three orders of magnitude lower than
1,000,000 mt/yr. Based on the very low production rates (0.5 tons/yr), the waste
generation rate is not expected to be as high as 1,000,000 mt/yr. A low of 100 mt/yr was
selected.
The waste stream may be ignitable (engineering judgment).
The methodology for estimating waste generation rates for the waste streams
listed below is provided at the end of the sector.
High:
Medium:
Low:
5,000 mt/yr
500 mt/yr
50 mt/yr
This waste may be toxic for selenium.
High:
Medium:
Low:
5,000 mt/yr
500 mt/yr
50 mt/yr
This waste may be toxic for selenium.
840
-------
Slag:
Tellurium Slime
Waste:
TELLURIUM
Slag:
High:
Medium:
Low:
5,000 mt/yr
500 mt/yr
50 mt/yr
This waste may be toxic for selenium.
High:
Medium:
Low:
5,000 mt/yr
500 mt/yr .
50 mt/yr
This waste may be toxic for selenium.
Selenium is produced from copper anode slimes or "tankhouse slimes." According to the
Newly Identified Waste Characterization Data Set, 1992, 4,000 metric tons of these
slimes are produced annually. Assuming a process efficiency of 50%, 2,000 metric tons
of wastes from selenium production is generated annually. Assuming each of the wastes
from selenium production is produced equally, a medium estimate of 500 metric tons of
each of the above wastes is produced annually. (Plant process wastewater was not used in
this calculation of medium waste generation rates.) The high and low estimates are one
order of magnitude above and below the medium estimate.
High: 4,500 mt/yr (4,500 * 1 facility)
Medium: 1,000 mt/yr
Low: 100 mt/yr
Solid Waste
Residues:
Waste Electrolyte:
No information about production rates or waste stream is available, therefore, high and
low estimates of 4,500 and 100 mt/yr were selected. A medium estimate of 1,000 mt/yr
was selected because the number of refineries in the U.S. (1) and uses of the metal
indicate that production rates and, therefore, waste generation rates would be low.
The waste stream may contain selenium.
High: 4,500 mt/yr (4,500 * 1 facility)
Medium: 1,000 mt/yr
Low: 100 mt/yr
See previous comment.
The waste may contain selenium since selenium is produced in the process.
High: 10,000 mt/yr (10,000 * 1 facility)
Medium: 1,000 mt/yr
Low: 100 mt/yr
No information about production rates was available. However, the number of refineries
in the U.S. (1) and the uses of the metal indicate that production rates and, therefore,
waste generation rates will be low, A medium value of 1,000 mt/yr was used for reasons
discussed above. High and low values of 10,000 and 100 mt/yr, respectively, were
selected for the same reasons.
The waste stream may contain selenium since selenium is produced in the process. Lead,
as an impurity, may also be present in the waste stream.
841
-------
Wastewater: High: 20,000 mt/yr (20,000 * 1 facility)
Medium: 10,000 mt/yr
Low: 100 mt/yr
See previous comment.
The waste stream may be corrosive. The waste may contain selenium since selenium is
also produced in the process.
TITANIUM
Sulfate Process
Waste Acids: High: 77,000 mt/yr (Newly Identified Document)
Medium: 39,000 mt/yr
Low: 200 mt/yr (100 * 2 facilities)
Chloride and Chloride-Ilmenite Processes
Waste Ferric High: 75,000 mt/yr
Chloride: Medium: 29,000 mt/yr
Low: 22,000 mt/yr
Ferric chloride is generated in the chloride-ilmenite process when gaseous titanium
tetrachloride is separated from other chlorides. Ferric chloride is removed as an acidic,
liquid waste stream through fractional condensation and treated with lime and either
landfilled or sold as a by-product. Volume estimated as 10% of Waste Solids volume.
This waste may exhibit the corrosivity characteristic.
Surface High: 6,700 mt/yr
Impoundment Medium: 3,400 mt/yr
Liquids: Low: 630 mt/yr
Surface impoundment liquids consist of various waste streams, such as chloride process
waste acids and solids in slurry form and wastewater treatment plant effluent. Waste
acids managed in surface impoundments are generally routed to a solids/liquids
separation process and then disposed by deep-well injection. Treated effluent is
discharged through NPDES outfalls after solids have settled.
This waste may be hazardous for chromium and lead.
Kroll Process for Ti Sponge (Metal) Production
Leach Liquor and High: 580,000 mt/yr
Sponge Wash Water: Medium: 480,000 mt/yr
Low: 380,000 mt/yr
Use discharge rates from Vol. IX of Eff. Guidelines Develop. Doc. for Acid Leachate and
Rinse Water (Table V-9, p. 4869) for 4 plants (unidentified). Because these two streams
are given as a combined stream in the Dev. Doc., we should combine them in our
analysis. Need to get an average value per plant for sponge (Ti metal) production. Use
sponge production value for 1991 from Gambogi (1993, p. 12) (1992 data withheld due
to CBI). This is for two plants. Calculate average water rate for the four reporting plants
and multiply by 2 plants and the sponge production number to get liters of wastewater.
842
-------
Smut from Mg
Recovery:
Ingot Production
Pickle Liquor &
Wash Water:
Convert to nitons using density of water at 20 °C. This gives a medium estimate; use the
±20% rule to estimate upper and lower bounds.
Based on EPA sampling and responses to the RTI survey, leach liquor is believed to
exhibit the hazardous characteristic of corrosivity (pH 0 and 1 recorded at Timet);
according to the Eff. Guidelines Dev. Doc., it also contains treatable concentrations of
copper, lead, nickel, thallium, and suspended solids.
High: 45,000 mt/yr (high vol. threshhold)
Medium: 22,000 mt./yr
Low: 100 mt/yr
This waste may be reactive in water.
High:
Medium:
Low:
3,200 mt/yr
2,700 mt/yr
2,200 mt/yr
Scrap Detergent
Wash Water:
Scrap Milling
Scrubber Water:
Use discharge rates from Vol. IX of Eff. Guidelines Develop. Doc. for Acid Pickle &
Wash Water (Table V-l 1, p. 4870) for 2 plants (unidentified). A third plant did not
report, so assume its value is average of other two. Use scrap consumption value from
Gambogi (1993, p. 12) to estimate volume of pickling liquor. Convert to mtons using
density of water at 20°C. This gives a medium estimate; use the ±20% rule to estimate
upper and lower bounds.
According to Eff. Guidelines Develop. Doc., this waste contains treatable concentrations
of antimony, cadmium, chromium, copper, lead, nickel, and zinc; no concentrations were
given. In absence of concentrations, assume potentially hazardous for cadmium,
chromium, and lead.. Because HF acid is used as pickling acid, may also contain high
concentration of fluoride and may exhibit corrosivity characteristic due to low pH.
High:
Medium:
Low:
540,000 mt/yr
450,000 mt/yr
360,000 mt/yr
Use discharge rates from Vol. IX of Eff. Guidelines Develop. Doc. for Scrap Detergent
Wash water (Table V-13, p. 4871) for 2 plants (unidentified). Use scrap consumption
value from Gambogi (1993, p. 12) to estimate volume of scrap detergent wash water.
Convert to mtons using density of water at 20 °C. This gives a medium estimate; use the
±20% rule to estimate upper and lower bounds.
According to Eff. Guidelines Develop. Doc., this waste contains treatable concentrations
of oil and grease, TSS, and toxic metals. No concentrations were given due to
confidentiality. In absence of concentrations, assume potentially hazardous for cadmium,
chromium, and lead. This waste may also exhibit the corrosivity characteristic because it
is caustic.
High:
Medium:
Low:
6,000 mt/yr
5,000 mt/yr
4,000 mt/yr
Use discharge rates from Vol. IX of Eff. Guidelines Develop. Doc. for Scrap Milling Wet
Air Pollution Control (Table V-l2, p. 4870) for 1 plant (unidentified). Use scrap
843
-------
consumption value from Gambogi (1993, p. 12) to estimate volume of scrap milling
scrubber water. Convert to mtons using density of water at 20°C. This gives a medium
estimate; use the ±20% rule to estimate upper and lower bounds.
According to Eff. Guidelines Develop. Doc., this waste contains treatable concentrations
of TSS, titanium, and low concentrations of toxic metals. No concentrations were given
due to confidentiality. In absence of concentrations, assume potentially hazardous for
cadmium, chromium, and lead.
TUNGSTEN
Spent Acid and
Rinse Water:
High:
Medium:
Low:
2,100mt/yr
Omt/yr
Omt/yr
Process Wastewater:
URANIUM
The Technical Background Document reports a production rate of 7,324 kkg for tungsten
metal powder. The Development Document for Effluent Limitations Guidelines provides
discharge rate's for 2 plants for rinsewater and spent acid from tungsten powder
production. An average of these 2 rates was used to calculate a waste generation rate. An
average waste-to-product ratio of 2,400 L/kkg of tungsten was calculated. Using the
annual production of tungsten metal above, this waste-to-product ratio corresponds to a
high value of 21,000 metric tons of scrubber water annually. Medium and low values
were set at 0 mt/yr since the waste is treated prior to discharge.
This waste may be corrosive.
High:
Medium:
Low:
7,300 mt/yr
3,700 mt/yr
1,800 mt/yr
The generation rate for a comparable waste stream is assumed to be an acceptable
medium estimate for wastes for which no generation rate information is available. Using
this assumption, the waste generation rates for tungsten carbide process wastewater were
set at those of water of formation.
This waste may be corrosive.
Note: Since the number of mineral processing facilities is currently unknown, we used the number of mining
facilities (17) to calculate the quantity of wastes generated.
Tailing Pond
Seepage:
High: 7,650,000 mt/yr (450,000 * 17 facilities)
Medium: 3,833,500 mt/yr ((7,650,000 + 17,000)/2)
Low: 17,000 mt/yr (1,000 * 17 facilities)
Seepage from one facility is estimated at 1,855 rrrVday (Werthman, P., Purdue Industrial
Waste Conference). Using this value, a high annual waste generation rate of 450,000
mt/yr was calculated as shown below. Since this seepage is treated, the low value was
estimated to be 1,000 mt/yr.
High Waste Generation Rate = 1,855 m3/day * 250 days/yr * 1.01 mt/m3
(using density for water) = Approximately 450,000 mt/yr per facility
844
-------
Barren
Lixiviant:
Waste Solvents:
Waste Acids from
Solvent Extraction:
Slimes from
Solvent Extraction:
Waste Nitric Acids
from the Production
ofUO,:
Sampling data from a facility (Werthman, P., Proceedings of the Purdue Industrial Waste
Conference) shows that this waste stream has a pH of 1.7 and may exhibit the
characteristic of toxicity for lead, chromium, arsenic, and selenium.
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 1,700 mt/yr (100 mt/yr * 17 facilities)
Low: 0 mt/yr
Barren lixiviant (raffinate) is recycled back to the leaching circuit. Therefore, a low of 0
mt/yr was selected. High and medium waste generation rates were estimated as 1,000
mt/yr and 100 mt/yr, respectively.
Engineering judgment suggests that this waste may exhibit the characteristics of toxicity
(arsenic, chromium, lead, and selenium) and corrosivity.
High: 1,700 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 0 mt/yr (100 mt/yr * 17 facilities)
Low: 0 mt/yr
Low and medium waste generation rates were set equal to 0 mt/yr since organic solvents
used in solvent extraction are recycled. However, due to incomplete phase separation, a
small amount may be lost (0.5 gallon per 1,000 gallons of solution passing through the
solvent extraction circuit). Therefore, a high waste generation rate of 100 mt/yr was
selected.
Waste stream may be ignitable (engineering judgment).
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 9,350 mt/yr ((17,000 + 1,700)/2)
Low: 1,700 mt/yr
High and low waste generation rates of 1,000 mt/yr and 100 mt/yr, respectively, were
selected based on the low production rates (1,361 mt/yr).
This waste stream may exhibit die characteristics of toxicity (arsenic, chromium, lead, and
selenium) and corrosivity.
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 9,350 mt/yr ((17,000 + l,700)/2)
Low: 1,700 mt/yr
High and low waste generation rates of 1,000 mt/yr and 100 mt/yr, respectively, were
selected based on the low production rates (1,361 mt/yr).
This waste stream may exhibit the characteristic of toxicity (arsenic, chromium, lead, and
selenium).
High: 3,400 mt/yr
Medium: 2,550 mt/yr ((3,400 + 1,700)72)
Low: 1,700 mt/yr
High and low waste generation rates of 200 mt/yr and 100 mt/yr, respectively, were
selected based on the low production rates.
This waste stream may be corrosive (engineering judgment).
845
-------
Vaporizer
Condensate:
Superheater
Condensate:
Slag:
Uranium Chips from
Ingot Production:
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 9,350 mt/yr
Low: 1,700 mt/yr
High and low waste generation rate of 1,000 mt/yr and 100 mt/yr, respectively, were
estimated based on the low production rates for uranium (1,361 mt/yr).
This waste may be corrosive since the process uses hydrofluoric acid.
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 9,350 mt/yr
Low: 1,700 mt/yr
High and Low waste generation rate of 1,000 mt/yr and 100 mt/yr, respectively, were
estimated based on the low production rates for uranium (1,361 mt/yr).
This waste stream may be corrosive (engineering judgment) since the process uses
hydrofluoric acid.
High: 17,000 mt/yr (1,000 mt/yr * 17 facilities)
Medium: 8,500 mt/yr
Low: 0 mt/yr
High waste generation rate of 1,000 mt/yr was estimated based on the low production
rates for uranium (1,361 mt/yr). The low generation rate was set equal to 0 mt/yr since
the slag is recycled.
This waste stream may be ignitable since it may contain uranium metal (engineering
judgment, DOT Emergency Response Guidebook).
High: 3,400 mt/yr
Medium: 2,550 mt/yr ((3,400 + 1,700)/2)
Low: 1,700 mt/yr
High and low waste generation rates of 100 mt/yr and 200 mt/yr, respectively, were
selected based on the low production rates.
This waste stream may be ignitable (engineering judgment) since it contains uranium
metal (DOT Emergency Response Guidebook).
ZIRCONIUM AND HAFNIUM
Spent Acid Leachate
Zirconium and
Hafnium Alloy
Production:
High:
Medium:
Low:
850,000 mt/yr
0 mt/yr
0 mt/yr
For spent acid leachate from zirconium alloy production, waste-to-product ratios were
given in the Effluent Guidelines, 1989. The waste-to-product ratios for acid leachate
were 12,617 to 18,925 L/kkg zirconium in alloys. A production rate for zirconium in
alloys was not available so the production rate for zirconium was used instead. (It is
assumed that the production of zirconium alloys does not exceed the production of
zirconium.) The above mentioned waste-to-product ratios were used to calculate an
average generation rate. This generation rate was used as the high rate. Low and medium
rates were set equal to zero since the waste may be treated prior to discharge.
846
-------
Spent Acid Leachate
Zirconium and
Hafnium Metal
Production:
This waste may be corrosive.
High:
Medium:
Low:
1,600,000 mt/yr
0 mt/yr
0 mt/yr
Leaching Rinsewater
from Zirconium Alloy
Production:
Leaching Rinsewater
from Zirconium
Metal Production:
For spent acid leachate from zirconium metal production, waste-to-product ratios were
given in the Effluent Guidelines, 1989. The waste-to-product ratio for acid leachate was
29,465 L/kkg zirconium produced. The production rate for zirconium used was 45,350
metric tons. Using the production of zirconium and the waste-to-product ratio, a high
sector wide estimate of 1,600,000 mt/yr was calculated. Low and medium rates were set
equal to zero since the waste may be treated prior to discharge.
This waste may be corrosive.
High:
Medium:
Low:
51,000 mt/yr
42,000 mt/yr
34,000 mt/yr
For leaching rinsewater, waste-to-product ratios (632 to 946 L/kkg zirconium in alloys)
were given in the 1989 Effluent guidelines. A production rate for zirconium was not
available so the production rate for zirconium was used instead. (It is assumed that the
production of zirconium alloys does not exceed the production of zirconium). The above
mentioned waste-to-product ratios correspond to low and high estimates.
This waste may be corrosive
High: 2,000,000 mt/yr (1,000,000 * 2 facilities)
Medium: 1,000,000 mt/yr
Low: 200 mt/yr
This waste may be corrosive.
847
-------
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848
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX B
Work Sheet for Waste Stream Assessment of
Recycling, Recovery, and Reuse Potential
849
-------
Page Intentionally Blank
850
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream:
Waste Generation Rate:
Waste Form: Liquid(Aq,/Non-Aq.)/Sluiry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major):
I • Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the following
questions for each major source of the same waste generated in the process. Complete a separate form for each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D, Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its management
practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical separation,
water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste streams,
results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at any of its
sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ,
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
851
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852
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX C
Definitions Formerly Used to Classify
Mineral Processing Waste Streams
853
-------
Page Intentionally Blank
854
-------
DEFINITIONS FOR CLASSIFYING MINERAL PROCESSING WASTESTREAMS
Sludge - any solid, semi-solid, or liquid waste generated from a municipal, commercial, or industrial
wastewater treatment plant, water supply treatment plant, or air pollution control facility exclusive of the
treated effluent from a wastewater treatment plant. Examples include:
• baghouse dusts
« cast house dusts
* wastewater treatment plant sludges and solids
* chlorinator wet air pollution control sludges
• scrubber wastewater
APC dust/sludges
Spent Material - any material that has been used and as a result of contamination can no longer serve the
purpose for which it was produced without processing (e.g., treatment or regeneration). Examples include:
• process wastewaters
• spent barren filtrate
• spent raffinate
* spent caustic soda
• spent electrolyte
* waste acid solutions
* waste liquors
• caustic washwaters
• spent bleed electrolyte
• contact cooling water
* slag quench water
• spent furnace brick
By-Product - a material that is not one of the primary products of a production process and is not solely or
separately produced by the production process. Examples are process residues such as slags or distillation
column bottoms. The term does not include a co-product that is produced for the general public's use and is
ordinarily used in the form it is produced by the process. Other examples include:
* anode or tankhouse slimes
* beryl thickener slurry
• post-leach filter cake
« furnace residues
* synthetic gypsum
Note: If a surface impoundment is used for pollution control, then both the liquid and solid components
are considered to be "sludge." If a surface impoundment is not used for pollution control, then the
liquid is probably a "spent material" and the solid is probably a "by-product."
855
-------
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856
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX D
Recycling Work Sheets for Individual
Mineral Processing Waste Streams
857
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858
-------
1997 UPDATE
Several of the recycling status conclusions and former RCRA waste type classifications detailed on the
following worksheets have been revised since December 1995 (the date of initial publication of this appendix) due to
comments received on the January 25, 1996 Supplemental Proposed Rule Applying Phase IV Land Disposal
Restrictions to Newly Identified Mineral Processing Wastes and the May 12,1997 Second Supplemental Proposed
Rule Applying Phase IV Land Disposal Restrictions to Newly Identified Mineral Processing Wastes, as well as other
new information received by the Agency. Changes in recycling status are summarized in Exhibit D-l, and changes
in former RCRA waste type classification are summarized in Exhibit D-2. Note that in Exhibit D-l, the symbols Y
and Y? are equivalent to the term "Recyclable," the symbol N is equivalent to "Not Recyclable," and the symbols YS
and YS? are equivalent to "Partially Recyclable" on the following worksheets.
EXHIBIT D-l
Changes in Recycling Status Since December 1995
Sector — Waste Stream
Beryllium — Spent Barren Filtrate
Elemental Phosphorous — Furnace
Scrubber Slowdown
Magnesium and Magnesia from
Brines — Smut
Mercury — Dust
Rare Earths — Solvent Extraction
Crud
Selenium — Tellurium Slime Wastes
Zinc -- WWTP Solids
1995 Recycling Status
YS?
N
Y? -
YS?
YS?
YS?
N
Current Recycling Status
YS
Y
N
N
N
Y?
YS
EXHIBIT D-2
Changes in Former RCRA Waste Type Classification Since December 1995
Sector — Waste Stream
Cadmium — Scrubber Wastewater
Copper ~ Acid Plant Slowdown
Elemental Phosphorous — Furnace
Scrubber Slowdown
Lead - WWTP Liquid Effluent
Rare Earths — Spent Scrubber
Liquor
Rare Earths — Wastewater from
Caustic Wet APC
Rhenium — Spent Barren Scrubber
Liquor
1995 Former RCRA Waste Type
Classification
Spent Material
By-Product
N/A
Sludge
Spent Material
Spent Material
Spent Material
Current Former RCRA Waste
Type Classification
Sludge
Sludge
Sludge
Spent Material
Sludge
' Sludge
Sludge
EXHIBIT D-2 (continued)
859
-------
Sector ~ Waste Stream
Titanium and Titanium Dioxide —
Scrap Milling Scrubber Water
Zinc — Acid Plant Slowdown
Zinc -- WWTP Solids
1995 Former RCRA Waste Type
Classification
Spent Material
Spent Material
N/A
Current Former RCRA Waste
Type Classification
Sludge
Sludge
Sludge
860
-------
omi£.i Z-VK »»*»**, aiK£AM ASSESSMENT TOR KECTCUNG, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process
'aste Strewn: Ov>T f^il.-'^. r\
I* Plummy / Qijjuunn ua-irn
, - I i ^
/aste Onenttton Rate: 1H OOP
Waste Form: Uqttid(Aq^dn-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C. R
Hazardous Constituents i major):
1. Process Flow Diagram & Waste Characterization: % looking at both documeDts. try to answer the
following questions for each major source of tie same waste generated in the process. Complete a separate form for
each major source.
A. Source: • CTL-'^ _
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ ~ _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ~ _ .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? *. . , , , , ,
Comment: _ ' [U U> • JTiOTi ^n\"^'^- _
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)? ~
Comment: .......................................
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _^ _
B. Water Use Reduction: Ye&No/Can't Tell
Comment: ........................
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _________^__^_____________-_____-____^___^__^________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ' """"
Conclusion: /_ Recyclable _ Non-Recyclable _ Partially Recyclable
- x
4. Material Qassificarion: { Sludge) Spent Material By-Product
( circk one) ^- — -^
861
-------
cmaE.1 rvm vinaix. aiK&AM nssaas&MWl *UK KECYCUNG, KECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process: ,^-x ,^,. »», .^»
Waste Stream: £X? ^TvOi' ,U M A \NPl
Waste Generation Rate: C3ft. QOQ pn4)' -
Waste Form: Liquid(Aq./Non-Aa;)/S]urry/SoIids(Wet/Dry)
Hazard Characteristics (ail):
Hazardous Constituents (major):_
Hazard Characteristics (ail): I C R
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: TJj^olU^A f.APC ?).': i;> )
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
Reasons for Waste Generation: Based on the description of the process, and waste feneration and its
management practices given for a sector, make the following assessment
A Is the same waste generated at every facility using the process?: (^esj'No/Can't Tell
l^/SV**«VltA«%*> - ^->^
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? ~
Comment: .............................
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ______________^ _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Ten
Comment: ................
B, Water Use Reduction: Yes/No/Can't Tell
Comment: _ ................... _ _
C On-sitc Waste Recycling/Recovery/Reuie: Yes/Mo/Can't Tell
Comment: _ ..........................
D. Off-site Waste RecydingMerave^Reose: (YeaNo/Can't TeB
Comment: ^- - -^ ^—^
Conclusion: \/_ Recyclable _ Non-Recyclable _ Partially Recyclable
4 Material Classification: f Sludge \ Spent Material By-Prodact
( circle one)
862
-------
WORK SHEET TOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
PW-Vr?c!!r\e-, v
- I C_ R JT_
Hazardous Coostttttoti neater): n£ , Cc^-» r7?» I-)*
Process Flow Diagram & Waste Characterization: iy looking at both documents, try to answer the
following questions tor cacti major source of tte same waste generated in the process. Complete a separate form for
each major source.
A. Source Au-ha GXAV'g-. _
B. Wasie generation is closest to: Raw MateriaiyMajor latennediatea/Fmal Prodiiq
C Wasie appears to have: recoverable producg/removabte conuminaotsyneitner
D. Comment Uaslf. .i-^v->w\ w..^t^ k? ygc_£,/ed(. -fey u^-tv fe yfe
"" ........ ~ ................ "~ «^™^^
2. Reasons for Waste Generation: Based on the descnptkn of tite process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: YeVNo/Can't Tell
Comment: __
B. What was the basic purpose for fenairmg this waste (e.g^ plant maintenance, chemical reaction, physical
sejttaiiQ.il, water hnsing. other porificatiOB steps)?
Comment: ____ __ — — _
C Why did this waste become hazardous (c,&, physical contact dating production, mixing with other waste
streams, results from imparity removal)?
Comment: ___-_________—_—__-______________^
3. Waste Management Alternatives; Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Gtat Ten
Comment: •
B. Water Use Redaction: YesAfo/Cant Tell
C On-site Waste Recyctog/RecoveryyReuse: Yes/Ho/Cant Tefl
Comment: • • '
D. Off-site Waste RecycMag/Recovery/Rease: Yes/No/Cant Ten
Comment: ________________._„__«_______«_»_»___»_««___»«__.__-__-_________
Condnsten: ; Recyclable Non-Recyclable \ Partially Recyclable
4. Material Classification; Sludge C Spent MateriaT) By-Product 863
(arete one) ^-~~~.
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and FTWMK fVwK wxpyxy . S'Wv.j
Waste
Waste
Waste Form: Uquid(Aq^Non-Aq.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (afl): __ I C R T
Hazardous Constituents (major):
I Process Flow Diagram & Waste Characterization: By looking at both documents, iry to answer s;
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
........................
B. Waste generation is closest to; Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: .
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: - ........
B. What was the bask purpose for generating this waste (e.&, plant maintenance, chemical reaction, physic
separation, water rinsing, other purification steps)?
Comment: .
C Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Coaunenc _______________ ____________________________________________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the fbQowiog waste management alternatives.
A. Waste Segregation: Yes/No/Cant Ten
Comment! __ ............
B. Water Use Reduction: Yes/No/Can't Tell
Comment! '
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: • _ •
D. Off-site Waste Recydmg/Recovery/Rense: Yes/No/Can't Tefl
Comment: ..........................................
Conclusion: _ ; Recyclable Y Non-Recyclable _ Partially Recyclable
4 Material Classification: Sludge Spent Material
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'qdnstrial Sector mad fneaK PrvxrHv^ve^x/ , V\^ jv*£>v
asttStt-aax S:WM^e£\ K^oWVe
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: qff l/ru .-vi
Waste Stream: S,oa/if 3&rn^ Fl/^jf, S-feso.^^
Waste Generation Rate: _
Waste Form:
Hazard Characteristics (all):
Hazardous Constituents (major):_
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A. Source: F/Mr*-^ eF &g.CO, v Be-CO'-i}- _
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ft Mr**ti; FrOfy^ &-C<3o <5 As*i-h*,e*, ^ej\Ce.fftlK~faA "fe
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same wastegenerated at every facility using the process?: /*?es/No/Can't Tell
Comment: > f«cJr
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector and Process:
steStream: Sg-w I ~fk,^k(-^~
Waste Generation Rate: BOOO
Waste Form: Uquid(Aq Jton-Aq
Hazard Characteristics (all): I (£>
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: Coun-f..- Cus-n^
B. Waste generation is closest to: RawMatenal/Major Intermediates/Final Product
C. Waste appears to have; recoverable products/removable contaminants/neiihej
D. Comment: '
2. Reasons for Waste Generation: Based on the description of the process, and waste generation amd its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: > r^c-ij/-^- """^
B, What was the basic purpose for generating this waste (e,g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _ _______^^__^___-__~____«_^___________..^__________^
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)? ~~
Comment: Lo<.e,k>/*«> A^.-.'vS QJ^ceJ a I-/
™"^ """S"""^*™™"""™*™ t^^mm^a^ .^•••MMIMIBHWMHMMWHWH
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ____________________________^____________^^
B, Water Use Reduction: Yes/No/Cant Tell
Comment: ____________________________-_______^___^^
C Cm-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ............... _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _ „ __ _ _ ' _ __
Conclusion: Recyclable _j(_ Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material ( By-ProdttcT%
{circle one) ^~ ^ 867
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: Bej-^l!,^^
Waste Stream: C*\\t&.. -frea-^t .%-f /^jag-f?.., *•.•*-»<-
Waste Generation Rate: loO.^rf/y,- ; .gO.gQg/^-^yr- i
Waste Form: <^u^S>>l6n-Aq.)/Slurry/Solids(Wet'Dry)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): *—f -
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: JL-JI;Um Akb^ "Hi^^*-
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminantsmeu&gr
D. ' "
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/Ho/Can't Tell
Comment: ________________________________________^^
B, What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _____________-_—______-_______________^
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: __________________________________________^^
3. Was^e Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives,
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tefl
Comment: _^________________________^_____________________
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Cant Tell
Comment: _________________________________________^
D. Off-site Waste Recyding/Recovery/Reusc: Yes/No/Can't Tell
Comment: ______,________________________—____J
Conclusion: Recyclable Non-Recydable 21 PartiaUy Recyclable
4 Material Classification: Sludge
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAJL
industrial Sector and Process: &ru}l,t_* M
»te Stream: F/ / •
*Vaste Generation Rate: ICO ^-^- ^ £-3-.(\QG
Waste Form: Uquid(AqJNon-Aq.)/51urry/Soiids(Wet/Dry)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): nb -
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: r1 • '''"'"' o^ fir^moniuf^ Fl<*o, />K-faf f-rc.**? o/*-g, ^ ts*.(j r r0rf> ii~ie\tta/*,
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment- ............
B. Water Use Reduction: Yes/No/Can't Tell
Comment . .
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment - _
D, Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeU
Comment: '
Conclusion: _ Recyclable J^Non-Recvdable _ Partially Recyclable
4. Material Classification: Sludge Spent Material /^^By-ProducfS
QCQ
(circle one) v-— ___— -^
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream: £ts\~t
Waste Generation Rate: 3ft0tO(X> /»-//y/-
Waste Form: Uquid(AqJNon-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I (c) R "
Hazardous Constituents (major): •££• •
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
U-~v£ tv
A. Source: ___
B. Waste generation is closest to: Raw Material/MaioX-Mtennediates/Fuial Product
C. Waste appears to have: recovei^le pnxlucisyrcmoyjable^contaminants/neither
D. Comment: ro/A-f>s AK«»«-; M . *t'**»»'.*_.»"i »^fusi^tM,
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste^generated at every facility using the process?: yes/No/Can't Tell
Comment: i r^ctlf*^
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, pbysicr
separation, water rinsing, other purification steps)?
Comment: ,
C Why did this waste become hazardous (e-g., physical contact during production, mixing with other waste
streams, results from impjirMjemoval)?
Comment: ______________—_____________________________________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Cant Tell
Comment: __________________________________________^
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site-Waste Recydfflg/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable J(_ Partially Recyclable
4; Material Classification: Sludge f Spent MateriiHv By-Prodna
..... _ —
-------
Page j of J_
WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY AND REUSE POTENTIAL
C
Industrial Sector and Process: Zy-Rtf-nttJ df j£U/?y/.uug UCc 4c figgy// tUM J/',_A?g
Waste Stream: fitrA.TRA+/T\m. THint^*^ .r-L.,tery
Waste Generation Rate: _^J_Q, aAr\ »VIT
Waste Form: I^iiid(Aq./Nop-Aq4/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): I ——
Hazardous Constituents (major):
1. Process Row Diagram & Waste Characterization: By looking at both documents, try to answer
the following questions for each major source of the same waste generated in the process.
Complete a separate form far each major source.
A. Source: £xn._p£&r* CVD -TVfrCfcfvat As A !njRA.y.._$tic*£.j>&)_ ~Tl
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: "$f-c.LuoG* Je-uPS fa£e$CT£DL/,n S"i-Lfi,ljC Af/f> of?
Reasons far Waste Generation: Based on the description of the process, waste generation and its
management practices given in a sector profile of the industry, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Don't Know
Comment:
B. What was the basic purpose for generating this waste (e,g., plant maintenance, chemical
reaction, physical separation, water rinsing, other purification steps, etc.)?
Comment: ^ASTF ^s-rj-eVg-fNfT ggStOth'k. 0^ ;OiTif tKJ W/l STb -
B. Water Use Reduction: Yes/Np/Don't Know
Comment mftv H^v/'r-TD "MLUTT WP-JT£ Tb <2ccg- fee iPti"
C On-site Waste Recycling/Recovery/Reuse: Yes/Np/Doat Know
Comment: ^Rg-rcLiA<> C
-------
-Ui-JbT M>K WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: \^\SYy\u"V'V\ .<
Waste Stream: f\ \ \ r>vJ ft -p <. •» A \J £ S _ __.
Waste Generation Rate: \do
Waste Form:
Hazard Characteristics (all); I C
Hazardous Constituents (major): _ ff JQ
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: Qy \deKT~i Ov\ P-T \>y\-g lArg. Cn S nn
B. Waste generation is closest to: Raw Material/Major Intennediates/Emal Product
C. Wasie appears to have: recoverable products/removable contaminants/neither
D, Comment: fig_-4->v\wv*\ ... y?v o b\K. e*a Q^-AQ^vn gv-^-g \r> \5 ' .
if » 5
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: .
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)? ~~ — —
Comment: _____ _________________________________________________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segreption: Yes/No/Cant Tell
Comment: _______________________________________^
B. Water Use Reduction: Yes/No/Caa't Tell
Comment: .......................
C On-site Waste RecycMng^Recovery/Rense: Yes/No/Can't Tell
Comment: ......... _ ..................
D. Off-site Waste Recycling/Recovety/Reuse: Yes/Np/Can*t Tell
Comment: .............. _
Conclusion: _ Recyclable V Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge Spent Material By-Prodnct
fdrcfe (me)
872
-------
FOK WASH; STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: ^SSYWU'
.aste Generation Rate: \ 0*3. ~}QOO koe>p
Waste Fonn: yqmd(Ag^lon-Aq.)/SIuny/Solids(Wgt/Diy)
Hazard Otoracteristics (all): 1C R T_
Hazardous Constituents (major): -£_g ^
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source; fixYVgj t^es » Wg C
B. Wasie generation is closest to: Raw Material/Major IntermedJata/Final Produa
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: < &th
Reasons for Waste Generation: Baaed on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Caa'.t
Comment:
B. What was the basic purpose for generating this waste (e,g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _ -
3. Waste Management Alternatives: Review tae potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation; Yes/No/Can't Ten
Comment: __^ _
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _______________i_________________^ __________________
C. On-site Waste Req«atog/Recovery/Reuse: Yes/Np/Can't Tell
Comment: [[[
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tefl
Comment:
Conclusion: _ _ Recyclable Non-Recyclable _ Partially Recyclable
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream: ^ K>e r-vx%-
Rate _ 1 O O __-, i£ \ 0 O t \ ~L D&O wv * /
_ __
Waste Form: yqaJd(Aqw^Non-Ag.)/Sliiny/SoUds(Wet/Dty)
Hazard Characteristics (all): — I C R T
Hazardous Constituents f major): g_)p
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer ihe
following questions for each major source of the same waste generated in the process. Complete, a separate form for
each major source.
A. Source: "Ex:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ^-oe^r^r c^rf ^ •W^A/S/-V "
^ J
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
U
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water linsiag, other purification steps)?
Comment: _____________ ^___^_^_
C Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
Comment: __________________________»___________________________»_____
B. Water Use Reduction: Yes/No/Can't Tell
Comment: i
C On-siie Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recycuag/Recovery/Rense: Yes/No/Cant Tell
Comment: __________________________________^
Conclusion: Y. Recyclable Non-Recydabte Partially Recyclable
4, Material Classification: Sludge /spent Material/ By-Product
-------
WORK SHUT FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'ndnstrial Sector and Process: P-^S\vuJ~H/> . e-VVs "E \-e
ute Stream: S-Q-P^^- TE \-e r --W o ) vV «£-
Wart* rrtneration Rate: ~^OO 6NO P -.
Waste Form: Uqujd(Aq./Nop-Aq.)/Sluny/Soiids(Wei/Dry)
Hazard Characteristics (ail): — 1C R _T
Hazardous Constituents (m^or):
i. Process Flow Diagram & Waste Characterization.- By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate farm for
each major source.
A. Source: 1: \-e.c -Vvp-^i c_
B. Waste generation is closest t& Raw Nfatenal/Major Intermediates/Final Product
C Waste appears to nave: recoverable products/removable contaminants/neither
D. Comment: ......................................
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: 15^ Wy fiv--*. pVc r}\jr?s\
•J - "*
B. What was toe basic purpose for generating this waste (e.gn plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? "
Comment: ___________.^_____________________-_____^
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation; Yes/No/Can't Tell
Comment: _____ _ _— _________«.^_^__________— _________^^__^___^_
B, Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: • _ . _ '
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: • '
Conclusion: _ Recyclable ~2f Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
(circle one) B7S
-------
VYOKK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: 1J>\Sw\U~V'K . fex-eA-Ny^v^^
Waste Stream: 'SsOeA/vV .^ fs C) f>*. <. r\ \J*~\
Waste Generation Rate: \ G o. ^ \ P O , \~l~QQC
Waste Form: Liquid(Aq./NoB-Aq.)/Sluny/SoUds(Wet^)iy)
Hazard Characteristics (all): I .C. R T_
Hazardous Constituents (major):
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: VX^e. V
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contamiaants/neither
D. Comment: 5t?ewV s>odo* SC^IA^CW v^g^ \g^ -<~t \jsej' e\-P4-e\<- C)-i"DCtS
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Ye/No/Can't Tell
Comment: avy'W rt-w-e rr>m n w C -e -v- _
0
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ' ................................. •
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: n
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _ . _
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _^ _
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ___________________— ___^_____— ^__________________________.___^_
D. Off-site Waste Recycling/Recovery/Rense: Yes/No/Can't Tell
Comment; ............
Conclusion: V Recyclable _ Non-Recyclable _ Partially Recyclable
4 Material Classification: Sludge ^Spent Material ^ By-Product
(circle erne)
876
-------
V? ORK SHEET VOX. WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: V^ \ _S V\ v ) "W H yl Vr ^ L "V\ gv\ -4ViJN^\ "£>\ 5 ]~w ^ic
ate Stream: v^)(
.aste Generation Rate; )0 Or 6/0Q, t~L.0Q&
Waste Form: _Liqind(AqJiNtm-Aq.)/Siuny/SoIids(Wet/Dry)
Hazard Characteristics (all): I C_ _R T
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: fiUYv-CkcJwVlay^ o£ O>^S•w^u-VU. o*\t C\A\py^ (j-g. ^ gxv'C\A^o\-xtt^ 9-fO
B, Waste generation is' closest to: Raw Material/Major Intermediates/Final Product ^
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: •
Z Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility usiag the process?: Yes/No/Can't Tell
Comment: QvsW ^rv\e_ oveAuce'/' •
B. What was the, basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: -
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: '
3. Waste Management Alternatives: Review the potential for reductaf the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segreption: Yes/No/Can't Tell
Comment -
B. Water Use Reduction: Yes/Np/Cant Tell
Comment
C On-site Waste Recyding/Recovery/Rease: Yes/No/Can't Telj
Comment: ...
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ^^_^_^___^______^^________^_^_^_____^_^__________..^_______
Conclusion: Recyclable X, Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
(circle one) 87?
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector aadPracns: &\ S fWu jrt\ -, €.vVygt£.4igv\
Waste SMBBK "^ \e_ji.A-^o\j-^-¥s c O iv-wg. s .
Waste Generation Rate.
Waste Form: Uquid(Aq7Non-Aq.)/SlurTy/Soli
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
ndustrial S-etor
Vaste Straw PAg.-Wg' . PWInv
"(V
Waste (^aeration Rate _,
Waste Form: Uquid(AqJNon-Aq.)/Sluny/SolJds(Wei/Diy)
Hazard Characteristics (all): -- [CRT
Hazardous Constituents (major):
i. Process Flow Diagram & Waste Characterization: iy looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intennediates/Fina] Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ______________________________________________
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: •
B. What was the basic purpose for generating this waste (e.g_, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ^^_^__^^__^..l^__--_^__^______^.^..l^^_—^-_—_^______m^_
C Why did this waste become hazardous (e.g_, physical contact daring production, mixing with other waste
streams, results from impurity removal)?
Comment: _^^_____^^^^.^__^^^^__-_—___.^_^_.m_^^_,..^^__...,^__^___^_
3, Waste Management Alternatives; Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant TeB
Comment:
B, Water Use Reduction: Yes/No/Can't Tell
Comment: .
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tdl
Comment: _______L^____—________^ ; '
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: , _^______
Conclusion: Recyclable X- Non-Rccydable Partially Recyclable
4. Material Classification: Sludge Spent Material i oy-rrooua \ 8;9
(circle one)
-------
WORK SHEET roi WASH STUAM ASSESSMENT FOB RECTCUMG, RXCOVEXY, AND REUSE POTENTIAL
«—a*— ^7. fPG, -2-00
, ptem matntenaAce, cacaMcal reacoon, physical
separation, water riasiai, other puriflcatioa step)?
Why ad this waste becone haaiitous (fc§» phyiical contaa dnring producooa, nunnj with other waste
streams, results iron unpuruy
ConoBeoc
3. Waste Management AJtTnBsfoffJ' Re*ln»dHtfOteatial for radocinf the quantities of waste generated at
nij nf in iniiiii i ti) rniiiiil) iiri| !•• ftinrming maiiii miiiiji MM in iln iniiini
A. Waste Sefrepttoo: Ye«^No)Can1t Tefl
& Water UM Rednotac Yei/NoCuft TeO
C OB^OJ Waste R*cjrtinf/!Ucovery/Rense: YesflWCanl Tefl
Conuneac •
D. Off-site^ Waste RecycantyRecafwery/Reas*: YesTNo/Caaft TeB
Comment:
Condosioo: RecydaWe Non-RecyctaWe J/ Partial* Recyctabie
(fffflf
^' ^-x
Spent Material ) By-Prodoct
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT TOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'oduatrtal Sector tut TfneaK .feyStv^'VU , O € "V^t v A-gVx - V-voM
/astt Stream: ^(a^y
Watt* numeration Rate ^
Waste Form: yquid(AqJNcro-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): ._ I C R T
Hazardous Constituents (major):
i.
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B, Waste generation is closest to: Raw Material/Major Istenaediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: •
B. What was the basic purpose for generating this waste (e.f_ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _________^_^^__^__________________._—^________-_-___^_____________
C Why did this waste become hazardous (e.g~ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Ten
Comment: _____________________________________________________
B. Water Ite Redaction: Yes/No/Can't Tell
Comment:
C. On-site Waste Recyding/Recovcry/Reuse: Yes/No/Can't Tell
Comment: -.. •
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: _________________________________________________^
Conclusion: Recyclable \ Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material f By-Prodact j 881
(drcleone) ^-—_
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIA
Sector nrf PTOCMK f*>n V cv\., "S> o v \ C A-CsA (V £? ^ \K "
Waste Generation Ratr
FOTK Uqi^AaJNon-AqO£luny/Solidsry)
Haarf Ch«»ettftet*e« W - I C R T
Hazardous CdMttaMtt (aator):
1. Process Flow Diagram A Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of UK same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D, Comment: __^^^________________^____^^_____
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the fallowing assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ plant "»iran*Bf!K*, chemical reaction, physi,
separation, water rinsing, other purification steps)?
Gonunene '_
C Why did this waste become hazardous (e.&, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ______________________________^»__«__.___»__««_«_______«_«_______^___..^^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering toe foOowing waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
B. Water Use Reduction: Yes/No/Cant Tell
Comment!
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recydiag/Recovery/Reuse: Yes/No/Cant Tell
Comment:
Conclusion: X Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge •'' Spent Material) By>Product
(circte one) ' ^ _—--^
-------
VT UK&. ajtutti I- UK TTASlt STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
C r\ (\Y~Y~] \ OPT)
Industrial Sector and Process:
Stream: C C\ I \rA\r \l\Tl Ah -.^ tl'&n
Generation Rate: F; C /I Q DO rrvf i J. g 91 ,.t . I
Waste Form: Liquid(AqJ«loriXAq.)/Sluny/SoUds(Wei/Diy)
Hazard Characteristics (all): I (8). R
Hazardous Constituents (major): CQdLV~njOrr*
I, Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. • Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B- What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? x ,
Comment: ; (jjOvr:?
>-*'
C. Why did this waste become hazardous (e.§., physical contact during production, mixing with other waste
streams, results, from impurity removal)? ——-,
Comment: '
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment: •
C On-site Waste RecycUng/Recovery/Reuse: Yes/No/Caa't Ten
Comment: ____-______-..^__—__________________________^
D. Off-site Waste Recyclmg/Recovery/Reuse: Yes/No/Can't TeD
Comment: ••....
Conclusion:^ Recyclable Non-Recyclable Partially Recyclable
4 Material Classification: Sludge . Spent Material > By-Product
(circle erne) ^——. -^
883
-------
f UK tTAaiE, aTKKAM ASSESSMENT FOR KECYCUNG, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: I (id fniJ AA _ _ ___
W]lsle stream: ^FtfM* ft nHI (9/1/1 ?H-t A'j (rr? J /~r\ V ni
Waste Generation Rate: )SO/i9O^ P~>* ( \- / &?%£} V
Waste Form: Liquid(AqJNon-j^q,Vsiurjy/Sou"djȣWet/Dry)
Hazard Cbaraeteristies (all): I C R
Hazardous Constituents (major):_
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: -Vtl
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ . ...................... . ' =="
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, nuke the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: '
B, What was the basic purpose for generating this waste (e,g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ______ ______________________________________________
C. Why did this waste become hazardous (e.g,T physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ..................
3. Waste Management Alternatives: Renew the potential tor reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/Ho/Cant Tell
Comment: ________________^____________________________________________^
B. Water Use Redaction: Yes/No/Can't Tea
Commenc
C On-site Waste Recyding/Reecwery/Reiise: Yes/No/Can't fell
Comment: i
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: __ ..... _ _ _ __
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4 Material QassiBcation: Sludge spent Material
(circle one)
884
-------
ru*. TfAaiJE, OTKi-AM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: CViflifV'i \(
Waste Strewn;
Waste Generation Rate: H&JlQr)O rrrt 1 L- / >rC?
-------
-MU-C.I evfi ™«aii!, aiKEAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
_ __
Waste Stream: _ ~LC\ f/Trrtq \ ni'nQ l/in,O I M
Waste K«ieration KsSKH3^O,^> m 4-
Waste Form: Liquid(AqJN«»-Aq.)^l«ny/SoU«is(Wet/Diy)
: I , C R (T ;
Hazard Cbaracteristks (all)
Hazardous Constituents (major)
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
n* < .
A. Source: fr i !"L? /
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to nave: recoverable products/removable contaminants/neither
D. Comment: ______________________________________^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make die following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ______________________________________
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: -
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: '
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes^Nc/Can't Tell
Comment: ______________^_^^___^__^___^.^^^^^^^^^^^^^^__^_^^^^^^^^_^^^^^^^^^^^^^
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ______________________________________^
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable V Non-Recyclable Partially Recyclable
4 Material Classification: Sludge Spent Material By-Product
(circle one)
886
-------
J-UR. TT/UIC. aiKJSAM ASSESSMENT FOR KJECTCLDIG, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
•Waste Stream: ^>nKDr i9f)r}r\ Pnl'-
•Vast* Generation Rate: f-K)/l9C)O AAf i 'J-Pfl/. /tMCO.v
Waste Fom: Uquid(Aq.^6n-Aq.)/Sluriy;$ops{Wet/Dry)
Hazard Characteristics (all): I . £c) R . Cj[)
Hazardous Constituents f major) : flhfST,!' -> C "1 ii'fY] p M '
1. Process Flow Diagram
-------
omuii rum. »T/_aij& oiKllAM ASSESSMENT *OR KECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: Lj^^lTi lOfTi
Waste Stream:
Waste flgneration R-MasHj/T^DO rnjj\^AJ_<&i
____ _ ^ _
Waste Form: * Ljqui«lin§!Recovery/Reuse: Yes/No/Cant Tell
Comment: ________________________________________________________
D. Off-site Waste Recyclinf/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
Conclusion: A^_ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material ( By-Product
(circle (me)
888
-------
I- UK RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Vaste Stream:
C_OArT\)l)fV)
) I
Waste Form:
Hazard Characteristics (all): I . C
Hazardous Constituents (major): CYlfifD \ _
B. Waste generation is closest-^6: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ...............
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: '.
B. What was the basic purpose for generating this waste (e.g_, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ..............
C. Why did this waste become hazardous (e.g., physical contact during production, miring with other waste
streams, results from impurity removal)?
Comment: .................
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: __^_________________________-______^_______^
B. Water Use Reduction: Yes/No/Can't Tell
Comment: • • . • •
C On-sfte Waste Reqrdmg/Recovery/ReBse: Yes/No/Can't Tell
Comment: .............
D. Off-site Waste Recycliag/Recovery/Reuse: Yes/No/Can't Tell
Comment:
-,
Conclusion: y Recyclable V-> Non-Recyclable _ Partially Recyclable ' S'TO Id i9C '"•"- '" r
4. Material Classification: Sludge Spent Material
( circle one) _ _
889
-------
ASSESSMENT FOR KECTCTJNG, RECOVERY, AND REUSE POTENTIAL
s~\ .
s: I C)JJ.ff} i
Industrial Sector and Process:
Waste Stream: Sr£jT>T T3l)fl"Vl'C1-f tfTn ?;~)i'Ot* tOlA.
Waste Generation Ratc:f y^Qc) TVm U# 3 A
Waste Form: Liquid(Aqon-A.)/Sluny^oUds(Wet/Diy)
Hazard Ca»aracteristics (ail): I sC\ R
Hazardous Constituents (major) : Cf\ t\ 10Q ' •
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g,, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: - . _
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: . ..............
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .^ ________________
B. Water Use Reduction: Yes/No/Can't Tell
Comment: .
C, On-site Waste Recyding/Reeovery/Reuse: Yes/No/Cant Tell
Comment: ______________________________________________^
D. Off-site Waste Recytitag/Recovery/Reuse: Yes/No/Cant Tell
Comment:
Conclusion: Recyclable y_ Non-Recyclable Partially Recyclable
4 Material Classification: Sludge Spent Material By-Product
(circle one)
890
-------
w«, *TA9iis.
Aaseasmiu* i roK JKJBCYCLING, KECOWRY, AND REUSE POTENTIAL
Industrial Sector and Process:
Taste Stream: S^H tVfA VVJ A fyg ^ ?rt? A
Vaste Generation
Waste Form: Liquid(Aq.^lon-Aq4/SlunySoiids(Wei/Dry)
Hazard Characteristics (all):
Hazardous Constituents (major): C
Hazard Characteristics (all): I . /E^ R (?)
"
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. ' Comment: _____________________________________^___^^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make (be following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g_ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _______________________________________^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _
B, Water Use Reduction: Yes/No/Can't Tell
Comment:
C. On-siie Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste RecydinfUecovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: V_ Recyclable Non-Recyclable Partially Recyclable
4, Material Qassification: Sludge ( Spent Material J, By-Product
(circle one) ~~ '—
"891
-------
r*M&33mut«i r«K KfcCjrujUNti, RECOVERY, AND REUSE POTENTIAL
/"**">. j
Industrial Sector and Process: I H/A-POlOY
Waste Stream: _ . «=sgJOT
Waste K«aieratioaR«te;H^>afE) mil' \XLfi ]
Waste Form: * Uquid(A(f?Non-Aq.)/SIuny/SolWs{Wet/Dry)
Hazard Characteristics (all): I (C~) R
Hazardous Constituents (major): CTX^lOr!''jTn ..
1, Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: €"[(> r-rp/J A!/)
B. Waste generation is closest to: Raw MateriaiyMajor latermediaiesgmal Product
C Waste appears to have: recoverable produos/removable contaminamsTneltnef^
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: •
B. What was the basic purpose tor generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
• • Comment: _________________.____________________________.___^^_^
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Cant Tell
Comment: ______________„_______________^__________^___
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
D. Off-site Waste Recycling/Recovery/Rease: Yes/No/Can't TeH
Comment:
Conclusion: Recyclable \/ Non-Recyclable Partially Recyclable
4- Material Classification: Sludge Spent Material By-Prodno
(circle one)
892
-------
, naanaamiiwi *UK KJiCXCOWU, RECOVERY, AND KEUSE POTENTIAL
s~> i ^
Industrial Sector and Process: (^A/JKTH'Ol'A
"Vaste Stream: . ^irY D'TC'/i p i i f~i~^fj ' '' "
" Rgneratton Rate: ^fO/ 1QQO n14 i' AO ft' .All"; Cgj'
Waste Form: Liquid(AqJNon^Aq.)/Sl^ny/SoUds(Wei/Diy)
Hazard Characteristics (all): ^ . C R (IP)
Hazardous Constituents (major): CfiA fKlUTM
1- Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverablejproduas/removable contaminants/neither
D. Comment: ________________________________..^^_^^_______^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment; _________________________^___^_____^_____^_________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A Waste Segregation: Yes/No/Can't Tell
Comment: ___«____________________^_______.«_______^___.
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ___^_________________________________—____^
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyctog/Recoverv/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
893
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT TOE RECYCLING, RECOVERY, AND REUSE POTENTIAL
"
O
"py 5 4- _*Ljn._-H~. f3 v >\ c
Ha
Form: Liquid(AqVNon-Aq.)/Sluny/SoikJ»:
1. Process Flow Djagptrrj A Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in die process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable produos/removabte contaminanc/neii&er
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment.
A. Is the same waste generated at every facfliry using toe process?: Yes/No/Can't Tell
Comment: __ —
B, What was the bask purpose for generating this waste (e^, plant maintenance, chemical reaction, physic
separation, water rinsing, other purification steps)?
Comment:
C Way did this waste become hazardous (e-g^ physical contact daring production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives; Review the potential
-------
ottCJti ri>K vfASTt aiKJsAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: _ :.:;hrcfHiu:n Fe-rroczhren i ufi* , •»
te Stream: Sus'f o
«ste Generation Rate:
Waste Form: Liquid{Aq./Non-Aq.)/Slurry,'SoIids(Wet/Dry}
Hazard Characteristics (all): I C R (¥)
Hazardous Constituents ( major >: SA.? . Cr9. Pb •? . Se£ . Jflc. 7
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
1.
each major source
A. Source:
B. Waste generation is closest to: Raw_MaieHal/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't TeU
Comment: _ : _ __
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment ______^______________________^^_________.__^^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Can't Tell
Comment: ____^_^^_____^^__^____^_^— ________^^^_______^^^_^__
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ^^___________^_.^___^_^______— _________^____^____.
C On-site Waste Recyding/Recovery/Reiise: Yes/No/Can*t Tell
Comment: ______________ _^^_____^_^___________________________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ^_________^_______^^^^___.____.^____-_.^________^_^__^^______
Conclusion: _ Recyclable _ Non-Recyclable _X Partially Recyclable
4- MateriaLQassification: \ Sludge 1 Spent Material By-Product
(circle one) \ J 895
-------
v? yiui auiifci ruK WASTE ant£AM ASSESSMENT FOR RECYCLING, KECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process:
Waste Strewn: _AkJ'Tia/& eff^rfc a.w.per-rfe'"
Waste Generation Rate: O.... O. f
Waste Form: Uquid(Aq./Non-Aq.)/Sluny/Solicls(Wet/Dry)
Hazard Characteristics (all): I (t?) R T
Hazardous Constituents (major): /U ? , -5e 7^~^ -
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: Kis c^/«^ ~r'fy»'f
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: j fgc.My
6. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: re/ao^c rjtPw.d^ _
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: /'or>^rlo o >.-» oroc»&&_'«*- Corcq r«ss"/<'- .... ce.oas^orT'tyx or '/
"
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives,
A. Waste Segregation: Yes/No/Can't Tell
Comment ............................
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _________^ _
C On-site Waste Recycling/RecoveryyReuse: Yes/No/Can't Tell
Comment . •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tefl
Comment: ......... _
Conclusion: _ Recyclable _ Non-Recyclable X Partially Recyclable
vs
4. Material Classification: Sludge Spent Material
-------
ruit TYAAit 31KJKAM ASSESSMlim *OR KKCYUJJNU, RECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process: CoJ G-
te Stream:
Generation Rate: _ 6 QcC mt/ r , i 7.
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Sj3lids(Wet/Dry) ?
Hazard Characteristics (all): I C (K/~' T
Hazardous Constituents (major):
1. Process Row Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: -S -
B. Waste generation is closest to: Flaw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: f ^cj.^ _ _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: £•.
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _ _
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _______________.^^^_____________________^_________
Conclusion: _ Recyclable X Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge <^Spent Material7 By-Product
(circle one) • -- — - - -^ 897
-------
l-UK WAS.It 3TKKAM ASSESSMENT FOR KECYCUNG, RECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process: C-r^oo ir~
•ste Stream:
_ste Generation Rate; iaoo /n*
Waste Form: Uquid(Aq^on-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R ^~
Hazardous Constituent (major): _Q_t - , Pfe7
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A, Source: UJurfP , ;*^ffJL[>;ffcr jo+rces -rki-c-^^'hc^ /psac*&s )
B. Waste generation is closest to: Raw Material/Major Intennediafes/Rnal Product
C. Waste appears to have: recoverable products/removable contaminants/cejther
D. Conunent: k,.k ^r^oir- g&n 4*-,^ b* Y* .vjJc^7
4. Material Classification: ( Sludged Spent Material By-Product
-------
onjcjti ruts, w»A3tr. OIKHAJVI /%3»|_SSMI_PU WK tUICYCLUMU, RECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process:
"Vaste Stream: UJUJTP /
-------
oiKHAM ASSiiSSMJSHl *OK KECYCUNG, KECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: (A LiT^ A'TJlX k'
Stream: f\ [
,/aste Generation Rate: _ '^A^T) kM I LUfa A
Waste Form: Uquid^Aq./Won-Aq.)/Shtrry/SoIids(Wet/Dry)
Hazard Characteristics (all): 1 C . R fr^s
Hazardous Constituents (major): C.(\r\fT\ '• "^ s '"
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: H/unS / v?.r.i -.'^.^'V
B. Waste generation is ciosest-to: Raw MateriaiyMajor Intermediates/Final Product
C. Waste api»ars to have: recoverable products/removable contaminants/neither
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _ .
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: .
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: •
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment ..........................................
B. Water Use Reduction: Yes/No/Can't Tell
Comment: :i
C On-site Waste Recyding/Recovery/Reuse: YesyNo/Can't Tell
Comment L
D. Off-site Waste Recycling/RecoveryyReuse: Yes/No/Can't Tell
Comment:
Conclusion: V_ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification; Sludge Spent Material /By-Product
(circle one) r , ;r— ""'
900 ' Kxrtcrwzcsjr rrftrfran ^
-------
SHEET FOK WASTE STREAM ASSESSMENT TOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: _ ....... ^ ) Q jrrijl jnlha U ^Cl^uT] Qi I
Waste Stream: _ ft-f .1A f1r\M4
Waste Form: Liqui(i(Ajq./Non-Aq.)/SIuny/SoU&{Wei/Diy)
Hazard Characteristics (afl): 11 C R ^Tji
Hazardous Constituents (major): Cl 1?T".' XT* n T^ Vf ' * I "•' )TA
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: ._
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to nave: recoverable products/removable contaminants/neither
D. Comment:
Z Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps}?
Comment: _________^
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ___________-..^__________________^____^
3. Waste .Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Can't Ten
Comment
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment ____^__________
D. Off-site Waste Recycling/Recovery/Reuse:
Comment:
Conclusion: Recyclable \/ Non-Recyclable Partially Recyclable
4 Material Classification: Sludge Spent Material By-Product
(circle one)
901
-------
Industrial Sector and Proes
Stream:
aiiuyun MaaussMCNi fOK tO£CYCLING, KECOVERY, AND REUSE POTENTIAL
S". i
i: ( I V H v;
.Vaste Generation Rate: 7^ ;/Tf)
Waste Form: Liquid(Aq./Non-Aq.)^luny/Solids(Wet/Dry)
Hazard Characteristics (ail): I C _ R
Hazardous ConstftDents (major): CYl:'l T^ •'. }f Y'
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ ___________________
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: '
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: •
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can*t Tell
Comment: ___________________________________^^
C On-site Waste RecycBng/Recoverv/Reuse: Yes/No/Can't Tell
Comment _____^______________________^___^_______________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment ___________________________________________^
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: j Sludge) Spent Material By-Product
(circle one)
902
-------
onu.i JPW* »f /win oiKtAM assiSSSUKKl TOR KEC¥CUNG5 KECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: 7 I CJT 0 JThkO ^h fTCfaTV i JV
Waste Sttwan: -FT 1 )T HO f g . SfD J X
Waste fatneratjon Bate: T/&I 7~^2.r^f^, rrrf | f >g.
Waste Form: UquidfAqJNon-Aq )/Slufty/SoIids(Wet/Dry)
Hazard Characteristics (all): I
Hazardous Constituents (major); _
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ___^
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _______._____„__^______^^^___________________^__.
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g.7 physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing .the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: •
B. Water Use Reduction: Yes/No/Can't Ten
Comment: -
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~
Conclusion: Recyclable \/ Non-Recyclable Partially Recyclable
4. Material Classification: . Sludge Spent Material By-Product
(circle one)
903
-------
aiiuyun aaSESSMKNi FOR KECTCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: l h £)ph HI i 1 Af
^aste Stream:
/Vaste Kaieratton EattQfc ..;ycD>Rtx>-j TrH
Waste Form: ** Liquid(Aq./Non-Af.)/Siimy/SoUds(Wet/Diy)
Hazard Characteristics (all): I C R
Hazardous Constituents rmaior): _ ............. /^Q q TT''' } .'• ' •O
i. Process Flow Diagram. ._4t Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
_
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ______________ _ '
B. What was the basic purpose for generating this waste (e,g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: -
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ________________________________________________^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segreption: Yes/No/Can't Tell
Comment .........................
B. Water Use Reduction: _Y_s/No/Can't Tell
Comment ......................
C On-site Waste RecycUng/RecoveryJleuse: Y^No/Can*! Tell
Comment: _ jr OV"
J
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: \/ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge • Spent Material By-Product
{circle tme) "^ ^
904
-------
*UK WASTt 3TK£AM ASSESSMENT FOR KECYCUNG, KECOVERY, AND KEUSE POTENTIAL
IndustrlaJ Sector and Process: h A^cgo&.r t |-(vgx£>.T'oonc-
Stream: O? ^--so*,
Generation Rate: ' O /5"O3O*vtXwr
Waste Form: Li^d(AqJ^an-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (aU): I (^> R T
Hazardous Constituents (major): _ ;
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: ^"tu- 5erubVr- _
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable e
D. Comment: vjlwv FWs^Lm, & »-f .•
2, Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Cant Tell
Comment: _
6. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _______^______^^________^_^________^____^^^^
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segreption: Yes/No/Can't TeU
Comment: ............................
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ^_____^^_^____ _______________^__^^^_^^^______________^^
C On-site Waste Reeydtaf/Recovery/Reuse: Yes/No/Can't TeU
Comment: _____^ ____^_^____________.«__«_________________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
Conclusion: _ Recyclable _ Non-Recyclable X Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one) '\ ^^ 905
-------
WOBE SBDT ro» WASII STMAJ* Aaaamata ro* R»CYCLB«G, RacovotY, AMI REUSE POTENTIAL
^•^ jg\rwxfl.v~au i/w. rYi W^Y/ ar 5
Process Flow Diagram & Waste Characterization: % lookiaf at both dootments, try to answer the
following questions for etch major source of the SUM waste generated in {te process. Compiae a separate form for
loch major source.
A. Source: ._ _
R Wastt penetauoB 8 ctaMtt to: Raw M«teml?»Uior buenaeduuaVF'auJ
C Waste appean m have resovenbte prartueo/remov»>rte amtuuAuts^eitber /, /;?
D. Commenc jjg >J-f " 4-t^ / j ^x-. .« -^ j*y ^>a? ^re.f C c /y &^y-d\ re u/e^r
- •- • --
2. Reasons for Waste Generation: Based OB the description of die process and waste geaentkm and
management practices pven Cor a sector, make the foUowinf ----
its
A. Is the same waste feaeraied at emy fiwlity osiaf the process?: Yes/No/Can't Tell
Consent: ;
B. What wts tiM basic porpose tot pamtfrg Qds vane (64, ptnt mamrmtncR, cfaemical reaction, pbysical
other jiuiificaiion steps)?
C Why did this waste become haartoai (e^, phyiictl contact dariag prodactioB. mniag with other waste
streams* results bom mxpwny resnovaT)?
Comment:
3. Waste Management Alternative*: Bane* the noaanial tor ntwemf tae yuatltMS of wane generated at
any of its sources by i
A. Waste SetrefBtiOK Ye*Wo/Catft Tefl
B. WaterUs«
Comment:
On-sitt Wwe Recyciiaffllflcovery/Rewe: YeyNcwOntTefl
Commenc •
D, Off-site Waste RecycUnf«ecovery/Rease: Yes/No/Cant Tefl
Comment:
CondusiotL __Recyd_bte Non-Recydabte V Panuliy RecycUWe
Qftssificatioii: Stedp ; Spent Mawi^N; By*Piodaa
^~— -^
-------
WOUE SHEET ro« WASTE STREAM ASSESSMENT FOB RECYCLING, RECOVERY, AND REUSE POTENTIAL
"2- f £? -, Lr-£> t?
Haawtf aarKtcristlei (aflfc ..1C _R. ^ T_
, Se ,
l Process Flow Disgrsin & ^Xfa*?te Ctt3r3Cter*^?*lOfl- By i*v
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
^ rv'ivwwt/ i ^e.COv\d.(^r
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
iDOQSlsMU S^KXXX^ H^nnj ••^•^^••v* ^_p^^-j(^JJ^_^^^—p,,^^^,,,^^^^.p^^.^^^^^^^^^^^^^^^••^^^^•••^•^^••""^•'^••"^^•^^^^^^"^•^^^^^^^^••"•^
Wast* Straw Lf.&df ttfJ-iJiSej I £___
Waste Generation RttK _ _
Waste Fora: Ij
-------
WORK SHUT FOB WASH SXUAM AsnannMT ro» RECYCLING* tacovonr, AND REUSE POTENTIAL
Process Flf"» T>feB?p & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: L?GO^\\>/^^r"
B. . Waste generation is closest to: Raw Matenal/Maior Intermedia lo/Fmal Protluct
C. Waste appeals to have itjBB»|gaMe_«?otfsfls/MttOMble contaminants/neither
D. Comment •
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the foUowmg assessment.
A. Is the same waste feaenied at every facility osiaf the process?: Yes/No/Can't TeU
Comment: .
What was the bane purpose for feaeratLaf this wane (e£, piaat maintenance, chemkal reaakm. physical
separation, water nnsmf. other jmHiatiou steps)?
Comment:
C Why did this waste becoow haantoas (e^. phiaicai cpaaa_d«nBg producbon. mixing with other waste
streams, results froai impurtty reaoval)?
Waste Mantgymffll Akeraativet: Re»«w the poteaoial to redneinf the quanntia of waste generaied at
any of its sources by considenaf the foftxvfem wasat Biaua^uiieut alternatives.
A. Wtste SepeptiOK Yea^p^aait Tea
& Water UaeR«d*atosc Y«flfaCw1Tei
COOUMBB
C On-Hte W«» Ro^dia«««oov«yyRc»e: Yes/NoXaat Tcfl
Commenc *
0. Off^ite Waste Reeydiat/Recovery/Reaae: Yes/No/Cant Tcfl
Condiuion: Recvdabte NoB-Recgrtabte ^ Partially Recydahte
4- ff*lfrnirtr?B7 Sl«*f= Spent MateraT ^, By-Prediaa
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
£>gv)v\fl.vMi/'W>' . rsi yviay 8"
Wast* Straw y&l~*-m S-h tl
Waste Focm: Liqaid(AqJNoa-Aq.)/Sluny/Solids(Wet/Dry)
Clianctarfetfes (al): .- I C R T
Constttuenti (major):
1. Process How Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for «acfa major source of the same waste generated is the process. Complete a separate farm for
each major source.
Source:
B. Waste generation is closest to; Raw Matenal/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment .
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?; Yes/No/Can't Tell
Comment:
B. What was the bask purpose for generating this waste (C.&, plant maintenance, chemical reaction, physica
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considerinf the foOowing waste management alternatives.
A. Waste Segregation: Yes/No/Caat Ten
Comment: ,____________________________________^^
B. Water Use Reduction: Yes/No/Caa't Tell
Comment:
C On-site Waste Recvding/Recovery/Reuse: Yes/No/Cant Tefl
Comment: •
D. Oftiite Waste Recyding/Recovery/Reuse: Yes/No/Cant Tefl
Comment: ____________________________________________________________
Conclusion: ; Recyclable V Non-RecydaWe Partially Recyclable
4. Material Classification: Sludge , Spent Material' By-Product an
(circle one) "^^_ ^/
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Sector and PIIKWS:
Stream: \?P4j^r^° IMfl. ArQ/v
Wast* Gencrmtion R_*s 1® / -J 3 2O i flOft Q-r4 h
Waste Form: L«p-id(Aq^on-Aq.)/Sluny/$6lids(Wet/Diy)
Hazard Characteristics (all): I S R '
Hazardous Constituents (major): S
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
anrh m/ji/jr tnurce..
i.
each major source
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ; _.
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ~'...
B. What was the basic purpose for generating this waste (e.g_, plant maintenance, chemical reaction, phystca'
separation, water rinsing, other purification steps)?
Comment; ___________________________________________
C Why did this waste become hazardous (e.f», physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment HCJ J
3. Waste Management Alternatives: Review the potential for reducing toe quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _________^___________________________________________________________
C. On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: _^_
D. Off-site Waste Recyding/Recovery/Reuse: Yes/Np/Can't Tell,
Comment: "TOO IfiUCflP \
Conclusion: Recyclable _ Non-Recyclable V Partially Recyclable
4. Material Classification: ( Sludge J Spent Material By-product
(circle one)
912
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Initastrial Sector and Proas*
Waste
&£>\<\ flltl Jll\llA
loocu
Waste Form: Uquid(AqJ^on-Aq.)/sfiny/sdiids(Wet/Dry)
Heard Characteristics (all): I C R
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable produce/removable contaminants/neither
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment
A. Is the same waste generated at every facility, using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.&, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ^_^__________iii^_
C Why did this waste become hazardous (e.g* physical contact during production, mixing with other waste
streams, results from impurity removal)?
. Comment: .
3. Waste' Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment
B. Water Use Reduction: Yes/No/Cant Tell
OofflSBfiOdtr
C On-site Waste Reeycfing/Recovery/Reuse: JYesyNo/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: TfiD 1/lKtf \/
Conclusion: Recyclable Non-Recydabte V Partially Recydabte
4: Material Classification: Sludge Spent Material By-Product
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
(?) O \d
W W5gqA / 7^-1 OR
Waste Form: Lk|ui
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream.' _ '\N \\ MP W
PHf* i Ml d / i "=f SCSPO
Waste Fona;
Hazard Characteristics (all): I. C R
Hazardous Constituents f rotor): cnhfPk. an.OPt^Ji rqd>TliAJ01, ^hil/THI Jj)/Yl» O^
" —-1 • / -"ji-^-jj- / — • .
1- Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions tor each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Wasie generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tel]
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment .
3. Waste Management Alternatives: Review the potential tar reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comments
B. Water Use Reduction: Yes/No/Can't Ten
Comment: ______^____i^^^^_^__ii^___^____^^___^_______^^__^^__^_^_^^^_
C On-site Waste Recycling/Recovery/Reuse: YeVNo/Can't Tell
Comment: _
D. Off-site Waste Recyding/Reoovery/Rease: Yes/Np/Caa't Tell
Comment:
Conclusion: \/_ Recyclable Non-Recyclable Partially Recyclable
4 Material Classification: f Sludge J Spent Material By-Product
(circle one) ^ ^ 915
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
ndnstrial Sector and
A'astt Streaav
. i--_a
Z&Lcn 1 vno, W A/rr£Zi
Waste Form: Uquid(AqJNon-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I n £T) R
Hazardous Constituents (major): <
L Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
....................
B. Waste generation is closest to: Raw Material/Major Intermediates/Filial Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _^_^______^___________________^__
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physka'
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: .
3, Waste Management Alternatives; Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ______________________—____________^___________________
B. Water Use Reduction: Yes/No/Canl Tell
Commenc _^
C On-site Waste Recycung/Recovery/Reose: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Rease: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recydable V Partially Recyclable
4. Material Classification: Sludge (Spent Materi4> By-Produa
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAI
W«ste
Hazard Chamteristiei (all):
Hazardous CoosttoeHtsi
i. Process Flow Diagram & Waste Characterization: % looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appeals to have: recoverable productsVremovable contaminants/neither
D. Comment: ..... _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is toe same waste generated at every frailty using toe process?; Yes/No/Can't Tell
Comment: ,
B. What was the bask purpose for gesenting this waste (04, plant maintenance, chemical reaction, physic
separation, water rinsing, other purification steps)?
Comment: ................................
C Why did this waste become hazardous (e^, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering tne foOowmg waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
Comment: '
B. Water U*e Redaction: Yes/No/Cant Tell
OfeHPilUfffltn
C On-site Waste Recycimg/Recoveiy/Reuse: Yes/No/Can't Tell
Comment • _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeD
Comment: ................
Conclusion: Recydanle _ Not-Recydabfcs _ Partially Recyclable
4 Material Classification: Sludge ( Spent Material ) By-Prodact 917
(circle one)
-------
aJUKET JfOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: \
tste Stream: P\C\ A n\OvvvV
(?o>rx <,vxAeA'V\y\ ^k cvwck VetM v\ -, v\
«aste Generation Rate: itf.ODO v^ /
Waste Form: Uquid(Aq./Noa-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I JC R T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the-
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: __________________________________________________^
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. - Comment: •S. \y-JLa, o_ vs >rg c we \e /^ acCos J^-T X S^
O 'J f\
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't TeU
Comment: •
B. What was the basic purpose for generating this waste (e.g_, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _______________________________________________
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/NcyCan't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _________________________________________
C, On-site Waste Recycfing/Recovery/Reuse: Yes/No/Can't Tell
Comment: _____________________________________________
D. Off-site Waste Recyctag/Recovery/Rense: Yes/No/Can't Tell
Comment: ________________________________________^
Conclusion: ^/Recyclable Non-Recyclable Partially Recyclable
Spent Material By-Product
918
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTUI
Industrial Sector aai
WssttStreuu &i
Waste Generation Rate!
Wise Font: Liqa«(AqJNon-Ai|.>SI«ny/SoWi(Wet/Diy)
Haoanl Cluuracueristia (ail): .. I C R T
H«artous Constttnents (major): _
i. Process Flow Diagram & Waste Characterization: By looking at both documents, tiy to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: -
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to nave: recoverable products/removable contaminants/neither
D. Comment- '
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is tie same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: • _ __
B. What was toe basic purpose for generating this waste (eg, plant maintenance, chemical reaction, physic;
separation, water rinsing, otter purification steps)?
Comment:
C Way did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from imparity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tefl
Comment: ..................
B. Water Use Reduction: Yes/No/Cant Tell
Comment .
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Cant Tefl
Comment: • ............................... - . *
D. Off-site Waste Recydiag/Recr^ery/Reuse: Yes/No/Cant Ten
Comment: ________^___— ,^______________________________,^__________
Conclusion: Recyclable _ Non-Recyclable _ Partially Recyclable
4- Material Classification: /^Sludfe) Spent Material By-Product 919
(circle one)
-------
-------
WORK SHUT! FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: \ _ £/X
B. Waste generatioo is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable conm«
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
vdostrtal Sector ui ^
<¥utt StnaoK ^ I y /"/?€ j^ A-PC-
Waste Font Uquid(AqjTJon-Aq.)^l"ny/Solkls plant maintenance, chemical reaction, physic
separation, water rinsing, other purification steps)?
Comment: -
C Why did this waste become hazardous (e.g_ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: . ...
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering die following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
Comment: i;
B. WatCT UK Reduction; Yes/NOCamt Tell
Comment: '
C On-site Waste Recyctrng/Recovery/Reuse: Yes/No/Cant Tell
Comment: • •
D. Off-site Waste Recyding/Recovery/Reus«: Yes/No/Cant TeO
Comment:
Conclusion: V Recyclable . Non-Recydaale Partially Recyclable
4 Material Classification: (''sludge ^} Spent Material By-Product
(ciKS one)
-------
SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: __L-ftQu7v * TV-v w\Wve 1-n v\ a, Ov/v--^ >xtj-^ v\<
Waste Stream: ScAx (5
Waste Generation Rate: |
Waste Form: LJquidfAq^Non-Aq.)/Sluny/Sotids(Wet/Dry)
Hazard Characteristics (all): I C R T_
Hazardous Constituents (major):_
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: S>^
B. Waste generation is closest toYjtaw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: oOg>.S^"e \V Vfccw: )<\c.'k- -V-p
^-
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given tor a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _^___^____________^_________^______________________^__
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: __________^___________^______^___________^^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Cant Tell
Comment: ' .
B. Water Use Reduction: Yes/NoVCai't Tell
Comment ^______________________-______^_____________.^^
C On-site Waste Recycling/Recovery/Reuse: Yes/NoiCan't Tell
Comment: __^ _ ____
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
Conclusion: Y Recyclable _ Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge Spent Material (-Product
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
idnslrtalSaetaraai
Strtmm: ^ O-f. ^T
Waste Generation Race,
Waste Waem: Liqiii4(Aq^Non-Aq.)/SHiny/Solids(Wet/Dry)
Hazard Characteristics (all): .. I C R T
Hazardous CoastMaentS fMtor):
I. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in me process. Complete a separate form for
each major source.
A, Source:
B. Waste generation is closest to: Raw Material/Major intermediates/Final Product
C Waste appeais to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: YesyNo/Can't Tell
Comment:
B. What was the basic purpose tor generating this waste (e.f_ plant maintenance, chemical reaction, physic,
separation, water rinsing, other purification steps)?
Comment: ____________________^______«___________
C Way did this waste become hazardous (tg_ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ____™—^________^^____^__________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant TeD
Comment: ^.^__^____________________________________«_-«_____••——
B. Water Uie Reduction: Yes/No/Cant Tell
Commenc
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tea
Commenc .._ •
D. Off-site Waste Recydmg/Recovery/Rcose: Yes/No/Can't TeD
Commenc
Conclusion: Y Recyclable Non-Recyclable Partially Recyclable
4- Material Classification: Sludge /Spent Material ) By-Product
. (afdeone} ^ ^
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: L-ea-JL . l?y xv\/MXY vf 5>Yvve.VT^Yv ^ cxfyxzA N*e.~Kva
Waste Stream: _ \jjr chowrdr* w<^ S"V-€. _
Waste G«oeration Rate: gpo, llQ,o$o „ 7-i--r, g^fl ^ •?- y1 ^-y- _
Waste Form: U(mid(Aq^Non-Aq.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): I C R T_
Hazardous Constituents f major): £Z-g-) , f 10 _
"•"*^^^™"™*"" --.r:_- --- —^— ^^^^^^^^^^—p—
1-
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A, Source: XJjk-ficnJ S / ^ tyo-£"W*< lyfic fc ? S^S. , ^'uee^ji^^J
B, Waste generation B closest'to: Raw Material/Major latennediates/Fmal Proiua
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment _
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and Its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was the basic purpose for generating this waste (e.g., giant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _^___________________________^____________________^____
C. Why did this waste become hazardous (e.&, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _____________^ ___________^________^___________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _
B. Water Use Reduction: Yes/No/Can't TeU
Comment: _________________________________________^
C On-site Waste Recycling/Recovery/Reuse: Yg/No/Can't TeU
Comment: _ •
D. Off-site Waste Recvding/Recovery/Reuse: Yes/No/Can't Tell
Comment: __________________^_______________________________
•Conclusion: _ Recyclable _ Non-Recyclable Partially Recyclable
4- Material Classification: Sludge ( Spent Material) By-Product
(circle one) ^ — — ' 925
-------
WORE SHEET FOE WASH STREAM ASSESSMENT pen RECYCLING, RECOVERY, AND REUSE POTENTIAL
WaattF
Haart CbamMrirtca («•): --
1. Process _¥]r** ^fogf?1" ^ Waste Characterization: By looking at both documents, try to answer the
following questions tat each major scarce of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: \f£^V*90t/S 5>DU^C£S
E Waste generation is doses: to: Rjw_Matehal/MajOT Intermediates/Final Product
C Waste appears to haw: recoverable products/removable contaminant&neitber
D. Comment: ________«_«______^_____^_^«-____.«^___^_^^«________«_________
2. ' Reasons for Waste Generation; Based on the description of the process, and waste generation and its
management practices giwn tar * sector, make the following assessment.
A. is the same waste generated at evwy facffity using the process?: Ys/No/Cant Tell
Comment:
B. • What was the basic purpose tor generating thai wane (tg, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification step*)?
- " Comment:
Why did this waste become hazaidoas (e^, physical contact during production, tninnt with other waste
streams, results from imparity removal)? " '
3. Waste Manag?pKnf ^Item^loegL ReOTawtfaroQaanalteMdnciM the quantities of waate generated at
3BV Of
A. Waste SejrefUio
Comoesc __ :
Water U«» Radacttoac YeVr^yCaat TeH
OB-stte Waste ReeydmfyRecovery/Reaae: Y»t4o/Cant TeO
Conunenc *
O, Off-site Waste RecycUng/Rjcomy/Reoe Yes/No/Caat Teg
CondusiOD: _ RecydaWe _ No«-Recjetabte J/ Pamalry RecydaWe
4 Ml*^! Cl^^*^^<»te "Slodfr^; SpeaiMatottl By-Prodnct
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOB RECYCLING, RECOVERY, AND REVSE POTENTIAL
Iadostt.il Sectoral
nhi. r^rmtiaa Rat-i V
Wart* Form: IJquid(AqyNon.Aq.>Slurry/Soiids(Wet^)ry)
Hmaml Cb«r»cterift-ci (*i): .. I C R T
HaanfcNH Coastttaaia (major): , _ ___
i. Process Flow Diagrarg & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: ; ._____»__»__________
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appeals to have recoverable products/removable contaminants/neither
D. Comment;
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the bask purpose for geaentiaf this waste («,&, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ________^____^_____^_______________________
C Why did this waste become hazardous (e-g., physical contact during production, mcaaf with other waste
streams, results tern impurity removal)?
Comment: •_.
3. "Waste ManagCTPCnt Alternatives: Renew the potential for reducinf -the Quantities of waste generated at
any of its sources by considerinf the following waste management alternatives.
A. Waste Sefrejaboa: Yes/No/Curt TeD
Comment: •
B. Water Us« Redaction: Yes/NoCant Tefl
Comment: .
C On-sitc Waste Recytiinf/Recovery/Reuse: Yes/No/Can't TeU
Comment: • ' • .. • •
D. Off-site Waste Recyding/Recovery/Rease: Yes/No/Cant Tefl
Comment: •
Conclnsion: )£ Rccydabte Non-Recydabk Partially Recydabie
4 Material Classification: Q Sludg«J) Spent Material By-Product 92/
(drcleone) —• -~^
-------
WORK SHEET TOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
le^A '
C11.1 da e. I So 11
Wane Gcaentfoa °— v
Bawd Ch«r»ct*Tistic» («fl): — I C R T
1. Process Flow DJafpm & Waste Characterization: ty looking at both documents, tiy to answer the
following questions far each major source of the same waste generated is the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have recoverable products/removable contaminants/neither
D. Coauaeat: ^ „ __« ___^______
2. Reasons for Waste Generation; Based on the description of tbe process, and waste generation and its
management practices given fa a sector, make the following assessment.
A. Is toe same wtstt generated ai every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was tbe basic pupae for geaentiBf this waste (e^ plant maintenance, chemical reaction, physical
separation, wwer rinsing, other jrorificanon steps}?
Comment: _^ •——.—•-•••••»«•«••—— ____^^..^__^________^________
C Why did this waste become hazardous (e^, physical contact daring production, miaog with other waste
streams, results from imparity removal)?
Comment* ,^^^mim—^^mil^l.^—^limi—mi^^mmim^l^^.^ilimimimim^l^—,^mm^miim^l^^im^mmimi^^m^im^l^^—
3. Waste Management Alternatives: Review the potential for reducing 'the quantities of waste generated at
any of its sources by considering the fbOowing waste management alternatives.
A. Waste Segregation: Yej/No/Cant Tell
Comment: •
B. Water UK RadnotoK Yea/No/Caat Tefl
^^O^Q^BCBC
C On-site Waste Recyetog/Recovery/Rewe: Yes/NoCant Tefl
Comment: •
D. Off-site Waste RecycUng/Recoveiy/Rense: Yes/No/Cant TeD
Comment: ___ ____
Conclusion: KRecydaWe Non-Recydabte PaniaDy RecydaNe
4 Material Classification: ( Stedge ) Spent Material By-Prodna
(arcie one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
• Stream: C 7i .of h/Yl f/pP f\ 1J23
Waste Form: Uquid(AqJNon-^.)/Siuny/Solids(Wei/Dry)
Hazard Characteristics (aB): I ,C R
Hazardous Constituents (mator): "
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A Source: CTLO _
B. Waste generation is cldsest to: Raw Mate^iaiyMajor Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ,______._._____^_^_..^_____.__^____________^_____^____^___
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment '
C Why did this waste become hazardous (e-g-, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste" Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A Waste Segregation: Yes/No/Can't Tell
Comment: _____________—___________________^______—^____^_^^
B. Water Use Reduction: Yes/No/Cant Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment: _^___________—^________-^_______^_______^__^^
D. Off-site Waste Recycimg/Recovery/Reasc Yes/No/Can't Tell
Comment:
Conclusion: \f Recyclable Non-Recyclable Partially RecydaWe
('sludge)
(circle one) \«_^X 929
Material Classification: . (sludge) Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
]| 1 n f\\ " /
Industrial Sector and Process: _ JU(LxnQM(I (
___
Vastest****: ffVYlii-r--'
Waste Generation R"** ZL> I &&. )-r>fh\jfeLA
Waste Form: Liquid(Aj|^«fon-Aq:ysluny/Solid^Wet/Dry)
Hazard Characteristics (all): 1C R
Hazardous Constituents (major): finJ^ IJ1 vn
1,
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: a" in
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appeals to have; recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g_, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: •
C Why did this waste become hazardous (e.g, physical contact during production, mixing with other waste
streams, results from imparity removal)?
. Comment: :
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tefl
Comment: 1_^^^__________________________1__________________
B. Water Use Reduction: Yes/No/Can't Tell
Comment ^
C On-site Waste Recydrng/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Ho/Can't Ten
Comment:
Conclusion: \/ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: . Sludge Spent Material
(drclf one)
930
-------
run TtASin. StKl_AM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream: f-> 1-kr
Waste Generation Rate: ^dQAi-f/^r. 3oo. uc-^-tl
-------
vTuitik ojuuii f UK n Aai-js aiKKAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
/M,
Industrial Sector and Process: '__ l^rt
*'aste Stream: ru-TAsci. fe^^,
•taste Generation Rate: \OO ,
Waste Form: Uquid(AqwNon-Aq.)^]uny/SoMds(Wet/Dry)
Hazard Characteristics (ail): I C R
Hazardous Constituents (major): rtf :
1, Process Flow Diagram & Waste Characterization: By looking ai both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Rav. MateriaiyMajor Intermediates/Final Produa
C. Waste appears to have: recoverable products'/removable contaminants/neither
D. Comment:
2- Reasons for Waste Generation: Based on tie description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't TeU
Comment: •
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g,, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: __________________________________________________^__
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Cant Tell
Comment: '_
C. On-site Waste Recydiag/Recovery/Reuse: Yes/NoCan't TeO
Comment: ..._
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable .x Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
932
-------
ruK r*ASTt STMEAM ASSSESSMEPt'l FOR RECYCLING, KECOVERY, AND KEUSE POTENTIAL
Industrial Sector and Process: Atcrcu/y __________
Vaste Stream:
.Vaste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Sluny^^®rWet/Diy)
Hazard Characteristics (all): If C R
Hazardous Constituents (major): 'he, '
1, Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A, Source: -v-~a-
B, Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable rontammants/neither
D. Comment: UaiOio^A pa
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: / «_
Vaste Stream: Atdli. toA c. Oiock. A-n.-v.-M
/Vaste Generation Rate:
Waste Form:
Hazard Characteristics (all): I
Hazardous Constituents (major): ftb •
1. Process Flow Diagram &. Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: fjg j_/\fo
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was tie basic purpose for generating this waste (e.g.t plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _____________________ ________________________________________
C. Why did this waste become hazardous (e.g., physical contact during production, meting with other waste
streams, results from impurity removal)?
Comment: ............................... _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ______________________________________________ _______
B. Water Use Reduction: Yes/No/Caa't Tell
Comment: .............
C On-site Waste Recyciing/Recovery/Reuse: Yes/No/Can't Tell
Comment ...........................
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: _ Recyclable _*_ Non-Recyclable _ PartiaUy Recyclable
4. Material Qassification: Sludge Spent Material C^ By-Prodwa/
(circle one)
934
-------
WORK. aMttT M>K WAS It STREAM ASSESSMENT FOR KECYCLJTNG, K1COVERY, AND KEUSE POTENTIAL
Industrial Sector and Process:
"Vaste Stream: FU/LW /6
j Generation Rate: i. 2=0 .*%,- • Q 7!vi;*\ is /** /rccp!-'s.'c-o
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: i .-no; j. r;"h; a. f> cr* _ ............................ [[[
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ____ ________^^_^___,,__^^^___^^^__^____.^___.____________
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _^_________________^____-______________________^
C. On-site Waste Recjding^Recovery/Reiise: Yes/No/Can't Tell
Comment: __________________^^^_^^__^^_________________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ...
Conclusion _ Recyclable * Non-Recydabie _ Partially Recyclable
4, Material Classification: Q^ Sludgej/ Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: ______
te Stream: I—U^ U ifx $&&&• K&
Generation Rate:
Waste Form: C^Lj§uj5^Aq./Non-Aq.)«lurty/SoUds(Wet/Diy)
Hazard Characteristics (ail): I C R (jf)
Hazardous Constituents (major): £s? . Cd ?.
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: LrgciigJs 'f-rcm ef^^cJ* OnM SCT<~, fe 6*r ibuj*rs/1khec.J«*<.''-* ( "'fg^y^r A.PC ^ .^f
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product fa^-.-t -iei ,-^t^T
C. Waste appears to have; recoverable products/removable contaminants/neither
D. Comment: ____________________________-__________^___^__
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Ye&Wo/Can't TeU
Comment: _^ ___^_^_^_^__^____
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mmng with other waste
streams, results from jmpuriiy removal)?
Comment: ' _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Cja't Tell
Comment: f c^
B. Water Use Reduction: Yes/No/CjnVTell
Comment
C. On-site Waste Recyding/Recovery/Reuse: Yes/Np/Can't Tell
Comment: C.rr^-fj^ sk,/n <£•-*!**. •£<•
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeU
Comment: ______
Conclusion: Recyclable * Non-Recyclable Partial^ Recyclable
4. Material Qassification: Sludge
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: .P\aAvvwVviv f^n-^rO\J-€> Ms-WJP
Waste Stream: ^pex/^-V- ^oAyfcwVs
Waste Generation Ratfe ^QO-, \~1~0~O, "^
Waste Form: UgmdrAqJNoja.Ag.^luny/SolMsfWet/Ptv)
Hazard Characteristics (tH): l_ C R _T_
Hazardous Constituents (major): Pfr ? A- ^4»w\. ..... _v#tf \f ... [&*-> 'ff^c?^~^n- -
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices fives tot a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .....
B. What was the basic purpose for generating this waste (&g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? ~~~
Comment: • _
C Why did this waste become hazardous (e,g^ physical contact during production, mixing with other waste
streams, results from impurity removal)? ~~ " ~~ ~~
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ___ _ :
B. Water the Reduction: Yes/No/Cant Tell
Comment: .___«__^_________— _____^_— ^__ _________^_____________._________
C On-site Waste Recj«aing/Recoveiy/Rense: Yes/No/Can't Tell
Comment: ___^ _____^_________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can'i Tell
Conclusion: ; Recydabte V Non-Reeydable _ Parually Recyclable
Material Qassification: Sludge Spent Material By-Prodact
(drdeone) 937
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: x \(XrV\v\uyvN &\-&2\)-p_ fAgAra-lS K.£ 4-
aste Stream: ^np^Ar A.r,v/i^ '" 7
• emigration Rate? ... ^ OO^ ) TO O _,_ ^ r> O O v^^ / V.Y"
Waste Form: Uqujd(Aq
Hazard Characteristics (all): I
Hazardous Constttneats fmajor): r b f f
Process Flow Diagram & Waste Characterization: % looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: Re.£\w\v A/Se^l 4o 0yo/vt£ ckbv^JU ^dV? o+ \fAYfovS
B. Waste generation is closed to:~Ttaw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ute yVe wi^ C^u\4&\y\ \te-r\s ./ s
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ...................................... _ _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? "
Comment: ...............................
C Why did this waste become hazardous (e.g_, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _____ ____^______________^_________^__________________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Sepegation: Yes/?to/CaBt Tell
Comment: ________________-__________________________^
B. Water Use Reduction: Yes/No/Can't Tell
Comment: .....................................
C On-site Waste Recyding/Recovery/Reuse: Ycs/No/Can't Tell
Comment: __ _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Cant Tell
Comment: ; _
Conclusion: _ Recyclable j>( Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge spent Material By-Product
( circle one)
938
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: A3 VxAxvwwy 6sKVOvJ NV.eAgQi<>
Waste Stream:
w»«t» njuM-ratian Rate
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
/aste Stream:
Waste Generation Rale: 2. / -4 B j }| K
B. Waste generation is closest toijRaw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _______________________________________________________
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. 2s the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ___________________________________-______________________•
B. What was the basic purpose for generating this waste (e.g-, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ____________________________________________________________
C Why did this waste become hazardous (e,g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Cant TeU
Comment: ~
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell ~ , . -,,
Comment ; l\Vpl "
Off-site Waste Recyding/Recovery^Reuse: Yes/No^§nVIieU
Comment:
Conclusion: Recyclable V Non-Recyciable Partial^ Recyclable
4 Material Classification: . Sludge Spent Material By-Product
(circle one)
940
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and '.
Waste Scream: WUJ
Waste Generation Ralg2./I01(IT) pfo 11 \t n */!£> .'(tD
Waste Form: Liquid(A(jJton-Aq;)/Sluny/SoU«Js(Wet/Diy)
Hazani Characteristics (all): I C
Hazardous Constituents fmaior): fTl [JrnKU )
i. Process Flow Diagram &. Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest dp: Raw Material/Major Intermediates/Final Product
C Waste appeals to have: recoverable produce/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g* plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ^________—____________________^_______^_____^^
C. Why did this waste become hazardous (tf, physical contact during production, mrang with oilier waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing toe quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _^^^^__^________-__^_______^_______________^^
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~~
Conclusion: \/ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge fspent Material^ By-Product
(circle one) 941
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'odnstrial Sector and Process: uXfl£ 0/iU-rVw: _ [ _ .
asteStnaun: <^Pnt nmrn/fYUlrm n'rfelfti-P
Waste r^ntian Rate: K 'i flPTl m \ )
WjV
r-A.)
Waste Form: Uquid(Afl^lor-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (ail): I ,£6) R T
Hazardous Constituents (major) , ,._
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: '
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B, What was the basic purpose for generating this waste (e,g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ^_____________
C. Why did this waste become hazardous (e.g,, physical contact during production, mixing with other waste
streams, results torn impurity removal)?
Comment: -
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Redaction: Yes/No/Can't Tell
Comment: ____________________^__________________
C On-site Waste ReCTding/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Ho/Can't Tell
Comment:
Conclusion: Recyclable V Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
{circle one)
942
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector «ni Freeway t/(l
Waste StreuK
i»—. n-^^tton B«te f^Tfl
Waste Form- Liqaid(Sq J
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
? ft, .A/H/lo"
•' rotit CfJjlr>-rn fAKf.^ AET.
Gii•Hmi
Wane F«t*K Uquid
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: tCTkAJ
Waste Generation Rate: ~>r?7F)
Waste Form: yquid(A
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: MJAii Ofi
'aste Strew* _ ..SQPJTlt StA LA
Waste Generation Rate l.glbfaDcfl-g£) (TS^ rrrrUi
Waste Fonn: ' Uquid(AqJNon.Aq.)/Sluriy/SQUds(WK/Dty)
Hazard Characteristics (an): __I , ("c) _ R,
Hazardous Constitnents (major):_
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A, Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ _ , _ _>____________________________
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: » — — _^— ___________
B. What was the basic purpose for generating the waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ...........................
C. Why did this waste become hazardous (e.g., physical contact during production, meting with other waste
streams, results from impurity removal)?
Comment: '. .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _________^_^^_^^_____^^_^__^______^__^__^_____^^____^^_____^____
B. Water Use Reduction: Yes/NcVCan't TeO
Comment ..................
C On-sitc Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~~_
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _ _ __ _
Conclusion: Recyclable Non-Recyclable V Partially Recyclable
4. Material Classification: Sludge ^Spent Material^) By-Product
(circle one] ^^ __--—^
(circle one)
946
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Waste Stream: _ S)h P n| f^ fl (fiy f A Aid
filtration Rate: l^J / ^QJ, rfi^ rp4-li JUJftyi
Waste Forai: Liquid(Ag'^Non-Aq,)/Slfey/Solids(Wet/Diy)
Hazard Characteristics (all):
Hazardous Constituents (major):.
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: SO\\)enrr fTHflfJIfSh _
B. Waste generation is closest to: Raw Material/Major Iniennediates/Fmai Product
C. Waste appears to Daw: recoverable products/removable contaminants/neither
D. Comment: _ , _
2. Reasons for Waste Generation: Based on toe description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A, Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ........................
B. What was the basic purpose for generating this waste (e,g*, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _____-__________________________________^ _____________
C Why did this waste become hazardous (e,&, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Commenc ................................
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: . . •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeD . , ,
Comment: _ - -- WWfDg W) in f\ , _
—
y
Conclusion: _ Recyclable _ Non-Recyclable y Partially Recyclable
4. Material Classification: Sludge ( Spent Material ^) By-Product
(circle one) ^_ _____ __ ^/ 947
-------
WORK SHEET FOR WASH: STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector and Process: IcQ/lQ PAATrVft _ . _
raste Stream;
_
Rate: "K^ f 1 rfibQSfr ulp-ft^ ...... __/ ,
Waste Form: • LiquM(Aq^Non-Af.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): (2l«*, R *&a*R / T
Hazardous Constituents < major): *//GOD I \ lID / 2TC&
.—
Hazardous Constituents (major):
1. Process How Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: M%TLt-"> -C X nQ IJlQh
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A, Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ~~. .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
, Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ....'..
C. On-site Waste Recyding/Recovety/'Reuse: Yes/No/Cant Tell •
Comment: (Df)'^'
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: \/_ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge / Spent Material ] By-Product
-------
WOEK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: *l(U£ 9/l/vtiVy
Waste Stream: \N(\T)dS UHthM -fir/mr fUJU>fiV -V\)PT
Waste c^raHoo Rate: ' _ . S flD / ~QO<3£> / / TH
LJquM(AqJNon-A4:)/S»uny/SoIids(WAPry)
Waste Form: LJquM(Aq
Hazard Characteristics (all): I
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A PC
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: KIQ 11 T\ ft ' "
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, miring with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment _________________^_^__________________________________________
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _______^—^^^^—-^—^^^^^^^^—_————-—-^^^^^^^^^^---..^^^.
C, On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell , i
Comment: ~ TOfiTHL
O
Conclusion: Recyclable Non-Recyclable V Partially Recyclable
4. Material Classification: . Sludge / Spent Material J By-Product
(circle one) ^ __^-~^ 949
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
I sector and Process:
,V»ste Stream: __ Vsi Afffe7iTK f /^YtfllTll JTi^d \ fTRVx mJMf HA]]
Waste Form: Uquid(Aq^on-Aq;>Sluny/sdli
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Wast* Sira*:
v~uL?'b-?v L
Waste Forw Laqiud(AqVNon-Aq.)/Sluny/Solids(WeoDry)
Characteristics (ail): — I C R T
Coastttaeatt f»dor): _ .
1. Process Flow Diaera^ A Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major laterBediates/Fmal Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _____________________________________^__
2. Reasons for Waste Generation: Based on the description of the process, and waste generation aad its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: r.
B. What was the basic purpose to generating this waste (tg, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _^^_^^___-_____.^_____—________________^_______
C Why did this waste become hazardous (e.g* physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering {he foUowing waste management alternatives.
A Waste Segregation: Yes/No/Cant Tell
Comment: .
B. Water U*e Reduction: Yes/No/Cant Tell
Comment: ^^___-__^_______________—__«»«_________________.__
C On-site Waste Recyctmg/Recovery/Reuse: Yes/No/Can't Tefl
Comment •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeO
Comment:
Conclusion: V RecvdaMe Noa-RecydiUe Partially Recyclable
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: R\XPV\\VIWN Q&C-ox/g-V oV" 'RW.vxww. -(-ygv^N (viD\v^OC^V^'i'e £-$•
'.te Stream: "
,,aste Generation Rate: SS i O P o vy^A V v
Waste Form: LiquidfAq./Non-Aq.)/Slurry/Solids(Wet/DTy)
Hazard Characteristics (aU): I C_ R _T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate farm for
each major source,
A Source: So\\^-Y)€C^ \ gvv -e
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: \5v\--e grg'Wgv^x^i?' -rpwif/v'g 5 ^S"0//. or- S^Vv-e v\> •>_; w^
-j
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B, What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? ~~
Comment: _
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A Waste Segregation: Yes/No/Can*t Tell
Comment: -_______^_^_________________^______^^^_____________________^
B. Water Use Reduction: Yes/Np/Can't TeD
Comment:
C On-site Waste Recyclia|/Recovery/Rense: Yes/Np/Can't Tell
Comment: _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Np/Can't Tell
Comment: _ ___
Conclusion: _ Recyclable X Non-Recyclable _ Partially Recyclable
4- Material Qassification: Sludge Spent Material By-Product
-------
WORK SHEET FOB WASTE STREAM ASSESSMENT FOE RXCYCUNG, RECOVERY, AND REUSE POTENTIAL
Ac^J
Seta*
Watte Sinare ftew- fgw
WuteFo
CbvMttristfcf (ID):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A Source: Ad
B, Waste generation is closest to: Raw Material/Major Intennediaua/FiaaJ Product
C Waste appeals to have: recoverable produas/removabte contaminants/neither
D. Comment:
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, mate the following assessment
A. L. the same waste generated at every facility usinj toe process?: Yes/No/Can't Tefl
Comment- ____ _ _ ^_^ ^___^___^_^__
B. What was the bask purpose for gcaeiariaf tna wane (e,g^ plant maintenance, cncmical reactioa, physical
separation, water riasug. otoer puntkukn steps)? _
Commeac -
C Why did this waste become hazardous (e.g-, physical contact during production^ minni with other waste
streams, results from imparity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for redacmf the quantities of waste generated at
any of its sources by considermg the foHowiaf waste managetneat altemadves.
A. Waste Sepegattoa: YewfteCaatTeO
Co
B. Water l^a Redncttom: YeaVNo/CaBt Tell
Commeoc
On-iite Waste RecydiatyRecovery/Rewe: Yo/No/Cant Tefl
Comment: •
D. Off-site Waste Recyciiag/Recovery/ReBse: Yes/No/Cant Tefl
Comment ..........................
Conclusion: _ Recyclable Non-Recydable V Partially Recyclable
_^^ 953
4, Material Classification: stud**
-------
WORK SHEET FOR WASH STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
W
Waste Fora: yq»kl(AqJNon-Aq.)/SIi»rry/SoIJds(WewDiy)
Haard Chancttftotlci (all): .- I C R T
Hazardous Coastftacitti <««j*r): _
Process Flow DiagramA ..Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: •
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appeals to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of toe process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Cin't Tell
Comment: _ ........................ ..................... _
B. What was tbe bask purpose fur generating this waste (e.g* plant maintenance, chemical reaction, physical
separation, water rinsing, otter purification steps)?
Comment: _______ ,.^______—. — _________________________________
C Why did this waste become hazardous (e.g* physical contact during production, mating with other waste
streams, results from impurity removal)?
Comment: ' .
3, Waste Management Alternatives: Revie«r the potential for reducing -the quantities of waste generated at
any of its sources by considering tbe following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
Comment: :
B. Water Ute Reduction: Yes/No/Cant Tell
CoinnicoJ*
C On-site Waste Recvctmg/Recovery/Reuse: Yes/No/Can't TeU
Comment: •
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't TeU
Comment: _ _
Conclusion: Y. Recyclable Non-Recyclable Partially Recyclable
4 Matfelial Classification: ( Sludge ) Spent Material By-Prodnct
oitel
-------
WORK SHEET FOR WASH STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
- .A-f-./J
industrial Swtor
Wastt Straw Sf f vAT A
Waste Fora
H«iMtl Cbarmcttrtrtto (mH):
Hazardous Coostttncati
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of UK same waste generated is the process. Complete a separate form for
each major source.
A. Source: ; .
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _____^__^_____^___________^^_________^__
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is toe same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose fat generating this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: • .
C Why did this waste become hazardous (e.£, physical contact daring production, mixing with other waste
streams, results from impurity removal)?
Comment ii:
3. Waste Management Alternatives: Review toe potential for reducing the quantities of waste generated at
any of its sources by considering tae following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tell
Comment
B. Water Uie Redaction: Yes/No/Cant Tell
Comment: ^»-_«____™_____«__»__^___.____.____—__.^____i,^—————————
C On-sfte Waste Recydmg/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recycting/Recovery/Reuse: Yes/No/Can't TeD
Comment: • __^___^_
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOE RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial -Sector and Process: Sr cwsfK LJW-% .. Sccwv^i;\i\v\ -^\rgws '^ovVxjf \-V\ Vg £?• \
iste Stream: "Pe^gA fit O. A S _ : _ _ _
:
aste Generation Rate: *7 O O *3. £>, "~7f)C>O
_
Waste Fonn: Uquid( Aq^NgihAt.)/Sluny.SoIids( Wet/Diy)
Hazard Characteristics (all): I C_ R T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By loolcing at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. ' Source: \}exv\o\j) S \— e^.cV"V'iS- CXv% a
_
B. Waste generation is closest to: Raw MateriafrKiajor Intemediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: <5V-pyv\V .AoU-o r^vg' •wgrr"
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was the basic purpose for generating this waste (e.f., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e,g,, phpical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3, Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/Np/Can't Tell
Comment:
B. Water Use Reduction: Yes/Np/Can't Tell
Comment ......................
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Njp/Can't Tell
Comment: __^ _
•Conclusion: _ Recyclable V Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: $>C/3L-v\'l''g-
Waste Stream:
Waste Generation Rate: 1 OO •, 3^g<9 / ~7£>g £>
Waste Form: IJguid(Ag./Non-Aq.)/Sluny/SoUds(Wet,€)ry)
Hazard Characteristics (aB): _|_ c R T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: S. o\ v -fWV5 £c?\)\ 3 k>€.
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ~
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ______
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment;
C, On-site Waste RecydiBg/Recovery/Rense: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Y. Recyclable Non-Recyclable Partially Recyclable
4. MaterialClassification: Sludge /Spent Material) By-Prod»_t
(circle one) V ^^-^ 957
-------
\
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
qdustrial Sector and Process: _
Waste Stream: .__, ^,1 _^^
Waste Generation Rate: '*-r- / PxDC) rriT I \&BLA / :-i^u,J
Waste Form: Ljquid(Aq^Non-Aq.)^uny/Solids(Wet/l::}ry)
Hazard Characteristics (all): I ( C R (Y)
Hazardous Constituents (major):_
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: _ 4 \ Hg/l'jjyvS _
B, Waste generation is closest 10: Raw MaieriaiyMajor Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _______________________^___ _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: YesTNo/Can't Tell
Comment: .............. _ .
B. What was the basic purpose for generating this waste (e.f, plant maintenance, chemical reaction, phvsica'
separation, water rinsing, other purification steps)? ~~~"
Comment: _______________________^^
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from imparity removal)?
; Comment: . _
3. Waste Management Alternatives! Review the potential for reducing the quantities of waste generated at
any of its sources by considering toe following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ............................
B. Water Use Redaction: Ycs/No/Can't Tell
Comment: _ _
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell v
Comment:
Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _ ' ' .-^4-hOA PfgfVlM l
ConciuslOP:\/ Recyclable Non-Recyclable Partially Recyclable
4- Material Oasslficarion: Sludge Spent Material
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: -=%Ll&h IU/U
Waste Stream: "plnuP.4- pOCO/T) Ny^fljqtfilXBtitBA
Waste Generation Rate: foU;/££} m4llipQyi
Waste Form: Uquid(Aq4/Non-Aq.)^lurry/Solids( Wet/Dry)
Hazard Characteristics (all): I . (C) R (T;
Hazardous Constituents (major; __
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Commentr
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g-, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ________^^^______^_^________^____________^_^^_____
C Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Caa't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Comment? ^ ; •
C. On-site Waste Recycling/Recovery/Reuse; Yes/No/Can't Tell
Comment: '
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable \,/ Partially Recyclable
4. Material Classification: Sludge /Spent Material ) By-Product 959
(circle one) ^—- ^^
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
: Sector «nd Process:
Stream:
Waste G«Kfa«oa Rate So 7 QC^cDD Frff lUp CIA / bOCO
Waste Form: Liquid(AqwNon-AqV)/Siurry/SoMds^Wet/Dry)
Hazard Characteristics («U): I q R
Hazardous Coostttneats (major): M-wfl l\i LA
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each malar source.
Source:
^
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ '"'
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: """" .
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physica:
separation, water rinsing, other purification steps)?
Comment: _______________^_______________________^^
C Why did this waste become hazardous (e,g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Ycs/No/Can't Tell
Comment: '.
B. Water Use Reduction: Yes/No/Cau't Tell
Comment: •
C On-site Waste Recydmg/Recovery/Reuse; Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyciing/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~ _____^_____
Conclusion: Recyclable Non-Recyclable V Partially Recyclable
4. Material Classification: , Sludge Spent Material
-------
WORK SHEET FOE WASTE STJIEAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Proas* JXLiQ/") ilUA
Waste Strewn: "^ftJ I l)Y ULU Dl IffiG
Waste Generation Rale ""/
Wast* Form: Liquid(AqJ*on-Aij5/SIurry/Solids(Wet/Dry)
Hazard Characteristks (all): I C , R
Hazardous Constituents (major): Sg\0 f}\V)irV\
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in tbe process. Complete a separate form for
each major source,
UlUlt /\Pl£
A, Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appeals TO Have: recoverable produos/removable contaminants/neither"
D. Comment: __________^____________________^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _ - '
B. What was the basic purpose for generating this waste (e.g, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment _ _
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
.' Comment: .
3. Waste Management Alternatives: Review the. potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives,
A. Waste Segregation: Yes/No/Cant Tell
Comment: .
B. Water Use Reduction: Yes/No/Cant Tell
Comment? _ .
C. Cm-site Waste Recyding/Recovery/Re^e: Yes/Np/Can't Tell
Comment: _________^ _
D. Off-site Waste Resyetog/RecovejyJ£suse: Yes/No/Can't Tell
Comment: _^ _ „ _ _______ _
Conclusion: Recyclable Non-Recyclable V_ Partially Recyclable
4. Material Classification: . Sludge Spent Material \ o7-riuw»** • g51
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
MiustriaJ Sector and Process:
Wast* Gencamttoo RattK S^/<=.QQ rr;\ llALftA /D
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: ^^doLt/vy
tYaste Stream: rg&Lss uJb.s-fe_ab-tiLr
Waste Generation Rate: \^°, CC& «A/' Z3*> °, Q
Waste Form: ^J^u^^/Non-Aq,)/Sluny/Solids(Wet/Dty) ;_/o%
Hazard Characteristics (all): I (CT" R T>
Hazardous Constituents (major): Ms
7
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: Sao^ ~^a #*> -tz> cxjuuT". . 6-^ta, ux- o>^no'f' cnPtt'i
j>VS«. \
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ........................
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _....
B, Water Use Reduction: Yes/No/Can't Tell
Comment: _
C. On-site Waste Recycliag/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: X Recyclable _ Non-Recyclable _ Partially Recyclable
4, Material Qassification: Sludge Spent Material "^j By-Product 963
(circle one) "~ ,x
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'-•dustrial Sector and Process:
ste Stream: _ DiA*.s"
Waste Generation Rate:
Waste Form: Ljgujd(Aq.yNon-Aq.)/SluiTy/Sfiyjag(W£t/Diy)
Hazard Characteristics (all): I /tp R T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: -Ws^e.-
B. Waste generation is closest to: Raw -Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: <~ecvo^c u-'i fae- ricynK'.r*.? tot^on-nnc. &'7~ rt-'gt i
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
* rf*^ -— «— — — ..................... .»
Comment: _ ; _ _________
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: t/\*£~tc,i<-ic.\r rf J^atioA g/^ver resT£jr,\ ^f^ i r
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)? ' ~" ~ ~
Comment: ^J fir
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering die following waste management alternatives.
A, Waste Segregation: Yes/No/Can't Tell
Comment: ______________________________________^
B. Water Use Reduction: Yes/No/Can't Tell
. Comment: _______________,.______>ii_______^
C. On-site Waste RecycUBg/Recowry/Rease: Yes/No/Can't Tell
Comment - _
D. Off-site Waste Recycling/Recovery^Reuse: Yes/No/Can't Tell
Comment:
Conclusion: _ Recyclable "^ Non-Recyclable _ Partially Recyclable
4. Ma||rial Classification: Sludge Spent Material
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'idustrial Sector and Process: ~u.rAJu^ Cai^A^i <- ^rrocol^g.Aj-M
/aste Stream: fSooAl' K«^t"irto-fe _-g.-,lud?s
Waste Generation Rate: CkZC/p^ /u ^ .
Waste Form: Liquid(Aq^Non-Aq.)/Slurry/SojMs(Wet/Dry) Co-
Hazard Characteristics (all): I ($ R T
Hazardous Constituents (major): ;
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A. Source: Kam^ /;at.rJ ^vtrcAA _
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: _ _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make tbe following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can^t Jell
Comment: _ _________^__________________^___^^
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purificaiipn steps)?
Comment:
C. Why did this waste become hazardous (e.g., ph^sjra^OTnacT^uring^roduaiori, mixing with other waste
streams, results from impurity removal)?
Comment: w ;-tH fftcie)- er _
3, Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: ____.,_^^___^^_________^________^^
B. Water Use Reduction: Yes/No/Can't Tell
Comment _____^ _
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeU
Comment: • _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: _ Recyclable "X Non-Recyclable _ Partially Recyclable
4, Material Oassification: Sludge Spent Material f By-Product ) 955
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
"7g )i W' i> w^ , /Jxf"/r7^ 71? AA t^r 7e )jUv~cUS.
Wane Fora: Uquid(Aq^on-Aq.ySlnrry/Solids(Wet/Dry)
Haard Ch*r*cttristk» («U): -- I C R 7
Huantoos Coosttoena fartor):
1. Process Flow Diagram &. Waste Characterization: By looking at both documents, tiy to answer the
following questions for each major source of the same waste generated in the process. Complete a. sepanat form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/FrnaJ Product
C Waste appeals to have: recoverable products/removable contaminants/neither
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _
B. What was die basic purpose for feaentmf this waste (e.&, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g* physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: ^g_^_______,_._____^___^_____-_-__^__^^_—_________,^_____^__
3. Waste Management Alternatives; Review the potential for reducing the quantities of waste generated at
any of its sources by considering die following waste management alternatives.
A. Waste Segregation: YesJNo/Cant TeD
\_/Ofll3tmB8c
B. Water U» Reduction: YeVNo/Can't Tell
CnBimettti
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can*t Ten
Comment: • ; •
D. Off-site Waste Recycting/Recovery/Reuse: Yes/No/Can't Tell
Comment: . •
Conclusion: Y- Recyclable __ Non-Recydable Partially Recyclable
Maftlftal Qasstfication: Sludge ( Spent Material
fczncfc aiift ^
-------
WORK SHEET FOB WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: ~Te,N\u \T\O\%A . P-^-f -<\\C-&~\-\ Sv^_ o-C- ~\p\\\j^'0v\ Ac.\".
Waste Stream: O a s¥j- 'E-N g,£.-Vv o ^
Waste Generation Rate: \OO \co.P... }DQQ
o
Waste Form: IJc{uid(Aq./Ngn-Aq.)/SluiTy/SoMds(Wet/Dry)
Hazard Characteristics (mil): — 1C R J_
Hazardous Constituents (major): *?b , S-€_
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A. Source: E > •& & -Vvo \ V S\^
B, Waste generation is closest to: Raw Material/Major Intermediates /Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _ _______
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? " "
Comment: _________________________________________^
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: _________________ _
B. Water Use Reduction: Yes/No/Can't Tell
Comment: __________________________________^
C. On-site Waste Recyding/Rectivery/(Re«se: Yes/No/Can't Tell
Comment: _ • _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/CanVTell
Comment: _ ~~~^
Conclusion: _ Recyclable ]/ Non-Recyclable _ Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product gg7
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
'adustruJ Sector and Process: "TeA\U VXUv^-x Reogv-e.v -Vv^jJVs^ Qrv?ev^ 5nvr>e.S
aste Stream: SrAifJ ^iJo. i Ve-
Waste Generation Rale: /co, /g g Z. <-/ S~p D
Waste Form: xIJquiil(Aq.?Non-Aq.)/SIuny/^olids(Wei/Diy)
Hazard Chararteristics (all): I C R_ T_
Hazardous Constituents (major): S €L
Process Flow Diagram _.& Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A. Source: VY e C i m~fev"il gvx
i
is'
B. Waste generation is' closest to: Raw Material/Major Intermediates/Final Produc
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: f/Jgt
3 ;
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: _^_____________._________
B. What was the bask purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: .........................
C Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: . _
Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/Np/Can't Tell
Comment: __________________ _______________________^_^^_____^________
B, Water Use Reduction: Yes/Np/Can't Tell
Comment: _ ~^ _
C On-site Waste Recyciing/Recovery/Reuse: Yes/No/Can't Tell
Comment: • . • _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Np/Can't Tell
Comment:
Conclusion: _ ^Recyclable Non-Recyciable _ Partially Recyclable
4, Material Classification: Sludge Spent Material By-Product
(c®3Bone)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT TOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: fe\\ov.\u>w-^ . Tvg^iO^-e^w -tv-gyvs. /^/osD-py" A_n v^^ € J
Waste Stream: S^'cy- , J *
Waste Generation Rate: U\CQ i ggo, '-t^QD ~ ;
Waste Form: Liquid(Aq./Non-Aq.)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
•te Stream: t^Jg^'hs fe/yv'c. OK- Cg-tr/
.ite Generation Rate:
Waste Form:
Hazard Characteristics (all):
Hazardous Constituents (major):
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: Tf ?**<•*-
'aste Stream: _ fukle i-»<
/Vaste Generation Rate: _ J^°° ~~ ~^>~'~&o ....-^
Waste Form: ^pqui^^i/Non-Aq.)/Sluny/SoUds(Wet/Dry)
Hazard Characteristics (all): I C R (T) .
Hazardous Constituents (major): _ C^ ; Cr> Kb _ fir5<< t U,
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of tne same waste generated in the process. Complete a separate form for
each major source.
A. Source: tffe^/a&y llfr $p&^^ACii^<^ h?7at-rifm<: (e.g., physical contact during production, mixing with other waste
streams,(results from impurity removal);?
Comment: ~~~ • ^ _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
^—~ -^
A. Waste Segregation: Yes/NOjfcan't TelT)
Comment: ^ -- — — _
B. Water Use Reduction: YeNo/Can't Tell
Commeat:
C. On-site Waste^Recyi^g/Recovery^eusetj^eyNo/Can't Tell
Comment:
D. Off-site Waste Re^clmg/Recovery/ReiKel^es^o/Can't Tell o
Comment:
Conclusion: Recyclable Noi-Recydable yf Partially Recyclable
4. Material Qassification: Sludge (Spent Material J By-Product
(circle one)
971
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
~te Stream:
f /?**_•'
,te Generation Rate: tcoe - (g^t ^y^__
\. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source. rttokv **
A. Source: *
A. Source: flc/tyr ^c^^lf^f^u^tJi Jfr jfrvw ^fe$r de^«aJ5y vO ' ' ^s the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction/physical
Separation, water rinsing, other purification steps)? < r -
omment: '><~*~-'>*>^
a
C. Why did tftyiwuw hprnme ^ayardnmi (e.g.T physical contact during production, mixing with other waste
streams.^esuhs^ from impurity renteyal)?
Comment:^ "~" —~ ~~ _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yesmo/Can't Tell
Comment:
B. Water Use Reduction: Yes/Nd/Can't Tell
Comment-
don: Yes/No/Can't
iHg/Recovery^Reusa:
C. On-site Waste Rfecycaiag/Recoverylleusa: nfes/No/Can't Tell
Comment:
D. Off-site Waste Recyeling/Recovery/Rease: Yes/No/^n't TOJ/
Comment: ^—-^
l/Pai
Conclusion: Recyclable Non-Recyclable y Partially Recyclable
4- Material Classification: Sludge /£spem N^teml By-Produa
(arete one) ^—-^^"^
972
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: //&*•'•
Vaste Stream: _ ft>'«£
-Vaste Generation Rate: j_______- 3fe).c£o — g>fe,gc*? MJ~/% /&_
Waste Form: (pquid(A^Non-^.)/Slurry/Soiids(Wet/Dry) '
Hazard Characteristics (all): I (c) R Q) _ , ^
Hazardous Constituents (major): _ C — HJfs"lirom impurity^
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/<&i*t TeO,
Comment: ^—-^
B. Water Use Reduction: Yes/No/|C"an't TeU>
Comment:
C, On-site Waste cliag/RecoveryisyYNo/Can't Tell
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/pm't
Comment
Conclusion: Recyclable Non-Recyclable \_/PartiaIIy Recyclable
4, Material Qassification: Sludge «-"fspent Materalj %-Product
(circle one)
973
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: _
" ~ -te Stream:
,t£ Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Sluny^S85dsi[Wet^i5;p
Hazard Characteristics (all): I C ^R)^—^f
Hazardous Constituents (major):
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
sack major source. f fru»^ €!«j?v*VJs'"5'
A. Source: tf&^-y&Q ^ rec^e^]^^!.- ^Cy $/&r* Mfl^l ft,U4'g>. MS^
B. Waste generation is closest to: Rawjrfaier'ial^jtjajor iinfenne^iiite^Finai Product
C. Waste appears to h*vef?Secoverable produclstemovable contaminants/neither
D, Comment:- " ~~^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?:£Y^s/No/Can't Tell
Comment:
-T?=- -v-"-"=> X
B. wjgrwas the basic purpose for generating this waste (e.g., plant maintenance/chemical reaction, physical^,-
j-^ggpition, water rinsing, other purification steps)? ^ >i——-—
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams(?esuits rrorn impurity removal)?
ConunentT -_•
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/fcjj»Can"t Tell
Comment:
B. Water Use Reduction: Yes/N_p/Can't Tell
Comment:
C, On-site Wast/R^cMg/Reajveiy/Reuse:x^»Wo/Caii't Tell
Comment: ^^^^ CoJvtayJ't-l t-gt^oLg-Ji *fz>
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
: j/ R
Conclusion: AX Recyclable Non-Recyclable Partially Recyclable
4- Material Qassification: Sludge Spent Material
(circle one)
974
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: f/'ftA •'«
¥aste Stream:
Waste Generation Rate: _ Ig^oco — S"g&>Q9q
Waste Form: CT^id{^./Non-Aq.),Sluny
Hazard Characteristics (all): I (^cT) R \j p
Hazardous Constituents (major): _ v <", ' b
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: <^-^ £^4 ~fl 77' vfifrt-igg. qfid r?*« V? f-e^
B. Waste generation is closest to: Raw Material/Ma'jor Intermediates^pal PfodujE
C. Waste appears to have: cficSverafale products/removable contaminanQ/neither
D. Comment: ~ ..... — — ----- • ^
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A Is the same waste generated at every facility using the process?: nfes/No/Can't Tell
Comment: _ " " _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation^water rinsing, other purification stepsg
Comment: _ \ _ ] _ _
_ '"_ ' ............................
C, Why did this^waste become hazardous (e.g., physical contact during production, mixing with other waste
streams^results from impurity removil)?^
CommentT ^ _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
jiT -- ^
A. Waste Segregation: Yes/No/£an't Telly
Comment:
B. Water Use Reduction: tt^/No/Can't Tell
Comment:
C. On-site Waste Recycling/RfecovervjReuse:l/No/Can't Tell
Comment:' V- — ^
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell fs
Comment:
Conclusion: Recyclable Non-Recydable y/PartiaUy Recyclable
4. Material Qassification: Sludge /%entMaterialx By-Product
(circle one)
975
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
~7~/f*A-
Industrial Sector and Process:
^e Stream:
>tc G«neration Rate:
Waste Form:
Hazard Characteristics (all): - „ ,
Hazardous Constituents (major): C i~, f £>
!. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw NJaterial/Maior Intenritediatesi^SajTroS
C. Waste appears to have: recoverable productsrfemovable contatninani^neither
D. Comment: _ _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
/"/'"\
A. Is the same waste generated at every facility using the process?: ¥es|No/Can'i Tell
Comment: _
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
• Comment:
C. Why didthis waste become hazardous (e,g., physical contact during production, mixing with other
Jstrsas»sr?esu]ts from impurity removal)? ' "~
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A Waste Segregation: ^eVNo/Can't Tell
Comment: ' —
B. Water Use Reduction: Yes/No/|
Comment:
'pn't TelTx
C. On-site Waste Recycling/Recovery/Reuse: nTesVNo/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: ^Recyctable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge (Spent Material ) By-Product
(circle one)
976
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: ~7~/t*A' '
Stream: _ £/3&*~T £<** •(Lj'.e J*~-fis*j .-.
.Vaste Generation Rate: _ 5"/, o^c-
Waste Fonn:
Hazard Characteristics (all): I C R /T ,
- - • • ^ Cr,
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest tfc Raw
C. Waste appears to have: recoverable products/removable contaminarits&ieither
D, Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?j^Yes/No/Can't Tell
Comment: *— :
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? , _
Comment: C*l'*/^<=~
hiS^ (ffer JT>
C. Why did this waste become hazardous (e.g., physical contact during production/mixing with other waste
sffelml^resuJts from impurity removal)? ^-=— -- — -
"CSinment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation:4Yey/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/pan't TeJ]
Comment:
C On-site Waste Eecyclingfllecovery/Reuse:
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes$gpf!an't Tel
Comment:
Conclusion: Recyclable _t_/Non-RecvcJable Partially Recyclable
4. Material Classification: f Sludge^ Spent Material By-Product
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: f/f*A •'«
' ' ste Stream: _ bJs
stz Generation Rate: ^ ^_
Waste Form: ^iqnid(Aq./Non-A^/8Iurry/SoUd5£Wet/Dry)
Hazard Characteristics (all): ^— —I-^ (C/ R (^)
Hazardous Constituents (major): (_ y~ _ T b ,
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: =_^_
B. Waste generation is closest toi^Raw MatemJTMgjo'r Intermediate/Final Produ6t
C. Waste appears to have: recoverable productsa^movaBie contamiiifig/neither
D. Comment: ; ^"" "•"'
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
-« Schl,*. £
J '' (
A. Is the same waste generated at every facility using the process?: (Te^/No/Can't Tell
Comment:
B. Wjjaj-waSj the basic purpose for generating this waste (e.g., plant maintenance^aiemical
j, water rinsing, other purification steps)? •
em:
C. Why did this waste become hazantous (e.g., physical contact during production, mixing with other waste
streams, ^trtlTrroin impurity i
CotmnentT ~ '
3. Waste Management Alternatives: Review the potential for reducing tne quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Ye^o/Can't Tell
Comment: ^—y
B. Water Use Redaction: Yes^ojcan't Tell
Comment: __________________
C. On-site Waste Recycling/Recovery/Reuse:
Comment: _____________________
D. Off-site Waste Recycling/Recovery/Reuse: Yes/Nrf^aln't'
Comment:
Conclusion: Recyclable Non-Recyclable "? Partially Recyclable
•*• Material Classification: Sludge /"spenTMatejSrl By-Product
(circle one)
978
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
Vaste Stream:
*Vaste Generation Rate: _ jo? -- ?-?-,ooo t
_ ^
Waste Form: ^Gquid(^/7*loTi-Ag.)/Sluny/SoIids(Wet/Dty)
Hazard Characteristics (aU): I (£) R
Hazardous Constituents (major): _ _
, C-r -, ->£, ' -
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: "V- '^U'gy, t^ 4iTgU'v<»-J
B. Waste generation is closest to: Raw Material^a}6r Jntem^tate^Final Product
C. Waste appears to have: recoverable productsgrpEovable contanilnamSjpeitrter
D. Comment:
Reasons for Waste Generation-. Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
jf—s
A. Is the same waste generated at every facility using the process?:/Yes^o/Can't Tell
Comment: . ^—~-^
B. What was the basic purpose forjenerating this waste (e.g., plant maintenance, chemical reaction, physical
? -
hat was the basic purpose forjenerating this was
separation, water rinsing, otierpurificai5rri|Bps)?
^ --------
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams^iSaRs from impurity removaT|§
Comment: ...................... _
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
r^
A. Waste Segregation: Yes^of Can't Tell
Comment: _ ^_ _
B. Water Use Reduction: Yes/IWCan't TeE
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/!M/Can't Tell
Comment: _ _ _
D. Off-site Waste Recycling/Recovery/Reuse: YesMj/Can't Tell
Comment;: _ . ......... _
Conclusion: _ Recyclable _/_ Non-Recyclable _ Partially Recyclable
4. Material Classification: . Sludge Tipent Material) By-Product
(circle one) V____~ -~^" 979
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
ste Stream:
Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/?!oIi£
Hazard Characteristics (all): I C R
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
A. Source: * u--- JA^ ~_ ...
I
^ _
B. Waste generation is closest to: Raw Material/Major Intermediateg^nal ProSu
C. Waste appears to have: recoverable productsffgrnovltble contammanwneitner
D. Comment: _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?:('YeVNo/Can't Tell
Comment: _ y
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ' _
C. Why did thiswa^KLhfiCDjneJiazardous (e.g., physical contact during production, mixing with other waste
strearas,
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: 7/£x» •'*
'aste Stream: ___
*Vaste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq,)/Sluny/Soiids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major): _
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try 10 answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C, Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g,, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion; Recyclable Non-Recyclable Partially Recyclable
4. Material Classification. Sludge Spent Material By-Product
(circle one) ggl
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: _
T" te Stream:
Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Siurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major):
1, Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B, What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification step)?
Comment:
C. Why did this waste become hazardous (e>g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't TeU
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
(circle one)
982
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
'aste Stream:
Waste Generation Rate: _ _ _ ;
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major): _
Process Flow Diagram &L Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives,
A. Waste Segreption: Yes/No/Can't Ten
Comment: ________________..^_____________^^^_______.__^________
B. Water Use Reduction: Yes/No/Caa't Tell
Comment:
C. On-site Waste RecycUng/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
(circle one) 983
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
' -dustnal Sector and Process: _
.Vast* Stream:
Af AH nnd Y /C
StP
Rate **: i .C I / I ,/^D rni 1 U-f ft
1 m^^^™,^wy*^^^^^^^— ^^^^— j Jy
Waste Form: ' Liquid(AqjNoa-Aq.)/Smny/Solids( Wet/Dry)
Hazard Characteristics (all): I (6) fc T
Hazardous Constituents (major): „ .^__^____________
1. Process Flow Diagram &. Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in tbe process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw MaieriaLMajor Intermediates/Final Product
C. Waste appears to nave: recoverable products/removable contaminants/neither
D. Comment: . '
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using tbe process?: Yes/No/Can't Tell
Comment: • ,
B. What was the basic purpose for generating the waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ____..^__________________________^__^__^
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Caat Tell
Comment: . .
B. Water Use Reduction: Ycs/No/Can't Tell
C-OTiiincnf *
C On-site Waste Recycling/Recovery/Reuse: JYes/No/Can't Tell
Comment
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~ „ ^___
Conclusion: Recyclable Non-Recyclable V Partially Recyclable
4. Material Classification: . Sludge (Spent Material ^> By-Product
(cffar one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTUL
Industrial Sector and Process:
Waste Stream: TflQCl^
Waste Generation Rate: 13C£ "gTf Or)
Waste Form: Uquid(Aq./Non-Aq.)/Sliitty/Solids"(Wet£)ry}
Hazard Characteristics (all): I f~C\ R T
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of toe same waste generated in the process. Complete a separate form for
each major source.
A. Source: -^mAlO G\fMC ?£*! Ll (Jl
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to bave: recoverable products/removable contaminants/neither
D. Comment: .............................................
2. Reasons for Waste Generation: Based on tie description of the process, and waste generation and its
management practices given for a sector, make me following assessment
A Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
.' Comment: _ , _
Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/CanVTdl
Comment: _
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ' _ __ ________ .........
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ' — • _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: __ _ _ ______
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge ( Spent Material) By-Product
(circle one) ^—-—
-------
WORK staar worn WASTE STREAM ASSESSMENT pom RECYCLING, RECOVERY, AND REUSE POTENTU'
' Sector Mi PnwHB \J 'fa^vx \ \J vv\ •> m? g^c-f? jv\ QJ-
Ctarr»ff""
Wan* Form- Laiiafl/uf7
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable conuaunanis/neuber
D. Comnwiit: '
2. Reasons for Waste Generation: Based on tn« description of the process, and waste generation and its
management practices given for a sector, make tne following assessment
A. Is tne same waste generated at every fatiliry using the process?: YeVNo/Can't Tell
B. What was die bask purpose for geaeratiaf this waste (e.g^ plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? _ ~"
Comment: .....................
C Why did this waste become hazardous (e^ physical contact daring production, mixing with other waste
streams, results from imparity removal)?
Comment: ___„ ______„ — .•• ___ ____^_^.^..^_— .___-___.^__-____________..____^_— ^^_
3. Waste Management Alternatives; Review the potential for reduonf the quantities of waste generated at
any of its sources by considenaf the foOowiaf wmste manageaeat alternatives.
A. Waste SegrefUiOB: Yo/Np/Cant Tefl
Commeac -_B-_,^_—__-_____________-________-____^^
B. Water UM Redwatot YesyNoCant Tell
XjOaflfflCQC
C On^ite Waste Recydini/Recovery/Reuse: Yes/No/Caat Tefl
Comment: • _
D. Off-site Waste Recyding/Recovery/Reme: Yes/No/Cant Tefl
Comment: _ __ __
Conclusion: Recyclable Non-Recydabte V Partially Recyclable
4 Material Classification: sludge ( Spent Material} By-Product
-------
WORK SHEET ron WASTE STREAM ASSESSMENT rot RECYCLING, RECOVERY, AND REUSE POTENTIAL
0^ v\nJW> A™& •> f/c? L g £ I
Wastt Focm- Liquid 0? / ^ $T
B. Waste generation is closest to: Raw Material/Major Lntenncdiates/Fuial Produa
C Waste appears to have; recoverable producgyreaovable contamtaaiits/iieitlief
D. Comment; -
t^
1 Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is tie same waste generated at every factory using toe process?: Yes/No/Can't TeU
B. What was the basic purpose for generatinf this waste (ef>, plant maintenance, cheaucai reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.f* Physical contact durum production, mixing with other waste
streams, results from impurity removal)? ~~~~~ ~~
Comment:
3- Waste Management AltCTnatTTf ' Review the potential for redocmf the quantities of waste generated at
any of its sources by considering the foOowing watte management alternatives.
A. Waste SegregatJoa: Yett4o/Can1 Tcfl
Conunett: ... '
B. WMCT Us* RednatoK Yes/N^Caat Tett
Comment: __
C On-site Waste Recyding/Recovery/Reuse: Yea/No/Can't Ten
Comment: • _
D. Off-site Waste R^cyding/Recovcry/Reose: Yes/No/Can't Tefl
Conclusion: _X Recydabie _ Non-Recydabte _ Partially Recyclable
/ i ' «— ~ «"i»
Material Classification: Sludge Spent Material {By-Product
987
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOB RECYCLING, RECOVERY, AND REUSE POTENTIAL
ostrial S*ewr «ai Preea*c (ArA vxij i v^ ; Pro Xy r -fj TTVI f) -T
\JA-fi as Ti
Waste
Waste Form:
Hazard Chaneteristte* (ail): ..
Hazardous Constituent* (major):_
i. Process Flow Diagram..& Waste Characterization: By looking at both documents, tiy to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major soune.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appeals to have: recoverable products/removable contaminants/neither
D. Comment _
2. Reasons for Waste Generation: Based on tbe description of the process, and waste generation and its
management practices given for a sector, make the foliowing assessment.
A. Is toe same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.&, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: _____________^_^_____________
C Why did this waste become hazardous (eg^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: r
3. Waste Management Alternatives: Review the potential for reducing -the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tefl
Comment: i:iri.
B. Water Use Reduction: YesWo/Canl Tell
Comment:
C On-site Waste Recydiag/Recovery/Reuse: Yes/No/Can't Tell
Comment: • •
D. Off-site Waste Recyding/Recovery/Rease: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable V Non-Recydable Partially RecydaWe
4 Ma^gftal QassificatJOIl: Sludge Spent Material fay-Product
(cvcle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
indaftrial Sartor mi ProeeaK U^CtX ^ I (J ^V) fJ-fft vt/iC'n ff\^ R'L
Waste Geaeratfoo Rate
Waste Fora: Liquid(Aq7Non-Aq.)/Slurry/SoUds(Wet^)ry)
Huard Oiarmcttrisliei (aB): .. I C R T
Haarooaa Coastttneatt (autor);
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
i.
each major source
A. Source: •
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't TeU
Comment:
B. What was the basic purpose for generating this waste (e.&, plant maintenance, chemical reaction, physical
separation, water rasing, other purification steps}?
Comment: .
C Why did this waste become hazardous (tg, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: __________________________________________________
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tefl
Comment: iri
B. Water Uie Redaction: Yes/No/Cant TeU
Comment: __^___________________^___»„____________________
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: •
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't TeH
Comment:
Conclusion: Recyclable Y Non-Recyclable Partially Recyclable
. -^ __
^-**= ^ ^ ggg
4. Material Classification: Sludge Spent Material ( By-Product
~"
-------
WORK SHEET FOB WASTE STREAM ASSESSMENT FOB RECYCLING, RECOVERY, AND REUSE POTENTIAL
?//
<-> I' 0^
Waste Generation Raac __
Wute FORK
Haard Ch*r*c*eristta («H): -
Hazardous Constttacnti (B«jor)
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the sane waste generated in the process. Complex a separate form for
each major source.
Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appeals to have: recoverable products/removable contaminants/neither
D. Comment: _
2. Reasons, for Waste Generation; Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated al every facility using the process?: Yes/No/Caa't Tell
Comment: •
B. What was the basic purpose for generating this waste (e.f, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: .
C Why did this waste become hazardous (e,g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Alternatives; Review die potential for reducing -the quantities of waste generated at
any of its sources by considering the foDowing waste management alternatives.
A. Waste Segregation: Yes/No/Cant TeU
Comment: •
B. Water Uie Reduction: Yes/No/Cant Tell
Comment:
C On-site Waste Recvding/Recovery/Rense: Yes/No/Can't TeU
Comment: • . • '
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Ten
Comment: ^______ .
Conclusion; r Recyclable Non-Recyclable Partially Recyclable
4. Matiifal Classification: Sludge Spent Material
f circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector ami Process: "CL^c.
Waste Stream: rlc,J r
Waste Generation Rate:
Waste Fora: CDjujd£Ag^Non-Aq.)/Slurry/Solidj|{Wet/Dry)
Hazard Characteristics (all): I (Cj "* ~
Hazardous Constituents (major):
3.
Process Flow Diagram &. Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
1?7 <-.
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
-L- ( 0 r
industrial Sector and Process: *—ty)c- ^ ' ^r ->l"
ste Stream: , .. kfafte..
waste Generation Rate:
Waste Form: L»q
Hazard Characteristics fall):
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: t^^- ~Y&j.s~>\&~3 //
B, Waste generation is closest to: Raw Material/Major Iniennediates$jnai
C. Waste appears to havexficoverable productsjtemovable contaminants/neiiher
D. Comment: ............
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the prcKess?:(iS/No/Can't Tell
Comment: ^—^
B. What was the basic purpose forjengrating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing^ttleTpurification stepsj?- n
Comment: " fc^s-df*
C. Whv did this waste become frarardrms (e g, physical contact during production, muring with other waste
streams ^results from impurity rettio^Jj^>
Comment: ^ J
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ____________^__^___________^___________^________________
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _^
D. Off-site Waste Recycling/Recovery/Reuse: ft^esj'No/Can't TeD
Comment: ^~^
Conclusion: ^Recyclable •__ Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
ial Sector and P«c«s:
Stream: ___ _ jSa&vJ' g «»c--'fax "f.^-
Waste Generation Rate: _ /s>^o r~T/y_/L..
Waste Form:
Hazard Characteristics (all):
Hazardous CoastlttieBts (major): _ .5, i.r, . r% ,->-,
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source,
/
A. ' Source:
B, Waste generation is closest to; Raw Materialijpapr MterfflediatisTRpal ifeioduct
C. Waste appears to have: recoverable products/removable contanjiaants/^eltE'
D. Comment:
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: (Yes/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, phemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams(^ulS^froni tapurily~relne¥al)?
Comment:
Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/C|n't Tell'
Comment: __ S — ^ __ _ , _ _
B. Water Use Reduction: Yes/No/Cafft TeU/
Comment: ^^
.^*<—>
On-site Waste Recycling/Recovery/Reuse: Yes/No/Can'tTell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes^Nfo/€ap't Te
Comment:
Conclusion: Recyclable - ^Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one) ' ^ "3
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
TZ^
industrial Sector and Process:
,tc Stream:
naste Generation Rate:
Waste Form:
Hazard Characteristics (all):
Hazardous Constituents i major):_
I"/
, /ffl-
1 Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
, ^L
B. Waste generation is closest tof <
C. Waste appears to have: recoverable products/fremovable contaminamsmtitEier
D. Comment: - ~ '
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make toe following assessment
A. Is the same waste generated at every facility using the process?:/Yes/No/Can't Tell
Comment:
B. What was theJjasic_gurpose for generating this waste (e.g., plant maintenance, Chemical reaoiojifphysical
separatipa.i^ater rinsmft other purification steps)? ^=
Comment: ___ _ .......................... _ _ _ , _ _________ _
C. Why did this wasteJ>ecgjne-hazardDus (e.g., physical contact during produaion/mixing with other
streamsnS»£'2S"55m impurity removal)? ^ _____ •.
• waste
3. Waste Management Alternatiyes: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/purt Teu)
Comment ^-——
B.
C.
D.
Water Use
Comment:
On-site Waste Recyding/Recovery/Reuse: /YesyNo/Can't Tell
Comment:
Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't TeU
Comment:
Concfosion: _f_ Recyclable Non-Recyciable Partially Recyclable
4. Material Classification:
Sludge
By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: "C-mc,
Vaste Stream: / .
Waste Generation Rate: tea?
Waste Form:
Hazard Characteristics (all):
Hazardous Constituents (major):_
Process Flow Diagram & Waste Characterization: By looking ai both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest
C. Waste appears to have: recoverable products/removable contaminant/neither •
D. Comment: ——
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: fYes/pfo/Can't Tell
Comment:
B, What was the basic purpose for generating this waste (e.g.(plant maintenance) chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become hazardous (e.g^/physical contact during production) mixing with other waste
streams, results from impurity removal)? ^~ •"'
Comment: ____^___________________________._____^_____^_^_
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Ten
Comment: ^
B. Water Use Reduction: Ye&*Q/Can't Tell
Comment: ___________________^__
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/^nrt Tell
Comment:
D, Off-site Waste Recycung/Recovery/Reuse: Yes/No/ptn't TelT
Comment: ^ —'
Conclusion: Recyclable • iXNon-Recyclable Partially Recyclable
4. Material Qassification: Sludge j^Spent Material By-Product
(circle one) '- -^ "5
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector an* Process: "fc-.'<. *^
B. Waste generation is closeTroCgaw Materiai/Major.IptCTimBaiitsyFtnal
C. Waste appears to have: recoverable productsTTefliuvaUle u>n uiminants/fie 1 1 be>
D, Comment: _ _~~"1
2. Reasons for Waste Generation: Based on the description of tae process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: (^feNo/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, -chemical reaction, physical
separation, water rinsing, other purification steps)? 'v- —-~~^
Comment:
C. Why did this waste become hazardous (e.g^physical contact during production, mixing with other waste
streams, results from impurity removal)? ^-— . __ —•
Comment: •
3. Waste Management Alternatives: Review the potential for reducing toe quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes^/Can't Tell
Comment:
B. Water Use Redaction: Yes£fe/eant Tell
Comment:
j^ \ \-^".
C On-site Waste Recyding/Recovery/Reuse:/V'eS/No^^m
Comment; (/ /
D. Off-site Waste Recycling/Recovery/Reuse:
Comment:
/ A
Conclusion: _£ Recyclable • Non-Recyclable _r> Partially Recyclable
4. Material Classification: Sludge (Spent Material ) By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: __ >e*
Vaste Stream: r.w^
Waste Generation Rate: ___,p^=___ ^^O,®0*
Waste Form: /x^Liquidj[A^Non-Aq.)^luny/Soligs{Wet/'Dry)
Hazard Characteristics (all): I f\j^) ^ Cj^
Hazardous Constltaents (major):
\. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: 1/^.c^S g^e/ptt < L±_^f_L^_.
B. Waste g eneration is closest to:fT^ MatliialJMifoT intennediates'/FiBal Produc?
C. Waste appears to have: recoverable product«reniovai>ie"contaniiiiants/deither
D. Comment: ____________ _ V- . „.. ............. „ ...... — — ; — ~~ ~~ • _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: f'rW/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g ., plan: maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? • ~~
Comment: " ~ _
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams, results from impurity removal)? ~~ " - • - : - - -
Comment: ~~
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation:
Comment
B. Water Use ItectactionjOfeflfo/ean't Ten
Comment:
C. On-she Waste Recycling/Recovery/Reiisef^^/No/Can't Tell
Comment: _ _ __ •
D. Off-site Waste Recycling/Recovery/Rense: Ye$/N<
Comment:
Conclusion: Recyclable - . Non-Recyclable iXpartiaUy Recyclable
4. Material Qassification: Sludge /^SSentMateriaK-, By-Product
" " / r j QQ7
(circle one) (^ _^~-^
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process:
iste Streua:
• *Vaste Generation Rate:
Waste Form: .
Hazard Characteristics (all): I C R (7 .
Hazardous Constituents (major): /7x • Ce< , Pb ,$ H&, /Sg, -^
' "' :^~^
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to^JSaw-MateriafeMajor Intemediates/Hnal
C. Waste appears to have: recoverable products(removaDie SoBiamuSftftrc
TN /""*«>%*•»*Maw**i« ^*""" " ' "•"" "•*
D. Comment
Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: (^es'/No/Can't Tell
f**r\ •"» i 'tin ^m *•
Comment:
B. What wasjhe basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, (physical
—sepifationTjJteter rinsing, other purification steps)?
C. Why did this waste become hazardous (e,g., physical contact during production, mixing with other waste
streams,(feiults from impurity removal)?
Comment: ".." "" _ ' "_
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation:
Comment
B. Water Use Ratactionf^^io/Can't Tell
Comment: _.
C On-site Waste RecydiBg/Recovery/Reuse:
Comment: -
D. Off-site Waste Recycling/Recovery/Reuse:
Comment: ________^_____________-_____^______________-__^._
Conclusion: Recyclable l/Non-Recyclable Partially Recyclable
4- Materiai Qassification: ^/*fludg^ Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector and Process: _ .. ">
Vaste Stream:
Waste Generation Rate: ^
Waste Form: Liquid(Aq./Non-AqO/Slurry/SoiiS(Wei/Dry)
Hazard Characteristics (all): I C R ~Q? * x-y r>/
Hazardous Constituents (major): /7s^ v.^ r P
i. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separaie form for
each major source.
A Source:
B. Waste feneraiion is closest/to: ROT Materiai/T@gr Interme^tes^inal Product "^
C. Waste appears to have: recoverable products/removable contammants^flfelfnerN
D. Comment: -
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: /^M/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing^ot&er purification step?)?
Comment: ^^~
C. Why did this waste become hazardous (e,g., physical contact during production, mixing with other waste
streams, ^esylts Ironrtmpurity removal)?..
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A, Waste Segregation: Yes/Na/^nVTe.
Comment:
B: Water Use Reduction: Yes/Nofl2alt Teji
Comment: v—-—-"^^
C On-site Waste Recydrnf/Recovery/Reuse: Ye^aFGau't Tell
Comment:
_/
D. Off-site Waste Recycling/Recovery/Reuse: Yes/NoCan't
Comment: _^
Conclusion: Recyclable • •^Non-Recyclable Partially Recyclable
4. Material Classification: Sludge /SpSTMateriaL/ By-Product
C „—•""""''' 999
(circle one) ^ —-^
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector ami Process: 'C-mc. _ __ _
ste Stream: Turf ife^cy- R f^
rtaste Generation Rate: ----- — ^ _ /one
Waste Form: £ UquidJ^/Non-A^4/Slurry/SoUds(Wet/Diy)
Hazard Characteristics (all): I Cs^ R Cp /- .- _/ .
Hazardous Constituents (major): . „' ''' v "n.' ^
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation & closest to: Raw Material/Major In termed iates/^ihal
C. Waste appears to have: recoverable prodacts^«nlo^fc^e^ntammiitsS^e^ther
D. Comment: v" -—— — - ~-J
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
>s-
A. Is the same waste generated at every facility using the processH^Yes^pCan't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation,jwaterrijiiligisother purification steps)?
Comment: ..__...
C. Why did this waste^ become hazardous (e.g.,(pnysical contact during proauaion, mixing with other waste
streams, <
Commentf
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering toe following waste management alternatives.
Waste Segregation: Yea^fo/fan'l Tell
Comment
B. Water Use Rfiduaton/""^No/Cai't Tell
Comment: —'
C On-site Waste Recydiag/Recovery/Re«se<®s/No/CaB'i Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Ye&^Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable c^artially Recyclable
» \fC, ^\,/VL j
--—•—~~-~^
4. Material Classification: Sludge (Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
•ndustrial Sector and Process: "C-mc. _ ..... _
*aste Stream: ._.
Waste Generation Rate: J_^_, _ _ J,, 52£>,Ccp iAiT
Waste Form:
Hazard Characteristics (all):
Hazardous Constituents {major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closes^to^Raw Material/Major Intermediates/Final
C, Waste appears to have; recoverable prodacts/removaBie
D. Comment:
2, Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A Is the same waste generated at every facility using the process?:/Y«/No/Can't Tell
Comment: _
B. What was the basic purpose for generating this waste (e.f., plant mainteggfice, cnenucalje^giogjjjhysical
separation, water rinsing,other purification steps)?
Comment: - .
c- Why did this waste become hazardous (e.g., physical contact during production,/mrong with other waste
ts from impurity removal)? ~~ " "~ -—
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A Waste Segregation:
Comment: __________________________________________
B. Water Use Red_ction:f^/No/Can't Tell
Comment: .
C. On-site Waste Recyding/Recovery/Reuser^Y^No/C^n't Tell
Comment: -
—=r- -x
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No^n't TeU/
Comment:
Conclusion: Recyclable • Non-Recyclable *Xpartiallv Recyclable
.^=======s^~~^
4. MaterialClassification: Sludge /Spent Material) By-Product
(circle one)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
industrial Sector and Process:
arte Stream:
rP *'„&
^bgQ 0
GeneratfoD Raw
Waste Forai:
Hazard Characteristics
C. Waste appears to have: recoverable products/removable " •
T"\ f**f\*r*wv*4n*t'
D. Comment
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facflify using the process?: ^?p/No/Can"t Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? " " ~~
Comment: .•
C. Why did tMsj^asteJ^eramfiJiazardous (e.g., physical contact during production, mixing with other waste
streamffres
Comment:
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
jf*~*~~~~~^
A Waste Segregation: Yes/No/can't TeJl)
Comment: ^ —
B. Water Use Redaction: rVes^No/Can't Tell
Comment:
>*=—~~v
C. On-site Waste Recydiag/Recoveiy/ReBse: Yes/No/eanVTeJl
Comment: .
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: ^~ —^
Conclusion: _j\__ Non-RecydaWe _ Partially Recyclable > **'
4- Material Qassification: ^'siudge'N Spent Material By-Product
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: "*•-—mc-
'Vaste Stream: 55-rHg f&i.n
i Generation Rate:
Waste Form: Liq
Hazard Characteristics (all): I C R
Hazardous Constituents (major):
Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: 4f^^4^ (\~ a*^.-fS&JA ••
B, Waste generation is closest to:
C. Waste appears to have:^fecbverable products/removable
"""^
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same'waste generated at every facility using the process?: W
Conclusion: tXRecvclable ; Non-Recyclable Partially Recyclable
4- Material Qassification: Sludge Spent Material /%-Product
(ca-cleme)
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
•wtestri«I Seen* and Process zil Y CaVl) U A K / H-Kt HIUM
Vaste Stream: ^pP ^"f Qriri iPrirl^Afk l^r^^^ 3 lyMn iUi_A A 11
Waste Generation :
Waste FOPBI: Uquid^jNon-Aq.)/Sluny/Solids( Wet/Dry) *
Hazard Charw«is«ics (all): I £c) P T
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated to the process. Complete a separate form for
each major source.
Source:
B. Waste generation is closest to; Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D, Comment: _ _____________ _
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ___________________________________________________________ ^
B. What was the basic purpose for generating this waste (e.g^ plant maintenance, chemical reaction, physica
separation, water rinsing, other purification steps)?
Comment: ____________________________________________^
C. Why did this waste become hazardous (e.g- physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: ________^_______________________,________^
3. Waste Management Alternatives; Review the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: —• . ....
B. Water Use Redaction: Yes/No/Can't Tell
Commote
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tel]
Comment: ~ ~—
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable V Non-Recyclable Partially Recyclable
4 Material Classification; Sludge Spent Material By-Product
-------
WORE SHEET FOR WASH; STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: . •^.\/0/)Vl UiU /
Waste Stream: S'pg'rrr /T Y \ ft I I uf Dmt ^ -fiTTT^. ^| y cAr\ [\ ip n J
Waste n«ieratloB Raas ''
_
Waste Form: LJqu6tAi|JNon-A},)/Sluny/Soli
-------
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Sector mA Process:
/
^^Efr v ^rpr^ j^arnKnV u frlftU m.AU
A\4 I V| C^ /t2£%SjQ-^: _ J
/Vaste Stnmm
Waste Generation
Waste Form: Uquid(A4^Non-Aq.)/Sl»i>Ty/SoUds(Wet/Dry)
Hazard Characteristics (all): I (gj K T,
Hazardous Constituents (major): ___
1, Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source: __ •
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: __^__^_
2, Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment.
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: ............................................
B. What was the basic purpose tor generating this waste (e.g» plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ____
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: _ .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated at
any of its sources by considering toe following waste management alternatives,
A. Waste Segregation: Yes/No/Can't Tell
Comment: . _
B, Water Use Redaction: Yes/No/Can't TeD
Comment: _ _ ,
C, On-site Waste Recydrng/Reccwry/Reuse: _Yes/No/Can't Tell . ,
Comment: _ 9 ft > 1 ft A C ; i />i AOTAP A 1 A./M wrAW _
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: _ __ _ _
Conclusion: Recyclable Non-Recyclable V Partially Recyclable
4. Material Classification: . Sludge / Spent Material; By-Product
-------
WORE SHEET won WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Industrial Sector and Process: g-lVCfiVn I\J A A
Waste Stream: I Oft ? )f\ru? Y I Y\rf Wj/X-te/V -£?7m -Zwrfi/K.A CUJUU
Waste Form: Uquid(AqJNon-Aij.)/&uriy/Soiids(Wet/Dry)
Hazard Characteristics (all): I ^ JR T
Hazardous Constituents (major) :_ _ •
\/
Process Row Diagram &. Waste Characterization: By looking at both documents, iry to answer the
following questions for each major source of the same waste generated in the process. Complete a separate form for
each major source.
A. Source:
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable coniaminants/neither
D. Comment:
2. Reasons for Waste Generation: Based on the description of the process, and waste generation and its
management practices given for a sector, make the following assessment
A. Is the same waste generated at every facility using the process?: Yes/No/Can't Tell
Comment: .
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
; Comment: .
3. Waste Management Alternatives: Review the potential for reducing the quantities of waste generated ai
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Can't Tell
Comment: .
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _.
C. On-site Waste RecydLng/Recovery/Reuse: Yes/No/Can't Tell r i
Comment: 010 i £ IH /XTTM 3 V~1
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: _ Recyclable _ Non-Recyclable \/ Partially Recyclable
4. Material Classification: Sludge /Spent Material ) By-Product
circle one — - — - __ ^
(circle one)
-------
Page Intentionally Blank
1008
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX E
Listing of Waste Streams Generated by
Mineral Production Activities by Commodity
Note: The failure to list a mineral processing waste on this table in no way assumes that the Agency has determined
that the waste is not a mineral processing waste. A company has an obligation to determine whether it is generating a
mineral processing wastestream subject to the 1989 rulemaking.
1009
-------
Page Intentionally Blank
1010
-------
EXHIBIT E-l
SUMMARY OF MINERAL PROCESSING WASTE STREAMS BY COMMODITY
Commodity
Alumina and Aluminum
Antimony
Beryllium
Waste Stream
Anode prep waste
APC dust/sludge
Baghouse bags and spent plant filters
Bauxite residue
Cast house dust
Cryolite recovery residue
Wastewater
Discarded Dross
Flue Dust
Eieclrolysis waste
Evaporator salt wastes
Miscellaneous wastewater
Pisolites
Serap fomace brick
Skims
Sludge
Spent cleaning residue
Spent potliners
Sweepings
Treatment Plant Effluent
Waste alumina
Gangue
Wastewater
APC Dust/Sludge
Autoclave Filtrate
Spent Barren Solution
Gangue (Filter Cake)
Leach Residue
Refining Dross
Slag and Furnace Residue
Sludge from Treating Process Waste Water
Stripped Anolyte Solids
Waste Solids
Spent Barren filtrate streams
Beryllium hydroxide supernatant
Chip Treatment Wastewater
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1011
-------
EXHIBIT E-l (Continued)
Commodity
Beryllium (continued)
Bismuth
Cadmium
Calcium Metal
Cesium/Rubidium
Waste Stream
Dross discard
Filtration discard
Leaching discard
Neutralization discard
Pebble Plant Area Vent Scrubber Water
Precipitation discard
Process wastewater
Melting Emissions
Scrubber Liquor
Separation slurry
Waste Solids
Alloy residues
Spent Caustic Soda
Electrolytic Slimes
Excess chlorine
Lead and Zinc chlorides
Metal Chloride Residues
Slag
Spent Electrolyte
Spent Material
Spent soda solution
Waste acid solutions
Waste Acids
Wastewater
Caustic washwater
Copper and Lead Sulfate Filter Cakes
Copper Removal Filter Cake
Iron containing impurities
Spent Leach solution
Lead Sulfate waste
Post-leach Filter Cakes
Spent Purification solution
Scrubber wastewater
Spent electrolyte
Zinc Precipitates
Calcium Aluminate wastes
Dust with Quicklime
Chemical Residues
Digester waste
Electrolytic Slimes
Pyrolytic Residue
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1012
-------
EXHIBIT E-l (Continued)
Commodity
Cerium/Rubidium (continued)
Chromium, Fenochrome, and Ferrochromium- Silicon
Coal Gas
Copper
Elemental Phosphorous
Waste Stream
Slag
Gangue and tailings
Dust or Sludge from ferroehromiurn production
Dust or Sludge from ferrochrom mm- silicon production
Treated Roast/Leach Residues
Slag and Residues
API Oil/Water Separator Sludge
API Water
Cooling Tower Slowdown
Dissolved Air Flotation (DAF) Sludge
Rue Dust Residues
Liquid Waste Incinerator Slowdown
Liquid Was:e Incinerator Pond Sludge
Multiple Effects Evaporator Concentrate
Multiple Effects Evaporator Pond Sludge
Sludge and Filter Cake
Spent Methanol Catalyst
Stretford Solution Purge Stream
Surface Impoundment Solids
Vacuum Filter Sludge
Zeolite Softening PWW
Acid plant blowdown
Acid plant thickener sludge
APC dusts/sludges
Spent bleed electrolyte
Chamber solids/scrubher sludge
Waste contact cooling water
Discarded furnace brick
Process wastewaters
Scrubber blowdown
Spent black sulfurk add sludge
Surface impoundment waste liquids
Tankhouse slimes
WWTP liquid effluent
WWTP sludge
Condenser phossy water discard
Cooling water
Furnace building washdown
Dust
Waste ferrophosphorus
Furnace offgas solids
Nature of Operation
Mineral Processing
Ex trac fion/B eoefic iatioo
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1013
-------
EXHIBIT E-l (Continued)
Commodity
Elemental Phosphorous (continued)
Fluorspar and Hydrofluoric Acid
Germanium
Gold and Silver
Iron and Steel
Lead
Waste Stream
Furnace scrubber blowdown
Precipitator slurry scrubber water
Precipitator slurry
NOSAP slurry
Sludge
Spent furnace brick
Surface impoundment waste liquids
Surface impoundment waste solids
Waste Andersen Filter Media
WWTP liquid effluent
WWTP Sludge/Solids
APC Dusts
Off-spec fluosilicic acid
Sludges
Waste Acid Wash and Rinse Water
Chloriaator Wet Air Pollution Control Sludge
Germanium oxides fumes
Hydrolysis Filtrate
Leach Residues
Roaster off-gases
Spent Acid/Leachate
Waste Still Liquor
Wgstewater
Spent Furnace Dust
Refining wastes
Retort cooling water
Slag
Wastewater treatment sludge
Wastswater
Wastewater
Acid Plant Blowdown
Acid Plant Slydge
Baghouse Dust
Baghouse Incinerator Ash
Cooling Tower Blowdown
Waste Nickel Matte
Process Wastewater
Slurried APC Dust
Solid Residues
Solids in Plant Washdown
Spent Furnace Brick
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Process:ng
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Miners! Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1014
-------
EXHIBIT E-l (Continued)
Commodity
Lead (continued)
Lightweight
Aggregate
Magnesium and Magnesia
from Brines
Manganese, Manganese
Dioxide, Ferromanganese
Manganese, Manganese
Dioxide, Fetiomanganese
and Silieonianganese (continued)
Mercury
Molybdenum,
Ferromolybdenurru and
Waste Stream
Stockpiled Miscellaneous Plant Waste
Surface Impoundment Waste Liquids
Surface tamoundment Waste Solids
SVG Backwash
WWTP Liquid Effluent
WWTP Sludgcs/Solid5
APC control scrubber water arid solids
AFC Dust/Sludge
Surface impoundment waste liquids
WWTP liquid effluent
APC Dust/Sludge
CaJciner offgases
Calcium sludge
Casthouse Dust
Casting plant slag
Cathode Scrubber Liquor
Slag
Smut
Spent Brines
APC Dust/Sludge
APC Water
Iron Sulfide Sludge
Ore Residues
Slag
Spent Graphite Anode
Spent Process Liquor
Waste Electrolyte
W'astewater (CMD)
Wastewater (EMD)
Wastewater Treatment Solids
Dust
Mercury Quench Water
Furnace Residues
APC Dust/Sludge
Rue Dust/Gases
Liquid Residues
H2 Reduction Furnace Scrubber Water
Molyhdic Oxide Refining Wastes
Refining Wastes
Roaster Gas Blowdown Solids
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1015
-------
EXHIBIT E-l (Continued)
Commodity
Molybdenum,
Ferromolybdenum, and
Ammonium Molybdaten (continued)
Phosphoric Acid
Platinum Group
Metals
Pyrobitumens,
Mineral Waxes,
and Natural Asphalts
Rare Earths
Rhenium
Scandium
Waste Stream
Slag
Solid Residues
Treatment Solids
Waste Scale
Slag
Scrubber offgases
S02 waste
Spent Acids
Spent Solvents
Still bottoms
Waste catalysts
Spent ammonium nitrate processing solution
Electrolytic cell caustic wet APC waste
Spent Electrolytic cell quench water and scrubber water
Spent iron hydroxide cake
Spent lead filter cake
Lead backwash sludge
Monazite solids
Process wastewater
Spent scrubber liquor
Off -gases from dehydration
Spent off-gases from electrolytic reduction
Spent sodium hypochlorite filter backwash
Solvent extraction crud
Spent surface impoundment solids
Spent surface impoundment liquids
Waste filtrate
Waste solvent
Wastewater from caustic wet APC
Waste zinc contaminated with mercury
APC Dust/Sludge
Spent Barren Scrubber Liquor
Spent Rhenium Raffinate
Roaster Dust
Spent Ion Exchangc/SX Solutions
Spent Salt Solutions
Slag
Crud from the bottom of the solvent extraction unit
Dusts and spent filters from decomposition
Spent acids
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1016
-------
EXHIBIT E-l (Continued)
Commodity | Waste Stream
Scandium (continued)
Selenium
Silicon and
Ferrosilicon
Sulfur
Synthetic Rutiie
Tantalum, Columbium
and Ferrocolumbium
Tellurium
Tin
Spent ion exchange resins and backwash
Spent solvents from solvent extraction
Spent wash water
Waste chlorine solution
Waste solutions/solids from teaching and precipitation
Spenl filter cake
Plant process wastewater
Slag
Tellurium slime wastes
Waste Solids
APC Dust Sludge
Dross discard
Siag
Airborne emissions from sulfuric acid production
Spent catalysts (Claus process)
Spent vanadium pentoxide catalysts from sulfuric acid
production
Tail gases
Wastewater from wet-scrubbing, spilled product and
condensates
APC Dust/Sludges
Spent Iron Oxide Slurry
Spent Acid Solution
APC Dust Sludge
Digester Sludge
Spent Potassium Titanium Chloride
Process Wastewater
Spent Raffinate Solids
Scrubber Overflow
Slag
WWTP Liquid Effluent
WWTP Sludge
Slag
Fumes of telluride dioxide
Solid waste residues
Waste Electrolyte
Wastewater
Brick Lining and Fabric Filters
Dross
Process Wastewater and Treatment Sludge
Slag
Slimes
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1017
-------
EXHIBIT E-l (Continued)
Commodity
Tin (continued)
Titanium and
Titanium Dioxide
Tungsten
Uranium
Waste Stream
Waste Acid and Alkaline baths
Spent Brine Treatment Filter Cake
FeCl Treatment Sludge
Waste Ferric Chloride
Finishing Scrap
Leach Liquor and Sponge Wash Water
Waste Non-Contact Cooling Water
Pickling Liquor and Wash Water
Scrap Detergent Wash Water
Scrap Milling Scrubber Water
Reduction Area Scrubber Water
Chlorination Off gas Scrubber Water
Chlorination Area - Vent Scrubber Water
Melt Cell Scrubber Water
Chlorine Liquefaction Scrubber Water
Chip Crushing Scrubber Water
Casting Crucible Contact Cooling Water
Smut from Mg Recovery
Spent Surface Impoundment Liquids
Spent Surface Impoundment Solids
T1C14 Purification Effluent
Spent Vanadium Pxychloride
Sodium Reduction Container Reconditioning Wash Water
Casting Crucible Wash Water
Waste Acids (Chloride process)
Waste Solids (Chloride process)
Waste Acids (Sulfate process)
Waste Solids (Sulfate process)
WWTP Liquid Effluent
WWTP Sludge/Solids
Spent Acid and Rinse water
Scrubber wastewater
Process wastewater treatment plant effluent
Water of formation
Waste Nitric Acid from Production of UCs
Vaporizer Condensate
Superheater Condensate
Slag
Uranium Chips from Ingot Production
Waste Calcium Fluoride
Nature of Operation
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1018
-------
EXHIBIT E-l (Continued)
Commodity
Vanadium
Zinc
Zirconium and
Hafnium
Waste Stream j Nature of Operation
Fillrate and Process Waste waters
Solid Waste
Spent Precipitate
S!a%
Wet scrubber wastewater
Acid Plant Slowdown
Spent Cloths, Bags, and Filters
Waste Ferrosilicon
Spent Goethite and Leach Cake Residues
Saleable residues
Process Wastewatcr
Discarded Refractory Brick
Spent Surface Impoundment Liquid
Spent Surface Impoundment Solids
Spent Synthetic Gypsum
TCA Tower Slowdown (ZCA Bartlesville. OK -
Electrolytic Plant)
Wastewater Treatment Plant Liquid Effluent
Wastewater Treatment Plant Sludge
Zinc -lean Slag
Spent Acid leachatc from zirconium alloy production
Spent Acid leachate from zirconium metal production
Ammonium Thiocyatiate Bleed Stream
Reduction area-vent wet APC wastewater
Caustic wet APC wasfccwater
Feed makeup wel APC wastewater
Filter cake/sludge
Furnace residue
Hafnium filtrate wastewater
Iron extraction stream snipper bottoms
Leaching rinse water from zirconium alloy production
Leaching rinse water from zirconium metal production
Magnesium recovery area vent wet APC wastewater
Magnesium recovery off-gas wet APC wastewater
Sand Chlorination Off-Gas Wet APC wastewater
Sand Chlorination Area Vent Wet APC wastewater
Silicon Tetrachloride Purification Wet APC wastewater
Wet APC wastewater
Zhcor.ium chip crushing wet APC wastewater
Zirconium filtrate wastewater
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
Mineral Processing
1019
-------
Page Intentionally Blank
1020
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX F
Mineral Processing Sectors
Generating Hazardous Wastes
This list is not exclusive. Other sectors may generate mineral processing wastes that are hazardous, A generator has
the obligation to test each wastcstream to determine if a waste has hazardous characteristics.
1021
-------
Page Intentionally Blank
1022
-------
EXHIBIT F-l
LIST OF SECTORS GENERATING HAZARDOUS MINERAL PROCESSING WASTE STREAMS*
Alumina and Aluminum
Antimony
Beryllium
Bismuth
Cadmium
Calcium
Chromium and Ferrochromium
Coal Gasification
Copper
Elemental Phosphorous
Fluorspar and Hydrofluoric Acid
Germanium
Gold and Silver
Lead
Magnesium and Magnesia from Brines
Mercury
Molybdenum, Ferromolybdenum, and Ammonium Molybdate
Platinum Group Metals
Rare Earths
Rhenium
Scandium
Selenium
Synthetic Rutile
Tantalum, Columbium, and Ferrocolumbium
Tellerium
Titanium and Titanium Dioxide
Tungsten
Uranium
Zinc
Zirconium and Hafnium
1023
-------
Page Intentionally Blank
1024
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX G
Mineral Processing Sectors
Not Generating Hazardous Wastes
1025
-------
Page Intentionally Blank
-------
EXHIBIT G-l
LIST OF SECTORS NOT GENERATING HAZARDOUS MINERAL PROCESSING WASTE STREAMS
Arsenic Acid
Boron
Bromine
Cesium and Rubidium
Gemstones
Iodine
Iron and Steel
Lightweight Aggregates
Lithium and Lithium Carbonate
Manganese, MnO2, Ferromanganese, and Silicomanganese
Phosporic Acid
Pyrobitumens, Mineral Waxes, and Natural Asphalts
Scandium
Silicon and Ferrosilcon
Soda Ash
Sodium Sulfate
Strontium
Tungsten
Vanadium
Note: This list is not exclusive. Generators of these waste streams should not assume that their wastes are non-
hazardous simply because they are found on this list. Each generator should test its wastes to determine if they are
hazardous.
1027
-------
Page Intentionally Blank
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX H
List of Commenters
January 25,1996 Supplemental Proposed Rule
May 12,1997 Second Supplemental Proposed Rule
1029
-------
Page Intentionally Blank
1030
-------
Commenter List, January 1996 Proposed Rule
Number
COMM1
COMM2
COMM3
COMM4
COMM5
COMM6
COMM7
COMM8
COMM9
COMM10
COMM1I
COMM12
COMM13
COMM14
COMM15
COMM16
COMMIT
COMM18
COMM19
COMM20
COMM21
COMM22
COMM23
COMM24
COMM25
COMM26
COMM27
COMM28
COMM29
COMM30
COMM31
COMM32
Name(s)
National Mining Association
PTI Environmental Services
The Ferroalloys Association
Heritage Environmental Services, Inc.
Marine Shale Processors, Inc.
U.S. Department of Energy
American Electric Power
Arizona Public Service Company
Institute for Interconnecting and Packaging Electric Circuits
Lead Industries Association, Inc.
New York State Department of Environmental Conservation
Anson County ACTUS, Chapter of the Blue Ridge Environmental Defense League
Avocet Tungsten, Inc.
Chemgold, Inc.
General Motors Corporation
Public Service Electric and Gas Company
Chemical Waste Management, Inc.
DuPont White Pigment and Mineral Products
Westinghouse Electric Corporation
U.S. Borax, Inc.
Association of Container Reconditioners
SCM Chemicals, Inc.
Montana Department of Environmental Quality
Homestake Mining Company
KRONOS, Inc.
Jersey Central Power & Light Company
Union Carbide Corporation
South Carolina Electric and Gas company
Sonora Mining Corporation
Chemical Waste Management
Laidlaw Environmental Services, Inc.
Kodak
1031
-------
Commenter List, January 1996 (continued)
Number
COMM33
COMM34
COMM35
COMM36
COMM37
COMM38 '
COMM39
COMM40
COMM41
COMM42
COMM43
COMM44
COMM45
COMM46
COMM47
COMM48
COMM49
COMM50
COMM51
COMM52
COMM53
COMM54
COMM55
COMM56
COMM57
COMM58
Name(s)
International Precious Metals Institute
Institute of Scrap Recycling Industries, Inc.
Metal Industries Recycling Coalition
ASARCO
Sierra Club's Midwest Office and the Mining Impact Coalition of Wisconsin, Inc.
Phelps Dodge Corporation
Solite Corporation
Kennecott Corporation
Environmental Defense Fund
Phosphorus Producers Environmental Council
Precious Metals Producers
Battle Mountain Gold Company
Barrick Gold Corporation
Echo Bay Mines
Independence Mining Company
Santa Fe Pacific Gold Corporation
Battery Council International
The Fertilizer Institute
Cyprus Amax Minerals Company
Safety-Kleen Corp,
SKW Metals & Alloys, Inc.
Kemira Pigments, Inc.
New Jersey Natural Gas Company
South Jersey Gas Company
Robert Lucht, Mining Engineer and Geologist
INCO LTD
INCO United States, Inc.
International Metals Reclamation Company, Inc.
RSR Corporation
Copper & Brass Fabricators Council, Inc.
Utility Solid Waste Activities Group
Edison Electric Institute
American Public Power Association
National Rural Electric Cooperative Association
Newmont Gold Company
National Mining Association
1032
-------
Commenter List, January 1996 (continued)
Number
COMM59
COMM60
COMM61
COMM62
COMM63
COMM64
COMM65
COMM66
COMM67
COMM68
COMM69
COMM70
COMM71
COMM72
COMM73
COMM74
COMM75
COMM76
COMM77
COMM78
COMM79
COMM80
COMM81
COMM82
COMM83
COMM84
COMM85
COMM86
COMM87
COMM88
COMM89
LCOMM1
Name{s)
Brash Wellman, Inc.
Brush Wellman, Inc.
Brush Wellman, Inc.
Brash Wellman
Brush Wellman, Inc.
Utah Mining Association
Aluminum Company of America
Rio Algom Mining Corp.
BHP Copper
Molycorp, Inc.
Molycorp, Inc.
FMC
U.S. Department of Defense
Uranium Resources, Inc.
Copper Range Company
U.S. Department of Interior
Recyclers of Copper Alloy Products, Inc.
Kerr-McGee Corporation
The Aluminum Association
Rhone-Poulenc
The Colorado Mining Association
Molten Metal Technology
OxyChem
Horsehead Resource Development Company, Inc.
Electronics Industries Association
Chemical Manufacturers Association
Nevada Mining Association
U.S. Borax
Kennecott
California Mining Association
Arizona Department of Environmental Quality
American Gas Association
1033
-------
Commenter List, January 1996 (continued)
Number
LCOMM2
LCOMM3
LCOMM4
LCOMM5
LCOMM6
LCOMM7
LCOMM8
Name(s)
Environmental Technology Council
U.S. Department of Agriculture
The Ferroalloys Association
Association of Battery Recyclers, Inc.
Northern Plains Resource Council
MISSING
State of Wyoming Department of Environmental Quality
1034
-------
Commenter List for May 12,1997 Second Supplemental Proposed Rule
Commenter #
COMM1001
COMM1002
COMM1003
COMM1004
COMM1005
COMM1006
COMM1007
COMM1008
COMM1009
COMM1010
COMM1011
COMM1012
COMM1013
COMM1014
COMM1015
COMM1016
COMM1017
COMM1018
COMM1019
COMM1020
COMM1021
COMM1022
COMM1023
COMM1024
COMM1025
COMM1026
COMM1027
COMM1028
COMM1029
COMM1030
COMM1031
COMM1032
COMM1033
Commenter Name
ASARCO Incorporated
American Wood Preservers Institute
Chemical Products Corporation
Occidental Chemical Corporation (OxyChem)
American Chrome & Chemicals, L.P.
Marine Shale Processors, Inc. (MSP)
Frontier Technologies Inc. (FTI)
Florida Phosphate Council
World Resources Company
International Metals Reclamation Company, Inc. (MMETCO) and INCO
United States, Inc.
CITGO Petroleum Corporation
The Ferroalloys Association (TFA)
GF Industries
Westinghouse Electric Corporation
Ms. Linda W. Pierce
Chemical Manufacturers Association
Battery Council International (BCI) and Association of Battery Recyclers
(ABR)
Collier, Shannon, Rill & Scott, PLLC for Specialty Steel Industry of North
America (SSINA)
The Doe Run Company (DRC)
American Portland Cement Alliance (APCA)
American Petroleum Institute
Eastman Kodak Company
U.S. Department of Energy (DOE)
Lead Industries Association, Inc. (LIA)
R.SR Corporation
Homestake Mining Company
Solite Corporation
l^aidlaw Environmental Services
Sfewmont Gold Company
Chemical Products Corporation (CPC)
r^lorida Institute of Phosphate Research (FIPR)
Savage Zinc, Incorporated
General Motors Corporation (GM)
1035
-------
Commenter List, May 12,1997 (Continued)
Commenter #
COMM1034
COMM1035
COMM1036
COMM1037
COMM1038
COMM1039
COMM1040
COMM1041
COMM1042
COMM1043
COMM1044
COMM1045
COMM1046
COMM1047
COMM1048
COMM1048-D
COMM1048-E
COMM1049
COMM105.0
COMM1051
COMM1052
COMM1053
COMM1054
COMM1055
COMM1056
COMM1057
COMM1058
COMM1059
COMM1060
COMM1061
COMM1062
COMM1063
Commenter Name
ASARCO Incorporated
Utility Solid Waste Activities Group (USWAG)
Okanogan Highlands Alliance (OHA)
CF Industries, Inc.
The Fertilizer Institute
American Iron and Steel Institute (AISI)
Molycorp, Inc.
Cyprus Amax Minerals Company
Law Office of David J. Lennett (for Environmental Defense Fund, Mineral
Policy Center, Southwest Research and Information Center, North Santiam
Watershed Council, Pamlico-Tar River Foundation, Siskiyou Regional
Education Project, Okanogan Highlands Alliance, and the Louisiana
Environmental Action Network
BHP Copper
National Lime Association
The Silver Council
Mineral Policy Center
American Gas Association (AGA)
National Mining Association
National Mining Association
National Mining Association
Lake Superior Alliance (LSA)
Reynolds Metals Company
Brush Wellman Inc.
Brush Wellman Inc.
Brush Wellman, Inc.
Kennecott
Mr. William R. Schneider, P.E. (Consultant to Macalloy Corp.)
Nexsen, Pruet, Jacobs & Pollard, LLP (Counsel to Macalloy Corporation)
Photo Marketing Association International
Menominee Indian Tribe of Wisconsin
Lake Michigan Federation
Mr. David Isbister
Ms. Marianne Isbister
Rolling Stone Lake Protection & Rehabilitation District
Ms. Laura Furtman
1036
-------
Commenter List, May 12,1997 (Continued)
Commenter #
COMM1064
COMM1065
COMM1066
COMM1067
COMM1068
COMM1069
COMM1070
COMM1071
COMM1072
COMM1073
COMM1074
COMM1075
COMM1076
COMM1077
COMM1078
COMM1079
COMM1080
COMM1081
COMM1082
COMM1083
COMM1084
COMM1085
COMM1086
COMM1087
COMM1088
COMM1089
COMM1090
COMM1091
COMM1092
COMM1093
COMM1094
COMM1095
COMM1096
COMM1097
COMM1098
Commenter Name
Mr. Gregory Furtman
Ms. Jennifer Pierce
Cement Kiln Recycling Coalition
Institute for Interconnecting and Packaging Electronic Circuits
Horsehead Resource Development Company, Inc.
Macalloy Corporation
Ms. Dori Gilels
Kenneth and Linda Pierce
Ms. Ellen Wertheimer
Mr. Earl Meyer
New York State Department of Environmental Conservation
United States Department of Defense (DoD)
Clean Water Action Council of Northeast Wisconsin, Inc.
Air Products and Chemicals, Inc.
EnviroSource Treatment and Disposal Services, Inc. (TDS)
Independence Mining Company Inc. (IMCI)
Uniroyal Chemical Company, Inc.
Eastman Chemical Company
Nevada Mining Association (NvMA)
[Cerr-MeGee Corporation
Elf Atochem North America Inc.
Slew Mexico Mining Association
DuPont
Waste Management
FMC Corporation
Phelps Dodge Corporation
Arizona Mining Association
Beazer East, Inc.
AlliedSignal Inc.
Placer Dome U.S., Inc.
Phosphorus Producers Environmental Council
U.S. Borax, Inc.
Appalachian Producers
Aluminum Company of America; Kaiser Aluminum & Chemical Corporation;
Ormet Corporation; and Reynolds Metals Company.
AM AX Metal Recovery, Inc.
1037
-------
Commenter List, May 12,1997 (Continued)
Commenter #
COMM1099
COMM1100
COMM1101
COMM1102
COMM1103
COMM1104
COMM1105
COMM1106
COMM1107
COMM1108
COMM1109
COMML1001
COMML1002
COMML1003
Comnienter Name
Barrick Resources, Inc.
Koppers Industries, Inc.
IMC-Agrico Company
Echo Bay Mines
Mining Impact Coalition of Wisconsin Inc.
Precious Metals Producers (PMP)
California Mining Association
Freeport-McMoRan
Shoshone-Bannock Tribe Land Use Department
Texaco
Occidental Chemical Corporation (OxyChem)
Photographic & Imaging Manufacturers Association, Inc.
Phosphorus Producers Environmental Council
Environmental Technology Council
1038
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