IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
United States Environmental Protection Agency
Office of Solid Waste
December 1995
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Table of Contents
Section Page
I. Executive Summary I
A. Methods and Data Sources 2
1. Background 2
2. Scope of the Report 3
3. Methodology and Major Data Sources 4
4. Caveats and Limitations of Data Analysis ¦. . 9
B. Mineral Operations That May Generate Hazardous Waste 10
1. Introduction 10
2. Alphabetical Listing of Mineral Commodities and Waste Streams 10
C. Summary of Findings 26
II. Introduction 29
A Background 29
B. Scope of Project 30
C. Structure of the Document 31
III. Methods and Data Sources 33
A Identify Mineral Commodity Sectors of Interest 34
B. Conduct Exhaustive Information Search on Mineral Commodity Sectors of Interest 34
B.l. Review of Hard Copy Reports, Comments, and Survey Instruments 37
B.2. Electronic Literature Search 37
B.3. Contacts with Bureau of Mines 43
B.4. Review of Outside Data/Reports >. 43
C. Prepare Mineral Commodity Analysis Reports on Each of the Identified Sectors 48
C.l. Bevill-Exclusion Status 49
C.2. Waste Stream Sources and Form 65
C.3. Waste Stream Characteristics 65
C.4. Waste Stream Generation Rates 66
C.5. Waste Stream Management Practices 68
C.6. Waste Stream Recyclability and Classification 68
D. Define Universe of "Mineral Processing" Waste Streams Potentially Affected by the
Phase IV LDRs 69
E. Define Universe of "Mineral Processing" Facilities Potentially Affected by the
Phase IV LDRs 73
Caveats and Limitations of Data Analysis 73
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Mineral Commodities .si
A- Individual Mineral Commodity Reviews XI
1. Alumina and Aluminum 83
2. Antimony 109
3. Arsenic Acid . 127
4. Beryllium 131
5. Bismuth 159
6. Boron 171
7. Bromine . . . 183
8. Cadmium 191
9. Calcium Metal 203
10. Cesium and Rubidium 209
11. Chromium, Ferrochrome, and Ferrochrome-Silicon 219
12. Coal Gas 235
13. Copper 247
14. Elemental Phosphorus 291
15. Fluorspar and Hydrofluoric Acid 315
16. Gemstones 323
17. Germanium 327
18. Gold and Silver 343
19. Iodine 363
20. Iron and Steel 369
21. Lead 383
22. Lightweight Aggregate 427
23. Lithium and Lithium Carbonate 445
24. Magnesium and Magnesia 453
25. Manganese, Mn02, Ferromanganese, and Silicomanganese 471
26. Mercury 493
27. Molybdenum, Ferromolybdenum, and Ammonium Molybdate 503
28. Phosphoric Acid . . . 521
29. Platinum Group Metals 537
30. Pyrobitumens, Mineral Waxes, and Asphalt (natural) 551
31. Rare Earths, and Cerium and Lanthanides 559
32. Rhenium 585
33. Rutile (Synthetic) 593
34. Scandium 599
35. Selenium 611
36. Silicon and Ferrosilicon 623
37. Soda Ash 631
38. Sodium Sulfate 643
39. Strontium 649
40. Sulfur 655
41. Tantalum, Columbium, and Ferrocolumbium 665
42. Tellurium 683
43. Tin 691
44. Titanium and Ti02 699
45. Tungsten 733
46. Uranium 75
47. Vanadium 767
48. Zinc 78
49. Zirconium and Hafnium 809
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V. Summary of Findings 823
Appendices 865
A. Detailed Explanations of Methodology Used to Estimate Annual Waste Generation
Rates For Individual Waste Streams 865
B. Work Sheet for Waste Stream Assessment for Recycling, Recovery, and. Reuse Potential . 893
C. Definitions for Classifying Mineral Processing Waste Streams 897
D. Recycling Work Sheets for Individual Mineral Processing Waste Stream's 901
E. Listing of Waste Streams Generated by Mineral Production Activities by Commodity . . 1051
F. Colocated Facilities and Generators of "Special 20" Wastes
- Hazardous Waste Streams 1067
G. Colocated Facilities and Generators of "Special 20" Wastes
- Non-Hazardous Waste Streams 1089
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I. Executive Summary
The purpose of this executive summary is to summarize EPA's review of mineral commodities
which may produce hazardous wastes as defined by RCRA Subtitle C. EPA studied mineral commodities
as part of the RCRA requirements to establish treatment standards for newly identified RCRA hazardous
wastes. Through a series of rulemakings (see Background below) EPA has established criteria for 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 of the four characteristics of a
hazardous waste must be made subject to the Land Disposal Restrictions (LDRs). Accordingly, EPA will
be proposing treatment standards (Best Demonstrated Available Technology, or BDAT) for newly
identified mineral processing wastes, and expects to promulgate these standards by 1996. This work has
required EPA to perform further data collection and analysis activities in order to better identify "newly
identified" wastes and to develop BDAT treatment standards that are both adequately protective and
achievable.
As part of this effort, 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 Mine's 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 this draft technical background
document on the production of particular mineral commodities and associated operations that generate
mineral processing wastes.
This document, available in . the RCRA docket, represents the Agency's view that the wastes
discussed are, in fact, mineral processing wastes, rather than beneficiation wastes (beneficiation wastes
would be exempt from Subtitle C, because all beneficiation wastes remain within the scope of the Mining
Waste Exclusion). The Agency will be soliciting comment on this document and expects to revise it during
the course of this-rulemaking. The Agency is also seeking comments as to whether this document, when
finalized, should be a binding Agency determination. The other alternative is for the discussions of the
wastes to be merely interpretive, as are letters that are sometimes provided to parties inquiring about the
regulatory status of particular wastes. Such letters are non-binding and are not considered to be "final
agency action" within the meaning of the Administrative Procedures Act, but provide useful guidance as to
the Agency's initial assessment of the matter.
The Agency cautions that this draft 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 exemption.
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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, which was added in the 1980 Solid Waste
Disposal Act Amendments (also known as the "Bevill Amendment"). The Bevill Amendment precluded
EPA from regulating these wastes until the Agency performed a study and submitted a Report to
Congress, as directed by §8002(f) and (p), 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 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 of Adamstown 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
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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), corrosivitv (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 BDAT) in several phases that would 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. The
specific, methodology that EPA employed for this effort is described in detail in Section 3, Methods and
Data Sources, below.
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Based on this information, EPA prepared 49 separate analyses covering the 62 commodity groups
presented in Exhibit 1-1. Each analysis includes the 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 non-uniquely associated waste
stream).
waste stream characteristics (total constituent concentration data, and statements
on whether the waste stream exhibited one of the RCRA hazardous waste
characteristics of toxicity, ignitability, corcosivity, 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 was 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 represent 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 above 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.
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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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 both the 1993, 1994, and 1995 "Mineral Commodity
Summaries" prepared by the Bureau of Mines (BOM) for salient statistics
on commodity production.
Partially 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 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.
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.
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EXHIBIT 1-1
Mineral Commodities Of Potential Interest
1)
Alumina
32)
Lightweight Aggregate
2)
Aluminum
33)
Lithium (from ores)
3)
Ammonium Molybdate
34)
Lithium Carbonate
4)
Antimony
35)
Magnesia (from brines)
5)
Arsenic Acid
36)
Magnesium
6)
Asphalt (natural)
37)
Manganese and Mn02
7)
Beryllium
38)
Mercury
8)
Bismuth
39)
Mineral Waxes
9)
Boron
40)
Molybdenum
10)
Bromine (from brines)
41)
Phosphoric Acid
")
Cadmium
42)
Platinum Group Metals
12)
Calcium Metal
43)
Pyrobitumens
13)
Cerium, Lanthanides, and Rare Earth metals
44)
Rhenium
14)
Cesium/Rubidium
45)
Scandium
15)
Chromium
46)
Selenium
16)
Coal Gas
47)
Silicomanganese
17)
Copper
48)
Silicon
18)
Elemental Phosphorus
49)
Soda Ash
19)
Ferrochrome
50)
Sodium Sulfate
20)
Ferrochrome-Silicon
51)
Strontium
21)
Ferrocolumbium
52)
Sulfur
22)
Ferromanganese
53)
Synthetic Rutile
23)
Ferromolybdenum
54)
Tantalum/Columbium
24)
Ferrosilicon
55)
Tellurium
25)
Gemstones
56)
Tin
26)
Germanium
57)
Titanium/Ti02
27)
Gold and Silver
58)
Tungsten
28)
Hydrofluoric Acid
59)
Uranium
29)
Iodine (from brines)
60)
Vanadium
30)
Iron and Steel
61)
Zinc
31)
Lead
62)
Zirconium/Hafnium
NOTE: This list represents EPA's best efforts at identifying mineral commodities which may
generate mineral processing wastes. Omission or inclusion on this list does not relieve
the generator from managing wastes that would be subject to RCRA Subtitle C
requirements.
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In preparing the commodity sector reports, we used EPA's 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. 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.
3. Establish whether the waste and the operation that generates it are
uniquely associated with mineral production.
4. Determine whether the waste is generated by a mineral extraction,
beneficiation, or processing step.
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.2
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). Where documented
waste generation rates and analytical data were not available, EPA used a step-wise methodology
for estimating waste characteristics for individual waste streams to present mineral commodity
profiles that were as complete as possible. Specifically, 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 exhibited 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. However, to account for the
general lack of data for many of the mineral commodity sectors and waste streams, the Agency
2 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. The TCLP as applied to mineral processing wastes was recently remanded
to the agency, for further discussion, see the Applicability of TCLP Technical Background Document
elsewhere in today's docket.
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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. Precise methodology 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. EPA's Effluent
Guideline Documents. EPA survey instruments, and the literature. Since 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 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.
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 wetc 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
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.
EPA, through the process of researching and preparing mineral commodity analysis
reports for the mineral commodities, identified a total of 527 waste streams that are believed to
be generated at facilities involved in mineral production operations. The Agency then evaluated
each of the 527 waste streams to remove waste streams that would not be affected by the Phase
IV LDRs. Specifically, EPA removed:
• All of the extraction and beneficiation waste streams;
• The "Special 20" Bevill-Exempt mineral processing waste streams;
• Waste streams that were known to be fully recycled in process; and
• 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).
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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 148 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 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).
In addition, to present mineral commodity profiles that were 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 was 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).
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
level3. In cases where 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.
3 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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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).
EPA identified a total of 527 waste streams from a review of all mineral sectors. After
careful analysis, EPA determined that 41 commodity sectors generated a total of 354 waste
streams that could be classified as mineral processing wastes, 148 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 the authoritative list of processes and waste
streams. Ihese reports represent a best effort, and clearly do not include every potential process
and wastejfeeam affected by today's proposed 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
determiningpwhether the particular waste is covered by the Mining Waste Exclusion.
2. Alphabetical Listing of Mineral Commodities and Waste Streams
Agisting of the mineral commodity sectors that are likely to generate 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.
-------
EXIUItIT 1-2
Listing of Hazardous Mineral I'roci<:ssin<; Wastes.by Commodity Sector
Commodity and Summary Description
Waste Stream
Reported
General (on
(1000
mt/yr)
Estimated Generation
(1000 ml/yr)
TC Metals
Oilier Hazardous
Characteristics Yj
Low
Med.
IHgh
As
Ba
Cd
Cr
Pb
"e
Se
Corr
Jgnlt
Rclv
Alumina and Aluminum
Metallurgical grade alumina is exlracted from bauxite by the Bayer
process and aluminum is obtained from this purified ore by electrolysis
via the I lall-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 Mall-llcroult 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.
Cast house dust
19
-
-
-
Y
Y
N? '
N?
N?
Electrolysis
waste
58
-
-
Y?
N?
N?
N?
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
telrahedritc or lead ore. Antimony can be produced using either
pyrometallurgical processes or a hydrometallurgical 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 hydrometallurgically by leaching and
electrowinning.
Autoclave
filtrate
0.38
32
64
Y?
Y?
Y?
Y'»
Y?
N?
N?
Slag and furnace
residue
32
-
-
-
Y7
N>
N'
N7
Stripped anolyle
solids
0.19
-
-
Y?
N?
N?
N7
Beryllium
Rertrandite and-beryl oies are treated using two separate processes to
produce beryllium sulfate, BcSO,: a counter-current extraction process
and the Kjcllgren-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 berliandite and beryl ores and converts tlie
beryllium sulphate to beryllium hydroxide, Bc(OM)2. The beryllium
hydroxide is further converted to beryllium fluoitdc, BePj, which is then
calalytically reduced to foim metallic beryllium.
Spent barren
filtrate streams
88
-
Y
N7
N?
N?
Beitrandile
thickener slurry
370
-
-
V
N?
N''
Beryl thickener
slurry
3
-
-
Y
N?
N?
Chip treatment
wastewater
0.2
100
2000
Y'
N?
N?
N'
Initiation
discaid
-
02
45
90
Y?
N?
N?
N'
Spent lalfinatc
380
-
Y
Y
N'
N?
-------
1X11IIU1 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
Tt Metals
Other lliiznrdous
Characteristics JJ
Low
Med.
High
As
Ba
Cd
Cr
Pb
lis
Sc
Ag
Corr
lgnit
Rctv
Bismuth
Bismuth is recovered mainly during the smelling of copper and lead
ores. Bismuth-containing dust from copper smelting operations is
transferred to lead smelting operations for recovery. At lead smelling
operations bismuth is recovered either by the Betterton-Kroll process or
the Belts Electrolytic process. In the Belterlon-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 Blectrolytic process, lead bullion is eleclrolyzed The resulting
impurities, including bismuth, are smelted, reduced and refined.
Alloy residues
-
0.1
3
6
Y?
N?
N?
N?
Spent caustic
soda
-
0.1
6.1
12
Y?
N?
N7
N?
Electrolytic
slimes
- '
0
0.02
- 0.2
Y?
N?
N?
N?
Lead and zinc
chlorides
-
0.1
3
6
Y?
N?
N7
N7
Metal chloride
residues
3
-
-
Y?
N'
N'>
N'
Slag
-
0 1
1
10
Y?
N?
N?
N?
Spent electrolyte
-
0.1
6.1
12
Y?
N?
N>
N?
Spent soda
solution
-
0.1
6 1
12
Y?
Y?
N?
N?
Waste acid
solutions
-
0 1
6 1
12
Y7
N7
N7
Waste acids
-
0
0.1
0.2
Y?
N7
N''
Boron
Boron (borax) is either recovered from ores or from natural mineral-
rich lake brines by two companies in the U S. Recovery from ores
involves the following steps: (1) ore is dissolved in water; (2) Ihe
resulting insoluble material is separated fiom the solution, and (3)
crystals of sodium borate arc separated from the weak solution and
dried Boron is recovered from brines involves solvent extraction,
acidification, and fractional distillation followed by evaporation.
Waste liquor
0.3
150
300
Y?
N?
N?
N7
-------
I XIIim i 1-2 (Continued)
Commodity and Summitry Description
Waste Stream
Reported
Generation
(1000
nit/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1j
Low
Med.
High
As
Itu
Cd
Cr
I'b
»g
Se
Ag
Corr
Ignit
Rctv
Cadmium
Cadmium is obtained as a byproducl of zinc metal production.
Cadmium metal is obtained from zinc fumes or precipitates via a
hydrometallurgical or a pyromctallurgical 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 pyromelallurgical 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.
Caustic
washwalcr
-
0 19
1 9
19
Y?
Y?
N?
N?
Copper and lead
sulfate filler
cakes
-
0.19
1.9
19
Y?
Y?
N?
N?
N?
Copper removal
filter cake
0.19
1.9
19
Y?
N?
N?
N?
Iron containing
impurities
-
0 19
1.9
19
Y?
N?
N?
N?
Spent leach
solution
0.19
1.9
19
Y?
Y?
Y?
Y?
N?
N?
Lead sulfate
waste
0 19
1 9
19
Y?
Y?
N?
N?
N?
Post-leach filter
cake
0 19
1.9
19
Y?
N?
N?
N?
Spent
purification
solution
0.19
1.9
19
Y?
Y?
N?
N?
Scrubber
wastewatei
0 19
1.9
19
Y?
Y?
N?
N?
Spent electrolyte
0 19
1.9
19
Y?
Y?
N?
N?
Zinc precipitates
0.19
1.9
19
Y?
N?
N?
N.'
Calcium Metal
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
')')% pure calcium metal which can be further purified Ihiough
distillation
Dust with
quicklime
-
0.04
0.04
0.04
Y?
N?
N?
-------
EXIIIIHT 1-2 (Continued)
Commodity and Summary Descripllon
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
At.
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignil
Rclv
Coal Gas
Coal is crushed and gasified in (he presence of steam and oxygen,
producing carbon dioxide and carbon monoxide, which further read to
produce carbon oxides, methane and hydrogen. The product gas is
separated from the flue gas, and is processed and purified to saleable
methane.
Multiple effects
evaporator
concentrate
0
0
65
Y
Y
N?
N?
N?
Copper .
Copper is recovered from ores using cither 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 clcctrowinning
Acid plant
blowdown
4800
-
Y
Y
Y
Y
Y
Y
Y
Y
N?
N7
APC
dusts/sludges
-
1
220
450
Y?
N?
N7
N?
Spent bleed
clectrolyle
310
-
-
Y
Y
Y
Y
Y
Y
Y
N?
N?
Waste contact
cooling water
13
-
Y?
N?
N?
N?
Process
wastewaters
4900
-
-
Y
Y
Y
Y
Y?
Y
N?
N?
Scrubber
blowdown
-
49
490
4900
Y
Y
Y?
Y
N>
N?
N?
Surface
impoundment
waste liquids
620
-
-
-
Y?
Y?
Y?
Y
N?
N?
Tankhousc
slimes
4
-
Y'
Y7
Y?
Y?
N?
N?'
N?
WWTP sludge
6
-
Y 7
Y?
N7
N?
N7
-------
EXHIBIT 1-2 (Continued)
Commodity and Suninmry Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
C'r
I*b
Hg
Se
Ae
Corr
Ignlt
Kctv
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 arc lapped. Dusts are removed from
the furnace offgases and phosphorus is removed from the dusts by
condensation
Dust
4.4
-
Y?
N?
N?
N7
AFM rinsate
2
-
-
Y
Y
N7
N7
N7
Furnace offgas
solids
24
-
-
Y
N?
N?
N?
Furnace
scrubber
blowdown
-
270
Y
YS.
N?
N?
Slag
quenchwater
-
0
0
1000
Y? -
Y7
N7
N?
N7
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.
Off-spec
lluosilicic acid
0
15
44
Y?
N?
N7
Germanium
Germanium is recovered as a by-product of other metals, mostly
copper, zinc, and lead Germanium-bearing residues from 7.inc-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 acid wash
and rinse water
0.4
2.2
4 ¦
Y?
Y?
V
Y?
Y?
Y?
Y?
N7
N7
Chlorinator wet
air pollution
control sludge
001
0 21
0.4
Y?
' Y?
Y?
Y?
Y?
Y?
N?
N?
N?
Hydrolysis
filtrate
-
0.01
0.21
0.4
Y9
Y'
Y?
Y>
Y7
Y?
N7
N7
N''
l each residues
001
-
-
Y7
Y?
N?
N7
N7
Spent
acid/lcachatc
04
22
4
Y?
Y7
Y?
N7
N7
Waste still
liquor.
-
001
0 21
0.4
Y'»
Y>
Y?
Y''
Y?
Y?
N?
Y?
N7
-------
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Oilier Hazardous
Characteristics ]_/
Low
Med.
High
As
»u
Cd
Cr
Pb
»S
Se
Ag
Corr
Ignil
Hclv
Gold and Sliver
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 by acid leaching or electrolysis. The Merrill Crowe process
consists 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 dor6 is sent to refining.
Spent furnace
dust
-
01
360
720
Y?
Y?
N?
N'
Refining wastes
-
0.1
360
720
Y?
N?
N?
N?
Slag
-
0 1
360
720
Y?
N?
N?
•tf?
Wastewater
treatment sludge
-
0.1
360
720
Y'
N?
N?
N?
Wastewater
440
870
1700
Y?
Y?
y
Y?
Y?
N?
N?
N7
Lead
Lead ores are crushed, ground, and concentrated Pclletized
concentrates are then fed to a sinter unit with oilier 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
drosscd to remove lead and other metal oxides The lead bullion may
also be dccoppcrizcd before being sent to the refining stages. Refining
operations generally consist of several steps, including (in sequence)
softening, desilverizing, dczincing, bismuth removal and final refining.
During final refining, lead bullion is mixed with various fluxes and
reagents to remove remaining impurities.
Acid planl
blowdown
560
-
Y
Y
Y
Y?
Y
Y
N?
N?
Acid planl
sludge
14
-
Y?
N?
N?
Daghouse dust
46
Y
Y
N?
N?
N?
Baghousc
incinerator ash
-
0.7
3
30
Y
Y
N?
N?
N?
Process
wastewater
4000
-
Y
Y
Y
Y?
Y
N?
N>
N?
Slurried APC
dust
7
-
Y
Y
N?
N'
N'>
Solid residues
04
-
Y?
N?
N?
N?
¦Spent furnace
brick
1
-
Y
N?
N?
N'
-------
EXHIBIT 1-2 (Continued)
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1j
Commodity and Summary Description
Waste Stream
Low
Med.
High
As
Ba
Cd
Cr
I'b
»g
Se
Ag
Corr
Ignif
Rclv
Lend (continued)
Stockpiled
miscellaneous
plant waste
-
04
80
100
Y
Y
N?
N?
N7
Surface
impoundment
waste liquids
1100
-
-
-
Y?
Y?
Y?
N?
N?
N?
WWTP liquid
effluent
3500
-
-
-
Y?
Y
N7
N?
WWTP
sludges/solids
380
-
Y?
y
Y
N?
N?
Magnesium and Magnesia
from Brines
Magnesium is recover 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
licl and HjSO^ 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 arc 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
Cast house dust
-
0.076
0.76
7.6
Y?
N?
N?
N?
Smut
26
Y
N?
N?
N?
Magnesia is produced by calcining magnesitc or magnesium hydroxide
or by the thermal decomposition of magnesium chloride, magnesium
sulfate, magnesium sulfite, nesquehonite, or the basic carbonate.
-------
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
, Estimated Generation
(1000 mt/yr)
TC Metals
Oilier Hazardous
Characteristics 1/
Low
Med.
High
As
Da
Cd
Cr
Pb
Jig
Se
Ag
Corr
Ignltf
Rclv
Mercury
Mercury currently is recovered only from gold ores. Sulfide-bearing
gold ore is roasled, and the mercury is recovered from the exhaust gas.
Oxide-based gold ore is crushed and mixed with water, and 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 clcclrowinning, 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.
Dust
0.01
-
-
-
Y?
N?
N?
N7
Mercury quench
water
81
99
540
Y?
Y?
N?
N?
N?
Furnace residue
0.1
-
Y?
N?
N?
N?
Molybdenum,
Ferromolybdenum, and
Ammonium Molybdale
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 metallolhermic
process using silicon and/or aluminum as the reductant.
Flue dust/gases
-
1 2
270
540
Y?
N?
N?
N?
Liquid residues
1
-
-
Y7
Y?
Y?
Y?
N?
N?
N?
Molybdic oxide
refining wastes
2
-
-
-
Y?
N?
N?
N?
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 ciushed and tiealed 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.
Slag
-
0 0046
0 046
0 46
Y'
Y?
N7
N?
N?
Spent acids
0.3
1.7
3
Y?
Y?
Y?
N?
N?
Spent solvents
-
0 3
1.7
3
Y?
Y?
N?
Y'
N?
-------
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
»S
Se
Ag
Corr
Ignit
Rctv
Pyrobitumens, Mineral
Waxes, and Natural Asphalt
The production process for pyrobitumens consists of cracking in a still,
recondensation, and grading. Mineral wax processing consists of solvent
extraction from lignite or cannel coal. To produce natural asphalt, ore
is processed through a vibrating bed dryer, and sorted according to
particle size. The material is cither loaded directly as bulk product, fed
to a bagging machine, or fed into a pulverizer for further size reduction.
Still bottoms
0.002
45
90
N?
Y?
N?
Waste catalysts
0.002
10
20
Y?
Y?
Rare Earths
Rare earth elements arc produced from monazile and baslnasitc ores by
sulfuric and hydrochloric acid digestion. Processing of rare earths
involves fractional crystallization and precipitation followed by solvcnl
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.
Spent
ammonium
nitrate
processing
solution
14
-
Y
N?
N?
Electrolytic cell
caustic wet Al'C
waste
0.07
07
7
Y?
N?
N?
Spent lead filter
cake
-
3.3
42
5
Y?
N?
N?
N?
Process
wastewater
7
-
Y
Y?
N?
N?
Spent scrubber
liquor
0.1
500
1000
YS
N?
N?
.Solvent
extraction crud
2
45
90
N?
Y?
N'
Waste solvent
2
1000
2000
N?
Y?
N?
Wastewater
fiom causlic wet
Al'C
0 1
500
1000
Y?
Y?
Y?
N9
N'>
Waste zinc
contaminated
with meicury
2
45
90
Y?
N9
N>
N7
-------
PO
o
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(100(1
mt/yr)
Estimated Generation
(1000 mt/yr)
I'C Metals
Oilier Hazardous
Characteristics 1j
Low
Med.
High
As
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignlt
Rclv
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 arc converted to molybdic oxide and rhenium is converted
to rhenium heploxide. The 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 II2S and 1 lcl) and filtration; (4)
oxidation and evaporation; and (S) reduction.
Spent barren
scrubber liquor
-
0
0.1
0.2
Y?
N?
N
N
Spent rhenium
raffinate
88
-
-
Y?
N?
N?
N?
Scandium
Scandium is generally pioduccd by small bench-scale balch processes.
The principal domestic scandium resource is fluorite tailings containing
thortveitite and associated scandium-enriched minerals. Scandium can
be lecovered from thortveilile 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.
Spent acids
0.7
3.9
7
Y?
N?
N>
Spent solvents
from solvenl
extraction
07
3.9
7
N?
Y?
N?
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 (he flue gas, or is incorporaled 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. To
purify the ciude selenium, il 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.
Spent filler cake
0.05
05
5
Y?
N?
N?
N?
Plant process
wastewater
66
-
-
-
Y
Y
N?
N''
Slag
-
0.05
0 5
5
Y?
N?
N>
N''
Tellurium slime
wastes
-
0 05
0.5
5
N?
Y?
N?
N''
Waste solids
-
0 05
05
¦5
Y?
N?
N7
N''
-------
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
"8
Se
Ag
Corr
Ignit
Rctv
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 Ihc ilmenite ore is completely reduced to metal and
separated either chemically or physically; (2) processes in which iron is
reduced to the ferrous stale and chemically leached from the ore; and
(3) processes in which selective chlorination is used lo remove the iron
In addition, a process called the Benelite Cyclic process uses
hydrochloric acid to leach iron from reduced ilmenite.
APC
dust/sludges
30
-
Y?
Y?
N7
N?
N?
Spent iron oxide
slurry
45
-
-
-
Y?
Y?
N?
N?
N?
Spent acid
solution
30
-
-
Y?
Y?
Y?
N?
N?
Tantalum, Columbium, and
Ferrocolumblum
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 lo 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.
Digester sludge
1
-
-
-
Y
N?
N?
Process
wastewater
150
-
-
-
Y?
Y?
Y?
Y?
Y9
Y
N?
N?
Spent raffiniite
solids
2
-
-
-
Y
N?
N?
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
Slag
-
0.1
1
4.5
Y?
N?
N?
N?
Solid waste
residues
-
0.1
1
4.5
Y?
N?
N?
Y?
Waste
electrolyte
-
0 1
1
10
Y?
Y?
N?
N?
N>
Wastewater
0 1
10
20
Y?
Y
N?
N>
-------
Ni
NJ
EXHIBIT 1-2 (Continued)
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Oilier Hazardous
Characteristics 1/
Commodity and Summary Description
Waste Stream
Low
Med.
High
As
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignit
Rciv
Titanium and
Titanium Dioxide
Waste ferric
chloride
-
22
29
35
Y
Y
Y
Y
Y?
N?
N?
Titanium ores arc utilized in the production of four major titanium-
based products: titanium dioxide (Ti02) pigment, titanium tetrachloride
Pickle liquor and
wash water
-
2.2
2.7
3.2
Y?
Y?
Y?
Y?
N?
N?
(T1CI4), titanium sponge, and Jitanium ingot/metal. The primary
titanium ores for manufacture of these products are ilmenite and rutile.
Ti02 pigment is manufactured through cither the sulfate, chloride, or
Scrap milling
scrubber water
-
4
5
6
Y>
Y?
Y?
Y?
N?
N?
N?
chloridc-ilmcnite process The sulfate process employs digestion of
ilmenite ore or Ti02-rich slag with sulfuric acid to produce a cake,
which is purified and calcined to produce Ti02 pigment. In the chloride
process, rutile, synthetic rutile, or high-purity ilmenite is chlorinated to
form TiCI4, which is purified to form Ti02 pigment. In the chloridc-
ilmenite process, a low-purity ilmenite is converted to T'iCI., in a two-
stage chlorination process. Titanium sponge is produced by purifying
TiCI4 generated by the chloride or cliloride-ilmenite process. Titanium
sponge is cast into ingots for further processing into titanium metal
Scrap detergent
wash water
360
450
540
Y?
Y?
Y?
Y?
Y
N?
N?
Smut from Mg
recovery
-
0.1
22
45
N?
N?
Y
Leach liquor
and sponge wash
water
-
380
480
580
Y?
Y?
Y
N>
Y?
Spent surface
impoundment
liquids'
-
.63
3.4
6.7
Y?
Y?
N?
N?
N?
Spent surface
impoundments
solids
36
-
-
-
Y?
Y7
N?
N?
N?
Waste acids
(Chloride
process)
49
-
-
Y?
Y?
Y?
Y
N
N
Waste acids
(Sulfate piocess)
0.2
39
77
Y
Y
Y
Y
Y
N
N
WWTP sludge/
solids
420
Y
N
N
N
-------
EXHIBIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
»g
Se
Afi
Corr
Ignit
Rctv
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.
Spent acid and
rinse water
-
0
0
21
Y?
N?
N?
Process
wastewater
-
1.8
3.7
73
Y?
N>
N?
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 nitric acid
from U02
production
-
1 7
25
3.4
Y?
N?
N?
Vaporizer
condensate
-
1.7
9.3
17
Y?
N'
N'
Superheater
condensate
-
1.7
93
17
Y?
N?
N?
Slag
0
85
17
N?
Y?
N?
Uranium chips
from ingot
production
-
1.7
25
3.4
N?
Y?
N?
rvj
UJ
-------
NJ
EXIIIHIT 1-2 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(i 000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
»g
Se
Ag
Corr
Ignlt
Rctv
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 electrotliermic 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.
Acid plant
blowdown
130
-
-
Y
Y
Y
Y?
Y?
Y
Y
Y
N
N
Waste
ferrosilicon
17
-
-
Y?
N?
N?
N?
Spent goethitc
and leach cake
residues
15
-
Y
Y
Y
Y?
Y?
Y
Y
N?
N?
N?
Process
wastewater
6600
-
-
Y
Y
Y
Y
Y
Y
Y
N?
N?
Discarded
refractory brick
1
-
-
r>
Y?
Y?
Y?
N7
N?
N7
Spent cloths,
bags, and filters
0.2
-
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
Spent surface
impoundment
liquids
2500
-
Y?
Y
N7
N?
Spent surface
impoundment
solids
1
-
-
Y?
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
Spent synthetic
gypsum
21
-
Y?
Y
Y?
N?
N?
N?
TCA tower
blowdown (ZCA
Bartlesville,
OK-Eleclrolytic
plant)
25
-
Y?
Y?
Y?
Y?
Y?
N7
N7
WWII' liquid
effluent
3500
-
-
Y?
N?
N?
N?
Zinc-lean slag
17
-
Y'>
N?
N7
N?
-------
EXHIBIT 1-2 (Continued)
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1J
Commodity and Summary Description
Waste Stream
Low
Med.
High
As
Da
Cd
Cr
Pb
HS
Se
A«
Corr
Ignit
Rctv
Zirconium and
llarnlum
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
Spent acid
leachate from
zirconium alloy
production
-
0
0
850
Y?
N?
N?
Spent acid
leachate from
zirconium metal
production
-
0
0
1600
Y?
N?
N?
dioxide employ reduction and purification steps only.
Leaching rinse
water from
zirconium alloy
production
-
34
42
51
Y?
N?
N?
Leaching rinse
water from
zirconium metal
production
-
0.2
1000
2000
Y?
N?
N?
1/ Corr., Ignit., and Rclv. refer lo the RCRA hazardous characteristics of corrosivity, lgnilabihly, and reachviiy
NJ
tn
-------
26
C. Summary of Findings
EPA has determined that 48 commodity sectors generate a total of 527 waste streams that
could be classified as either extraction/beneficiation or mineral processing wastes. After careful
review, EPA determined that 41 commodity sectors generated a total of 354 waste streams that
could be classified as mineral processing wastes.
Of the 354 mineral processing waste streams identified by the Agency, EPA has sufficient
information (based on either analytical test data or engineering judgment) to determine that 148
waste streams (from 31 commodity sectors) are possibly RCRA hazardous wastes-because they
exhibit one or more of the RCRA hazardous waste characteristics: toxicity, ignitability,
corrosivity, and reactivity. Exhibit 1-3 identifies the mineral processing commodity, sectors that
generate RCRA hazardous mineral processing wastes that 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
Estimated Annual Generation Rate {1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Mineral Processing Commodity Sectors
Number of
Waste
Streams 1/
Low Estimate
Medium Estimate
High Estimate
Alumina and Aluminum
2
77
77
77
Antimony
3
33
64
96'
Beryllium
6
740
990
2,900
Bismuth
10
3.7
35
73
Boron
1
0.30
150
300
Cadmium
11 '
2.1
21
210
Calcium Metal
1
0.040
0.040
0 040
Coal Gas
1
0
0
65
Copper
9
10,000
11,000
15.000
Elemental Phosphorus
5
30
30
1.300
Fluorspar and Hydrofluoric Acid
1
0
15
44
Germanium
6
0.84
5.0
9.2
Gold and Sliver
5
440
2.300
4,600
Lead
12
9,600
9,700
9.800
-------
EXHIBIT 1-3 (Continued)
Mineral Processing"Commodity Sectors
Number of
Waste
Streams V
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
Magnesium and Magnesia from Brines
2
26
27
34
Mercury
3
81
99
540
Molybdenum, Ferromolybdenum, and
Ammonium Molybdate
3
4.2
270
540
Platinum Group Metals
3
0.60
3.5
65
Pyrobitumens. Mineral Waxes,
and Natural Asphalt
2
0.0040
55
110
Rare Earths
9
39
2,100
4.200
Rhenium
2
88
88
88
Scandium
2
1.4'
7.8
14
-Selenium
5
66
68
86
Synthetic Rutile
3
100
100
100
Tantalum, Columbium, and Ferrocolumbium
3
150
150
150
Tellurium
4
0.40
13
39
Titanium and Titanium Dioxide
11
1,300
1,500
1,800
Tungsten
2
1.8
3.7
28
Uranium
5
6.8
32
58
Zinc
12
13,000
13,000
13,000 '
Zirconium and Hafnium
4
34
1.000
4,500
TOTAL;
148
36,000
43,000
60.000
In calculating the total number of waste streams per mineral sector, EPA included both no'n-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).
-------
28
-------
p##/ , -
Pfl q/l-SMl-B
-------
PHM-A-5ocol.f
29
II. Introduction
A. 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, which was added in the 1980 Solid Waste
Disposal Act Amendments (also known as the "Bevill Amendment"). The Bevill Amendment precluded
EPA from regulating these wastes until the Agency performed a study and submitted a Report to
Congress, as directed by §8002(f) and (p), 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 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 of Adamstown 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 these 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
-------
30
promulgated special wastes criteria; all other mineral processing wastes were removed from the Mining
Waste Exclusion. The 20 special wastes were studied in a 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 BDAT) in several phases that would 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 is 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.
B. Scope of Project
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 effort.
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 ctontractors, 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. The
specific methodology that EPA employed for this effort is described in detail in Section III, Methods and
Data Sources, below.
Based on this information, EPA prepared 49 analyses covering 62 commodity groups. Each
mineral commodity analysis report consists of a summary describing the uses of the commodity, a detailed
process description and process flow diagram, and a process waste section that identifies ~ to the.
maximum extent practicable - individual waste streams, sorted by the nature of the operation (i.e.,
-------
31
extraction/beneficiation or mineral processing). Within the process waste section, EPA also identified:
waste stream sources and form; Bevill-Exclusion status of the waste stream; waste stream characteristics:
annual generation rates; management practices; and, whether the waste stream was being (or could
potentially be) recycled, and thus be classified as a sludge, by-product, or spent material. 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. Tliese 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.
C. Structure of the Document
The remainder of this document is organized into three additional sections. Section III 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 IV presents the 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 V summarizes the findings of this study.
-------
f 44-50001. C
3
o *
la
o »
id a
» 3
2.
O
a
**
OJ
-------
34
A.
Identify Mineral Commodity Sectors of Interest
Identify Mineral Commodity
Sectors of Interest
J
r
Conduct Exhaustive Information Search
on s^ireral Commodity Sectors of Interest
r
i
r
i
r
I
EPA reviewed the 36 industrial sectors (commodities) and
97 different general categories of wastes previously developed
under this contract and published in the October 21, 1991
Advanced Notice of Public Rule Making (ANPRM). EPA also
reviewed the U.S. Bureau of Mines's 1991 Minerals Yearbook,
1995 Mineral Commodities Summary, and the 1985 Mineral Facts
and Problems. The Agency reviewed this comprehensive listing of
all of the mineral 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 3-2.
The Agency notes that Exhibit 3-2 represents EPA's best
efforts at identifying mineral commodities which may generate
mineral processing wastes. Omission or inclusion on this list does
not relieve the generator from managing wastes that would be
subject to RCRA Subtitle C requirements.
Step One
B. Conduct Exhaustive Information Search on Mineral Commodity Sectors of Interest
EPA researched and obtained information characterizing the mineral processing operations and
wastes associated with the mineral commodities listed in Exhibit 3-2. 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.
1 Sectors that employ operations that mill (e.g., grind, sort, wash), physically separate (e.g., magnetic, gravity, or
electrostatic separation, froth flotauon), 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 digesuon) are unaffected by the proposed Phase IV LDRs.
-------
P^q. A" 6^oDi,d
33
III. 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 in order to assure 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 3-1.
EXHIBIT 3-1
Overview of the Agency's Methodology for Defining the Universe of Potentially
Affected Mineral Processing Waste Streams
STEP 1
STEP 2
STEP 3
STEP 4
STEP 5
Define Universe of Mineral
Processing Facilities Potentially
Affected by the Phase IV LDRs
-------
r
Identify Mineral Commodity
Sectors of Interest
>
Conduct Exhaustive Information Search
on Mineral Commodity Sectors of Interest
~
^ Prepare Mineral Commodity Analysis
| Reports on Each Sector
r
>
r
>
Step Two
Reviewed numerous documents provided bv
EPA (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 through out
the United States.
Reviewed sampling data collected by EPA's
Office of Research and Development (ORD).
EPA's Office of Water (OW), and Agency
survey data collected to support the
preparation of the 1990 Report to Congress.
Reviewed both the 1993, 1994, and 1995
"Mineral Commodity Summaries" prepared by
the U.S. Bureau of Mines (BOM) for salient
statistics on commodity production.
Partially 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 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.
-------
EXHIBIT 3-2
Mineral Commodities Of Potential Interest
1)
Alumina
32)
Lightweight Aggregate
2)
Aluminum
33)
Lithium (from ores)
3)
Ammonium Molybdate
34)
Lithium Carbonate
4)
Antimony
35)
Magnesia (from brines)
5)
Arsenic Acid
36)
Magnesium
6)
Asphalt (natural)
37)
Manganese and Mn02
7)
Beryllium
38)
Mercury
8)
Bismuth
39)
Mineral Waxes
9)
Boron
40)
Molybdenum
1Q)
Bromine (from brines)
41)
Phosphoric Acid
11)
Cadmium
42)
Platinum Group Metals
12)
Calcium Metal
43)
Pyrobitumens
13)
Cerium, Lanthanides, and Rare Earths
44)
Rhenium
14)
Cesium/Rubidium
45)
Scandium
15)
Chromium
46)
Selenium
16)
Coal Gas
47)
Silicomanganese
17)
Copper
48)
Silicon
18)
Elemental Phosphorus
49)
Soda Ash
19)
Ferrochrome
50)
Sodium Sulfate
20)
Fenochrome-Silicon
51)
Strontium
21)
Ferrocolumbium
52)
Sulfur
22)
Ferromanganese
53)
Synthetic Rutile
23)
Ferromolybdenum
54)
Tantalum/Columbium
24)
Ferrosilicon
55)
Tellurium
25)
Gemstones
56)
Tin
26)
Germanium
57)
Titanium/Ti02
27)
Gold and Silver
58)
Tungsten
28)
Hydrofluoric Acid
59)
Uranium
29)
Iodine (from brines)
60)
Vanadium
30)
Iron and Steel
61)
Zinc
31)
Lead
62)
Zirconium/Hafnium
-------
EXHIBIT 3-3
Summary of On-line Databases Searched
Databases*
Description
Subjects Covered
Sources
NTIS
Dates 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 their 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 -- Atmospheiic
Sciences -- Behavior and Society -- Biomedical
Technology and Engineering -- Building Industry
Technology - Business and Economics -
Chemistry -- Civil Engineering -- Communication
- Computers, Control, and Information Theory --
Electrotechnology -- Energy -- Enviionmenlal
Pollution and Control -- Health Planning --
Industrial and Mechanical Engineering -- Libiary
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 llic
repoils of four major U.S. fcdeial
government agencies: US Depaitmciil
of Energy (DOE), U S. Department ol
Defense (DoD), U.S. Environmental
Protection Agency (EPA), National
Aeronautics and Space Adminisiralion
(NASA), plus.many other agencies
COMPENDEX PLUS
Dates Covered
1970 to the present.
File Size
3,015,116 records as of 1/93.
Update Freauencv
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 El ENGINEERING MEETINGS aie included.
Aeronautical and Aerospace Engineering -
Applied Physics (High Energy, Plasma, Nuclear
and Solid State) - Bioengirieering and Medical
Equipment -- Chemical Engineering, Ceramics,
Plastics and Polymers, Food Technology -- Civil
and Structural Engineering, Environmental
Technology - Electrical, Instrumentation, Contiol
Engineenng, Power Engineering -- Electronics,
Computers, Communications - Energy Technology
and Petroleum Engineering Engineenng
Management and Industrial Engineering - Light
and Optical Technology - Marine Engineenng,
Naval Aichiteclure, Ocean and Underwater
Technology -- Mechanical Engineenng, Automotive
Engineering and Transpoitalion -- Mining and
Metallurgical Engineering, and Matcnals Science
Publications from around the woild aie
indexed, including appioximately 4,5011
journals, publications of engineering
societies and oigamzations,
approximately 2,000 conferences per
year, technical reports, and monographs
-------
37
B.l 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 reasonably detailed process flow diagrams for the
following 27 commodities:
• Alumina
• Aluminum
• Antimony
• Bismuth
• Cerium/Lanthanides/Rare Earth Metals
• Cesium/Rubidium
• Coal Gas
• Copper
• Elemental Phosphorus
• Germanium
• Gold and Silver
• Hydrofluoric Acid
• Iron and Steel
• Lead
Lightweight Aggregate
Magnesium
Mercury
Molybdenum
Phosphoric Acid
Rhenium
Scandium
Soda Ash
Synthetic Rutile
Titanium/Ti02
Tungsten
Uranium
Zinc
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 were 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 3-3.
Using the on-line databases summarized in Exhibit 3-3, we searched for relevant
information (published since 1990) on the mineral commodities listed in Exhibit 3-2 using the
keywords presented in Exhibit 3-4. 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 Amendment to cover
truly "high volume, low toxicity" wastes.
-------
o
EXHIBIT 3-3 (Continued)
Summary of On-mnk Databases Searciikd
Databases
Description
Subjects Covered
Sources
POLLUTION ABSTRACTS
Dales Covered
1970 to the present.
File Size
POLLUTION ABSTRACTS is a leading resource for references
to environmentally related literature on pollution, ils 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 woild, including luniks,
conference papers/proceedings,
periodicals, research papers, and
technical reports.
185,551 records as of 1/93.
Update Freoucncv
Bimonthly.
ENVIRONMENTAL
BIBLIOGRAPHY
Dales Covered
1973 to llie presenl.
ENVIRONMENTAL BIBLIOGRAPHY provides access lo 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
wanning, and many other specialized subjects of environmental
consequence.
Air - Energy -¦ I luman and Animal Ecology -
(.and Resources -- Nutrition ami Health — Water
Resources
More than 400 <>l 1 lie woild's journals
concerning the enviioninenl aic .scanned
lo create ENVIRONMENTAL
BIBLIOGRAPHY
File Size
451,702 records as of 1/93.
Update Freauencv
Bimonthly (4,000 records per
update).
-------
EXHIBIT 3-3 (Continued)
Summary of On-link Databases Searched
Databases
Description
Subjects Covered
Sources
METAUEX
Dates Covered
1966 (o the present.
File Size
911,907 records as of 1/93.
Update Frequency
Monthly.
The M FT AD EX (Melals Abslracls/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 Melal Literature (1966-1967),
Metals Abstracts (1968 to the present), Alloys Index (1974 to
the present), Steels Supplement (1983-1984), and Steels Alert
(January - June 198S). 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 intcrmetalhc
compounds found within these systems.
Materials -- Processes -- Properties -- Products --
Forms - Influencing Factors.
Each month over 3,000 new documents
from a variety of international soiuccs
are scanned and abstracted lor the ASM
database, with intensive coveiagc >>l
appiopriate journals, conference papers,
reviews, technical reports, and books.
Dissertations, U.S patents, and
government reports' have been included
since 1979, British (OB) 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'Mechamcal Metallurgy --
Business Information -- Extractive Metallurgy --
Metalworking, Fabrication, and Finishing -
Engineering Properties and Tests -- Quality
Control and Tests -- End Uses of Aluminum --
Aluminum Intermetalhcs - Patents
'Hie AIA database includes information
abstracted from approximately 2,300
scientific and technical journals, patents,
government reports, confeience
proceedings, dissertations, books, and
othei publications.
ENVIROL1NE
Dales Covered
January 1, 1971 to the present.
File Size
165,000 records as of 10/93.
Update Frequency
Monthly
ENV1ROLINE 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 & Uiban
Ecology -- Energy - Environmental Education -
Food and Drugs -- General Environmental Topics
-- International F.nvitonmenlal Topics -- Land Use
& Pollution - Noise Pollution - Non-Renewable
Resources - Oceans and Estuaries -- Population
Planning & Control -- Radiological Contamination
-- Renewable Resources - Teiiestnal - Walei --
Toxicology & Envuonihcntal Safety -
Transportation -- Waste Management -- Water
Pollution - Weather Modihcation & Geophysical
Change -- Wildlife.
ENV1ROLINE draws material trom
over 1,000 scientific, technical, li.ide,
professional, and general periodicals;
confeience papers and pioceedmgs,
government documents; industry
leports, newspapers; and project
reports.
UJ
-------
42
Accordingly, using the strategy outlined in Exhibit 3-4, 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 3-2 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 the full text). This modification allowed for a more manageable number of citations -
1,242 titles.
EXHIBIT 3-4
Keywords and Search Strategy
Keywords
Modifiers
Industrial Sector with
Waste
with
Characteristics
or
or
Residue
Composition
°r
or
Wastewater
Properties
or
or
Sludge
Recovery
or
or
Slag
Recycling
or
or
Dust
Reduction
or
or
Blowdown
Reuse
or
Generation
or
Management
or
Treatment
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
-------
EXHIBIT 3-3 (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 updale).
GEOREF, Ihe 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 — Eneigy
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
Ihe U S. Publications of international
organizations represent about 7 peiccnt
of the file. The database includes
coverage of over 3,500 journals as well
as books and book chapters, eonfeienet
papers, government publications, theses,
dissertations, reports, maps, and meeting
papers
MATERIALS BUSINESS FILE
Dales Covered
1985 to the present.
File Size
83,228 records as of 1/93.
Update Freauencv
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 icpoits,
dissertations, and conference
proceedings are reviewed and ab.Miacled
from worldwide sources
-------
43
one or more of the commodities listed in Exhibit 3-2. 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). Not surprisingly, the top five industrial sectors that
appear to be the most studied (based on number of citations meeting our search strategy
specifications) are:
• Iron and Steel (1,460 titles);
• Alumina/Aluminum (1,242 titles);
• Copper (1,081 titles);
• Chromium (833 titles); and
• Lead (800 titles).
Lastly, 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 T- and $3 per minute of on-line time), we only attempted to retrieve
information on the following ten commodities:
• Arsenic Acid
• Asphalt (natural)
• Ferroalloys (all of them)
• Manganese
• Pyrobitumens
Limited process information was only
waxes (natural), and zirconium/hafnium.
B.3 Contacts with Bureau of Mines
• Rare Earths
• Rubidium
• Tantalum/Columbium
• Waxes (mineral)
• Zirconium/Hafnium
available for ferroalloys, manganese, rare earths,
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
several commodity specialists were able to provide technical information. We present below in
Exhibit 3-5, a listing of the Bureau of Mines personnel contacted by EPA.
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 91' ANPRM was published, EPA also reviewed:
• 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
-------
EXHIBIT 3-5
List of Personal Communications
Contacts
Telephone Nos.
Commodity Sectors
John Blossom
202-501-9435
Molybdenum
Rhenium
Larry Cunningham
202-501-9443
Columbium (niobium)
Tantalum
Joseph Gambogi
202-501-9390
Zirconium/Hafnium
James Hedrick
202-501-9412
Cerium
Lanthanides
Rare Earths
Scandium
Henry Hillard
202-501-9429
Vanadium
Steve Jasinski
202-501-9418
Mercury
Selenium
Tellurium
Thomas Jones
202-501-9428
Manganese
Deborah Kramer
202-501-9394
Beryllium
Peter Kuck
202-501-9436
Cadmium
Roger Loebenstein
202-501-9416
Arsenic Acid
Platinum Group Metals
John Lucas
202-501-9417
Gold
Phyllis Lyday
202-501-9405
Bromine
Iodine
McCaulin
202-501-9426
Antimony
Dave Morris
202-501-9402
Elemental Phosphorus
Phosphoric Acid
Joyce Ober
202-501-9406
Lithium
John Papp
202-501-9438
Chromium
Ferrochrome
Ferrochrome-silicon
Robert Reese
202-501-9413
Cesium
Rubidium
Silver
Erol Sehnke
202-501-9421
Alumina
Aluminum
Germanium
Gerald Smith
202-501-9431
Tungsten
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related wastes may be explained by the age of the data evaluated. Specifically, the most recent
data available are from the 1991 Biennial Reports. Thus, many of the respondents (and potential
respondents) may not have yet been required to manage their mineral processing-derived wastes
as if they were no longer considered "high volume, low toxicity wastes."
EXHIBIT 3-6
Summary of SIC Codes Searched in the 1991 BRS
SIC Code
INDUSTRIAL COMMODITY SECTOR
REPORTED
IN L991 BRS
RANKIN
BRS
1011
Iron Ores
Yes
8
1021
Copper Ores
Yes
7
1031
Lead and Zinc Ores
Yes
19
1041
Gold Ores
Yes
9
1044
Silver Ores
Yes
17
1051
Bauxite and Other Aluminum Ores
No
-
1061
Ferroalloy Ores, Except Vanadium
Yes
22
1092
Mercury Ores
No ,
-
1094
Uranium-Radium-Vanadium Ores
Yes
21
1099
Metal Ores Not Elsewhere Classified
Yes
16
1446
Industrial Sand
Yes
20
1452
Bentonite
No
-
1453
Fire Clay
No
-
1455
Kaolin and Ball Clay
No
-
1459
Clay, Ceramic, and Refractory Minerals, Not
Elsewhere Classified
No
-
1472
Barite
Yes
15
1473
Fluorspar
No
-
1474
Potash, Soda, and Borate Minerals
Yes
23
1475
Phosphate Rock
Yes
14
1477
Sulfur
No
-
1479
Chemical and Fertilizer Mineral Mining, Not
Elsewhere Classified
Yes
24
1499
Miscellaneous Nonmetallic Minerals, Not Elsewhere
Classified
Yes
10
2812
Alkalies and Chlorine
Yes
4
2819
Industrial Inorganic Chemicals, Not Elsewhere
Classified
Yes
1
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45
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.
- Location (City & State)
- Source Code
- Waste Volume
- EPA Hazardous Waste ID No.(s)
- Facility Name
- Origin Code
- Form Code
- On-site/Off-site Management
As shown in Exhibit 3-6, the 1991 BRS contained data for 24 (71 percent) of the 34
mineral processing related SIC numbers. We note that several of these SICs encompass a wide
variety of mineral/inorganic chemical products. For example, SIC 2819 represents the "Industrial
Inorganic Chemicals, Not Elsewhere Classified," which includes over 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 3-6 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.
It is not surprising that the above SIC number categories comprised the top five because these
industries are: (1) known to generate listed hazardous wastes such as K061, K062, K064, K065,
K066, K071, K088, K090, K091, 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
-------
D006
D035
K087
U080
D007
D036
P010
U144
D008
D038
P012
U154
D009
D039
P022
U159
DO 10
D040
P029
U161
D011
F001
P030
U196
D018
F002
P039
U201
D019
F003
P048
U210
D021
F004
P098
U211
D022
F005
P104
U218
D026
F006
P105
U220
D027
F007
P106
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 recovery
(e.g., subjected to 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 on Each of the Identified Sectors
As discussed above, EPA embarked on a very
ambitious 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 49 analyses
covering 62 mineral commodities. Each mineral commodity
analysis report consists of:
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).
• 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
I
I
t__:
Conduct Exhaustive Information Search
| on Mineral Commodity Sectors of Interest
t
Prepare Mineral Commodity Analysis
Reports on Each Sector
J
I"" Define Uruverse of Vlmeral Processing Waste
| Streams Potentially Affected by
' The Phase IV LORs
7
I
Step Three
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47
EXHIBIT 3-6 (Continued)
Summary of SIC Codes Searched in the 1991 BRS
SIC Code
INDUSTRIAL COMMODITY SECTOR
REPORTED
IN 1991 BRS
RANK IN
BRS
2874
Phosphatic Fertilizers
Yes
12
3274
Lime
Yes
18
3295
Minerals and Earths, Ground or Otherwise Treated
Yes
13
3312
Blast Furnaces (Including Coke Ovens), Steel Works,
and Rolling Mills
Yes
2
3313
Electrometallurgical Products
Yes
6
3331
Primary Smelting and Refining of Copper
Yes
11
3332
Primary Smelting and Refining of Lead
No
-
3333
Primary Smelting and Refining of Zinc
No
-
3334
Primary Smelting and Refining of Aluminum
Yes
3
3339
Primary Smelting and Refining of Nonferrous Metals,
Not Elsewhere Classified
Yes
5
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 D028 F008 PI 19
D002 D029 F012 U002
D003 D030 K060 U012
D004 D032 K061 U019
D005 D034 K062 U044
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50
EXHIBIT 3-7
Process Summary for Exclusion Determinations
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49
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 exhibited 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 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 straight-forward and involved
little interpretation on the part 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.l 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 3-7).
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
2 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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52
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 tetrachloride, 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 maiterial 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, since 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 subjecMo RCRA. 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.
Once it has been determined that a material is a solid waste produced 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 clearly and 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.
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."
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51
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 at what point mineral
processing first occurs; all wastes generated after that initial processing step are considered
processing 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 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
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).
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. The TCLP as applied to mineral processing wastes was recently remanded
to the agency, for further discussion, see the Applicability of TCLP Technical Background Document
elsewhere in today's docket.
-------
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.
Because mineral production typically
involves movement of large quantities of
material, as well as the use of heavy machinery,
large vehicles, and material testing and analysis,
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.
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 fbut are not limited to) the follovving:
• Cleaning wastes (e.g., spent solvents);
• Used oil and antifreeze from motor vehicles anc 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);
Highlight i. Lebcicatic-n Wastes and
Cfeeaucat Sfifk
EPA: reviewed the cfcims of arkroojpaayin
the mfcerals industry in 1952. regarding t&e
regufetory status of several wastes generated at its
laathanide prccuetioo facility. Among me wastes
cttscassed wer pinion .gear grease aad residues
from-cleanup =uf spi& of clean solvents tbat are
used in solvent extraction, operations. EPA
concluded thai these wastes were not uniquely
associated vwtfc ainerat extraction, benefication, or
processing operations; dad thus, were not excluded
wastes. EPA based this ore&, minerals or oeneftciaied
ores or nanerak
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53
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."1 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. That is, it must be
indigenous to the production of saleable commodities from naturally occurring ores or minerals,
including brines. Determining what is indigenous to mineral production requires some judgment
on the part of EPA or other regulator. Nonetheless, the Agency believes that the following
summary of the uniquely associated concept can enable persons to understand the required site-
specific decisions unambiguously:
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, and, in some cases, reagents required to
convert an ore, mineral, or beneficiated ore or mineral to one or more saleable
products. 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. Wastes from all
ancillary operations 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 recent example provided in Highlight 1.
In this notice, EPA stated that
[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)
5 Reportable quantity substances, limits, and requirements may be found at 40 CFR Part 301.
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56
Definitions of Mineral Beneflciation and Processing - Finding the Line
Once it has been established that primary mineral 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 aH 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),7
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 specific activities. 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.
Highlight 3. Decisions on Regulatory Status Made Prior to
September 1, 1989 Must be Reevaluated and
Should not be Reited Upon
In 1985, EPA was asked to clarify the special waste status
of leachaie derived from certasi smelter wastes. Because at that time
smefter wastes were considered to be special wastes (and; thus,
excluded from Subtitle C regulation under the Mining Waste
Exclusion) and because wasies derived Iron special wastes were also
deemed special wastes EPA cnnctaded that leacfaate from smelter
slag and pyrkic cinders (tfee smelter wastes in question) were covered
by tiie Mining Waste Exclusion and; accordingly, were exempt from
regutetiog under RCRA Subtitle €, Sabsequentiy, however, the
scope of the Exclusion for mineral processing wastes (such as those
from sroelting)was narrowed cotBHterably, to a fist of20 specific high
volume,, few hazard solid wastes. Wastes derived from these 20
wastes {or atif other processing wastes, Gar that matter) were
explicitly removed from the scope of fee Exclusioa in 1989 and 1990
fS4 FR 36623V That is, BFA's earlier findtags notwithstanding,
feachaies and other wastes derived. front any mineral processing
wastes are got excluded from RCRA Subtitle € regulation under the
Mining WaSe Exclusk)8v aoJess 'tfcey are one of the 20-wastes listed
in Figure i-1, above.
7 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.
8 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.
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55
Wastes from maintenance, repair, or regeneration of production
equipment, reagents, or supplies (e.g., wastes from carbon column
regeneration); and
Certain types of wastewater treatment sludges.6
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 contact with ores or minerals, and/or other raw materials needed
to transform ores or minerals into useful products. 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 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.
Consequently, the need to
Highlight x Off-Specification Products
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.
In respoase la an mquiry related to tiw specM waste status
of several material generated at. a fariSty that prodaces boron aad
related products from ferine^ at 1992EPA staled "The: Bevilf
Exclusion does aot apply, to soSd wastes suck as discarded
«Hnnjetttaf daesacais; ineyare Botwnqu^assocfetedwth mineral:
eaftac&m, beaeficiatjon, or pgcessntg. Discar&d; commercial
cfceratcals ffflis&ed mineFtiikferfYtd products t&at are
generated at these plants but foaad to be off-sjx^ciScatiGnaiid, th-os,
are tSscarded. Ot&er wastes not uaiqaeiy associated with pilaefal
extraction, beaefciation, OrprOcesscHg include many cJeautngwasiej
(sucfj as spent commercial solvent.. thai was esedcteaaiog
production vessefe) and used fcbocatias
6 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.
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58
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.
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 analytic process:
crushing
sorting
sintering
calcining
washing
grinding
sizing
pelletizing
drying
filtration
briquetting
flotation
gravity concentration
magnetic separation
electrostatic separation
roasting, autoclaving, and/or
chlorination9
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)
9 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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All uniquely associated wastes from mineral extraction and beneficiation operations as well
as 20 specific mineral processing wastes are exempt from Subtitle C under the Mining Waste
Exclusion.
Moreover, 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 "BeneBdatkm* Follows Processing
The primary copper industry provides an interesting illustration of the distinctions that exist between
mineral benefication and processing.' At a aamtiet of active primary copper fariBties, copper & recovered from
ores in two different ways: dump leaching is used to sctebilize copper values in mined and stockpiled tow grade
ores, and conventional mkung, naltiRgj flotation, smelting, and refining are used to process higher grade ores.
Metal-bearing Solution from t&e dtssp fcadbtog operation is* in many cases, sent to eleetrowinjBng (a type of
beoeSdatioa operation), wfeicb yields. pariSed metaffic copper. Ja contrast, after smelting, conventional copper
production yfefds partially poriged copper, theforin of "awaes," wfiieft is then further purified man electrolytic
refining process that is femctiona&y very sinalar to that used to recover copper values torn the damp leac&ng
solution. Because, however theanode cropper is produced &y operations that are defined as mineral process#^
wastes generated ty tbis steatolytic refining operation are mineral processing wastes, while wastes generated by
the electrowiniangof copper from tfce dump teach: soJutioa ate defined as fcenefieiaseai wastes and are excluded
from SutaiSeC regulation/ BecaaSe wastesfrQm regrang of anede copper are not amocg tbe 20 wastes listed in
Figure 1-1, they are not exempt from Subtitle C regulation. *fhus, ia dus case and mothers, waste streams from
similar opetationsmay be: subject to tgfferetu regulatory requffements, even if thsy are generated at the same
facility, depending upon the points ® tfae; production sequence froaa whicb ibsy 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 in Sections a.
and b., 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
beneflciation/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-
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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 Beneftetaiion
A facility produces deskcani and adsorbent products from, calcium mantmonlloniie clay using a sequence
of steps thai inctudescrushing, drytog, acid treatment, washing and filtration, drying, and sizing. In response to an
inqmry from the-relevant state agency tn 1989, EPA reviewed the available information regarding the acid treatment
operation and concluded fiat it is a beneficiation operation, for the fallowing 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 substantia^ change the physical structure of
the day.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 abave}tsa heaefroatfon waste that is exempt
front hazardous waste regulation under the Mining Waste Exclusion.
Highlight & Bauxite Refining is Mine rat Processing
Bauxite refining in ike 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 hydroxtde) solution under
elevated temperature and pressure cond&wns. lbs yields soluble sodium afucntriate, which e cooled, diluted, and
hydrotyzed to form insoluble aluminum hydroxide, which can then be filtered out and calcined to produce
alumina {aluminum oxide). Because hj 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: ts chemtcaiy altered^ EPA concluded in its rulemaking activities tn 1989 that
this operation constitutes mineral processing, rather than beneficiation. Even though strong ackfc and extreme
temperatures are not employed in the Bayer process, the combination of the strongly a&aline (ra£ber than acidtc)
reagent .and. tfee h^h pressures (several times atmospheric) appSed to the Ore slurry are sufficient to change .the
chemical form of the mineral value and the 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 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.
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• 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 provided in the Glossary, 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 where a production
sequence involves the use of heat or acid (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
other than by 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
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hazardous waste.11 No changes were made to the mixture rule as it applies to mixtures of
excluded wastes and listed hazardous wastes; that is, solid wastes that are^also excluded wastes are
regulated in the same manner as any other solid waste when they are mixed with a listed
hazardous waste that has been listed for reasons other than "characteristics," i.e., such mixtures are
hazardous wastes.
For mixtures of excluded wastes and other solid wastes that exhibit one or more
characteristics of hazardous waste, EPA revised the mixture rule such that
any mixture of a waste from the extraction, beneficiation, and processing of ores
and minerals excluded under §261.4(b)(7) and any other solid waste exhibiting a
characteristic of hazardous waste under subpart C of this part [is a hazardous
waste] only if it exhibits a characteristic that would not have been exhibited by the
excluded waste alone if such mixture had not occurred or if it continues to exhibit
any of the characteristics exhibited by the non-excluded wastes prior to mixture.
(40 CFR 261.3(a)(2)(i))
Or stated another way, a solid waste that is a mixture of an excluded waste and a "characteristic"
hazardous waste is a hazardous waste unless it does not exhibit any of the same "characteristics" as
the non-excluded hazardous waste. This relationship is illustrated in the following examples and
in Exhibit 3-8:
• A waste mixture that exhibits the characteristic of toxicity for
arsenic and is a combination of an excluded waste and a hazardous
waste, both of which were characteristic/toxic for arsenic before the
mixing occurred, is a hazardous waste.
• A waste mixture that exhibits the toxicity characteristic for arsenic
(and only arsenic) and is a combination of an excluded waste
(characteristic/toxic for arsenic) and a hazardous waste
(characteristic/toxic for lead) is not a hazardous waste.
For mixtures of excluded wastes and solid wastes that are listed hazardous wastes because
they, exhibit one or more characteristics of hazardous waste, EPA revised the mixture rule such
that the mixture is a hazardous waste unless
the resultant mixture no longer exhibits any characteristic of hazardous waste
identified in subpart C of this part for which the hazardous waste listed in subpart
D of this part was listed. (40 CFR 261.3(a)(2)(iii))
As a result, the rules that apply to a mixture of an excluded waste and a "characteristic" hazardous
waste are the same as those for a mixture of an excluded waste and a hazardous waste that is
"listed" because it exhibits one or more characteristics of hazardous waste.
11 It should be noted that the Agency's test method for evaluating the hazardous waste characteristic of
toxicity, the Toxicity Characteristic Leaching Procedure (TCLP), has been remanded to EPA on procedural
grounds as it applies to mineral processing (and coal combustion wastes). The Agency is responding to
the remand as part of today's proposed Phase IV LDR standards. Until any changes in the testing method
are promulgated, the current method (TCLP) remains in effect.
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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.
The Subtitle C "Mixture" Rule and Active Management - Co-Disposal and Disturbing
Old Wastes Can Influence Regulatory Status
[Note to reviewers: This section may be deleted or substantially altered, based on upcoming EPA
decision making.]
In the mineral production industry, large on-site waste management units, such as tailings
impoundments, are quite common. For a variety of reasons, including convenience and
economies of scale, these units have historically been used, and in some cases may still be used,
for disposal of many, if not most, of the wastes generated at a particular facility. As discussed in
the previous sections, not all wastes generated at such facilities may be excluded wastes, so co-
disposal may create wastes that are hazardous as a result of the "mixture" rule (currently 40 CFR
261.3(a)(2)(iv).10 This issue will be of particular interest when, after implementing the steps
outlined earlier, the regulator has identified new, non-exempt waste streams. In addition, the act
of mixing the wastes may meet the definition of hazardous waste treatment and. as a result,
require a Subtitle C treatment permit. Because of these consequences, the mixture rule can be
important in determining the regulatory status of co-managed wastes and corresponding waste
management units at mining and mineral production facilities. Moreover, many facilities have
very large historical accumulations of these waste mixtures or other newly non-excluded wastes.
The regulatory status of these historical accumulations is determined, in part, by whether or not
they are "actively managed." The mixture rule and the issue of active management are discussed
below.
The Subtitle C Mixture Rule
In 1989, when EPA promulgated its revised interpretation of the scope of the Mining
Waste Exclusion as it applies to wastes from mineral processing operations, the Agency also
revised the "mixture" rule (40 CFR 261.3(a)(2)) as it applies to mixtures of excluded wastes and
other solid wastes that exhibit one or more hazardous characteristics, or are listed hazardous
wastes (40 CFR Part 261, Subpart D) because they exhibit one or more characteristics of
10 As promulgated in 1980, the mixture rule required that a mixture that included a listed hazardous
waste be managed as a hazardous waste unless and until it had been "delisted," unless the hazardous waste
was listed only because it exhibited a hazardous characteristic (in this situation, the waste would not be
considered hazardous when and if it no longer exhibited any of the four characteristics of hazardous
waste). "Delisting" is a procedure whereby a person may file a petition with EPA to remove a specific
waste from the hazardous waste listing by demonstrating that the waste in question does not pose a hazard
(see 40 CFR 260.22). Similarly, in most cases, if a "characteristic" hazardous waste is mixed with an
excluded solid waste, the mixture is subject to the requirements of Subtitle C if it exhibits a hazardous
characteristic (40 CFR 261.3(b)(3)).
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EXHIBIT 3-8
Application of the RCRA Subtitle C Mixture Rule to Mineral Production Wastes
Waste Status and Characteristics
Characteristics
Excluded
I Non-Hazardous
Non-Excluded
Hazardous
Excluded
Hazardous
|(TC Constituent 1)
Excluded
Hazardous
|(TC Constituent 1)
Non-Excluded
Hazardous
I (TC Constituent 2)
Hazardous
Hazardous
I (TC Constituent 2)
Assuming the characteristic is exhibited by the special waste alone.
Excluded?
YES
NO
YES
YES
NO
YES
NO
NO
YES
NOTE: Mixtures of listed hazardous waste and other wastes (excluded or otherwise) are hazardous wastes unless the
mixture is delisted. This Figure applies only to "characteristic" hazardous wastes.
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As noted above, mixing of a hazardous waste and an excluded waste that meets EPA's
definition of treatment (See 40 CFR Part 264) requires a Subtitle C treatment permit. This
requirement has not been modified by any of the recent rulemakings and applies irrespective of
whether the resulting mixture is or is not a hazardous waste.
To determine if the mixture rule is important to resolution of the regulatory status of
wastes that are co-managed at a mineral production facility, EPA poses and answers the following
questions:
(1) Does the waste mixture include any solid wastes that are not
excluded wastes?
If yes, then answer question #2.
If no, then the mixture is an excluded waste.
(2) Does the waste mixture include any solid wastes that are listed
hazardous wastes (40 CFR Part 261, Subpart D) that were listed for
reasons other than exhibiting one of the four characteristics of
hazardous waste?
If yes, then the mixture is a hazardous waste subject to
Subtitle C requirements.
If no, then go to question #3.
(3) Does the waste mixture include any solid wastes that are
"characteristic" or are listed hazardous wastes because they exhibit a
hazardous characteristic?
If no, then compliance with Subtitle C requirements is not required.
If yes, then go to question #4.
(4) Does the waste mixture exhibit any characteristic of hazardous
waste that was also exhibited by the hazardous waste?
If no, then compliance with Subtitle C disposal requirements is not
required, but a Subtitle C treatment permit may be required.
If yes, then compliance with Subtitle C is required.
The current version of the mixture rule will remain in effect until the Agency takes final
action.
Active Management of Previously Disposed Wastes
In its final rule establishing the contours of the Mining Waste Exclusion for mineral
processing wastes (54 FR 36592), EPA stated that Subtitle C regulation arising from the
withdrawal of Bevill status from affected mineral processing wastes would not be imposed
retroactively. That is, Subtitle C requirements would apply only to newly generated or actively
managed mineral processing wastes that are removed from the Bevill exclusion and that exhibit
one or more characteristics of hazardous waste, not to existing accumulations of these materials
unless they are actively managed after the effective date of the .rule or are subject to regulation
as waste mixtures, as discussed above. EPA noted further that this is consistent with standard
Agency policy regarding the imposition of new regulatory requirements.
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This provision ensures that those mineral processing wastes that were originally excluded
from Subtitle C under the Bevill Exclusion, and are now considered hazardous wastes under the
reinterpretation of the Bevill Exclusion, will not be subject to Subtitle C closure and post-closure
care requirements if the wastes were disposed prior to the effective date of the final rule.
EPA defines active management as physically disturbing the accumulated wastes within or
disposing additional non-Bevill hazardous wastes into existing waste management units after the
effective date of the final rule. EPA does not intend to bring under Subtitle C regulation waste
management units containing newly non-Bevill wastes to which only Bevill wastes or other non-
hazardous solid wastes are subsequently added (i.e., this practice will not constitute active
management of the non-Bevill waste(s)). For example, a waste management unit receiving a high
volume slag excluded from Subtitle C regulation may continue to receive additional slag (or other
non-hazardous or Bevill waste streams) even if it has also, received (prior to the effective date of
the rule) newly non-Bevill hazardous waste, provided that no additional non-Bevill wastes that
exhibit characteristics of hazard or are listed as hazardous are managed in the unit. Continued
use of an existing unit for treatment, storage, or disposal of additional quantities of a newly
hazardous waste is considered active management and subjects the entire unit and its contents to
Subtitle C regulation. Similarly, disturbing (e.g., removing for additional processing previously
disposed, non-exempt wastes subjects the operator to Subtitle C requirements if the waste(s) in
question are listed or exhibit characteristics of 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.
C3 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 where
actual data indicated that a waste did exhibit one of the characteristics of a hazardous _waste, the
specific characteristic(s) was designated with a Y. However, despite 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 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 exhibited one of the characteristics of a RCRA hazardous waste (i.e., toxicity, corrosivity,
ignitability, and reactivity).
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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.12 In cases where 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. However, due 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)
arid determined input material quantities or concentration ratios from published market
specifications. In parallel with this activity, EPA reviewed process flow diagrams for information
12 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 1/20th of the total constituent concentration.
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67
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 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 arid 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 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 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. 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.
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C.5 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 recycled. When information showing that a particular waste
stream was being either fully or partially recycled was found, the recyclability of the waste stream
was 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 3-2, identified a total of 527 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.
-------
69
D. Define the Universe of "Mineral Processing" Waste Streams Potentially Affected by the
Phase IV LDRs
r
~
r
I
Prepare Mineral Commodity Analysts
Reports on Each Sector
i
Delme Univcne of Mineral Prociwnng W«
Stresms PoteuoaDy Affected by
The Ptac IV LDRa
J
I OefiM Udtwm of Maai
IProcong Fidtn Poqsb&bBjt
Aftctad by the Pfaaaa (V LOR*
Step Four
The Agency then evaluated each of the waste streams
listed in Appendix E using the process outlined in Exhibit 3-
9, to remove waste streams that would not be affected by the
Phase IV LDRs. Specifically^ EPA removed:
• All of the extraction and beneficiation waste
streams;
• The "Special 20" Bevill-Exempt mineral
processing waste streams;
• Waste streams that were known to be fully
recycled in process; and
• 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).
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 148
hazardous mineral processing waste streams presented below
in Exhibit 3-10.
-------
EXHIBIT 3-9
Schematic of the Agency's Process for Defining the Universe of Mineral Processing Waste Streams
Includes Extraction/Beneficiation and the "Special 20" Waste Streams
Listed hazardous wastes are excluded from further analysis because they are already subject to all relevant
Subtitle C requirements
-------
EXHIBIT 3-10
Potentially Hazardous Mineral Processing Waste Streams by Commodity Sector
Alumina and Aluminum
Process wastewaters
Cast house dust
Scrubber blowdown
Electrolysis waste
Surface impoundment waste liquids
Antimony
Tankhouse slimes
Autoclave filtrate
WWTP sludge
Slag and furnace residue
Elemental Phosphorus
Beryllium
Dust
Spent barren filtrate streams
AFM nnsate
Bertrandite thickener slurry
Furnace offgas solids
Beryl thickener slurry
Furnace scrubber blowdown
Chip treatment wastewater
Slag quenchwater
Filtration discard
Fluorspar and Hydrofluoric Acid
Spent rafSnate
Off-spec fluosilicic acid
Bismuth
Germanium
Alloy residues
Waste acid wash and rinse water
Spent' caustic soda
Chlorinator wet air pollution control
Electrolytic slimes
sludge
Lead and zinc chlorides.
Hydrolysis filtrate
Metal chloride residues
Leach residues
Slag
Spent acidAeachate
Spent electrolyte
Waste still liquor
Spent soda solution
Gold and Silver
Waste acid solutions
Refining wastes
Waste acids
Slag
Boron
Wastewater treatment sludge
Waste liquor
Wastewater
Cadmium
Lead
Caustic washwater
Acid plant blowdown
Copper and lead sulfate filter cakes
Acid plant sludge
Copper removal filter cake
Baghouse incinerator ash
Iron containing impurities
Process wastewater
Spent leach solution
Solid residues
Lead sulfate waste
Spent furnace brick
Post-leach filter cake
Stockpiled miscellaneous plant waste
Spent purification solution
Surface impoundment waste liquids
Scrubber wastewater
Magnesium and Magnesia from Brines
Spent electrolyte
Cast house dust
Zinc precipitates
Smut
Calcium
Mercury
Dust with quick lime
Dust
Coal Gas
Mercury quench water
Multiple effects evaporator concentrate
Furnace residue
Copper
Molybdenum, Ferromolybdenum, and Ammonium
Acid plant blowdown
Molybdate
Spent bleed electrolyte
Flue dust/gases
Waste contact cooling water
Liquid residues
Molybdic oxide refining wastes
-------
72
EXHIBIT 3-10 (Continued)
Platinum Group Metals
Titanium and Titanium Dioxide
Slag
Pickle liquor and wash water
Spent acids
Scrap milling scrubber water
Spent solvents
Scrap detergent wash water
Pyrobitumens, Mineral Waxes, and Natural Asphalts
Smut from Mg recovery
Still bottoms
Leach liquor and sponge wash water
Waste catalysts
Spent surface impoundment liquids
Rare Earths
Spent surface impoundments solids
Spent ammonium nitrate processing solution
Waste acids (Chloride process)
Spent iron/lead filter cake
Waste acids (Sulfate process)
Lead backwash, sludge
WWTP sludge/solids
Process wastewater
Tungsten
Spent scrubber liquor
Spent acid and rinse water
Solvent extraction crud
Process wastewater
Waste solvent
Uranium
Wastewater from caustic wet APC
Waste nitric acid from U02 production
Waste zinc contaminated with mercury
Vaporizer condensate
Rhenium
Superheater condensate
Spent barren scrubber liquor
Uranium chips from ingot production
Spent rhenium raffinate
Zinc
Scandium
Acid plant blowdown
Spent acids
Waste ferrosilicon
Spent solvents from solvent extraction
Process wastewater
Selenium
Discarded refractory brick
Spent filter cake
Spent cloths, bags, and filters
Plant process wastewater
Spent surface impoundment liquids
Slag
Spent surface impoundment solids
Tellurium slime wastes
Spent synthetic gypsum
Waste solids
TCA tower blowdown
Synthetic Rutile
Wastewater treatment plant liquid
Spent iron oxide slurry
effluent
Spent acid solution
Zinc-lean slag
Tantalum, Columbium, and Ferrocolumbium
Zirconium and Hafnium
Digester sludge
Spent acid leachate from zirconium
Process wastewater
alloy production
Spent raffinate solids
Spent acid leachate from zirconium
Tellurium
metal production
Slag
Leaching rinse water from zirconium
Solid waste residues
alloy production
Waste electrolyte
Leaching rinse water from zirconium
Wastewater
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.
-------
73
E. Define the Universe of "Mineral Processing" Facilities Potentially Affected bv the Phase
IV LDRs
r
r
r
i
i
+
Define Uruvene of Mineral Processing W*
Stream* Potentially Affected by "
The Phase IV LDRa
f
Define Univwie of Mmcni
Ftatoet Potentafly
EPA then used the information contained in the
individual sector analysis reports to identify the number of
facilities, by commodity, that potentially generated the
hazardous mineral processing wastes listed in Exhibit 3-10,
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. However, in cases where 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 and/or extraction/beneficiation
facilities.
Step Five 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 3r 11 presents the final mineral processing database developed using our
methodology discussed above. Appendix F presents a summary of the mineral processing facilities
by mineral commodity sector that 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.
Caveats and Limitations of Data Analysis
The results and information presented in this report 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
-------
74
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 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 was 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).
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
level13. In cases where 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.
13 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.
-------
rcxiimiT 3-11
Final Mineral Processing Waste Stream Database
Reported
Est /Reported
No. of
RCRA
RCRA Waste Typ
Wasto Form
Generation
Generation {1000mt/yi)
Facilities
TC Metals
Cliaractonstics
Current
By-
Spont
Waste
1-10%
Commodity
Waste Stream
(1000mt/yr)
Mm
Avg
Max
w/ Process
As
Bb
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignit
Rctv
Recycle
Prod
Mat'l
Sludg
Water
Solids
Solid
Alumina and Aluminum
Cast house dust
19
19
19
19
23
Y
Y
N?
N?
N?
Y?
Y
Y
Electrolysis waste
58
58
58
58
23
Y?
N?
N?
N?
Y?
Y
Y
Antimony
Autoclave liltrate
NA
0 38
32
64
7
Y?
Y?
Y?
Y?
Y?
N?
N?
YS?
Y
Y
Slag and furnace residue
32
32
32
32
9
Y?
N?
N?
N?
N
Y
Stripped anolyte solids
0.19
0.19
0 19
0 19
2
Y?
N?
N?
N?
Y
Y
Y
Beryllium
Spent barren filtrate streams
68
88
88
88
1
Y
N?
N?
N?
YS?
Y
Y
Beilrandite thickener slurry
370
370
370
370
1
Y?
N?
N?
N
Y
Beryl thickener slurry
3
3
3
3
1
Y
N?
N?
N
Y
Chip treatment wastewater
NA
0 2
100
2000
2
Y?
N?
N?
N?
YS?
Y
Y
Filtration discard
NA
0 2
45
90
2
Y?
N?
N?
N?
N
Y
Spent raffinate
380
380
380
380
1
Y
Y
N?
N?
YS?
Y
Y
Bismuth
Alloy residues
NA
0 1
3
6
1
Y?
N?
N?
N?
N
Y
Spent caustic soda
NA
0 1
6 1
12
1
Y?
N?
N?
N?
Y?
Y
Y
Electrolytic slimes
NA
0
0 02
0 2
1
Y?
N?
N?
N?
Y?
Y
Y
Lead and zinc chlorides
NA
0 1
3
6
1
Y?
N?
N?
N?
N
Y
Metal chloride residues
3
3
3
3
1
Y?
N?
N?
N?
N
Y
Slag
NA
0 1
1
10
1
Y?
N?
N?
N?
N
Y
Spent electrolyte
NA
0 1
6 1
12
1
Y?
N?
N?
N?
N
Y
Spent soda solution
NA
0 <
6 1
12
1
Y?
Y?
N?
N?
Y?
Y
Y
Waste acid solutions
NA
0 1
6.1
12
1
Y?
N?
N?
N
Y
Waste acids
NA
0
0 1
0 2
1
Y?
N?
N?
YS?
Y
Y
Boron
Waste liquor
NA
0 3
150
300
3
Y?
N?
N?
N?
Y
Y
Y
LD
-------
CT»
ICXIIIIUT 3-11 (Continued)
Commodity
Waslo Stream
Reported
Generation
(lOOOmt/yr)
Est./Repoiled
Generation (lOOOmt/yr)
No of
Facilities
w/ Procoss
TC Metals
- RCRA
Characteristics
Cuiiunt
Rucyclu
RCRA Waste Typ
Waste Foiiii
By-
Piod
Spent
Mat'l
Sludg
Waste
Water
1-10%
Solids
Solid
Min
Avg
Max
As
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
fgnit
Rclv
Cadmium
Caustic washwater
NA
0 19
1 9
19
2
Y?
Y?
N?
N?
Y?
Y
Y
Cu and Pb sulfate filter cakes
NA
0.19
1 9
19
2
Y?
Y?
N?
N?
N?
Y?
Y
Y
Copper removal filter cake
NA
0 19
1 9
19
2
Y?
N?
N?
N?
Y?
Y
Y
Y
lion containing impurities
NA
0 19
1 9
19
2
Y?
N?
N?
N?
N
Spent leach solution
NA
0 19
1 9
19
2
Y?
Y?
Y?
Y?
N?
N?
Y?
Y
Y
Lead sulfate waste
NA
0 19
1 9
19
2
Y?
Y?
N?
N?
N?
Y?
Y
Y
Post-leach filter cake
NA
0 19
1 9
19
2
Y?
N?
N?
N?
N
Y
Spent purification solution
NA
0 19
1 9
19
2
Y?
Y?
N?
N9
N
Y
Scrubber wastewater
NA
0.19
1.9
19
2
Y?
Y?
N?
N?
Y?
Y
Y
Spent electrolyte
NA
0.19
1 9
19
2
Y?
Y?
N?
N?
N
Y
Zinc precipitates
NA
0 19
1 9
19
2
Y?
N?
N?
N?
Y'
Y
Y
Calcium
Oust with quicklime
0.04
0 04
0 04
0 04
1
Y?
N?
N?
Y
Y
Y
Coal Gas
Mult, effects evap. concentrate
NA
0
0
65
1
Y
Y
N?
N? .
N?
YS
Y
Y
Copper
Acid plant blowdown
4B00
4800
4800
4800
9
Y
Y
Y
Y
Y
Y
Y
Y
N?
N?
YS
Y
Y
Y
APC dust/sludge
NA
1
220
450
10
Y?
N?
N?
N?
Y
Y
Y
Spent bleed electrolyte
310
310
310
310
6
Y
Y
Y
Y
Y
Y
Y
N?
N?
YS
,
Y
Waste contact cooling water
13
13
13
13
10
Y?
N?
N?
N?
Y
Y
Y
Process wastewaters
4900
4900
4900
4900
10
Y
Y
Y
Y
Y?
Y
N?
N?
Y
Y
Y
Scrubber blowdown
NA
49
490
4900
10
Y
Y
Y?
Y
N?
N?
N?
YS
Y
Y
SI waste liquids
620
620
620
620
10
Y?
Y?
Y?
Y
N?
N?
YS'
Y
Y
Tankhouse slimes
4
4
4
4
14
Y?
Y?
Y?
Y?
N?
N?
N?
YS
Y
Y
Y
WWTP sludge
B
6
6
6
10
Y?
Y?
N?
N?
N?
YS
Y
Elemental Phosphorus
Dust
4 4
4 4
4 4
4 4
2
Y?
N?
N"?
N?
N?
Y?
Y
Y
Y
AFM nnsate
2
2
2
2
2
—
Y
Y
Y
N?
N?
N
Y?
Furnace offgas solids
24
24
24
24
2
N?
N?
N?
Y
Y
Furnace sciubbei blowdown
NA
0
0
270
2
Y
YS
N?
N?
N
Y
Slag quenchwater
NA
0
0
1000
2
Y?
Y?
N''
N'>
N?
Y?
Y
Y
Fluorbpar and Hydrofluoric Acid
Olf-spec lluosihcic acid
NA
0
15
44
3
Y?
N'>
N''
YS
Y
Y
-------
I'XIIUUT 3-11 (Continued)
Repoitod
Est ./Reported
No. of
RCRA
RCRA Wasto Typ
Wasto Form
Generation
Generation (lOOOmt/yr)
Facilities
TC Motals
Characteristics
Cunont
By-
Spent
Waste
1-10%
Commodity
Waste Stream
(tOOOmt/yr)
Min
Avg.
Max
w/ Process
As
Ba
Cd
Cr
Pb
Hg
So
Ag
Corr
Ignit
Rctv
Recycle
Piod
Mali
Sludg
Water
Solids
Solid
Geimamum
Waste acid wash and rinse water
NA
0.4
2.2
4
4
Y?
Y?
Y?
Y?
Y?
Y?
Y?
N?
N?
YS?
Y
Y
Chlonnator wet APC sludge
NA
0 01
0 21
0 4
4
Y?
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
YS?
Y
Y
Hydrolysis filtrate
NA
0.01
0 21
0 4
4
Y?
Y?
Y?
Y?
Y?
Y9
N'
N?
N?
N
Y
Leach residues
0.01
0.01
0 01
0 01
3
Y?
Y?
N?
N?
N?
N
Y
Spent acid/leachate
NA
0 4
2 2
4
4
Y?
Y?
Y?
N?
N?
YS?
Y
Y
Waste still liquor
NA
0.01
0 21
0.4
4
Y?
Y?
Y?
Y?
Y?
Y?
N?
Y?
N?
N
Y
Gold and Silver
Refining wastes
NA
0 1
360
720
16
Y?
Y?
N?
N?
N
Y
Slag
NA
0.1
360
720
16
Y?
N?
N?
N?
YS?
Y
Y
Spent Furnace Dust
NA
0 1
360
720
16
Y?
N?
N?
N?
Y
Y
Y
Wastewater treatment sludge
NA
0.1
360
720
16
Y?
N?
N?
N?
YS'
Y
Y
Wastewater
NA
440
870
1700
16
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
Y?
Y
Y
Lead
Acid plant blowdown
560
560
560
560
3
Y
Y
Y
Y?
Y
Y
N?
N?
Y
Y
Y
Acid plant sludge
14
14
14
14
3
Y?
N? .
N?
Y?
Y
Y
Baghouse dust
46
46
46
46
3
Y
Y
N?
N?
N?
Y
Y
Y
Baghouse incinerator ash
NA
0.3
3
30
3
Y
Y
N?
N?
N?
N
Y
Process wastewatei
4000
4000
4000
4000
4
Y
Y
Y
Y?
Y
N?
N?
N?
YS?
Y
Y
Slurried APC Oust
7
7
7
7
3
Y
Y
N?
N?
N?
Y
Y
Y
Solid residues
0.4
0.4
0.4
0 4
3
Y?
N?
N?
N?
Y?
Y
Y
Spent furnace buck
1
1
1
1
3
Y
N?
N?
N?
Y
Y
Y
Stockpiled misc plant waste
NA
0.4
88
180
4
Y
Y
N?
N?
N?
YS'
Y
Y
SI waste liquids
1100
1100
1100
1100
1
Y?
Y?
Y?
N?
N?
N?
YS?
Y
Y
WWTP liquid effluent-
3500
3500
3500
3500
4
Y?
Y
N?
N?
Y
Y
Y
WWTP sludges/solids
380
380
380
380
4
Y?
Y?
Y
N?
N?
Y
Y
Y
Magnesium and Magnesia
Cast house dust
NA
0.076
0.76
7 6
1
Y?
N?
N?
N?
Y?
Y
Y
from Billies
Smut
26
26
26
26
2
Y
N?
N?
N?
Y?
Y
Y
Meicury
Dust
0.01
0 01
0.01
0 01
9
Y?
N?
N?
N?
YS?
Y
Y
Mercury quonch wator
NA
81
99
540
9
Y?
Y?
N?
N?
N?
Y7
Y
Y
Furnace residue
0 1
0 1
0 1
0 1
9
Y?
N?
N?
N?
N
Y
-------
00
KXIII1UT3-1I (Continued)
Commodity
Waste Stream
Reported
Generation
(1000mt/yr)
Est /Repoited
Generation (fOOOmt/yr)
No. of
Facilities
w/ Procoss
TC Metals
RCRA
Cliaiactonstics
Current
Recycle
RCRA Waste Typ
Waste Foim
By-
Prod
Spout
Mat'l
Sludg
Waste
Water
1-10%
Solids
Solid
Min
Avg
Max
As
Ba
Cd
Cr
Pb
Hg
So
Ag
Corr
tgnit
Rctv
Molybdenum, Ferromolybdenum
and Ammonium Molybdate
Flue dust/gases
NA
1.2
270
540
12
Y?
N?
N?
N?
N
Y
Liquid residueE
1
1
t
1
2
Y?
Y?
Y?
Y?
N?
N?
N?
N
Y
Molybdic oxide refining wastes
2
2
2
2
2
Y7
N9
N9
N?
N
•Y
Platinum Group Metals
Slag
NA
0.004
0 046
0 46
3
Y?
Y?
N?
N?
N?
Y?
Y
Y
Spent acids
NA
0 3
1 7
3
3
Y?
Y?
Y?
N?
N?
N
Y
Spent solvents
NA
0 3
1 7
3
3
Y?
Y?
N?
Y?
N?
N
Y
Pyrobitumens, Mineral Waxes,
and Natural Asphalts
Still bottoms
NA
0 002
45
90
2
N?
Y?
N?
N
Y
Waste catalysts
NA
0.002
10
20
2
Y?
Y?
N?
N9
N9
Y9
Y
Y
Rare Earths
Spent ammonium nitrate proc sol
14
14
14
14
1
Y
N?
N?
N
Y
Electrolytic cell caustic wet APC slu
NA
0 07
0 7
7
1
Y9
N9
N9
Y
Y
Y
Spent lead filter cake
NA
3 3
42
5
20
Y?
N9
N?
N?
N
Y
Process wastewater
7
7
7
7
1
Y
Y 7
N9
N?
YS?
Y
Y
Spent scrubber liquor
NA
0 1
500
1000
1
YS
N9
N?
YS?
Y
Y
Y
Solvent extraction crud
NA
2
45
80
20
N?
Y?
N9
YS?
Y
Waste solvent
NA
2
1000
2000
20
N?
Y9
N9
Y?
Y
Y
Wastewater from caustic wet APC
NA
0 1
500
1000
1
Y?
Y?
Y9
N9
N9
YS9
Y
Y
Y
Waste zinc contaminated with Hg
NA
2
45
90
20
Y?
N?
N?
N?
YS?
Y
Rhenium
Spent barren scrubber liquor
NA
0
0 1
0 2
2
Y?
N?
N
N
Y9
Y
Y
Spent rhenium raffinate
88
88
88
88
2
Y?
N?
N?
N?
N
Y
Scandium
Spent acids
NA
0 7
3 9
7
7
Y?
N9
N9
N
Y
Spent solvents from S/X
NA
0 7
3 9
7
7
N?
Y9
N9
Y9
Y
Y
Selenium
Spent filter cake
NA
0 05
0 5
5
3
Y?
N?
N?
N?
Y?
Y
Y
Plant process wastewater
66
66
66
66
2
Y
Y
N9
N?
YS9
Y
Y
Slag
NA
0 05
0 5
5
3
Y?
N9
n9
N9
YS9
Y
Y
Y
Y
Tellurium slime wastes
NA
0 05
0 5
5
3
— -
Y?
—
N
N9
N9
N9
N9
N9
YS9
Y
Waste solids
NA
0 05
0 5
5
3
Y?
N
Synlhnttc Rutile
Spent iron oxide slurry
45
45
45
45
1
Y?
Y?
Y'>
Y?
Y?
Y9
—
—
N9
N9
N9
N9
N9
YS9
Y
Y
Y
Y
Y
APC dusl/sludgus
30
30
30
30
1
—
—
N9
YV
N9
N9
Y
Y
Spent acid solution
30
30
30
30
1
Y
-------
EXHIBIT 3-11 (Continued)
Commodity
Wa6te Stream
Reported
Generation
(lOOOmt/yr)
Est /Reported
Generation (lOOOmt/yi)
No of
Facilities
w/ Process
TC Metals
RCRA
Characteristics
Cuiront
Recycle
RCRA Waste Typ
Waste Form
By-
Prod
Spent
Mali
Sludg
Waste
Water
1-10%
Solids
Solid
Min
Avg.
Max
As'
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignit
Rctv
Tantalum, Columbium,
and Ferrocolumbium
Digester sludge
1
1
1
1
2
Y .
N?
N?
N
Y
Process wastewater
150
150
150
150
2
Y?
Y?
Y?
Y?
Y?
Y
N?
N?
Y?
Y
Y
Spent raffinate solids
2
2
2
2
2
Y
N?
N?
N
Y
Tellunum
Slag
NA
0 1
1
4.5
1
Y?
N?
N?
N?
YS?
Y
Y
Solid waste residues
NA
0 1
1
4 5
1
Y?
N?
N?
N?
N
Y
Waste electrolyte
NA
0.1
1
10
1
Y?
Y?
N?
N?
N?
N
Y
Wastewater
NA
0 1
10
20
1
Y?
Y
N?
N?
Y
Y
Y
Titanium and Titanium Dioxide
Pickle liquor and wash water
NA
2.2
2 7
3.2
3
Y?
Y?
Y?
Y?
N?
N?
YS?
Y
Y
Scrap milling scrubber water
NA
4
5
6
1
Y?
Y?
Y?
Y?
N?
N?
N?
YS?
Y
Y
Scrap detergent wash water
NA
360
450
540
2
Y?
Y?
Y?
Y?
Y
N?
N?
YS'
Y
Y
Y
Smut from Mg recovery
NA
0 1
22
45
2
N?
N?
Y
Y?
Y
Leach liquor and sponge wash H20
NA
380
480
580
2
Y?
Y?
Y
N?
N?
YS?
Y
Y
Spent SI liquids
NA
0.63
3 4
67
7
Y?
Y?
N?
N?
N?
Y?
Y
Y
Spent SI solids
36
36
36
36
7
Y?
Y?
N?
N?
N?
N
Y
Waste acids (Chloride process)
49
40
49
49
7
Y?
Y?
Y?
Y
N
N
YS?
Y
Y
Waste acids (Sulfate process)
NA
0 2
39
77
2
Y
Y
Y
Y
Y
N
N
N
Y
Waste ferric chloride
NA
22
29
35
7
Y
Y
Y
Y
Y?
N?
N?
Y
Y
Y
WWTP sludge/solids
420
420
420
420
7
Y
N
N
N
N
Y
Tungsten
Spent acid and rinse water
NA
0
0
21
6
Y?
N?
N?
YS?
Y
Y
Process wastewater
NA
1 8
3 7
73
5
Y?
N?
N?
YS?
Y
Y
Jtanium
Waste nitric acid from U02 prod.
NA
1 7
2.5
34
17
Y?
N?
N?
YS?
Y
Y
Vaporizer condensate
NA
1.7
93
17
17
Y?
N?
N?
N
Y
Slag
NA
0
8 5
17
17
N?
Y?
N?
Y
Y
Y
Superheater condensate
NA
1 7
9 3
17
17
Y?
N?
N?
N
Y
Uranium chips from ingot prod
NA
1 7
2 5
34
17
N?
Y?
N?
Y?
Y
Y
KO
-------
CO
o
EXHIBIT 3-1 i (Continued)
Commodity
Waste Stroam
Reported
Generation
(1000mt/yi)
Est /Reported
Generation (lOOOmt/yr)
No. of
Facilities
w/ Process
TC Metals
RCRA
Characteristics
Current
Recycle
RCRA Waste Typ
Waste Form
By-
Prod
Spont
Mat I
Sludg
Waste
Water
1-10%
Solids
Solid
Min
Avg.
Max
As
Ba
Cd
Cr
Pb
Hg
Se
Ag
Corr
Igmt
Rctv
Zinc
Acid plant blowdown
130
130
130
130
1
Y
Y
Y
Y?
Y?
Y
Y
Y
N
N
Y
Y
Y
Waste ferrosilicon
17
17
17
17
1
Y7
N?
N?
N?
Y?
Y
Y
Process wastewater
6600
6600
6600
6600
4
Y
Y
Y
Y
Y
Y
Y
N?
N?
Y?
Y
Y
Discarded refractory brick
1
1
1
1
1
Y?
Y?
Y?
Y?
N?
N?
N?
N
Y
Spent cloths, bags, and tillers
0 2
0 2
0 2
0 2
4
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
Y
Y
Y
Spent goethite & leach cake residue
15
15
15
15
3
Y
Y
Y '
Y?
Y?
Y
Y
N?
N?
N?
Y
Y
Y
Spent Si liquids
2500
2500
2500
2500
4
Y?
Y
N?
N?
YS?
Y
Y
Spent SI solids
1
1
1
1
4
Y?
Y?
Y?
Y?
Y?
Y?
N?
N?
N?
N
Y
Spent synthetic gypsum
21
21
21
21
4
Y?
Y
Y?
N?
N?
N?
N
Y
TCA tower blowdown
0.25
0 25
0 25
0.25
1
Y?
Y?
Y?
Y?
Y?
N?
N?
YS
Y
Y
WWTP liquid effluent
3500
3500
3500
3500
4
Y?
N?
N?
N?
YS?
Y
¦ Y
Zinc-lean slag
17
" 17
17
17
1
Y?
N?
N?
N?
Y?
Y
Y
Zirconium and Hafnium
Spent acid leachate - z alloy prod
NA
0
0
850
2
Y?
N?
N?
N
Y
Spent acid leachate - z metal prod
NA
0
0
1600
2
Y?
N?
N?
N
Y
Leaching rinse water - z alloy prod
NA
34
42
51
2
Y?
N?
N?
YS?
Y
Y
1.
Leaching rinse water - z metal pro
NA
0 2
1000
2000
2
Y?
N?
N?
YS?
Y
Y
'' * EPA does not have enough information to determine whether Bromine, Gemstones, Iodine,
Lithium and Lithium Carbonate, Soda Ash. Sodium Sulfate, and Strontium produce mineral processing wastes
-------
-------
rv. Mineral Commodities
A. Individual Mineral Commodity Reviews
PHhA-€>O£>0|.j£
81
-------
82
¦ I{\ • >r,s.
¦ikfiOU (
.'iCT-t'i
riXiK
-------
83
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 is, with rare exceptions, 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.1
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%
of the total bauxite consumed in the United States during 1994 was for the production of alumina.
Primary aluminum smelters received 88% of the alumina supply. Fifteen companies operate 23 primary
aluminum reduction plants. In 1994, Montana, Oregon, and Washington accounted for 35% of the
production; Kentucky, North Carolina, South Carolina, and Tennessee combined to account for 20%;
other States accounted for the remaining 45%. The United States is both the leading producer and the
leading consumer of primary aluminum metal in the world. Domestic consumption in 1994 was as follows:
packaging, 30%; transportation, 26%; buijding, 17%; electrical, 9%; consumer durables, 8%; and other
miscellaneous uses, 10%. 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
Summary Of Alumina, Processing Facilities
Facility Name
Location
Process Methods
ALCOA
Point Comfort, TX
Bayer
Kaiser (1992 alumina prod, was 1.06 mt4)
Gramercy, LA
Bayer
Martin
St. Croix, VI
Bayer
Ormet
Burnside, LA
Bayer
Reynolds
Corpus Christi, TX
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.
-------
EXHIBIT 2
Summary Of Aluminum Processing Facilities
Facility Name
Location
Type of
Operations
1992 Production
Capacity5
(1000 metric tons)
ALCOA
Warrick, IN
Massena, NY
Badin, NC
Alcoa, TN
Rockdale, TX
Wenatchee, WA
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Hall-Heroult
Unknown
Unknown
Unknown
Unknown
Unknown
. Unknown
ALUMAX
Mt. Holly, SC
Hall-Heroult
275
Alcan Aluminum Corp.
Henderson, KY
Hall-Heroult
Unknown
Colombia Aluminum Corp.
Goldendale, WA
Hall-Heroult
Unknown
Eastico
Frederick, MD
Hall-Heroult
Unknown
Intalco
Ferndale, WA
Hall-Heroult
Unknown
Kaiser Aluminum Corp.
Spokane, WA
Tocoma, WA
Hall-Heroult
Hall-Heroult
Unknown
Unknown
Columbia Falls Aluminum Corp.
Columbia Falls, MT
Hall-'Herouit
Unknown
National South Wire
Hawesville, KY
Hall-Heroult
Unknown
Noranda
New Madrid, MO
Hall-Heroult
215
Northwest
The Dalles, OR
Hall-Heroult
82
Ormet
Hannibal, OR
Hall-Heroult
Unknown
Ravenswood
Ravenswood, WV
Hall-Heroult
Unknown
Reynolds
Massena, NY
Troutdale, OR
Longview, WA
Hall-Heroult
Hall-Heroult
Hall-Heroult
123
121
204
Venalco
Vancouver, WA
Hall-Heroult
Unknown
5 Ibid.
-------
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 other 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 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 the process can be carried out in a variety of ways depending upon bauxite properties and optimum
economic tradeoffs. Each step of the Bayer process is discussed in further detail below.7
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.
6 V.J. Hill, "Bauxite," from Industrial Minerals and Rocks. 6th ed., Society for Mining, Metallurgy, and
Exploration, 1994, pp. 135-147.
7 "Aluminum Compounds," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. II,
1991, pp. 254-261.
8 Ibid.
-------
86
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. Virtually all the 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. Na2C03 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.9
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 are not subject to regulation.10 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.11
Aluminum Hydroxide Precipitation
Precipitation is the heart of the Bayer process where recovery of the Al(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% of it was calcined to metallurgical grade alumina (A1203). 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.12
9 Ibid.
10 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.
. ¦} h
1 "Aluminum Compounds," Op.Cit.. pp. 254-261.>
12 Ibid.
-------
87
Calcination to Anhydrous Alumina
Calcination, the final operation in the Bayer process for production of metallurgical grade
alumina, is done either in rotary kilns or fluid bed stationary calciners. Prior to calcination, the process
liquor is washed from the Al(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.13
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 Al(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 impurities.14
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 is15:
2A1203 + 3C -» 4A1 + 3 C02
Cryolite is the primary constituent of the Hall-Heroult cell electrolyte. Because of its rarity and
cost, synthetic cTvolite 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 Na20 brought into the cell
as an impurity in the alumina using aluminum fluoride. Thus, the operating cells need 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% 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.
13 ]bid.
14 Ibid-
15 Ibid.
-------
00
00
EXHIBIT 3
THE BAYER PROCESS
(Adapted from: Development Document for Effluent Limitations, 1989.)
Atmosphere
H,0
Condensate
to Boilers, or
I lydrute
Filtration
Limestone
Digester
Condensate
lljO ¦
Hauxite ¦
lime Fillet
Aid
Mud
Settling &
Thickening
A
Mud
Washing &
Filti ation
li,o
Red Mud
lo
Disposal
Kcco\cicil Soiliiiin Viuniin.ilc
-------
EXHIBIT 3 (Continued)
THE BAYER PROCESS
Spent Caustic
-------
l£>
O
EXHIBIT 4
THE HALL-HEROULT PROCESS
(Adapted from: Development Document Tor Effluent Limitations Guidelines, 1989.)
-------
91
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.16
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.17
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.18
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.19
16 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.
17 Ibid.
18
Ibid.
19 Ibid.
-------
92
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 nerfnrated openings. The droplets are cooled
in a quench tankr
Anode Paste Plant
Fabrication fOf-Lanodes takes place in the .anode paste plant where coal tar pitch and ground
petroleum coke .are bLended together to formrp.asteri During electrolysis, the prebaked anode is gradually-
consumed andebecomes-itoo short to be effective. iThe resulting anode "butts" are recycled for use in the
paste plant. ii.Qperationsein the paste plant include crushing, screening, calcining, grinding, and mixing.
The paste isrthen 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 isjused 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
furnaces 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 unburned 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.21
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
Spent potliner wastes (SPL) from aluminum reduction have become one of the aluminum
industry's biggest environmental concerns., Reynolds developed a process for detoxifying SPL in which the
SPL was blended with limestone and an antiagglomeration agent and thermally treated in a rotary kiln.
The process is successful in destroying cyanides and reduced the concentration of soluble fluorides in the
20 Ibid.
21 Ibid.
-------
93
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.22
In fact, Reynolds received a RCRA delisting variance for this waste stream.
An alternative treatment known as the COMTOR process was developed at Comalco'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 the fluorides either recovered or stabilized, the residue reportedly passed the
standard leach tests and was no longer considered toxic.23
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 polyacryiamide flocculent. The fibers assist in the
formation of large floes that have the physical stability to withstand normal industrial dewatering
techniques.24
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.25
Research on carbon removal from Bayer liquors has also been studied. Manganese dioxide
treatment also was 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.26
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.,
22 Patricia Plunkert, 1992, Op. Cit., pp. 183-203.
23 Ibid.
24 Ibid-
25 Ibid.
26 Ibid.
-------
smelting) or chemical reactions (e.g., acid digestion, chloririation) 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 wnicn operationsvare'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 poin'&and quantities presented above in Section B.
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'tecnniques 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
Cooling tower blowaown was generated at a rate of 8,000 metric tons per year in 1991.27 Since .
this waste stream is non-uniquely associated, the Agency did not evaluate it further.
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.28 Since 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 judgement suggest mat ine materials listed oeiow irom alumina
production do not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
these materials further.
27 Ibid.
28 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.
-------
95
Evaporator salt waste. The 1991 total waste volume generation rate for this waste stream was
2,000 metric tons per year.
Bauxite residue. The 1991 total waste volume generation rate for this waste stream was 137,000
metric tons per year.30 Lagooning behind retaining dikes built around clay-lined ground is commonly
used for disposal of bauxite residue. Leaks into aquifers have motivated 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 residue is concentrated by vacuum filtration or other means to 35-50% 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 call 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%, bulldozers can work on the deposit.31
Waste alumina. The 1991 total waste volume generation rate for this waste stream was 7,000
metric tons per year.32
Spent cleaning residue. The 1991 total waste volume generation rate for this waste stream was
3,000 metric tons per year.33
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-situ clay barrier.34
Wastewater. There are four sources of wastewater from bauxite production--(l) 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 special
wastes. The 1991 total waste volume generation rate for this waste stream was 2,800,000 metric tons per
year.35 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 arid 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
29 Ibid.
30 Ibid.
31 "Aluminum Compounds," Op. Cit., pp. 254-261.
32 U.S. Environmental Protection Agency, 1992, Op. Cit., pp. 1-2 - 1-8.
33 U.S. Environmental Protection Agency, Op. Cit.. 1992, pp. 1-2 - 1-8.
34 RTI Survey, Kaiser, Gramercy, LA, 1988, ID# 100339.
35 Ibid.
-------
96
from 1 to 16 meters and averages 7 meters. As of 1988, the quantity/ofemuds 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.36
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 borons 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.
Aluminum Production
APC dust/sludge is a possible waste streamifrom aluminum production-operations including
electrolysis, fluxing, degassing, and anode productions Emissions may consist of unreacted chlorine and
aluminum chloride gas, aluminum oxide, sulfur, fluoride; hydrocarbons, and organics.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.
Flue dust. The 1991 waste generation rate was 39,000 metric tons per year.38 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.
Sweepings. The 1991 waste generation rate was 23,000 metric tons per year.39 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.
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 backintoithe cell.40 Hydrocarbon fumes are generally
disposed of by burning. This waste is generated fat 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.41 This waste is
classified as a sludge.
Baghouse bags and spent plant filters. The 1991 waste generation rate was 19,000 metric tons per
year42 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.
36 U.S. Environmental Protection Agency, Op. Cit.. 1990, 3-1 - 3-15.
37 U.S. Environmental Protection Agency, 1989. Op. Cit.. Vol. II.
38 Ibid.
39 Ibid.
40 "Aluminum Alloys," 1992, Op. Cit., pp. 190-212.
41 'UiSa Environmental Protection rAgency, 1992., Op. Cit.. pp. 1-2 -.1-8.
-conomic. and Small Business Impacts Arising
linerai Processing Ibid.ies.
-------
97
Skims. The 1991 waste generation rate was 20,000 metric tons per year. This waste may contain
traces of sodium, calcium, lithium, and aluminum oxide.43 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.
Discarded Dross. The 1991 waste generation rate was 126,000 metric tons per year. This waste
may contain traces of sodium, calcium, lithium, and aluminum oxide.44 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.
Anode prep waste. The 1991 waste generation rate was 20,000 metric tons per year45 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.
Scrap furnace brick. The 1991 waste generation rate was 77,000 metric tons per year.46
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.
Cryolite recovery residue. The 1991 waste generation rate was 30,000 metric tons per year47
This waste may contain high levels of lead. Management of this waste includes disposal in an unlined
surface impoundment.48 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. This waste is generated at a rate ot 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 is classified as a sludge. Attachment 1 presents waste
characterization data for casthouse dust.
Spent potliners. The 1991 waste generation rate was 118,000 metric tons per year.50 This waste
stream may contain toxic levels of arsenic and selenium as well as detectable levels of cadmium, chromium,
barium, lead, mercury, silver, sulfates, and cyanide. 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
43 Ibid-
44 Ibid.
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.
50 Ibid.
-------
98
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 back to the front of the process and used for leaching. Blowdown
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, K088.
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 judgement 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 judgement 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 judgement 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 is Attachment 1.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants.
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.
-------
99
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. II. 1991.
pp. 254-261.
Hill, V.J. "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. 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. 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. II. 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.
-------
100
-------
ATTACHMENT 1
-------
^Liflliruim
AijUlljtJOOV
A^iSeinc
Bariui
Boroi<
Cadniiu!-
dluoiri"
<®u
tfolP
K*a'yhesmr<
fulaWianebf-
MBrcuiv
Molvbrtenij
Nickpi
.SfllflOHH1
Silvo;
Ihamm-
.»!lnn •
.^apaatu
ZlfK
1 Ul>»
Cyamu*
Uu >M ' •
Sulfiijb
siii'faiir-
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i(5hlonp-
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-------
L. .dARY*OF EPA/ORDr3007. AND RTI SAMPLING DATA WASTEWATER uUMINA/ALUMINUM
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
It Values
Constituents
Minimum
Average _
Maximum
H Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.0005
0.298
1.5
20/20
-
-
0/0
-
-
Arsenic
0.001
0.333
1.5
20/20
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.0001
0.033
0.4
20/20
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.001
0.057
0.2
20/20
-
-
0/0
1.0
0
.Chromium
0.004
0.074
0.6
20/20
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
CoDDer
0.01
0.285
1.6
20/20
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.008
0.491
5
20/20
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercuiy
0.0001
0.001
0.0062
19/19
-
-
0/0'
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.004
0.682
4
20/20
-
-
0/0
-
-
selenium
0.0005
2.488
44
20/20
-
-
0/0
1.0
0
Silver
0.0005
0.075
0.36
20/20
-
-
0/0
5.0
0
^Thallium
0.0005
0.191
0.69
20/20
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.01
0.168
1
20/20
-
-
0/0
-
-
Cyanide
0.002
39.44.
180
22/22
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
(fluoride
-
-
-
0/0
-
-
0/0
-
-
PhosDhate
-
-
-
0/0
-
.
0/0
-
-
silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
--
-
PH '
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the deletion limit TCLP data are currently unavailable; therefore, only EP data are presented
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - CASTHOUSE DUST - ALUMINA/ALUMINUM
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
0/0
-
-
-
0/0
-
-
Antimony
7.5
7.5
7.5
1/1
0.42
0.42
0.42
1/1
' -
-
Arsenic
32
32
32
1/1
0.001
0.001
0.001
0/1
5.0
0
Barium
10
10
10
1/1
0.28
0.28
0.28
1/1
100.0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
7.2
7.2
7.2
1/1
3.5
3.5
3.5
1/1
1.0
1
Cnromium
110
110
110
1/1
0.086
0.086
0.086
1/1
5.0
0
boeait"
-
-
-
0/0
-
-
-
0/0
-
-
copper
510
510
510
1/1
0.25
0.25
0.25
1/1
-
-
irorr
93000
93000
93000
1/1
0.47
0.47
0.47
1/1
-
-
17
17
17
1/1
0.024
0.024
0.024
1/1
5.0
0
Magnesium
-
-
-
0/0
-
-
-
0/0
-
-
Manganese
1100
1100
1100
1/1
19
19
19
1/1
-
-
Mercury
0.0001
0.0001
0.0001
0/1
0.84
0.84
0.84
1/1
0.2
1
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
Nickel
260
260
260
1/1
0.74
0.74
0.74
1/1
-
-
S^enium
0.92
0.92
0.92
1/1
0.001
0.001
0.001
0/0
1.0
0
Silver
1.9
1.9
1.9
1/1
0.15
0.15
0.15
1/1
5.0
0
JhaHi.um
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
4inc
120
120
120
1/1
0.58
0.58
0.58
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sumae
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
-
0/0
18
18
18
1/1
-
-
FlU'orlde
-
-
-
0/0
61
61
61
1/1
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
27000
27000
27000
1/1
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH '
-
-
-
0/0
2l2
0
Organics (TOC)
-
'
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 - TREATMENT PLANT EFFLUENT - ALUMINA/ALUMINUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis
PPM
TC
ft Values
Constituents
Minimum
Average Maximum
H Detects
Minimum Average
Maximum
tt Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.0005
0.3438
1.1
15/15
-
-
0/0
-
-
Arsenic
0.002
0.3326
1.9
15/15
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.001
0.0191
0.06
15/15
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.002
0.0690
0.2
15/15
-
-
0/0
1.0
0
Chromium
0.004
0.0434
0.24
15/15
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.006
0.0975
0.744
15/15
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.02
0.2222
0.6
15/15
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Md'hganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0001
0.0019
0.0213
14/14
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.005
0.1985
0.56
15/15
-
-
0/0
-
-
Selenium
0.001
0.3743
3
15/15
-
-
0/0
1.0
0
Sliver
0.002
0.1416
0.7
15/15
-
-
0/0
5.0
0
Thallium
0.001
0.2288
0.69
15/15
-
-
0/0
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.056
0.2561
2
15/15
-
-
0/0
-
-
Cyanide
0.004
37.0253
200
17/17
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
pH *
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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 - MISCELLANEOUS WASTEWATERS - ALUMINA/ALUMINUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average Maximum
# Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
_
Antimony
0.0005
0.377
2
11/11
-
-
0/0
-
-
Arsenic
0.01
0.512
2.3
11/11
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.0005
0.019
0.08
11/11
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.001
0.037
0.1
11/11
-
-
0/0
1.0
0
Chromium
0.004
0.029
0.2
11/11
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.008
0.299
1.3
11/11
-
-
0/0
-
_
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.01
0.438
3
11/11
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0001
0.001
0.003
11/11
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.005
0.326
1
11/11
-
-
0/0
-
-
Selenium
0.001
3.964
40
11/11
-
-
0/0
1 0
0
Silver
0.002
0.129
0.5
11/11
-
-
0/0
5.0
0
Thallium
0.0005
0.189
0.73
11/11
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.02
0.108
0.6
11/11
-
-
0/0
-
-
Cyanide
0.004
95.24
180
11/11
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
_
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
pH '
-
-
-
0/0
212
0
.Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therelore; only EP data are presented.
-------
..MARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SLUDGE - Alumina/alUMINUM
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
U Detects
TC
Level
tt Values
In Excess
Aluminum
-
-
-
0/0
-
-
-
0/0
-
-
Antimony
0.64
1.68
3
3/5
0.032
0.032
0.032
1/1
-
-
Arsenic
0.72
7.18
16
5/5
0.001
0.014
0.026
1/2
5.0
0
Barium
4
31.2
78
5/5
0.01
0.024
0.037
2/2
100.0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.0465
1.04
2
3/5
0.001
0.013
0.025
1/2
1.0
0
Chromium
1.3
13.7
33
5/5
0.002
Q.005
0.008
2/2
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.38
95.40
380
5/5
0.001
0.011
0.021
2/2
-
-
Iron
730
2386
5300
5/5
0.27
0.300
0.33
2/2
-
-
Lead
5
30.98
63
5/5
0.001
0.002
0.003
1/2
5.0
0
Magnesium
-
-
-
0/0
-
-
-
0/0
-
-
Manganese
0.41
24.96
60
5/5
0.12
0.235
0.35
2/2
-
-
Mercury
0.0001
0.06
0.32
3/5
0.0001
0.0002
0.0002
1/2
0.2
0
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
Nickel
15
224
520
5/5
0 045
0.045
0.045
1/1
-
-
Selenium
0.05
0.32
0.78
4/5
0.001
0.004-
0.006
1/2
1.0
0
Silver
0.04
1.02
2
3/5
0.001
0.002
0.002
1/2
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
1.4
82.48
320
5/5
0.011
0.056
0.1
2/2
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
-
0/0
2
436
870
2/2
-
-
Fluoride
-
-
-
0/0
0.48
48.74
97
212
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
2 2
12.60
23
2/2
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. 1CLP data are currently unavailable, therefore, only EP data are presented
-------
109
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 pres. 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 mainlv
in flame retardants, transportation (including batteries), chemicals, ceramics, and glass.1
Antimony is generally found in association with other elements in complex ores as the sulfide
mineral stibnite. Antimony is made available commercially as antimony tnoxide. Most of the antimony
trioxide produced is derived from imported original sources.
EXHIBIT 1
Summary of Antimony Facilities
Facility Name
Location
Type of Operations
Amspec Chemical Corp
Gloucester, NJ.
Pyrometallurgical
Ant. Process (inactive)
Moscow, TN
Pyrometallurgical
Anzon, Inc.
Laredo, TX
Pyrometallurgical
ASARCO Incorporated
Omaha, NE
Pyrometallurgical
ASARCO (inactive)
El Paso, TX
Electrowinning
Chemet (inactive)
Moscow, TN
Pyrometallurgical
Laurel Ind.
LaPorte, TX
Pyrometallurgical
M&T Chemical (inactive)
Baltimore, MD
Pyrometallurgical
McGean Chemical
Cleveland OH
Pyrometallurgical
Sunshine Mining Company
Kellogg, ID
Electrowinning
US Antimony Corp.
Thompson Falls, MT
Pyrometallurgical
1 Antimony Specialist, "Antimony," from Mineral Commodity Summaries. U.S. Bureau of Mines, 1995,
p. 18.
-------
110
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 hvdrometallurgical
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 hvdrometallurgical 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
bnquetted 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
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.
-------
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)
Antimony Metal
-------
112
EXHIBIT 3
ANTIMONY SMELTING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Medium Grade Antimonv Ore
Fuel
Blast
Slag
Furnace
Waste or
Reprocessing
T
Antimonv Metal
EXHIBIT 4
ANTIMONY LIQUATION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
I
Antimony Ore
(40 - 60% Sb)
Perforated Pot or
Reverberatory Furnace
(550 - 600 °C)
Gangue
(12- 30% Sb)
Needle Antimonv
Metal
Reduction
Product
T
To Oxide Volatilization
-------
113
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
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 Na2S04. 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."
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 arid sulfur. Although lead is not readily removed from antimony,
material containing lead may be used for lead based alloy applications.9
6 Ibid.
7 Ibid.
8 Ibid.
9Ibid.. pp. 372-373.
-------
114
EXHIBIT 5
ANTIMONY IRON PRECIPITATION REDUCTION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
High Grade Antimony Ore
(40 - 60%) or
Needle Anttmonv.
Iron Scrap ¦
Carbon + Na2S04-
Salt -
Needle Antimony
Salt
^"fron Sulfide Matte
Fusion
Antimony Metal
Waste or
Blast Furnace
Smelting
4
Secondary
Fusion
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.)
Soda, Potash, or
Sodium Sulfate
T
Antimony Metal
-------
115
EXHIBIT 7
ANTIMONY REFINING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, pp. 3-31 - 3-45.)
Charcoal + Na2S04
or
Stibmte
NaOH
Na2C03
NaN03
Antimony Metal From
Pyrometallurgic Process
Antimony Metal
(85 - 90% Sb)
-------
Hvdrometallurgical Recovery "fil !
"rtjuiinwiiy can also bfKrecoverecr using the hvdrometallurgical process outlined in Exhibit 8, which
involv.es .leaching,followed bvjdectrowinning^and autoclaving. The hydrometallurgical process is based on
the knowledge mat: (1) 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).10 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
fr&inf. 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
t
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
ia,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 thai 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 solution by thickening and filtration.
The leached residue is either disposed of or processed further to recover other metals.11
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 tfiat might
interfere with acid pressure leaches downstream when the resultant solid filter cake is sent to the Sunshine
silver refinery.12
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.
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.
-------
Electrowinning. As shown in Exhibit S, 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 catholvte. in this case the pregnant
solution from the leaching process, surrounds the cathode and the anolvte, a combination of barren
catholvte 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.1-1
After the antimony has been removed, the barren catholvte 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 catholvte 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
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
13 Corby G. Anderson, 1991, Op. Cit.. p. 360.
14 U.S. Environmental Protection Agency, 1989. Op. Cit., p. 2063.
15 Corby G. Anderson, 1991, Op. Cit., p. 361.
-------
118
EXHIBIT 8
HYDROMETALLURGICAL ANTIMONY PRODUCTION PROCESS
(Adapted from: Residues and Effluents - Processing and Environmental Considerations, 1991, pp. 349 - 366.)
Mill Concentrate
-------
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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-produci 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.
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.
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120
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 ofr.toxicity for lead,
Waste Solids. Wastes produced from fluxing during the refining process contain arsenic (As) and
sulfur (S). Existing d£j.a and .engineering judgment suggest that this material does not exhibit anv
characteristics of hazardous waste. Therefore, the Agency did not evaluate this material further
Hvdrometallurgical Recovery
Leach Residue. The, leach residue contains antimony,sulfur, sodium, pvrite, 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.1' 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.
I- liiv.l -u.i.1 -!• -1.., .. - -U .
Gangue (Filter-Cake): At,the Kellogg plant, slurry, from the1 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 anolvte 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(As04) 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
unhned on-site surface impoundment. Natural sedimentation removes solids under the liquid
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 Ibjd.. p. 2-2.
19 Ibid.
-------
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. 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
20 Ibid
-------
122
BIBLIOGRAPHY
Anderson. Corbv 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.
-------
123
ATTACHMENT 1
-------
124
-------
MARY OF EPA/ORD. 3007. AND RTI SAMPLING DATA - AUTOCLAVE F
ATE - ANTIMONY
Total Constituent Analysis -
PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average Maximum
# Detects
Minimum Average
Maximum
'# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
3.7
40.59
120
8/8
-
-
0/0
-
-
Arsenic
260
1977.75
3700
8/8
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.002
0.069
0.3
8/8
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.2
0.391
0.8
8/8
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.01
0.457
3.05
8/8
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.015
5.30
12.6
7/7
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.01
0.110
u.27
8/8
-
-
0/0
-
-
Cyanide
-
-
-
0/0
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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.
-------
126
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ARSENIC
4. Commodity Summary
The most common source of arsenic is as a byproduct from the smelting of copper and lead
concentrates as arsenic trioxide (As-j03). Arsenic trioxide. is commonly converted to arsenic acid for use in
producing arsenical wood preservatives, which accounted for 75% of the U.S. demand for arsenic in
1992.1 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 3% of demand 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 (As20?) 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 100°C or less, to condense the arsenic trioxide vapor
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.
-------
128
EXHIBIT 1
ARSENIC TRIOXIDE PRODUCTION PROCESS
Cleaned Gases to Stack
-------
129
to concentrations of 90-95%. This crude trioxide is either pvrometallurgicallv refined through
resublimation in a reverberatorv furnace or hvdrometallurgically 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.'
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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.s In
1981. Equity Silver Mines Limned 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. Beneflciation/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.
7 "Arsenic and Arsenic Alloys," 1992, Op. Cit., pp. 626-628.
8 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.
9 Edwards, C., "The Recovery of Metal Values from Process Residues," Journarof Mines. June 1991,
p. 32.
-------
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." t-Journal of Mines. June 1991. p. 3
Gritton, K., D. Steele, and J. Gebhardt. "Metal Recovery from Copper Processing Wastes." Presented at
the Second International Symposium, Recvcling of Metals and Engineered Materials.
Williamsburg, Virginia, October 28-31,,_19,90.. SponsoredlkyJhe_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. ^
-------
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-copper alloys account
for about 75 percent of the Unites 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.2
Beryllium is a recognized constituent in some 40 minerals. Only beryl, an aluminosilicate
(3Be0»Al203»6Si02) containing 5 to 13 percent beryllium oxide (BeO), and bertrandite
(Be4Si207(0H)2), which occurs as tiny silicate granules containing less than one percent BeO, are
commercially available as beryllium ores.3 A BeO content of 10 percent is considered necessary for the
economic extraction of beryllium from beryl and bertrandite ores. However, bertrandite ores are still
considered a commercially viable source of beryllium because of the large reserves present, open-pit
mining, and the fact that beryllium may be extracted bv leaching with sulfuric acid. In fact, the majority of
beryllium produced is now obtained from bertrandite/
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.5 Its plant in Delta, Utah, is the only commercial beryllium extraction and production plant
operating in the Western world.6 The Delta plant uses both beryl and bertrandite ores as inputs for the
production of beryllium hydroxide. While the 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.7 Three other facilities process the beryllium
hydroxide to produce beryllium metal, alloy or oxide. Exhibit 1 presents the name, 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.
1 Deborah A. Kramer, "Beryllium," from Mineral Commodity Summaries. U.S. Bureau of Mines,
January 1995, p. 28.
2 U.S. Bureau of Mines, "Beryllium in 1992," Mineral Industry Surveys. April 1993, p. 3.
3 Brush Wellman, Comments of Brush Wellman Inc. on EPA's Proposed Reinterpretation of the
Mining Waste Exclusion. December 30, 1985, p. 1.
4 "Beryllium and Beryllium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol.
IV, 1992, p. 126:
5 "From Mining to Recycling," Metal Bulletin Monthly — MBM Copper Supplement. 270, 1993, p. 27.
6 Deborah A. Kramer, January 1995, Op. Cit.. p. 28.
7 "Beryllium and Beryllium Alloys," 1992, Op. Cit.. p. 126.
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132
EXHIBIT 1
Summary of Primary and Secondary Beryllium Ore Processors3
Facility Name
Location
Type of Process
Input Material
Products
Brush Wellman
Delta, UT
Primary
Ores
Be(OH)2
Brush Wellman
Elmore, OH
Secondary
Be(OH)2
Be Metal and Alloys
NGK Metals
Revere, PA
Secondary
Be(OH)2
Be Metal
3 - 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 facility located 10 miles north of
Delta, Utah
• Nearest resident lives 5 miles from Brush
Wellman facility
• Brush Wellman facility is not located in: a 100-
year floodplain,' area designated as wetland, Karst
terrain, fault area, or an endangered species
habitat
• No public drinking water wells are located within
1 mile of the Brush Wellman facility
• Private drinking water wells are located within 1
mile of the Brush Wellman facility
B. Generalized Process Description
I. Discussion of Typical Production Processes
At its mining site in Delta, Utah, Brush Wellman treats bertrandite ore using a counter-current
extraction process to produce beryllium sulfate, BeS04. 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 convened to beryllium fluoride; BeF2, which is then catalytically reduced to form metallic
beryllium, converted to Beryllium oxide, or converted to beryllium alloys.
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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.8
Bertrandite Ore. The bertrandite ore is crushed, sized, and wet milled to provide a pumpable
slurry of particles below 840 /u,m.9 The slurry is leached with sulfuric acid, H2S04, 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.10
Bervl 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 for the extraction of
beryllium from beryl. In this process, the ore is crushed, melted at 1650°C, 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 jxm, a slurry of the frit powder
is reacted with concentrated sulfuric acid at 250-300°C to produce soluble beryllium sulfate and aluminum
sulfate, Al2(S04)3.n The spent solid fraction is separated from the beryllium sulfate solution using
thickeners and CCD and discarded to a tailings pond. The beryllium sulfate solutions from the two
extraction procedures are combined and continue to the next step of the process, the production of
beryllium hydroxide.12
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 and triethanolamine, were added to the alum-free solution
in the presence of sodium hydroxide to form a solution of sodium beryllate. Heating the solution to just
below its boiling point precipitated a granular beryllium hydroxide which was recovered by continuous
centrifugation.
8 U.S. Environmental Protection Agency, "Beryllium," 1988 Final Draft Summary Report of Mineral
Industrial Processing Wastes. 1988, p. 3-47.
9 Crushing, sizing, and wet milling are shown as physical processing in Exhibit 1.
10 Brush Wellman, Comments of Brush Wellman Inc. on EPA's Proposed Reinterpretation of the
Mining Waste Exclusion. Revised November 21, 1988, p. 8.
11 Crushing, melting, quenching, heat treating, and grinding are shown as physical treatment in
Exhibit 1.
12 Brush Wellman, 1988, Op. Cit.. pp. 8-9.
13 "Beryllium and Beryllium Alloys," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed.. Vol.
IV, 1978, p. 808.
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IXIIIHII J
I'koi Kss Row Uia<;kam h>k I'kodikiion or Mki au.k Hkkym.ium (i-aki I of J)
Tailings Pond
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i xniitri 3
l'KO( | SS I'l.OW I)|A«.KAM KOK l*KOI>ll( 11ON OK MKTAI.I.H IllKYI.I.ItIM (I'AKI 2 Ol 3)
Deionized Waler
BeSO 4
Kerosene
Solvent
Extraction
BeSO
Stripping
Mg, Al
Sump Waler
Raffinate
Discard
Tailings Pond
H SO
2 4
r
1— Ammonium Cait>onale
Steam ¦
BeSO
Sludge
Leaching
Fe. Al
Saubber Waler
Slurry
Tailings Pond
ABC = Ammonium Beryllium Carbonate
Iron
Hydrolysis
BeSO
Fe, Al
Tailings Pond
\ Banen /
/ Filiala \
Tailings Pond
\ Waste /
Uranium
Product
/ Waters \
Extraction
uo4
Drumming
Tailings Pond
UJ
ui
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UJ
(Tt
i:\iiiiii I 3
I'KIX KSS I'l.OW |)IA(>KAM K)R I'ROIMKIION OK MKTAUJC HKKYI.MIIM (I'AKI ^ Ol J)
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137
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. Kerosene containing di(2-ethylhexyl)phosphate is used to remove some of the
impurities from the beryllium sulfate solution. By repeatedly mixing the aqueous solution and the organic
extractant in a counter-current flow pattern at a slightly elevated temperature, all of the beryllium is
extracted into the organic phase. The aqueous stream (i.e., raffinate) from the extraction operation
contains all of the magnesium (Mg) and most of the aluminum (Al) found in the beryllium sulfate
solution. The raffinate is discarded to a tailings pond.14
The most concentrated organic relative to beryllium in the system is referred to as the loaded
organic. By contacting the loaded organic stream with a solution of ammonium carbonate, the extraction
process is reversed. -The beryllium is stripped from the organic phase to the aqueous phase as ammonium
beryllium carbonate. Use of a small volume of aqueous ammonium carbonate, in relation to the loaded
organic stream, produces an almost 10-fold increase in beryllium concentration.15 Heating the strip
solution to about 70°C causes the iron (Fe) and remaining aluminum to precipitate as hydroxides or
carbonates, which are removed by filtration. These precipitates are leached with sulfuric acid to solubilize
any additional beryllium sulfate.16 A portion of the leaching solution is recycled to the beginning of the
extraction process, while the balance is discarded as slurry to a tailings pond. The stripped organic phase
is treated with sulfuric acid to recover the di(2-ethylhexyl)phosphate. Some of the organic phase is
recycled to the beginning of the extraction process, while the remainder is discarded with the raffinate.17
Heating the ammonium beryllium carbonate solution to 95°C liberates part of the ammonia (NH4)
and carbon dioxide (C02) 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.18 The barren filtrate streams ftom the
two filtration operations are discarded to a tailings pond. The stream from the first filtration operation
contains the uranium which was solubilized in the ore extraction processes. Instead of disposing of the
uranium-bearing waste, in a tailings pond, the stream is sometimes transferred to solar ponds for storage
and concentration of the uranium. The uranium is subsequently extracted as uranium oxide, U04, and
drummed. The wastewater generated in the uranium extraction process is disposed of in a tailings
pond.19
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).
14 "Beryllium and Beryllium Alloys," 1992, Op. Cit.. p. 129.
15 Brush Wellman, 1988, Op. Cit.. p. 11.
16 ICF Incorporated, Brush Wellman: Mineral Processing Waste Sampling Visit — Trip Report. August
1989, p. 2.
17 "Beryllium and Beryllium Alloys," 1992, Op. Cit.. p. 129.
18 Ibid.
19 Brush Wellman, December 30, 1985. Op. Cit.. p. 6.
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138
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 solid calcium carbonate, CaC03, and then
heated to 80°C to precipitate^any residual aluminum. Lead dioxide, Pb02, is added to the solution to
precipitate manganese as insoluble manganese dioxide, Mn02, and chromium-as insoluble lead chromate,
PbCr04. After filtration, ammonium sulfide is added to the filtrate to remove any heavy-metal impurities
and any solubili!zed lead from the lead dioxide treatment. Following another 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.20 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'Hhe bottom of the furnace and solidified as a glassy product on water-cooled
casting wheels.21
The beryllium fluoride is then reduced by magnesium metal (Mg) at a stoichiometric ratio of 1
BeF2 : 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
also dissolves beryllium oxide, which prevents the formation of an oxide film on the beryllium particles and
assists in the coalescence of the metal.22
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
97 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.23
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 an evaporator followed by two crystallizers in parallel where
beryllium sulfate crystals are formed. The crystals are separated from the mother liquor in a centrifuge,
20 Evaporation, centrifugation, and washing are shown as processing in Exhibit 1.
21 "Beryllium and Beryllium Alloys", 1992, Op. Cit.. pp. 129-130.
22 Ibid., p. 130.
23 "Beryllium and Beryllium Alloys," 1978, Op. tit', p. 810.
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EXHIBIT 4
PROCESS FLOW DIAGRAM FOR PRODUCTION OF BERYLLIUM OXIDE
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 36-47.)
Beryllium Wastewater
Oxide
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140
>dite and theimother liquor is recycled to the beryllium hydroxide dissolver. 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 treatment.24
Production of Bervllium-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 allov ingots with additional copper and
other alloying elements yields the desired bervllium-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
licktritubeiuiod, bar, and wire products.25
Identification/Discussion of Novel (or otherwise distinct) Process (es)
The'Fluoride process, an alternative to the Kjellgren-Sawyer process, converts the beryllium oxide
found in beryl ore to a water-spluble 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 out 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 3.26
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
24 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.
25 Deborah A. Kramer, "Beryllium Minerals," from Industrial Rocks and Minerals. 6th Ed., Society for
Mining, Metallurgy, and Exploration, 1994, p. 152.
26 "Beryllium and Beryllium Alloys," 1978, Op. Cit.. pp: 808-809.
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141
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.
Bertrandite Ore Process
EPA determined that for the production of beryllium via the bertrandite ore process, mineral
processing occurs when the bertrandite ore is leached (acidified) with sulfuric acid due to the chemical
substitution reaction that 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.
Bervl Ore Process
EPA determined that for the production of beryllium through the beryl ore process, the
beneficiation/processing line occurs between grinding and reacting with sulfuric acid due to the chemical
substitution that occurs here. 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
Since 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.
Parts 1 and 2: Extraction of Ore and Processing to Beryllium Hydroxide
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.
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Bertrandite thickener slurry. Approximately 370.000 metric tons of bertrandite thickener slurry were
discarded to a tailings pond in 1992.27 The pH of the bertrandite thickener sluny has been reported
between 2.5 and 3.5. Therefore, this waste may exhibit the hazardous characteristic of toxicity. We
used best engineering judgement to determine that this waste stream may be recycled to
extraction/beneficiation units. Bertrandite thickener slurry is classified as a by-product. This waste stream
is combined with approximately 250,000 metric tons of miscellaneous water streams prior to disposal.29
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.
Beryl-thickener1 slurry. In 1992, beryl thickener slurry was discarded to a tailings pond at a rate of 3,000
metric tons/yr-.'30 The beryl thickener slurry has a pH of 2.31 Therefore, this waste exhibits the
hazardous characteristic of toxicity. We used best engineering judgement to determine that this waste
stream may be recycled to extraction beneficiatiori units. Beryl thickener slurry is classified as a by-
product. This waste stream is combined with about 21,000 metric tons of sluice water prior to
disposal.32 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.
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.33 The
raffinate has a pH of 1.4.34 This aqueous waste stream also contains magnesium and aluminum,35 and
may contain treatable concentrations of beryllium, other metal impurities, total suspended solids, and low
levels of organics.36 We used best engineering judgement to determine that this waste stream may be
partially recycled. Spent raffinate is classified as a spent material. This waste stream is combined with
approximately 82,000 metric tons of sump water and roughly 33,000 metric tons of an acid conversion
stream prior to disposal37 See Attachment 1 for waste characterization data.
Sump water. This waste is generated during the solvent extraction process which removes metal impurities
from the beryllium sulfate solution. Existing data and engineering judgement suggest that this material
27 U.S. Environmental Protection Agency, Newlv Identified Mineral Processing Waste Characterization
Data Set. Office of Solid Waste, Volume I, August, 1992, p. 1-2.
28 Brush Wellman, 1988, Op. Cit., p. 8.
29 RTI Survey 101006, National Survey of Solid Wastes From Mineral Processing Facilities. Brush
Wellman Co., Delta, UT, 1989, p. 2-4.
30 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
31 Ibid., p. 6-61.
32 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
33 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
34 Brush Wellman, 1988, Op. Cit., p. 11.
35 "Beryllium and Beryllium Alloys", 1992, Op. Cit.. p. 129.
36 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 3569.
37 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
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143
does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
Acid conversion stream. This waste is the portion of the stripped organic phase which is not recycled to
the beginning of the solvent extraction process. 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.
Separation slurry. In 1992, the separation slurry was discarded to a tailings pond at a rate of 2,000 metric
tons/yr.38 The separation slurry has a pH of 3. The slurry contains iron and aluminum which have
been precipitated as hydroxides and carbonates from the aqueous ammonium beryllium carbonate
stream.40 This waste stream is combined with about 39,000 metric tons of scrubber water prior to
disposal.41 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. "Hiis waste exhibits the hazardous characteristic of toxicity for selenium.42 The
barren filtrate streams have a pH of 9.8.43 We used best engineering judgement to determine that this
waste stream may be partially recycled. The streams are classified as spent material. The barren filtrate
stream from the filtration of beryllium carbonate operation contains uranium which 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.44
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. 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.
38 U.S. Environmental Protection Agency, 1992, Op. Cit., p. 1-2.
39 Brush Wellman, 1988, Op. Cit.. p. 9.
40 "Beryllium and Beryllium Alloys," 1978, Op. Cit.. p. 807.
41 RTI Survey 101006, 1989, Op. Cit.. p. 2-4.
42 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-2.
43 Brush Wellman, 1988, Op. Cit.. p. 10.
44 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 3660.
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144
Neutralization discard. This waste stream contains precipitated aluminum. 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.
Precipitation discard. This waste stream contains precipitated manganese dioxide and lead chromate.
Existing data and engineering judgement suggest that thisrmaterial 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 heavyrmetal 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 100, metric tons/vr. 23,000 metric ,tons/yr, and,45,000.metric tons/yr, respectively. We
used best engineering- judgement to, determine that this waste may exnioit rne cnaracteristics of toxicity for
lead. This waste stream is not recycled.
Leaching discard. 1 nis waste stream contains insoluble magnesium fluoride. 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.
Dross discard. This waste stream contains nonvolatiles, such as, beiyllium oxide, magnesium fluoride, and
beryllium carbide which separate from the molten beryllium metal during the final melting process.
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.
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 judgement
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, fir 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.45
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 tot he 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.46 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. See Attachment 1 for waste characterization
data.
45 U.S. Environmental Protection Agency, 1989, Op. Cit., p. 3661.
46 Ibid., p. 3662.
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145
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.47 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/vr,
respectively. We used best engineering judgement to determine that this waste may exhibit the
characteristics of toxicity for chromium. See Attachment 1 for waste characterization data. We also used
best engineering judgement to determine that this waste stream may be partially recycled and classified as
a spent material.
Production of Beryllium Oxide
Scrubber liquor. This waste contains the sulfur dioxide that was removed from the furnace exhaust gas.
and is 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.4S
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.
Waste Solids. This waste stream contains the impurities filtered from beryllium sulfate solution. 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.
Production of Bervllium-copper allovs
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. Ancillary 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, 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.
47 Ibid., p. 3661.
48 -Ibid., p. 3660.
-------
146
BIBLIOGRAPHY
"Beryllium and Beryllium Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. IV.
1978.
"Beryllium and Beryllium Alloys." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV.
1992.
Brush 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.
"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.
-------
ATTACHMENT 1
-------
iiia'TiH"
Constituent
•AftirHinum
ftilllfH&hy
AfHe/ffii:1
BSiltiVrt
BHiWfum
Bbron
G&ilhuurn
'Ghrri/riliiir
tidtialf1'"
'c'dftpQi
hW"1-
tfeirtf''
Mlaflfibisiii:
Manganesir
fAcflVbiiem..'
Nfdhol.
§'3i(jhlbn>
Sitva^'
T^ffiVo"
Viinaniun
Zinc1
Suitaif
Ruruiilt,
(^Itlonor.
pH '
.Otyanii-a
ft I) <1 Wr t/l
u/!
11
"1
¦(ih »M i
•x> •'¦n [
~ i ;
. J3t\
00
-------
S AFrTOF'EPA/ORD, 3007, AND RTI SAMPLING DATA - BERTRANDITL CKENER SLURRY - BERYLLIUM
t " k'
iB'arii'!-
Constituents
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Minimum
Average
Maximum
U Delects
Minimum
Average
Maximum
H Delects
Level
In Excess
AlUfriihum
200.00
454.50
709.00
2/2
6.80
6.80
6.80
1/1
-
-
A'lMirrtony ¦
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
-
Arsenic
5.00
5.00
5.00
0/1
0.05
0.05
0 05
0/1
5.0
0
Barium
5.00
5.00
5.00
0/1
0.05
0.05
0 05
0/1
100 0
0
Beryllium
9.70
3,209.90
9,320.00
3/3
0.84
0.84
0.84
1/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
Cadmium
0.50
0.50
0.50
0/1
0.01
0.01
0 01
0/1
1.0
0
Ghr&mium
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
5.0
0
Cobalt
5.00
5.00
5 00
0/1
0.05
0.05
0.05
0/1
-
-
Cooper
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
-
Irofi
7.00
186.00
365.00
2/2
0.12
0.12
0 12
1/1
-
-
Lead
17.20
17.20
17.20
1/1
0.03
0.03
0.03
0/1
5.0
0
Maghesium
300.00
340.00
380.00
2/2
16.00
16.00
16.00
1/1
-
-
Manganese
308.00
308.00
308.00
1/1
0.49
0.49
0.49
1/1
-
-
Mercury
0.0500
0.0500
0.0500
0/1
0.0001
0.0001
0.0001
0/1
0.2
0
MoiyDdenum
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
-
Nickel
5.00
5.00
5.00
0/1
0.05
0 05
0.05
0/1
-
-
Setenium
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
1 0
0
Sliver
5.00
5.00
5.00
0/1
0.05
0.05
0 05
0/1
5 0
0
T;halliurn
25.00
25.00
25.00
0/1
0.25
0.25
0.25
0/1
-
-
Vanadium
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
Zinc
65.30
65.30
65.30
1/1
1.19
1.19
1.19
1/1
-
-
Sulfate
1,900.00
2,450.00
3,000.00
2/2
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
18.20
18.20
18.20
1/1
-
-
pH *
2.00
2.50
3.00
2/2
212
2l2
1
Organics (TOC)
385.00
385.00
385.00
1/1
-
-
Non dotocts were assumed to be present at 1/2 the detection limit TCLP data are cuirently unavailable, therefore, only EP data are presented
-------
SUMMARY OF EPA/ORD, 3007. AND RTI SAMPLING DATA - BERYL PLANT SLURRY DISCHARGE - BERYLLIUM
Barratry
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
H Values
Constituents
Minimum
Average
Maximum
It Detected
Minimum
Average
Maximum
U Detected
Level
In Excess
ARMIhum
0.62
0.62
0.62
1/1
0.22
0.22
0.22
1/1
-
-
Antimony
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
-
-
Arsenic
0.30
0.30
0.30
1/1
0.13
0.13
0.13
1/1
5.0
0
B&H6RV
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
100.0
0
0.05
4.660.02
9,320.00
2/2
0.19
0.19
0.19
1/1
-
-
BWon
-
-
-
0/0
-
-
-
0/0
-
-
QftCtfnium
0.005
0.005
0.005
0/1
0.005
0.005
0.005
0/1
1.0
0
bniomium
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
5.0
0
beoait
0.05
0.05
0.05
0>1
0.05
0.05
0.05
0/1
-
-
fcqppw'
0V05
0.05
0.05
oh
0.15
0.15
0.15
1/1
-
-
Wow
0.05
0.05
0.05
oh
0.05
0.05
0.05
0/1
-
-
Luad
0.03
0.03
0.03
oh
0.03
0.03
0.03
0/1
5.0
0
Magnesium
5.29
5.29
5.29
\h
4.13
4.13
4/13
1/1
-
-
Manaanese
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
-
-
Mercurv
0.0003
0.0003
0.0003
0/1
0.0001
0.0001
0.0001
0/1
0.2
0
Molvbdenum
0.05
0.05
0.05
o/i
0.05
0.05
0.05
0/1
-
-
Nickel
0.05
0.05
0.05
o/i
0.05
0.05
0.05
0/1
-
-
seiBIiflim
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
1.0
0
iSnver
0.05
0.05
0.05
o/i
0.05
0.05
0.05
0/1
5 0
0
VhartTium
0.25
0.25
0.25
o/i
0.25
0.25
0.25
0/1
-
-
Vanadium
0.05
0.05
0.05
0/1
0.05
0.05
0.05
0/1
-
-
Zirit
0.05
0.05
0.05
0/.1
2.32
2.3 2
2.32
1/1
-
-
Sulfate
8.740.00
8.740.00
8,740.00
1/1
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
155.00
155.00
155.00
i/i
-
-
PH*
2.00
2.00
2.00
i/i
212
1
Or games (TOC)
579.00
579.00
579.00
1/1
-
-
Non-detecls were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented
-------
MARY OF EPA/ORD, 3007, AND RTI.SAMPLINGDATA - SPENT RAFf TE - BERYLLIUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average Maximum
# Detects
Minimum
Average
Maximum tt Delects
Level
In Excess
'Aluminum
1570
1610
1650
2/2
3050
3050
3050 1/1
-
-
Antimony
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
-
-
Arsenic
3.05
3.05
3.05
1/1
1.19
1.19
1 19 1/1
5.0
0
Barium
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
100.0
0
beryllium
2.62
5.52
8.00
5/5
2.83
2.83
2.83 1/1
-
-
Bbfon
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.01
0.01
0.01
0/1
0 10
0.10
0.10 1/1
1.0
0
Gnromium
0.81
0.81
0.81
1/1
1 00
1.00
1.00 1/1
5.0
0
Gtibalt
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
-
-
Gdpper
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
-
-
Iron
2.88
2.88
2 88
1/1
3 16
3.16
3.16 1/1
-
-
Leaa
0.05
0.05
0.05
0/1
0.69
0.69
0.69 1/1
5.0
0
Magnesium
1690
1690
1690
1/1
1640
1640
1640 1/1
-
-
Manganese
60.70
60.70
60.70
1/1
61.10
61.10
61.10 1/1
-
-
Mercury
0.0001
0.0001
0.0001
0/1
0.0002
0.0002
0.0002 1/1
02
0
Molybdenum
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
-
-
Nicnel
0.46
0.46
0.46
1/1
1.00
1.00
1.00 1/1
-
-
Selenium
0.41
0.41
0.41
1/1
1.00
.1.00
1 00 1/1
1.0
1
Sliver
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
5.0
0
Ytfalllum
0.50
0.50
0.50
0/1
5.00
5 00
5.00 1/1
-
--
Vanadium
0.10
0.10
0.10
0/1
1.00
1.00
1.00 1/1
-
-
Zinc
141.00
141.00
141.00
1/1
125
125
125 1/1
-
-
sulfate
55900
55900
55900
1/1
-
-
Fluoride
7000
7000
7000
1/1
-
-
Chloride
298.00
298.00
298.00
1/1
-
-
PH *
0.90
0.95
1.00
2/2
212
2
Organics (TOC)
-
-
-
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.
-------
S.aMMSfiL^OE.ERAyORD..300Z„A^D,RII.SAMELING.DATA^SEBARATION,SLURBY BERYLLIUM-,
GStf&tilCfents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum # Detects
TC tt Values
Level In Excess
Aiumrnum
1110
1110
1110
1/1
54.10
54.10
54.10
1/1
-
-
Antimony
64.60
64.60
64.60
1/1
0.12
0.12
0.12
1/1
-
Arsenic
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
5 0
0
5.00
5.00
5.00
0/1
0.10
0.10
0.10
1/1
100.0
0
B&piUta
180.00
262.80
320.00
5/5
34.80
34.80
34.80
1/1
-
-
BGVdnloi
-
-
-
0/0
-
-
-
0/0
Cadmium
0.50
0.50
0.50
0/1
0 02
002
0.02
1/1
1.0
0
Opeefflium
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
5 0
0
Gobalii
5.00
5.00
5.00
0/1
0.05
0.05
0 05
0/1
-
-
CflPOflf:
5.00
5.00
5.00
0/1
0.11
0.11
0.11
1/1
-
-
ICPJRi
28000
47300
66600
2/2
3.21
3.21
3.21
1/1
-
-
26.50
26.50
26.50
1/1.
0.03
0.03
0.03
1/2
5.0
0
Magnesium
15.80
15.80
15.80
1/1
3.21
3.21
3.21
2/2
-
-
Manganese
5.00
5.00
5.00
0/1.
0.13
0.13
0.13
1/1
-
-
Mercury
0.1300
0.1300
0.1300
1/1
0.0001
0.0001
0.0001
0/1
D.2
0
Moiyuaenum
10.70
10.70
10.70
1/1
0.05
0.05
0.05
0/1
-
-
tMICKSI
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
-
Sei&nium
12.80
12.80
12.80
1/1
0.05
0.05
0.05
0/1
1.0
0
buyer
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
5.0
0
Tnaittuhv
25.00
25.00
25.00
0/1
0.25
0.25
0.25
0/1
-
0
Van&tiium
5.00
5.00
5.00
0/1
0.05
0.05
0.05
0/1
-
0
Zinci'aib
28.30
28.30
28.30
1/1
1.60
1.60
1.60
1/1
-
-
Sullateo-
8030
8030
8030
1/1
-
-
fluoride
7.00
7.00
7.00
1/1
-
-
Phlnride
-
-
-
0/0
-
-
RH,-
3.00
3.08
3.15
2/2
212
0
Organics (TOC)
475.00
475.00
475.00
1/1
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only bP data are presented.
-------
SL ARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - BARREN FILTh
- BERYLLIUM
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum H Detects
TC H Values
Level In Excess
Aluminum
0.30
579.88
2,290.00
4/4
14.70
293.85
573.00
2/2
-
-
Ann many
1.35
3.18
5.00
1/2
0.79
0.90
1.00
2/2
-
-
Arsenic
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
5.0
0
Barium
Beryllium
0.05
2.53
5.00
0/2
0.15
0.58
1.00
2/2
100 0
0
7.90
48.04
76 30
5/5
2,66
15.03
27.40
212
-
-
Horon
-
-
-
0/0
-
-
-
0/0
-
-
uaamium
0.03
0.26
0.50
1/2
0.02
0.06
0.10
2/2
1.0
0
enromium
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
5.0
0
GoBalt
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
-
-
Copper
0.10
2.55
5.00
1/2
0.05
0.53
1.00
1/2
-
-
Iron/
0.20
222.13
886.00
4/4
0.34
108.67
217.00
2/2
-
-
Lead
0.03
7.56
15.10
1/2
0.03
0.27
0.52
1/2
5.0
0
Magnesium
2.72
516.36
1.030.00
2/2
2.48
147.74
293.00
2/2
-
-
Manganese
0.05
101.03
202.00
1/1
0.05
6.63
13.20
1/2
-
-
Mercury
0.0001
0.0251
0.0500
0/2
0.0001
0.0002
0.0002
1/2
0.2
0
Molybdenum
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
-
-
Nickel
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
-
-
Selenium
0.05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
1 0
1
Silver
0 05
2.53
5.00
0/2
0.05
0.53
1.00
1/2
5.0
0
Thallium
0.25
12 63
25.00
0/2
0.25
2.63
5.00
1/2
-
-
Vanadium
0.05
2.53
5.00
0/2
0.05
0.53
1 00
1/2
-
-
Zinc
0.76
57.38
114.00
212
0.78
13.29
25 80
2/2
-
-
Suuaie
710.00
14,705.00
28.700.00
2/2
-
-
Fluoride
81.00
121.00
161.00
2/2
-
-
Chloride
175.00
178.50
182.00
2/2
-
-
PH*
9.00
9.38
9.60
4/4
212
0
Organics (TOC)
370.00
1,405.00
2,440.00
2/2
-
-
Non-detects were assumed (o 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 - BERVLLIUM HYDROXIDE SUPERNATANT RAW-WASTEWATER. BERYLLIUM
. 1 —I - 1 ¦ — ¦ ¦
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
ti Values
(nriosjliuents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
H Delects
Level
In Excess
'/jmimtnum
-
-
-
0/0
-
-
0/0
-
-
^'nHmony'
0.003
0.003
0.003
1/1
-
-
0/0
-
-
/prsemc
0.003
0.003
0.003
1/1
-
-
0/0
5.0
0
BaHOm
-
-
-
0/0
-
-
0/0
100.0
0
Befyuiam
12
12
12
1/1
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
tidbmium
Chromium
0.004
0.004
0.004
1/1
-
-
0/0
1.0
0
0.11
0.11
0.11
1/1
-
-
0/0
5.0
0
GtlBail
-
-
-
0/0
-
-
0/0
-
-
GQW6t
1.4
1 4
1.4
1/1
-
-
0/0
-
-
-
-
-
0/0
-
-
0/0
-
-
0.168
0.168
0.168
1/1
-
-
0/0
5.0
0
Magnesium
-
•-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0002
0.0002
0/0
-
-
0/0
02
0
kftdty&tenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.12
0.12
0.12
1/1
-
-
0/0
-
-
SelaHlum
0.003
0.003
0.003
1/1
-
-
0/0
1.0
0
jsln/dr
0.32
0.32
0.32
1/.1
-
-
0/0
5.0
0
ithalllOm
0.002
0.002
0.002
1/1
-
-
0/0
-
_
VSrttfdttim
-
-
-
0/0
-
-
0/0
-
_
Zinc
0.19
0.19
0.19
1/1
-
-
0/0
_
eyanide
-
-
-
0/0
-
-
0/0
-
_
Stiitiae
-
-
-
0/0
-
-
0/0
-
-
sulfate
-
-
-
0/0
-
-
0/io
-
_
Fluoride
-
-
-
0/0
-
-
0/0
-
_
Phosphate
-
¦-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
_
_
TSS
-
-
-
0/0
-
-
0/0
-
_
PH'
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-delects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
'ARVLOF EPA/ORD. 3007. AND RTI SAMPLING DATA - PROCESS WA
VATER BERYLLIUM
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
tt Values
Constituents
Minimum
Average
Maximum
H Detects
Minimum Average
Maximum
U Delects
Level
In Excess
Aluttilnum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.003
00030
0.003
4/4
-
-
0/0
-
-
Arsbnic
0.003
0 0790
0.19
4/4
-
-
0/0
5 0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
36
109.00
230
4/4
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.005
0.0205
0.047
4/4
-
-
0/0
1.0
0
Chromium
0.058
0.0793
0.11
4/4
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
1.1
1.3500
1.6
4/4
-
-
0/0
-
-
Iron1
-
-
-
0/0
-
-
0/0
-
-
Lead
0.16
0.1640
0.168
4/4
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0006
0.0007
0.0009
4/4
-
0/0
0 2
0
Moiyoaenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.019
0.0363
0.067
4/4
-
-
0/0
-
-
Selenium
0.003
0.0030
0.003
4/4
-
-
0/0
1.0
0
Silver
0.0005
0.0035
0.007
4/4
-
-
0/0
5.0
0
Thallium
0.002
0.0020
0.002
4/4
-
-
0/0
_
Vanadium
-
-
-
0/0
-
-
0/0
-
Zinc
0.041
0.0698
0.1
4/4
-
-
0/0
_
_
Cyaniae
-
-
-
0/0
-
-
0/0
_
Sulfide
-
-
-
0/0
-
-
0/0
_
_
Suiiate
-
-
-
0/0
-
-
0/0
_
_
Fluoride
-
-
-
0/0
-
-
0/0
-
_
Phosphate
-
-
-
0/0
-
-
0/0
_
Silica'
-
-
-
0/0
-
-
0/0
-
_
Chloride
-
-
-
0/0
-
-
0/0
_
TSS
-
-
-
0/0
-
-
0/0
-
PH*
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-delecls were assumed to be preseni at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP daia are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PEBBLE PLANT ARFA VENT SCRUBBER WATFR - BERYLLIUM
>seiii<
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
tt Values
.Constituents
Minimum
Average
Maximum
U Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.003
0.0030
0.003
2/2
-
-
0/0
-
-
Arsenic
0.042
0.0510
0.06
2/2
-
-
0/0
5.0
0
Barium*
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
210
210
210
2/2
-
-
0/0
-
-
Opfon
-
-
-
0/0
-•
-
0/0
-
-
Gadmium
0.033
0.0335
0.034
2/2
-
-
0/0
1.0
0
Chromium
0.093
0.1165
0.14
2/2
-
-
0/0
5.0
0
Ggbatti
-
-
-
0/0
-
-
0/0
-
-
Copper:
0.5
0.5400
0.58
2/2
-
-
0/0
-
-
Iroa
-
-
-
0/0
-
-
0/0
-
-
Le^di
0.168
0.1680
0.168
2/2
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0003
0.0004
0.0004
2/2
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickelm
0.064
0.0640
0.064
2/2
-
-
0/0
-
-
Selenium
0.003
0.0030
0.003
2/2
-
-
0/0
1.0
0
Silver/1
0.0005
0.0043
0.008
2/2
-
-
0/0
5.0
0
JJtaUium
0.002
0.0020
0.002
2/2
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
ZinciUH
0.096
0.1130
0.13
2/2
-
-
0/0
-
-
Cyanide
-
-
-
0/0
-
-
0/0
-
Sullide
-
-
-
0/0
-
-
0/0
-
-
Sulfate.
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
Chloride
-
-
-
0/0
-
-
0/0
-
_
TSS
-
-
-
0/0
-
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organics (TOC)
.
-
-
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.
-------
y|ARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - CHIP TREATK
WASTEWATER - BERYLLIUM
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
ff Values
Constituents
Minimum
Average
Maximum
ft Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0 003
0 003
0.003
1/1
-
-
0/0
-
-
Arsenic
0.003
0.003
0.003
1/1
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
3300
3300
3300
1/1
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.063
0.063
0.063
1/1
-
-
0/0
1.0
0
Chromium
7.4
7.4
7.4
1/1
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
1.4
1.4
1.4
1/1
'
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.2
0.2
0.2
1/1
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0002
0.0002
1/1
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.78
0.78
0.78
1/1
-
-
0/0
-
-
Selenium
0.003
0.003
0.003
1/1
-
-
0/0
1.0
0
Silver
0.04
0.04
0.04
1/1
-
-
0/0
5.0
0
Thallium
0.002
0.002
0.002
1/1
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
_
Zinc
7.2
7.2
7.2
1/1
-
-
0/0
-
_
Cyanide
-
-
-
0/0
-
-
0/0
-
-
Sulfide
-
-
0/0
-
-
0/0
_
Sulfate
-
-
-
0/0
-
-
0/0
-
_
Fluoride
-
-
-
0/0
-
-
0/0
-
_
Phosphate
-
-
-
0/0
-
-
0/0
-
_
Silica
-
-
-
0/0
-
-
0/0
_
_
Chloride
-
-
-
0/0
-
-
0/0
_
TSS
-
-
-
0/0
-
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-delecls were assumed to be present at 1/2 the detection limit. TCLP data are curramly unavailable, therefore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SCRUBBER LIQUOR - BERYLLIUM
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
tt Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
0
Antimony
0.003
0.0067
0.015
6/6
-
-
0/0
-
_
Arsenic
0.003
0.0030
0.003
6/6
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.49
1.0733
2
6/6
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
_
Cadmium
0.004
0.0073
0.015
6/6
-
-
0/0
1.0
0
Chromium
0.042
0.0675
0.13
6/6
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
_
_
Copper
0.12
0.4100
1.5
6/6
-
-
0/0
-
_
Iron
-
-
-
0/0
-
-
0/0
-
_
Lead
0.16
0.1667
0.166
6/6
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
_
Manganese
-
-
-
0/0
-
-
0/0
-
_
Mercury
0.0002
0.0002
0.0002
6/6
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
Nickel
0.019
0.0297
0.043
6/6
-
-
0/0
-
_
Selenium
0.003
0.0030
0.003
6/6
-
-
0/0
1.0
0
Silver
0.024
0.0655
0.1
6/6
-
-
0/0
5.0
0
Thallium
0.002
0.0020
0.002
6/6
-
-
0/0
_
Vanadium
-
-
-
0/0
-
-
0/0
_
_
Zinc
0.039
0.0553
0.087
6/6
-
-
0/0
_
_
Cyanide
-
-
-
0/0
-
-
0/0
-
Sulfide
-
-
-
0/0
-
-
0/0
_
Sulfate
-
-
-
0/0
-
-
0/0
_
_
Fluoride
-
-
-
0/0
-
-
0/0
_
Phosphate
-
-
-
0/0
-
-
0/0
-
_
Silica
-
-
-
0/0
-
-
0/0
_
Chloride
-
-
-
0/0
-
-
0/0
_
TSS
-
-
-
0/0
-
-
0/0
_
_
pH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
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 Drasantari
-------
159
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.1
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
Betts Electrolytic Process (shown in Exhibit 3).2 Bismuth can also be recovered from other bismuth -
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 Betts Electrolytic
Process.
2. Generalized Process Flow Diagram
Betterton-Kroll Process
As shown in Exhibit 2, the Betterton-Kroll process is based on the formation of high-melting
compounds such as Ca2Bi2 and Mg3Bi2 that separate from the molten lead bullion bath 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., CaMg2Bi2). 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 Allovs 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.
-------
160
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
~
Bismuth
Extraction
-------
161
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
Molten Compound
Cooling Process
Lead Bullion
Dross Containing Intermetallic Bismuth. Calcium, Magnesium, and Lead
I
Heat
t
Lead-Free Dross
Residual Lead
Chlorine
Chlorination
T
Bismuth-Lead Alloy
Magnesium and Calcium
Chlorides
\
Refining
I
Bismuth Metal
-------
Belts Electrolytic Process
As shown in Exhibit 3, in the Betts Electrolytic Process the lead bullion with impurities is
electrolvzed 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-Kxoll 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, bismuth is
precipitated as bismuth oxvchlonde. Further purification is achieved by redissolving the bismuth
oxvchloride in hydrochloric acid. The bismuth oxvchloride is reprecipitated, dried, and reduced with
carbon using soda ash flux to produce crude bismuth bullion.s
Refining
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) Process(es)
None Identified.
3 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.
' Funsho K. Ojebuoboh, 1992, Op. Cit., p. 47.
8 Funsho K. Ojebuoboh, 1992, Op. Git., p. 47.
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163
EXHIBIT 3
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
I
Anode Slimes
I
Spent Electrolyte
Slag
Copper Matte to
Cu Processing
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164
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.)
Hvdrochlonc Acid
Bismuth-bearing
Materials
Hydrochloric Acid
Soda Ash
Carbon
*
Leaching
Process
T
Leach Liquid
T
Bismuth OxvchJonde (ppt)
T
Purification
Bismuth Oxvchlonde (wet)
f
Dryer
Reduction With
Carbon
Spent Material
Wastewater
Waste Acid Solution
Fe, Zn, and HC1
\
Oxvchloride Process
Bi Metal
More
Refining
Waste Acid Solution
f
Bismuth Metal
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165
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 Allov
Mixer
Spent Soda Solution
Zinc
Punfied Metal Mix
~
Parkes
Disilvenzation
Silver. Zinc, and Gold
to Processing
Chlorine Gas
500 °C
t
Impure Bismuth
Lead and Zinc ChJondes
Excess Chlonne
Air Caustic Soda
Oxidation
Alloy Residue Spent
Caustic Soda Solution
Bismuth Metal
99.999% Pure
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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 leachingis 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 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/vr, 6.100 metric tons/Vr, 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/vr, 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.
Betis 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 determine that this waste may exhibit the characteristic of toxicity for
lead.
Slag. Slag is generated from carbon reduction as shown in Exhibit 3.
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/vr, 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/yr, 150 metric tons/yT, 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polvchlorinated biphenyls from electrical transformers and
capacitors. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage, and
waste oil (which may or may not be hazardous) and other lubricants.
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169
BIBLIOGRAPHY
"Bismuth " Kirk-Othmer 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.
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170
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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 colemanite.1 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
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 Kern,
, California.7
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 Ibid., p. 183.
6 Phyllis A. Lyday, "Boron," from Mmeiai ujinmuuuv amwnancs. uo. Duieau uf Mines, 1995, pp. 32-
33.
7 Phyllis A. Lyday, "Boron," from Minerals Yearbook Volume 1. Metals and Minerals, 1992, p. 249.
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172
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 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. One facility produces sodium borate from the ore and the other
produces boric acid. Since the ore used is principally tincal, which 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. As mentioned above, some 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 dissolved into an aqueous stream. Since
kernite, the primary borate mineral present, is not soluble in water, sufficient sulfuric acid must be added
to the dissolving unit. Next the clay and other insolubles must be 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.11 The remaining liquor
can be further evaporated to recover a sodium sulfate co-product. If the desired product is ammonium
borate, this can be prepared by reacting boric acid with ammonium hydroxide. The ratio of raw materials
used determines whether the resulting product is diammonium tetraborate or ammonium pentaborate.12
8 U.S. Environmental Protection Agency, "Boron," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. ,2-77-2-84.
9 Versar, 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.
11 "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.
12 Versar, Inc., 1980, Op. Cit.. p. 2-11.
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173
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.)
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174
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. Notxall 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.
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 pentahvdrate, 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
decahvdrate. 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 heated to its melting point
to remove hvdrated water, thus producing anhydrous sodium borate, which can either be packaged and
sold or sent to further processing. 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.13
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 NaCI 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.14
Liquid-Liquid Extraction. The Trona facility uses a proprietary liquid-liquid extraction process to
remove borate compounds from the brine. 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.15
13 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.
14 Ibid
15 Ibid.
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175
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.)
Brine
I .
Sodium borate decahydrate
and
Sodium borate pentahvdrate
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176
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.)
Evaporated Brine
I
Mixed Sulfate Cake (sent to potash/borax line)
-------
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 from 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.16 At Searles Lake the same
processes 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.1'
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
None Identified.
4. Beneficiation/Extraction Boundary
EPA established the criteria for determining \vhich 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 activitie.s 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 boric acid production process within this specific mineral commodity
sector, the beneficiation/processing line occurs between preparation and acidification of ore. EPA
16 Ibid.
17 Versar Inc., 1980, Op. Cit.. p. 2-7.
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178
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 ore occurs (sodium borate (ore) reacts with
sulfuric acid to produce boric acid and sodium sulfate). EPA also determined that the sodium borate and
the brine extraction production processes do not generate any 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/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
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.18
Wastewater. Process wastewater from washing contains dissolved borax and other salts may be
sent to lined evaporation ponds.19
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.20
Particulate Emissions. Particulates generated from drying operations are collected in drv bags and
recycled. In 1980, the wastes were generated at approximately 14 kg per kkg of product.^1
18 Ibid.
19 Versar, Inc., 1980, Op. Cit.. p. 2-7.
20 California Department of Toxic Substances Control, Memorandum from William Soo Hoo,
Director, to Sylvia IC Lowrance, Office of Solid Waste, U.S. Environmental Protection Agency, May 8,
1992.
21 Versar, Inc., 1980, p. 2-5.
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179
EXHIBIT 4
BORIC ACID PRODUCTION AT SEARLES LAKE, CALIFORNIA
TRONA PLANT (POTASH/BORAX PRODUCTION)
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-77 - 2-84.)
Evaporated Brine
~
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180
2. Mineral Processing Wastes
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.
Waste Liquor. 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 the sodium pentahydrate. Another site reported returning the arsenic-containing wastes to
the original subterranean brine source. Low. 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 is classified as a spent material.
Underflow Mud. 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polvchlorinated biphenvls from electrical transformers and
capacitors.
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181
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, 199.1.
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.
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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 Ludingtcm, 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 I
SumjMary of Bromine Facilities
Facility Name
Locations
Type of Operations
Dow Chemical Company
Ludington, Ml
Brine extraction prior to production of
magnesium chloride. Sent to Ethyl
Corporation for purification.3
Ethyl Corp.
Magnolia, AR
Brine Extraction
Great Lakes Chemical Corp.
El Dorado, AR (3 plants)
Brine Extraction
a Personal communication between Jocelvn Spielman. ICF Incorporated and Phyllis Lvday. 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.
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184
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 (H,S) 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 H2S04 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 the brine is greater than
1.000 ppm. The advantage of this method 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.'
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-Qthmer Encyclopedia of Chemical Technology. 4th ea., vol. iv, iyyz, p. :>48.
5 Ibid., pp. 548-549.
6 Ibid.
' Phyllis Lyday, "Bromine," from Minerals Yearbook Volume 1. Metals and Minerals. 1992, p. 259.
8 Ibid., pp. 259-260.
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185
EXHIBIT 2
BROMINE EXTRACTION FROM WELLS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1992, pp. 547 - 550.)
Bnne from Wells
H,S
H2S04 (98%) •
Skimming
hydrocarbon Removal
Acidification and
Stripping
Chlorination
1
Bromine Vapor
Extraction
1
Condensation
(Br:)
}
'
Drying
.H-,S to Na^S Recoverv
NHjOH (Neutralize)
T
Cooling
Spent Brines
(to disposal wells)
Spent H2S04 (70%)
T
Dry Bromine
(to sale or use)
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186
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 Bnne
T
Bromine
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187
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 H2S04 can be added, resulting in the
generation of a spent solution containing 70 percent H2S04. The resultant dry bromine is sent to sale or
use.
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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. Extraction/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.11
Slimes. Slimes are generated from the settling step in the steaming out process.
9 Ibid., p. 260.
10 "Bromine," Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed., Vol. IV, 1992, p. 550.
11 Phyllis Lvday, 1992, Op. Cit., p. 260.
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188
Water Vapor. Some chlorine and water vapor are captured at the top of the tower during
steaming out.
2. Mineral Processing Wastes
Bromine is used to make several organic chemical compounds in operations in close proximitv to
the brine extraction process. EPA does not have enough information to determine where in the
production sequence mineral processing begins.
D. Ancillary 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
naphtha), acidic tank cleaning wastes, and polvchlorinated biphenvls from electrical transformers and
capacitors.
-------
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.
Lydav. 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 Wijliams, K.C. "Bromine Resources." From Industrial Minerals and Rocks. 6th ed
1994. pp. 187-189.
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190
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191
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 Of Cadmium Producing Facilities
Facility Name
Location
ASARCO
Denver, CO
Big River Zinc Corporation
Sauget, IL
Jersey Miniere Zinc Company
Clarksville, TN
ZCA
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 panicles 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.
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 Volume 1. Metals and Minerals, U.S.
Bureau of Mines, 1992, pp. 271-276.
3 Ibid.
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192
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 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 (hvdrometallurgical process) or as cadmium-lead fume
(pvrometallurgical 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 hvdrometallurgical 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
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.
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193
EXHIBIT 2
PRELIMINARY CADMIUM ROASTING PROCESSES
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1992, pp. 749 - 754.)
Zn Concentrates Zn - Pb Concentrates
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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
Spent Zinc X
Electroivre Y
Cast Shape
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195
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
Water
Sulfuric Acid
NaHS
Waste Purification Solution
Iron Sulfate
Permanganate
Calcium Hydroxide
Sodium Carbonate
Mixer
7
T
Crusher
T
Leach Tank
J
Filter
J
Purification
7
Filter
J
Purification
J
Filter
J
Roaster
Fumes
450 - 600 °C
Scrubber ~ Wastewater
Waste Leach Solution
Lead Sulfate (solid)
}
Alternative # 1 • Galvanic Precipitation
With Zinc
Copper Sulfide (solid)
Waste Purification Solution
Iron Cake, Containing Impurities
Purified Leach Solution
i
T
Alternative #2: Galvanic Precipitation with Zinc
Alternative #3 Electrolvsis
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196
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. However the leach solution is obtained, it must generally be purified to
remove arsenic, iron, copper, thallium, and lead. The cadmium may also be galvanicallv 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.11
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) Process(es)
None identified.
8 Ibid.
9 Ibid.
10 Ibid.
11 Thomas Llewellyn, 1992, Op. Cit.. pp. 271-276.
12 Ibid.
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197
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
Galvanic Precipitation
pH = 2. 70 °C
Zinc
Precipitate
Cadmium Sponge
Wash Solution
(usually NaOH)
Wash
Waste Wash Solution
Compactor
T
Cadmium Briquettes
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198
EXHIBIT 6
ALTERNATIVE 3
ELECTROLYSIS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-64 - 3-71.)
Punfied Leach Solution
Electrolysis
High Silicon-Iron Anodes
Aluminum Cathodes
/
Spent Solution
Melting Pot
T
Cast Shapes
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199
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.
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-bearing 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 tonstyr, 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/fyr, 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.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
190 metric tons/yr, 1,900 metric tons/tyr, and 19,000 metric tons/yT, respectively. We used best engineering
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.
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200
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/vr, 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/tyr, 1,900 metric tons/yT, 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.
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.
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201
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. Ancillary 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), acidic tank cleaning wastes, and polychlorinated biphenvls 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.
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202
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.
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203
CALCIUM METAL
A. Commodity Summary
Pure calcium is a bright silverv-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
AJuminothermic Process
As shown in Exhibit 1, high calcium limestone, CaC03, 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 the 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.
3 Ibid., p. 777.
4 Ibid-, pp- 779-780.
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204
EXHIBIT 1
LIME AND LIMESTONE PRODUCTION
(Adapted from: Industrial Minerals and Rocks, 1994, p. S92.)
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EXHIBIT 2
ALUMINUM REDUCTION PROPCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. IV, 1992, pp. 777 -
Limestone
I
Calciners
Aluminum
Powder
Vacuum
Sublimation
T
Residue
Calcium
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206
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 quicklv 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 Ti02, ZrO?. Cr03 to form
nonvolatile Na20 and K20.
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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
5 Ibid., pp. 780-781.
6 Ibid.
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207
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
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 C02 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/Vr.
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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
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208
BIBLIOGRAPHY
"Calcium." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. IV. 1992. pp. 777-782.
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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.1 Exhibit 1 presents the names and
locations of the facilities once involved in the production of cesium/rubidium.
EXHIBIT 1
Summary Of Cesium/Rubidium Facilities
Facility Name
Location
Type of Operations
Cabot Corp
Revere, PA
Recovery of both cesium and rubidium
Callery Chem
Pittsburgh. PA
Uncertain
Carus Corp
La Salle, IL
Acid Digestion
Corning Glass
Corning, NY
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 (Rb02), 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. 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-Othmer 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.
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210
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
Water
Sulfiiric Acid
Hydrofluoric Acid
Aluminum sulfate
Cationic Reagent
Hydrochloric,
Hydrobtonic, or ¦
Sulfuric Acid
Ball Mill
Gnndina
^Slurry"
Frotli
Flotation
Flotation
Pulp
Pollucite
Concentrate
Acid
Digestion
T
Cesium Salt
Solution
Waste Solids
Non-Pollucite
Mineral Waste
Digestor
Waste
Evaporation
I
Dried Cesium Salt
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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 wafer 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.
9 "Rubidium," 1982, Op. Cit.. p. 493.
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212
EXHIBIT 3
RUBUDIUM ALUMS. EXTRACTION
(Adapted from: 1988 Final Draft Summan Report of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Ruhidium-
Bearing —
Ores
Sullianc
Acid —
Calciner
Residue
Calcined
1
Ore
Sulfiiric
Leach
.Alkali AJum
Solution
Spent Ore
Fractional
Recrvstallization
Rubidium
Alum
Unwanted Alkali Alums
Neutralizing
Agent
Neutralization
Rubidium Hydroxide
in Solution
Precipitated
Aluminum
Barium
Hvdroxide
Purification
Precipitated
Sulfate
(BaS04)
Pure Rubidium
Oude
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213
EXHIBIT 4
RUBIDIUM STANNIC CHLORIDE PRECIPITATION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Purified
Rubidium Chloride
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214
EXHIBIT 5
RUBIDIUM FROM ALKALI METALS
(Adapted from: 1988 Final Draft Summan of Mineral Industry Processing Wastes, 1988, pp. 3-179 - 3-186.)
Spent Metals
Spent Solvent
Spent Solution
t
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
Lepidohte -
Ores
Reduction
Spent Ore
Spent Metal
Pure Rubidium Metal
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215
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
Cesium
In the process used by Carus 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, permangante 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.
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.
10 "Cesium," 1993, Op. Cit.. p. 753.
11 ]bid., p. 754.
12 "Rubidium," 1982, Op. Cit.. p. 493.
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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 pyTOlysis, electrolysis, 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/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 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
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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.
Acid Digestion
Digester waste
Stannic Chloride Precipitation
Pyrolytic Residue
Electrolytic Slimes
Chemical Residues
Reduction
Slag
D. Ancillary 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
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
waste oil (which may or may not be hazardous)'and other lubricants.
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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.
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CHROMIUM, FERROCHROMIUM, AND FERROCHROMIUM-SILICON
A. Commodity Summary
Chromite ore, the starting material for chromium metal, alloys, and other chromium products, is
not produced in the United States.1 The metallurgical and chemical industry consumed 93 percent of the
imported chromite 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-
allov steel (8 percent), superalloys (2 percent) and other miscellaneous uses (12 percent). Exhibit 1
summarizes the producers of chromium products in 1992. Only a small amount of the chromite is
processed to produce ductile chromium; the rest is used in an intermediate form.^
EXHIBIT 1
Summary of Producers of Chromium Products (in 1992)a
Facility Name
Location
Industry
American Chrome & Chemicals Inc.
Corpus ChriSti, TX
Chemical
Elkem AS, Elkem Metals Co.
Marietta, OH
Metallurgical
Elkem AS, Elkem Metals Co.
Alloy, WV
Metallurgical
General Refractories Co.
Lehi, UT
Refractory
Harbison-Walker Refractoriesb
Hammond, IN
Refractory
Macalloy Corp.
Charleston, SC
Metallurgical
National Refractories and Mining Corp.
Moss Landing, CA
Refractory
National Refractories and Mining Corp.
Columbiana, OH
Refractory
North American Refractories Co. Ltd.
Womelsdorf, PA
Refractory
Occidental Chemicals Corp.
Castle Hayne, NC
Chemical
Satra Concentrates Inc.
Steubenville, OH
Metallurgical
a - 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
Ferrochromium, 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
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.
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220
ladle refining techniques such as argon oxygen decarburization, 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 has been produced
in the United States since 1982, 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. Generalized 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 fluxmaterials
(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.11 The production of low carbon ferrochromium requires
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.
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221
EXHIBIT 2
CONCEPTUAL DIAGRAM OF CHROMITE ORE PROCESSING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1993, p. 275.)
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222
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 carbon and oxygen form carbon monoxide,
leaving a pure ferrochromium with a carbon content of about 0.01 weight percent.12
Sodium Chromate and Dichromate
Sodium chromate and dichromate are produced at two facilities by a hvdrometallurgical 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 3.13 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 (C02) 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.16
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 the 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
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 al., editors, Encyclopedia of Chemical Technology. Wiley Interscience, New York, NY,
1978, pp. 93-94.
16 U.S. Environmental Protection Agency, Report to 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.
-------
EXHIBIT 3
SODIUM CHROMATE AND SODIUM DICHROMATE PRODUCTION
(Adapted from: KJrk-Othmcr Encyclopedia of Chemical Technology, 1993, p. 275.)
Chromic Acid Flakes Sodium Dichromate Chromic Acid Ciyslals
-------
224
boric acid recovery unit. The product with some of the final washwater is filtered, rewashed, dried,
ground, screened and packaged.18
Chromium Metal
Chromium metal can be made either pyrometallurgically or electrolvtically. In the
pyrometallurgical method (not shown), chromium oxide (Cr->03) 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 1,400°C.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) Process (es)
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 ores.21
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.
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.
19 "Chromium and Chromium Alloys," 1993, Op. Cit.. pp. 232-234.
20 Ibid., pp. 234-236.
21 J.E. Goodwill, "Developing Plasma Applications for Metal Production in the USA," Iron and
Steeimaking, 17, No. 5, 1990, p. 352.
-------
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 Section B.
Ferrochromium
EPA determined that for ferrochromium, 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 beneficiation/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 beneficiation/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
beneficiation/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 beneficiation/processing boundary occurs for this mineral commodity, please see the
ferrochromium and chromium oxide sections above.
-------
EXHIBIT 4
ELECTROLYTIC CHROMIUM METAL PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1993, p. 235.)
-------
227
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.
2. Mineral Processing Wastes
The following waste streams have been associated with the production of sodium dichromate,
ferrochromium, and ferrochromium-silicon.
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.22
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 residue is composed primarily of metallic oxides, such as those of iron, aluminum,
silicon, magnesium, and chromium, as well as sulfates.23 Using the available data on the composition of
treated roast/leach residue, EPA evaluated whether the 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.24
Ferrochromium
Dust or Sludge was a listed hazardous waste that has been remanded, therefore, the agency did not
evaluate this material further. Data from, the Newly Identified Mineral Processing Waste Characterization
Data Set indicate the following constituents above detection limits for untreated and treated K091
(baghouse dust): aluminum, antimony, barium, chromium, magnesium, manganese, molybdenum, nickel,
selenium, thallium, vanadium, and zinc. Other EP Toxicity leachate analyses indicated many of the same
constituents, as well as lead and silver. In addition, the data set indicated that organics were found in the
22 U.S. Environmental Protection Agency, 1990, Op. Cit., p. 4-2.
23 Occidental Chemical Corp., Company Responses to the "National Survey of Solid Wastes from
Mineral Processing Facilities", U.S. EPA, 1989.
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.
-------
228
dust or sludge, but did not list them by name or concentration.25 The data set aiso indicated that
approximately 3,000 .metric tons of dust or sludge are produced annually in the United States.26
Additional data is provided in Attachment 1.
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.
Terrochromium-silicon
Dust or Sludge was a listed hazardous waste that has been remanded, therefore, the Agency did
not evaluate this material further.28 According to the Newly Identified Mineral Processing Waste
Characterization Data Set, there is no domestic production of ferrochromium-silicon currently. Additional
data is provided in Attachment 1.
D. Ancillary 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, 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.
25 Ibid, pp. 15-1 - 15-10.
26 Ibid, p. 1-4.
27 Ibid.
28 Ibid.
-------
229
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 Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed.
Vol VI. 1993. pp. 228-263.
Goodwill, J.E. "Developing Plasma Applications for Metal Production in the 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. Newlv 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.
-------
230
-------
231
ATTACHMENT 1
-------
Aluminum
Aniimoii'
AiSbl>"
jBaHup
jBoror.
iCadnrit"-
Ichroirv-
Coba'
Coppes
lion
Leaii
Magnet
Mangaf:-
Mercu'
Molytxir.
Ntcsei
Seibiiiu"
Stivei
Thallii.'"
Vanadin'
Ziin
Cyanic--
jSulia^
jFiuonn-
if'iiosoft--
(3uii.a
jCnioiii1--
(TSS
jPH
jOrydiiu ,
LaJ
NJ
-------
summary of epa/ord, 3007. and rti sampling data - dust or sl^oE - ferrochrome-silicon
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
tt Detects
_ Level
In Excess
Aluminum
12.100
12.100
12,100
1/1
1.39
1.39
1.39
1/1
-
-
Antimony
0.60
0.60
0.60
0/1
0.023
0.023
0.023
1/1
-
-
Arsenic
50.00
50.00
50.00
0/1
0.40
0.40
0.40
0/1
5.0
0
Barium
138
138
138
1/1
0 60
0.60
0.60
1/1
100.0
0
Beryllium
0.52
0.52
0.52
1/1
0.00050
0.00050
0.00050
0/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.15
0.15
0 15
0/1
0.0015
0.0015
0.0015
0/1
1.0
0
Chromium
41.00
801
1.560
2/2
2.07
12.69
27.00
3/3
5.0
2
Cobalt
1.00
1.00
1.00
1/1
0.0015
0.0015
0.0015
0/1
-
-
Copper
3.50
3.50
3.50
1/1
0.0015
0.0015
0.0015
0/1
-
-
Iron
1,270
1,270
1,270
1/1
0.0020
0.0020
0.0020
0/1
-
-
Lead
273
273
273
1/1
0.0010
0.02
0.03
2/2
5.0
0
Magnesium
121,000
121,000
121,000
1/1
954
954
954
1/1
-
-
Manganese
1,510
1,510
1,510
1/1
5.08
5.08
5.08
1/1
-
T
Mercury
0.049
0.049
0.049
0/1
0.00010
0.00010
0.00010
0/1
0.2
0
Molybdenum
0.145
0.145
0.145
0/1
0.0082
0.0082
0.0082
1/1
-
-
Nickel
16.20
16.20
16.20
1/1
0.033
0.033
0.033
1/1
-
-
Selenium
5.50
5.50
5.50
1/1
0.069
0.069
0.069
1/1
1.0
0
Silver
0.15
0.15
0.15
0/1
0.0015
0.0015
0.0015
0/1
5.0
0
Thallium
23.90
23.90
23.90
1/1
0.029
0.029
0.029
0/1
-
-
Vanadium
1.50
1.50
1.50
1/1
1.011
0.011
0.011
1/1
-
-
Zinc
3,270
3,270
3,270
1/1
1.63
1.63
1.63
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
0/0
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
¦-
0/0
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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.
NJ
UJ
UJ
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - DUST OR SLUDGE - FERROCHROME
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
# Detects
TC
Level
# Values
In Excess
Aluminum
28,100
29,200
30,300
2/2
0.017
0.068
0.12
2/2
-
-
Antlmpny
.3.85
11.43
19.00
1/2
0.039
0.047
0.055
2/2
-
-
Arsenic
2.65
2.85
3.05
0/2
0.006
0.014
0.040
1/4
5.0
0
Barium
75.60
76.00
76.40
212
0.083
0.575
1.60
4/4
100.0
0
Beryllium
0.66
1.33
2.00
2/2
0.00050
0.00050
0.00050
012
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.70
0.78
0.85
0/2
0.0015
0.0027
0.0050
0/3
1.0
0
Chromium
3,390
5,360
6,470
3/3
0.010
17.99
63.20
18/21
5.0
12
Cobalt
9.20
9.20
9.20
1/1
0.00150
0.00150
0.00150
0/2
-
-
Copper
9.20
24.35
39.50
2/2
0.0020
0.0020
0.0020
0/2
-
-
Irani
6,240
15,170
24,100
2/2
0.0020
0.0020
0.0020
0/2
-
-
Lead
300
1,290
1,860
3/3
0.0050
0.57
4.73
10/17
5.0
0
Magnesium
168,000
188,500
189,000
2/2
409
880
1,350
2/2
-
-
Manganese
5,750
5,770
5,790
2/2
0.013
0.72
1.43
212
-
-
Mercury
0.26
0.32
0.38
1/2
0.00010
0.00053
0.00100
0/3
'0.2
0
Molybdenum
3.20
3.75
4.30
2/2
0.022
0.037
0.052
2/2
-
-
Nickel
128
130
131
2/2
0.003
0.006
0.009
1/2
-
-
Selenium
37.00
42.90
48.80
2/2
0.02
22.79
68.20
2/3
1.0
1
Silver
5.60
5.95
6 30
2/2
0.0020
0.0050
0.010
2/4
5.0
0
Thallium
27.10
130
232
2/2
0.066
0.077
0.088
2/2
-
-
Vanadium
17.70
19.35
21.00
2/2
0.0015
0.0025
0.0035
1/2
-
-
Zinc
13,600
14,300
15,000
2/2
0.0010
0.0015
0:0020
1/2
-
-
Cyanide
0.59
0.59
0.59
1/1
-
-
-
0/0
-
-
Sulfide
5.05
5.05
5.05
0/1
-
-
-
0/0
-
-
Sulfate
--
-
-
0/0
-
-
-
0/0
-
-
Fluoride
485
485
485
1/1
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH'
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
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.
-------
235
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.1 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
Location
Type of Process
Great Plains Coal Gasification Plant, Dakota Gasification Co.a
Beulah, ND
Synthetic Gas
Louisiana Gasification Technology, Inc.3
Placamine, LA
IGCC
Tennessee Eastman6
NA
IGCC
3 - U.S. EPA, Report to Congress on Special Wastes from Mineral Processing. July 1990, p. 5-1.
b - "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.
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236
EXHIBIT 2
Summary of Clean Coal Technology Demonstration Projects3
Project Name
Sponsor
Location
Technology
Project Stage
Self-Scrubbing Coal: An
Integrated Approach to
Clean Air
Custom Coals
International
Central City,
PA
Coal
Preparation
Design/
Permitting
Advanced Coal Conversion
Process Demonstration
Rosebud SynCoal
Partnership
Colstrip, MT
Coal
Preparation
Operating
ENCOAL Mild Coal
Gasification Project
ENCOAL
Corporation
Near
Gillette, WY
Mild
gasification
Operating
Commercial Scale
Demonstration of the
Liquid-Phase Methanol
(LPMEOH) Process
Air Products and
Chemicals, Inc.
Kingsport,
TN
Indirect
Liquefaction
Project
Definition
Combustion Engineering
IGCC Repowering Project
ABB Combustion
Engineering, Inc.
Springfield,
IL
IGCC
Assessing
Project Options
Camden Clean Energy
Demonstration Project
Duke Energy
Corp.
Camden, NJ
IGCC
Negotiating
Cooperative
Agreement
Pinon Pine IGCC Power
Project
Sierra Pacific
Power Company
Reno, NV
IGCC
Design
Toms Creek IGCC
Demonstration Project
TAMCO Power
Partners
Coeburn, VA
IGCC
Project
Definition
. Tampa Electric Integrated
Gasification Combined
Cycle Project
Tampa Electric
Company
Lakeland, FL
IGCC
Design/
Permitting
Wabash River Coal
Gasification Repowering
Project
Wabash River
Coal Gasification
Repowering
Project Joint
Venture
West Terre
Haute, IN
IGCC
Construction
a - U.S. Department of Energy, "Clean Coal Technology Demonstration Program: Program Update 1993," December 31. 1993. pp
6-22, 6-23, & 6-27.
B. Generalized 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 ui 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|fie 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 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 coai 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
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.
-------
NJ
UJ
00
EXHIBIT 3
PROCESS FLOW DIAGRAM OF SYNTHETIC GAS PRODUCTION
-------
EXHIBIT 4
SCHEMATIC DIAGRAM OF LURGI MARK IV GASIFIER
(Adapted from: Dakota Gasification Company, July 29,1991.)
-------
240
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.11
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 of ten.
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 svstem.12-13
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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
11 CDM Federal Programs Corporation, 1987, Op. Cit.. pp. 14-27.
12 North Dakota State Department of Health, Letter to Robert L. Duprey, Director, Waste
Management Division, EPA, June 10, 1986. p. 1.
13 CDM Federal Programs Corporation, 1987, Op. Cit.. pp. 41-42.
-------
241
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 straightforwiard 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.
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. Extraction and Beneficiation Wastes
Wastes from the extraction and beneficiation of coal may include gangue, fines, uagnuusc cuai
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. According to the Newly
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.
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242
Identified Mineral Processing Waste Characterization Data Set, approximately 301,000 metric tons of
gasifier ash are produced annually in the United States.17
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. 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.
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, the1 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, the Agency did not evaluate this 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
1' 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. OD.Cit.. D. 5-3.
19
U.S.
Environmental
Protection
Agency,
1992. OD.Cit.. D. 1-3.
20
U.S.
Environmental
Protection
Agency,
1990. OD.Cit.. d. 5-3.
21
U.S.
Environmental
Protection
Agency,
1992, Od. Cit., d. 1-3.
22
U.S.
Environmental
Protection
Agency,
1990. Op.Cit., d. 5-4.
23
U.S.
Environmental
Protection
Agency,
1992. Od. Cit.. p. 1-3.
-------
243
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 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/Vr, 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 that 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 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. LWI 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 methanation 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.
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.
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 CDM Federal Programs Corporation, 1987, Op. Cit.. p. 6.
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244
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.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 tohs/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.
^Oilv 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 (API) 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.
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
AJ'I/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.
31 Ibid., pp. 52-58.
32 Ibid., pp. 36-37.
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245
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. 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. 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. Ancillary Hazardous Wastes
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
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, Op. Cit.. p. 7.
37 Ibid, p. 39.
38 Ibid., pp. 73-76.
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246
BIBLIOGRAPHY
GDM 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.
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247
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 geologic environments, which depend on 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.3,4
Copper occurs in about 250 minerals; however, only a few of these are commercially important.3
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.'
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
valued at about S4.4 billion. The principal mining states, in descending order, Arizona, Utah, New
Mexico, Michigan, and Montana, accounted for 98 percent of domestic production; copper was also
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 years end. 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 Ibjd., p. 7.
7 Ibid., p. 9.
8 Edelstein, Daniel L, from Minerals Commodities Summaries, U.S. Bureau of Mines, January 1995,
pp. 50-51.
-------
fsj
CO
EXHIBIT 1
Summary of Copper Mining, Smelting, Refining, and Electrowinning Facilities"
Facility Name
Location.
Type of Operations
Potential Factors Related to Sensitive Environments
ASARCO
131 Paso, TX
Smelting
ASARCO
Amarillo, TX
Electrolytic Refining
ASARCO
Ray, AZ
Elecliowinning
ASARCO
llayden, AZ
Smelling and Eleclrowinning
Burro Chief Copper Mine
Tyrone, NM
Extraction ,md Elcctrowinning
Chino Mines Company
Hurley, NM
Smelting/Fire Refining
100 year floodplain, karst terrain, fault area, private wells
within 1 mile
Copper Range
White Pine, MI
Open Pit Mining, Smelting and Refining
fault area
Cyprus Pinos Altos Mine
Silver City, NM
Extraction
Cyprus
Claypool, AZ
Smelting, Refining, and Eleclrowinning
Cyprus Casa Grande Mine
Casa Grande, AZ
In-situ Extraction and Roasting
Cyprus Miami Mining Corp.
Claypool, AZ
1 leap Leaching
fault area, privale wells within 1 mile
Cyprus Mineral Park Corp.
Kingman, AZ
Dump Leaching
Cyprus Sierrila/IXvin Buttes
Green Valley, AZ
I leap Leaching
Cyprus Mining
Bagdad, AZ
Eleclrowinning
Cyprus Bagdad Copper Mine
Bagdad, AZ
Heap Leaching and Milling
Flambeau Copper Mine
Salt l.ake City, UT
Extraction
Gibson Mine
Mesa, AZ
Strip and In-situ Extraction
Johnson Camp Mine
Tucson, AZ
Heap Leaching
Kennecolt
Garfield, UT
Smelting and Refining
low pi 1 and metals contamination of ground water
Magma Mine
Superior, AZ
Undercutting and Filling (Mining)
Magma
San Manuel, AZ
Smelting, Refining, and Eleclrowinning
public and private wells within 1 mile
Mineral Park Mine
Kingman, AZ
Extraction
!Ov Incoipoiatcd, Mining and Mmeial Processing Facilities Database. August 19*>2.
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IEXHIIUT I (Continued)
Facility Name
location
Type or Operations
Potential Factors Related to Sensitive Environments
Mission Unit
Sahuarita, AZ
Extraction
Montanore Mine
Libby, MT
Extraction
Morenci Mine
Morenci, AZ
Heap Leaching
Noranda
Casa Grande, AZ
Electrowinning
Oracle Ridge Mine
San Manuel, AZ
Extraction
Phelps Dodge
Morenci, AZ
Electrowinning
Phelps Dodge
Playas, NM
Smelling
fault area
Phelps Dodge
El Paso, TX
Refining
fault area, public and private wells within 1 mile
Phelps Dodge
Hurley, NM
Smelting and Electrowinning
Pinos Alios Mine
Silver City, NM
Extraction
Pinlo Valley Operations
Miami, AZ
Extraction and Electrowinning
Pinto Valley
Pinto Valley, AZ
Electrowinning
Ray Complex
Hayden, AZ
Extraction
San Manuel Div. Mine
San Manuel, AZ
Extraction
San Pedro Mine
Truth or Consequence, NM
Extraction
Silver Butte Mine
Riddle, OR
Extraction
Silver Bell Unit
Marana, AZ
Exlraclion
Si. Cloud Mining Co.
Truth or Consequence, NM
Extraction
Sunshine Mine
Kellog, ID
Exlraclion
Tennessee Chemical
Coppcrhill, TN
Closed
Tyrone Branch Mine
Tyrone, NM
Dump Leaching and Electrowinning
Western World Copper Mine
Marysville, CA
Extraction
Yerington Mine
Tucson, AZ
Extraction
a - KT' Incorporated, Mining and Mineral Processing I¦acililies Database. August 1992
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250
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), it:
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 ana tanks), and in other activities where endurance and resistance to corrosion are
required.9
Primary production of copper-in the United States has steadily increased in the early 1990s. Total
apparent consumption has risen 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.1 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 being based
upon fiber optics technology rather than copper to a significant degree. Continued re-opening of
mothballed facilities, expansion .of existing facilities, and development of new mines could lead to copper
supplies increasing faster than demand.1"2
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, although they do
not entirely eliminate the problems found in pyrometallurgical processing. For example, in 1984 100,180
tons of copper was produced by solvent extraction and electrowinning (SX/EW), while in 1992 439,043
tons were produced by SX/EW.13 Many within the industry believe that hydrometallurgical operations
are only economically attractive for producing 30,000 metric tons of copper product per year or
less.14'15
9 Ibid.
10 Ibid.
11 Ibid.
12 UiS. 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.
13 "Copper," 1993, Op. Cit.. p. 412.
14 1M-, P- 408.
15 Keith R. Suttill, "Pyromet or Hydromet?" Engineering and Mining Journal. 191, May 1990, p. 31.
-------
2. Generalized Flow Diagram
Exhibit 2 presents a flow diagram of the typical operations involved the production of copper from
ore.
Extraction and Beneflciation Operations
Prior to either pyrometallurgical or SX/EW hydrometallurgical operations, the ore (which often
contains less than one percent copper) is crushed and ground with water and placed in a concentrator.
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.16
The material remaining on the bottom of the flotation tank (waste rock or "gangue"), is partially
dewatered and then discharged to tailing ponds for subsequent disposal.17 In cases where 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.18'19
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 or SX/EW
hydrometallurgical operations.20'21 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.
At a molybdenum recovery plant, sucn 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. 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
16 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.
17 Ibid., p. 6.
18 "Copper," 1993, Op. Cit.. pp. 388-92.
19 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 53.
20 "Copper," 1993, Op. Cit.. pp. 388-92.
21 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 53.
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fsj
i_n •
ro
i ximu i 2
I'rocess Flow Diugram for Hie Production of Copper
• Bevill - Exempt Wastes
Bleed Electrolyte
Contact Cooling Water
Gases to Atmosphere
Cooling
Oases
Scrubbing
Gases
Add
HjO Reagent*
r
f
Production
Overburden
\ Disposal /
J Pile V
Ore
Crushing
Fines
Flotation
and Grinding
Slag L
Ljl
3 [
Anodas
Furnaclng
Malts
Conversion
H20 H2904
Dump
Leaching
—|
Pregnant
Solution
Bleed
Electrolyte
•
Electrowinning
Slimes
Precious Metals
Recovery
•
Anode
~ Electrolytic
Casing
1
C Reining
Retrnedi
Copper
Metal
-------
253
beginning of the recleaner circuit. The filtered, dry molybdenum disulfide product (95 percent) is packed
into 55-gallon drums and sold as molybdenite.22
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.23 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 electrorefining. 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.24 Roasting dries, heats, and
partially removes the sulfur and volatile contaminants from the concentrated ore to produce a calcine
suitable for smelting.2^ 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.26
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.27 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.28-29 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 S02 gas, which is difficult to use in sulfur recovery.30 The
gases produced by electric smelting are smaller in volume, lower in dust (less than 1 percent), and have a
higher S02 concentration, which allows better sulfur recovery in an acid plant.31 Gases from smelting
operations contain dust and sulfur dioxide. The gases are cleaned using electrostatic precipitators and
22 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 7.
23 Office of Technology Assessment, Copper: Technology and Competitiveness. OTA-E-67,
Washington, DC: U.S. Government Printing Office, September 1988, p. 133.
24 U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 6-2.
25 Office of Technology Assessment, 1988, Op. Cit.. p. 134.
26 "Copper," 1993, Op. Cit.. p. 394-95.
27 Process upsets sometimes require the copper concentrate to be diverted from the smelter. EPA is
investigating the current management techniques, and their environmental implications.
28 "Copper," 1993, Op. Cit.. p. 393.
29 U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 6-3.
30 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.
31 Ibid., p. 27.
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254
then are sent to the acid plant, which converts the sulfur dioxide-rich gases to sulfuric acid (a useable
and/or saleable product).
Magma has constructed a new flue dust leaching (FDL) facility to recover copper from several
smelter by-product streams. Feedstocks to the FDL facility 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 the 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 are stored in bins or slurry
tanks prior to entering a series of agitator leach vessels. Sulfuric acid (93 percent concentration) is added
to dissolve the copper into solution. The remaining solids are thickened, washed, and filtered. The
resulting filter cake is sent back to the flash furnace for smelting. The copper sulfate-rich leachate is
purified in a dedicated solvent extraction unit, where an extremely concentrated copper sulfate solution
(one that can easily be crystallized into commercial grade copper sulfate crystals) is generated. The
crystals are either sold "as is" or are sent to the main solvent extraction circuit.
In the converter (the most common being the Peirce-Smith converter, followed by the Hoboken
converter and the Mitsubishi continuous convener), 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
convener 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 S02 are emitted to
the atmosphere. Some facilities have combined the smelting furnace and convener into one operation,
such as the one used by Kennecott (i.e., the Kennecott-Outokumpo flash converting process).34,35 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.36
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.3'38
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
32 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 8.
33 ]bid-, P- 9.
34 "Copper," 1993, Op. Cit.. p. 396.
35 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 6-3 - 6-4.
36 "Copper," 1993, Op. Cit.. p. 396.
37 Ibid., p. 399-400.
38 U.S. Environmental Protection Agency, 1990, Op. Cit., p. 6-4.
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255
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
(e.g., copper is removed from the electrolyte in electrowinning cells), and the resulting impurities (left on
the bottom of the electrolytic cells and electrowinning cells - often referred to as "anode slimes" and
"muds or slimes", respectively) are processed for recovery of precious metals (gold, silver, platinum,
palladium), bismuth, selenium, and tellurium.39'40 Electrorefining also produces various 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.41
Hydrometallurgical Beneficiation
Hydrometallurgical copper recovery is the extraction and recovery of copper from ores using
aqueous solutions. Hydrometallurgical operations include the following: (1) acid extraction of copper
from oxide ores; (2) oxidation and dissolution of sulfides in waste rock 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.42 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).43
The simplest form of hydrometallurgical beneficiation of low grade ores, waste rock, and
overburden practiced at large, open-pit copper mines is dump leaching. In dump leaching, the raw
material is leached using a dilute sulfuric acid solution. There are several other types of leaching
operations (progressing from least capital intensive and inefficient - using the rock "as is" - to most
capital intensive and efficient - using ground ore): m situ, heap or pile, vat, and heat or agitated 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 panicles. The roasted material is then subjected to leaching (as described
above). The copper-rich leachate (referred to as "pregnant 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 agitated leaching). The major potential
environmental impact of hydrometallurgical beneficiation involves acid seepage into the ground. In
addition, hydrometallurgical sludges may contain undissolved metals, acids, and large quantities of
water.44
39 Note to the reader: we are currently trying to resolve conflicting information obtained from EPA's
recent site-visits and that found in various literature to determine whether slimes are generated in
electrowinning cells.
40 "Copper," 1993, Op. Cit.. pp. 401-404.
41 U.S. Environmental Protection Agency, 1990, Op. Cit.. p. 6-4.
42 Copper," 1993, Op. Cit.. p. 408.
43 Office of Technology Assessment, 1988, Op. Cit.. p. 140.
44 K. Yoshiki-Gravelsins, J. M. Toguri, and R. T. Choo, 1993, Op. Cit.. p. 27.
-------
Copper is removed from the pregnant leachate 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 pregnant leachate, 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
hvdrometallurgical refining (electrowinning) or pvrometallurgical processing 45 46
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 kerosene) and is mixed with the
pregnant leach solution. The copper-laden organic solution is separated from the leachate in a settling
tank. Sulfuric acid 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 refined copper metal. When the iron concentration becomes too high in the
electrowinning cells, 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. This operation is functionally equivalent to electrolytic
refining.47-48
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 ui-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.49
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
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 Kennecott, is a one-step smelting process designed to eliminate the hot matte and slag
transfers between smelting and converting, thereby reducing their attendant fugitive emissions. In the total
pressure oxidation process, chalcopyrite (CuFeS^ 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
45 "Copper," 1993, Op. Cit.. p. 410.
46 Office of Technology Assessment, 1988, Op. Cit.. pp. 140-142.
47 "Copper," 1993, Op. Cit.. pp. 412-13.
48 Office of Technology Assessment, 1988, Op. Cit.. p. 142.
49 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 16.
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257
proceed directly to smelting. The acid solution can be used in heap or dump leaching.50 Total pressure
oxidization is especially well-suited for concentrates with a high copper to sulphur ratio.51
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 in Section B.
EPA determined that for this specific 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 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
As discussed above (and shown in Exhibit 2), 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.
50 Robert W. Bartlet, "Copper Super-Concentrates-Processing, Economics, and Smelting," EPD
Congress, 1992, pp. 652-653.
51 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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258
1. Extraction/Beneficiation Wastes
Wastes generated from the extraction and beneficiation of copper from copper-bearing ores are
exempt from RCRA Subtitle C and the scope of BDAT determinations. Wastes from the
extraction/beneficiation of copper-bearing ores are discussed below.
Waste rock. 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. These
materials are typically hauled from the mine site and are disposed of in on-site waste rock dumps. At
Magma Copper (Arizona), waste rock is left in place; at other facilities, however, the waste rock may be
hauled to the surface and disposed.52 In 1980, more than 282 million tons of waste rock were
disposed.53
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.54 In 1985, the
industry disposed of more than 189 million tons of gangue.55
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.56 We note that this "slime" is
much different in composition than the "slimes or muds" generated by electrolytic refining (see below).
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 non-uniquely associated and, therefore, not subject to the Bevill
Exclusion:
52
U.S. Environmental Protection
Agency,
1994b,
Op. Cit.,
p. 10.
53
U.S. Environmental Protection
Agency,
1993d,
Op. Cit..
pp. 50-51
54
U.S. Environmental Protection
Agency,
1994b,
Op. Cit..
p. 10.
55
U.S. Environmental Protection
Agency,
1993d,
Op. Cit..
p. 53-54.
56 "Copper," 1993, Op. Cit., p. 388-92.
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Slimes or "muds'. These materials result from the deposition of sediment in electrowinning
cells. These materials often contain valuable quantities of precious metals and are either
processed on-site or are drummed and sent off-site for recovery.57 Approximately 3,000 metric
tons of slimes are generated annually.58 (See footnote no. 39.)
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 form 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 clay and then is returned to the SX circuit. The
resulting solids and aqueous material are disposed of in the tailing ponds.59 In some cases,
however, the resulting solids contain sufficient quantities of precious metals to warrant recovery
(off-site).60 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.61,62 Approximately 2,000 metric
tons of crud is generated annually.63
Raffinate or barren ieachate. 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.64'65 At Cerro Copper Products Company (a secondary copper facility) in
Sauget, IL, an electrolyte purification - nickel recovery system was installed and began operating in
late 1990, thereby allowing the recovery of nickel sulfate and cessation of the discharge of
raffinate.66
57 "Copper," 1993, Op. Cit„ pp. 401-404.
58 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization
Data Set. Volume I, Office of Solid Waste, August 1992, p. 1-3.
59 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.
60 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 54.
61 RTI Survey 100750, National Survey of Solid Wastes from Mineral Processing Facilities. Magma
Copper Co., San Manuel, AZ, 1989.
62 Tom Burniston, James N. Greenshield, and Peter E. Tetlow, 1992, Op. Cit.. p. 34.
63 U.S. Environmental Protection Agency, 1992, Op. Cit., p. 1-3.
64 The 1992 NIMPW Characterization Data Set indicates that 70,036,000 metric tons of raffinate are
generated annually. We are currently trying to verily this number and will revise it in the near future (if
appropriate).
65 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-3.
66 John L. Sundstrom, "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. 527-537.
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Spent Kerosene. Commonly used as the organic material in solvent extraction, spent kerosene is
purified using filter clay. The resulting impurities or "grungies" are either sent to the heap-
leaching area or are disposed of with tailings.67
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 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. Copper in the solution is deposited on copper starting sheets. As the copper in the solution is
depleted, the quality of the copper deposit is degraded. Liberator cathodes containing 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 in tailing
ponds or pumped to a raffinate pond, from which it is pumped to on-site copper leaching dumps. Sludge
that falls on the floor of the liberator cell is returned to the smelter or sold. 69
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. Magma Copper Company's
San Manuel facility recycled the bleed electrolyte to the solvent extraction/electrowinning plant for copper
recovery.71 Kennecott Utah Copper's Bingham Canyon, UT facility treats the bleed electrolyte in their
wastewater treatment plant.72 Phelps Dodge Refining Corp. in El Paso, TX sends bleed electrolyte to an
electrowinning plant, which produces commercial sulfuric acid, commercial grade nickel sulfate crystals,
and water vapor.73 Approximately 307,000 metric tons of bleed electrolyte are generated annually.
Bleed electrolyte exhibits the hazardous characteristics of toxicity (for arsenic, cadmium, chromium, lead,
67 U.S. Environmental Protection Agency, 1993d, Op. Cit„ pp. 114-115.
68 U.S. Environmental Protection Agency, Revised Draft Wastes from Primary Cooper Processing
Characterization Report for Cyprus Miami Mining Corporation. Claypool. AZ. Office of Solid Waste, May
1991, p. 5.
69 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.
70 RTI Survey 100156, National Survey of Solid Wastes from Mineral Processing Facilities. Cyprus
Miami Mining Corp., Clay Pool, AZ, 1989.
71 RTI Survey 100750, 1989, Op. Cit.
72 RTI Survey 100834, National Survey of Solid Wastes from Mineral Processing Facilities. Kennecott
Utah Copper, Bingham Canyon, UT, 1989.
73 RTI Survey 101741, National Survey of Solid Wastes from Mineral Processing Facilities. Phelps
Dodge Refining Co., El Paso, TX, 1989.
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selenium, and silver) and corrosivity.'4 This waste stream is partially recycled and classified as spent
material. Additional data are included in Attachment 1.
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.75 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 dor6 furnace, followed by
refining.76 A new method of metals recovery gaining popularity is wet chlorination, which uses
chlorination and solvent extraction to recover these values.77 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.78 Although no
published information regarding waste characteristics was found, we used best engineering judgement,to
determine that this waste may exhibit the characteristics of toxicity for selenium, silver, arsenic and lead.
This waste stream is partially recycled land classified as a by-product.
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.79 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 l).80 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.81 This waste is partially recycled and classified as a
by-product.
Site-specific management information is available for several facilities. Cyprus Miami Mining Corp. in
Claypool, AZ recycles the solid fraction to the smelter and the liquid portion to the solvent extraction
74 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-3.
75 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.
76 M. Devia and A. Luraschi, "A Study of the Smelting and Refining of Anode Slimes to Dor6 Metal,"
Copper 91 fCobre 911. Ottawa. Ontario. Canada, 18-21 Aug. 1991. Pergamon Press, Inc., New York, 1992
p. 210.
77 James E. Hoffmann, 1991, Op. Cit.. p. 23.
78 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-3.
79 U.S. Environmental Protection Agency, 1991, Op. Cit.. pp. 5-7.
80 U.S. Environmental Protection Agency, Study of Remanded Mineral Processing Wastes Draft
Report, Office-of-Solid-Waste, April 1994c, p. 19.
81 U.S. Environmental Protection Agency, 1992, Op. Cit., p. 1-3.
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plant.82 The Hidalgo smelter in'Playas, NM was scheduled to make process modifications by January
1993. Previously, acid plant blowdown was sent to an evaporation unit. Radial flow scrubbers and
additional technology to be determined were scheduled to be installed in the acid plants, thereby
eliminating the wastewater.83 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. At the Magma Copper Company's San Manuel, AZ facility, the blowdown is neutralized
with lime and alkaline tailings, and the resulting mixture is sent to tailings dams.85 Kennecott Utah
Copper in Bingham Canyon, UT sends the blowdown to the wastewater treatment plant and then to the
tailings pond.8
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 evaporation
pond. Recent site-specific information, 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).87 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.88 Site-
specific management information is available for several companies. The Magma Copper Company's San
Manuel, AZ facility recycles the copper anode cooling water to the concentrator.89 "Hie Kennecott Utah
82 RTI Survey 100156, 1989, Op. Cit.
83 RTI Survey 100487, National Survey of Solid Wastes from Mineral Processing Facilities. Hidalgo
Smelter, Playas, NM, 1989.
.84 RTI Survey 100495, National Survey of Solid Wastes from Mineral Processing Facilities. Chino
Mining Co. Hurley, NM, 1989.
85 RTI Survey 100750, 1989, Op. Cit.
86 RTI Survey 100834, 1989, Op. Cit.
87 U.S. Environmental Protection Agency, 1994c, Op. Cit.. pp. 3-4.
88 U.S: Department of Commerce, Industrial Process Profiles for Environmental Use: Chapter 29
Primary Copper Industry. Industrial Environmental Research Lab, July 1980. p. 89.
89 RTI Survey 100750, 1989, Op. Cit.
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Copper's facility in Bingham Canyon, recycles all but a small fraction to the ore concentrator. The
remaining small fraction is discharged under NPDES after treatment.90 At Cyprus Miami Mining Corp.,
Claypool, AZ, contact cooling water is returned to the Industrial Water System.91 Approximately 13,000
metric tons of contact cooling water is generated annually.92 Although no published information
regarding waste characteristics was found, we used best engineering judgement to determine that this waste
may exhibit the characteristics of toxicity for arsenic. This waste stream is recvled and classified as 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, therefore it is not
included in the analysis. Approximately 4,590,000 metric tons of WWTP liquid effluent is generated
annually.93 We used best engineering judgement to determine that this waste may exhibit the
characteristics of toxicity for lead. Additional data are included in Attachment 1.
Process wastewaters. Various wastewaters result from conveyance, flotation, mixing, dissolution, and
cooling operations. Water is used for many things including, seal water in crushers and pumps, for dust
suppression and gas scrubbing, 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.94 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.95 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.96 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.97
Approximately 4,891,000 metric tons of process wastewaters are generated annually. This waste exhibits
the hazardous characteristics of toxicity (for arsenic, cadmium, lead, and mercury) and corrosivity.98 We
used best engineering judgement to determine that this waste may also exhibit the characteristics of
toxicity for selenium. This waste stream is recycled and classified as spent material. Additional data are
included in Attachment 1.
90 RTI Survey 100834, 1989, Op. Cit.
91 U.S. Environmental Protection Agency, 1991, Op. Cit.. p. 3.
92 U.S. Environmental Protection Agency, 1992, Op. Cit., p. 1-4.
93 Ibid.
94 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.
95 U.S. Environmental Protection Agency, 1991, Op. Cit.. p. 5.
96 RTI Survey 100750, 1989, Op. Cit.
97 RTI Survey 101782, National Survey of Solid Wastes from Mineral Processing Facilities. Copper
Range Co., White Pine, MI, 1989.
98 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4.
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Scrubber blowdown. This waste results when low volumes of high total dissolved solids (TDS) materials
are removed from the gas scrubbing system. At the Hidalgo smelter in Playas, NM, the scrubber had
processed electric furnace dust and the wastewater was routed to the acid plants, followed by an
evaporation unit. However, the system was scheduled to be taken off-line by 1993." 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.100 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.101 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.102 This waste exhibits the
characteristic of toxicity for arsenic, cadmium, and selenium, and may also be toxic for mercury.103 This,
waste stream is partially recycled and classified as spent material. 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.
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.104 Approximately 3,000 metric tons of furnace brick is generated annually.105 Revert
(molten matte that is spilled during its transfer in the smelting process) also contains significant
conceptrations of copper and is returned to the crushing/grinding circuit.106 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.107
99 RTI Survey 100487, 1989. Op. Cit.
100 RTI Survey 100495, 1989, Op. Cit.
101 RTI Survey 100750, 1989, Op. Cit.
102 ICF Incorporated, Mineral Processing Waste Sampling Survey Trip Reports. Prepared for U.S.
Environmental Protection Agency, Office of Solid Waste, August 1989, p. 2.
103 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4.
104 U.S. Environmental Protection Agency, 1991, Op. Cit.. p. 7.
105 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4.
106 U.S. Environmental Protection Agency, 1994b, Op. Cit.. p. 11.
107 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.
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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.108 Site-specific
management information is available for several companies. Magma Copper (Arizona), has constructed a
new flue dust leaching (FDL) facility to recover copper from several smelter by-product streams.
Feedstocks to the FDL facility 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 the Lurgi
scrubbers (3.6 g/L copper, 0.4 g/L arsenic, 3.5 g/L acid pH 1.6).109 At Kennecott Utah Copper,
Bingham Canyon, UT, only some of the copper-containing flue dust is returned to the smelting vessel: the
majority of the flue dust-is stockpiled for future recycling.110
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 caught 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.111112 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 tonsfyr, 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 waste stream is fully recycled
and classified as sludge.
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 waste exhibits the hazardous characteristic of corrosivity.113 We used best
engineering judgement to determine that this waste may also exhibit the hazardous characteristics of
toxicity for arsenic, lead, and selenium. Also, we used best engineering judgement to determine that this
waste stream is partially recycled. This waste is classified as spent material. Additional data are included
in Attachment 1.
108 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.
109 U.S. Environmental Protection Agency, 1994b, Op. Cit., p. 9.
110 ICF Incorporated, 1989, Qp.Cit.. p. 2.
111 "Indium and Bismuth," ASM International Materials Handbook. Tenth Edition, Vol. 2: Properties
and Selection: Non-ferrous Alloys and Special-Purpose Materials, 1990, p. 753.
112 Funsho K. Ohebuoboh, "Bismuth-Production, Properties, and Applications," Journal of Mines. 44,
No. 4, 1992. pp. 46-49.
113 Ibid.
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Non-recyclable APC dusts. APC dusts are collected by baghouses, electrostatic precipitators, and cottrell
systems. If the APC dusts contain insufficient concentrations of copper or other values, the material is
judged not to be economically recoverable. At Kennecott's Bingham Canyon, UT facility, the majority of
its flue dust is stockpiled for future recycling.114 Approximately 7,000 metric tons of non-recyclable
APC dusts are generated annually.115 Existing (lata and engineering judgement suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
this "material further.
Chamber solids/scrubber sludge. Approximately 31,000 metric tons of chamber solids and scrubber
sludges are generated annually.116 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 black sulfuric acid sludge. This material is obtained from the vacuum evaporation of decopperized
electrolyte. The black acid liquor may be also be used in leaching operations or be sold to fertilizer
manufactures.117 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 both the Phelps Dodge Hurley facility, which uses magnesium
hydroxide, and the Kennecott's Bingham Canyon plant, which uses lime.118,119 Approximately 6,000
metric tons of solids and sludges are generated annually.120 Although no published information
regarding waste characteristics was found, we used best engineering judgement to determine that this waste
may exhibit the characteristics of toxicity for cadmium and lead. This waste stream is partially recylced and
classified as 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. Ancillary Hazardous Wastes
Ancillary 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.
Samples of electrolyte are recycled to the plant.121 Other hazardous wastes may include spent paints
and solvents (non-chlorinated solvents such as "140 Stoddard" and petroleum naphtha, and "Safety
114 ICF Incorporated, 1989, Op. Cit.. p. 2.
115 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-4.
116 Ibid.
117 U.S. Environmental Protection Agency, 1984, Op. Cit.. p. 3-12.
118 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 13-74.
119 RTI Survey 100834, 1989, Op. Cit.
120 U.S. Environmental Protection Agency, 1992, Op. Cit.
121 U.S. Environmental Protection Agency, 1993d, Op. Cit.. p. 308.
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267
Kleen" solvents) generated from facility maintenance operations, spent batteries, asbestos, and
polychlorinated biphenyls (PCBs) from electrical transformers. 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 produced in the acid plant. The spent vanadium
pentoxide catalyst is either sent off-site for recycling, or disposed 'of either on- or off-site.
122 U.S. Environmental Protection Agency, 1994b, Op. Cit., p. 12.
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-------
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Chemical Characteristics in the Primary Copper Smelting and Refining Industry. Industrial
Environmental Research Laboratory, Office of Research and Development. October 1984.
U.S. Environmental Protection Agency. Newly Identified Mineral Processing Waste Characterization Data
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. II. Office of Solid Waste. July 1990. pp. 6-1 - 6-66.
U.S. Environmental Protection Agency. Pvrite Flotation: Magma Copper Company's Superior Facility
Draft. Office of Solid Waste. March 1993a.
U.S. Environmental Protection Agency. RCRA Mining and Mineral Processing Waste Outreach Support
Document - Draft. Office of Solid Waste. January 1994a.
-------
270
U.S. Environmental Protection Agency. Revised Draft Wastes from Primary Copper Processing
Characterization Report for Cyprus Miami Mining Corporation. Clavpool. A7. Office of Solid
Waste. May 1991.
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,
Pan II: Environmental Impact." Journal of Mines. 45, No. 8. August 1993. pp. 23-29.
-------
ATTACHMENT 1
-------
272
-------
SUMJ&. JF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT BLEED ELE 3LYTE - COPPER
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum
# Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
U Delects
TC
Level
tt Values
In Excess
Aluminum
6.20
145.04
356.00
5/5
10.00
139.73
361.00
3/3
-
-
Antimony
23.20
203.50
565.00
9/9
20.50
67.37
98.50
3/3
-
-
Arsecuc
0.02
2,218.50
11,500.00
10/10
10.00
347.00
1,100.00
4/4
5.0
4
Barium
0.25
7.19
1800
3/4
0.40
5.23
10.00
3/4
100.0
0
Bery|lium
0.03
0.36
1.00
2/3
0.05
0.68
1.00
2/3
-
-
Bordn
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.03
0.52
1.00
3/4
0.02
1.27
3.07
4/4
1.0
3
Chromium
0.84
12.59
38.00
4/4
0.80
5.55
10.00
4/4
5.0
2
Cobalt
1.90
39.15
124.00
4/4
1.69
55.56
126.00
3/3
-
-
Copper.
10.00
26,787
120,380
14/14
485.00
10,991 25
22,200.00
4/4
-
-
Iron
54.30
386.54
1,360.00
8/8
89.40
443.85
1,390.00
4/4
-
0
Lead
0.25
19.68
90.60
6/6
0.25
3.20
5.00
3/4
5.0
2
Magnesium
9.13
196.76
503.00
4/4
14.40
195.53
505.00
3/3
-
-
Manganese
0.62
9.04
32.60
4/4
0.79
11.43
33.00
4/4
-
-
Mercury
0.0001
0.0050
0.0100
3/4
0.0001
0.0019
0.0062
2/4
b.2
0
Molybdenum
0.25
62.58
187.00
2/3
0.50
67.83
193.00
2/3
-
-
Nickel
10.00
6,357.30
33,050.00
10/10
10.00
200.67
365.00
3/3
-
-
Selenium
0.01
4.25
10.60
5/5
0.01
7.18
10 00
4/4
1 0
3
Silver
0.23
2.75
10.00
3/4
0.19
5 17
10.00
3/4
5.0
2
Thallium
1.25
17.92
50.00
2/3
2.50
34.17
50.00
2/3
-
-
Vanadium
0.25
3.58
10.00
2/3
0.50
6.83
10.00
2/3
-
-
Zinc
2.73
25.84
62.40
5/6
2.73
28.48
63.00
4/4
-
-
Sulfate
18,301
218,273
786,653
11/11
-
-
Fluoride
1.00
1.00
1.00
1/1
-
-
Chloride
32.50
121.63
285.00
6/6
-
-
TSS
95,650
224,330
308,000
5/5
-
-
pH '
1.00
1.93
2.72
4/4
212
3
Organics (TOC)
7.29
153.63
382.00
3/3
-
-
Non-detects assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
f5PMRWh«Y 0FJEPA/0RD, 3007, AND RTI SAMPLING DATA - ACID PLANT BLOWDOWN -COPPER
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
It Detects
Minimum
Average
Maximum
tt Detects
Level
In Excess
Aluminum
1.16
870.32
5,200.00
8/8
0.78
750.39
1.500.00
2/2
-
-
Antimony
0.26
36.44
140.00
2/4
0.17
2.58
5.00
1/2
-
-
Arsenic
0.05
855.76
5,800.00
10/15
0.04
884.35
12,800
12/15
5.0
10
Barium
0.05
1.38
5.90
7/12
0.05
2.54
10.90
8/15
100.0
0
Beryllium
0.005
0.07
0.13
1/2
0.01
0.25
0.50
0/2
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.20
62.93
620.00
16/16
0.05
4.26
24.50
14/15
1.0
9
Chromium
0.10
3.62
21.00
14/14
0.00
0.41
5.00
11/15
5.0
1
Coball
0.02
3.35
9.00
4/5
0.05
5.03
10.00
1/2
-
-
Copper
1.80
3.151.86
40,000
20/20
1.89
144.53
1.190 00
9/9
-
-
Iron
7.90
2,402.62
10,000
12/12
0.22
103.82
1,010.00
10/10
-
-
Lead
0.20
1,061.28
17,900
19/19
0.04
2.83
6.74
13/15
5.0
3
Magnesium
2.10
638.49
2,070.00
10/10
60.60
1,015.30
1,970.00
2/2
-
-
Manganese
0.05
40.61
140.00
8/9
0.02
10.20
100.00
7/10
-
-
Mercury
0.00
0.32
1.50
6/11
0.0001
0.0426
0.3100
8/15
0.2
2
Molybdenum
0.50
70.68
390.00
5/6
5.91
15.86
25.80
2/2
-
-
Nickel
0.01
221.33
1,450.00
10/11
0.02
1.83
5.00
2/3
-
-
Selenium
0.00
78.97
1,000.00
6/13
0.01
1.21
7.63
11/15
1.0
3
Silver
0.00
11.52
124.00
6/11
0.01
0.41
5.00
6/15
5.0
1
Thallium
0.25
1.38
2.50
0/2
0.25
8.50
25.00
0/3
-
-
Vanadium
0.05
1.39
2.72
1/2
0.05
2.53
5.00
0/2
-
-
Zinc
5.10
1,737.16
10,000
13/13
3.16
100.70
467.00
10/10
-
-
Sulfate
766.00
23,198
135,570
12/12
-
-
Fluoride
20.60
761.02
1.780.00
6/6
-
-
Chloride
0.10
793.01
2,740.00
6/7
-
-
TSS
170.00
13,593.70
58,600.00
5/5
-
-
pH *
0.99
2.21
5.00
17/17
212
10
Organics(TOC)
1.39
436.30
1,300.00
3/3
-
-
Non-detecls were assumed (o be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
Si '*RY OF. EPA/ORD, 3007, AND RTI SAMPLING DATA - ACID PLANT T[ ENER SLUDGE - COPPER
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
H Values
Constituents
Minimum
Average
Maximum
H Detects
Minimum
Average
Maximum
» Delects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
-
0/0
-
-
Antimony
200.00
1,600.00
3,000.00
212
-
-
-
0/0
-
-
Arsenic
90.00
2.795.00
5,500.00
2/2
0.18
52.44
193.00
in
50
5
Barium
400.00
2,700.00
5,000.00
2/2
0.04
3.69
10.90
5/7
100.0
0
Beryinum
-
-
-
0/0
45.00
45.00
45.00
1/1
-
-
boron
-
-
-
0/0
-
-
-
0/0
Cadmium
250.00
1,875.00
3,500.00
2/2
0.16
7.97
24.50
6/6
1.0
4
encomium
50.00
760.00
1,470.00
1/2
0.00
0.03
0.17
7/7
5.0
0
CODait
20.00
210.00
400.00
2/2
-
-
-
0/0
-
-
caober
21,000
89,500
158,000
2/2
-
-
-
0/0
-
-
iron
39,000
163,000
287,000
2/2
0.22
23.50
150.00
7/7
-
-
Ldaa
56,000
275,500
495,000
2/2
0.04
1.94
3.80
7/7
5,0
0
Maanesium
-
-
-
0/0
-
-
-
0/0
-
-
Manganese
-
-
-
0/0
0.03
0.36
1.03
4/5
-
-
Mercury
-
-
-
0/0
0.0003
0.1038
0.3100
4/6
6.2
2
Moiyoaenum
50.00
625.00
1,200.00
2/2
-
-
-
0/0
-
-
Nickoi
40.00
1,355.00
2,670.00
2/2
-
-
-
0/0
-
-
Selenium
5.00
307.50
610.00
1/2
0.03
0.24
0.61
7/7
1.0
0
Silver
67.30
217.00
366.70
2/2
0.02
0.04
0.10
2/5
5.0
0
Thallium
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
Zinc
2,230
13,315
24,400
2/2
3.16
193.64
500.00
7/7
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
10.00
740.00
1,470.00
2/2
-
-
Chloride
620.00
9,310
18,000
2/2
-
-
TSS
-
-
-
0/0
-
-
PH '
1.81
1.81
1.81
1/1
212
1
Organics (TOC)
-
-
-
0/0
-
"
Non-detecls were assumb&u iu uo |jiuaeiii m mc. mo uoioliium num. i uaia are currenuy unavanaoie; inereiore, oniy tr aaia are presented.
NJ
•vj
lti
-------
StJMWtftRY*OPEPA/ORD, 3007, AND RTISAMPLING DATA - WASTEWATER-TREATMENT PLANT LIQUID EFFLUENT—GOPRER
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
H Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
tt Detecls
Level
In Excess
Aluminum
0.798
0.798
0.798
1/1
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenica
-
-
-
0/0
-
-
0/0
5 0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
Cadmium
0.002
0.151
0.300
212
-
-
0/0
1.0
0
Chromium
0.023
0.023
0.023
1/1
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
130.00
130.00
130.00
1/1
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.050
3.53
7.00
2/2
-
-
0/0
5.0
0
Magnesium
0.354
25.18
50.00
2/2
-
-
0/0
-
-
Manganese
0.060
0.060
0.060
1/1
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0 2
0
Molybdenum
0.011
0.011
0.011
1/1
-
-
0/0
-
-
Nickel
0.014
0.207
0.400
2/2
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1 0
0
Silver
-
-
-
0/0
-
-
0/0
5 0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.600
0.600
0.600
1/1
-
-
0/0
-
-
Sulfate
1889.00
2744.50
3600.00
2/2
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
740.00
1794.00
2848.00
2/2
-
-
pH *
3.10
7.48
11.80
5/5
212
-
Organics(TOC)
-
-
-
0/0
-
-
Non-detecls were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable, therefore, only LI* data are presented
-------
ft flRY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WA /VATER - COPPER
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
H Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
U Delects
Level
In Excess
Aluminum
0.050
1.23
7.71
7/7
0.05
1.02
4.91
5/5
-
-
Antimony
0.050
0.73
1.51
6/6
0.05
0.38
0.95
5/5
-
-
Arsenic
0.005
14.90
191.00
14/15
0.0003
4.75
23.20
11/12
5.0
3
Barium
0.005
27.57
318.60
12/12
0.0027
0.26
1.20
12/12
100.0
0
Beryllium
0.005
0.02
0.05
5/5
0.0050
0.01
0.01
5/5
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.0003
1.26
10.00
15/15
0.0050
7.31
32.00
12/12
1.0
5
Chromium
0.005
1.86
22.02
15/16
0.0001
0.12
0.53
12/12
5.0
0
Cobalt
0.010
0.15
0.50
6/6
0.0500
0.05
0.05
5/5
-
-
Copper
0.050
227.31
1,410:00
12/12
0.0500
159.88
664.00
7/7
-
-
Iron/
0.090
957.33
8.466.00
8/9
0.0001
33.69
139.00
9/10
-
-
Ltead
0.003
36.39
402.50
16/16
0.0020
1.39
7.30
12/12
5.0
1
Magnesium
0.221
485.67
3,643.00
8/8
3.3600
24.39
59.00
5/5
-
-
Manganese
0.050
803
63.07
8/8
0.0250
0.43
1.80
10/10
-
-
Medoury
0.0001
0.0010
0.0050
11/12
8.00E-07
0.1910
1.0600
5/11
0.2
2
Molybdenum
0.005
14.77
100.30
7/7
0.0500
0.51
2.33
1/5
-
-
Nickel
0.050
1.15
5.30
9/9
0.0500
0.15
0.40
3/6
-
-
Selenium
0.0005
0.55
7.00
15/15
0.0002
0.03
0.05
5/12
1.0
0
Silver
0.004
0.10
0.50
12/12
1.50E-05
0.03
0.05
11/12
5.0
0
Thallium
0.250
1.13
4.00
6/7
0.1000
0.32
0.81
6/6
-
-
Vanadium
0.050
0.18
0.50
5/5
0.0500
0.05
0 05
5/5
-
-
Zinc
0.01
8.72
42.00
11/11
0.0170
43.50
202.00
12/12
-
-
Sulfate
216.00
2.152.63
7,519.00
8/8
-
-
Fluoride
5.40
8.20
11.00
2/2
-
-
Chloride
28.40
363.39
1,862.00
7/7
-
-
TSS
1.50
55,080
270,800
13/13
-
-
PH*
1.35
6.37
8.50
28/28
212
3
Or games (TOC)
0.60
257.13
1,280.00
5/5
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 EEA/OBD 3007 AND RJI SAMPLING DATA SCBUBBEB.BLO.WDOWN COPPER
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum ft Detects
TC H Values
Level In Excess
Aluminum
1.84
1.84
1 84
1/1
1.63
1.63
1.63 1/1
-
-
Antimony
0.73
0.73
0.73
1/1
0.65
0.65
0.65 1/1
-
-
Arsenic
0.05
13.98
27.90
212
27.40
27.40
27.40 1/1
5.0
1
Barium
0.05
0.73
1.40
2J2
0.05
0.05
0 05 1/1
100.0
0
Beryllium
0.01
0.01
0.01
1/1
0.01
0.01
001 1/1
-
-
Boron
-
-
-
0/0
-
-
0/0
Cadmium
2.10
3.75
5.40
2/2
1 93
1 93
1.93 1/1
1.0
1
Chromium
0.17
0.28
0.40
2/2
0.17
0.17
0.17 1/1
5.0
0
CoDan
0.05
0.05
0.05
1/1
0.05
0.05
0.05 1/1
-
-
Copper
4.90
4.90
4.90
1/1
3.05
3.05
3.05 1/1
-
-
iron
11.50
11.50
11.50
1/1
9.50
9.50
9.50 1/1
-
-
Lead
4.90
11.60
18.30
2/2
4.88
4.88
4.88 1/1
5.0
0
Magnesium
15.80
15.80
15.80
1/1
14.80
14.80
14.80 1/1
-
-
Manganese
0.05
0.05
0.05
1/1
0 05
0.05
0.05 1/1
-
-
Mercury
0.01
0.49
0.98
2/2
0.022
0.022
0.022 1/1
0 2
0
MoiyDdenum
0.90
0.90
0.90
1/1
0.85
0.85
0.85 1/1
-
-
Nickel
0.47
0.47
0.47
1/1
0.44
0 44
0.44 1/1
-
-
Selenium
0.01
7.20
14.40
2/2
7.71
7.71
7.71 1/1
1 0
1
Silver
0.02
0.04
0.05
2/2
0.05
0.05
0.05 1/1
5 0
0
Thallium
0.25
0.25
0.25
1/1
0.25
0 25
0 25 1/1
-
-
Vanadium
0.05
0.05
0.05
1/1
0.05
0.05
0.05 1/1
-
-
Zinc
6.24
6.24
6.24
1/1
6.28
6.28
6.28 1/1
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
pH *
-
-
-
0/0
212
-
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present al 1/2 the detection limit. TCLP data are currently unavailable, therefore, onlv EP (Jala are Dresenipri
-------
S ARY OF EPA/ORD, 3007, AND Rll SAMPLING DATA - SURFACE IMF DMENT LIQUIDS - COPPER
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
U Detects
Minimum
Average
Maximum
H Detects
Level
In Excess
Aluminunri
-
-
-
0/0
-
-
-
0/0
-
-
Antimony
2 20
2.45
2.70
212
-
-
-
0/0
-
-
Arsenic
0.06
33.23
150.00
5/5
0.25
0.25
0 25
212
5 0
0
Barium
0.001
0.001
0.001
1/1
5.00
5.00
5 00
2/2
100 0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
Cadmium
0.01
0.15
0.30
272
0.05
0.05
0.05
2/2
1.0
0
Chromium
0 02
1.61
4.00
3/3
0.25
0 25
0.25
2/2
5 0
0
Cobalt
-
-
-
0/0
-
-
-
0/0
-
-
Copper
0.01
25.41
90 00
7/7
T
-
-
0/0
-
-
Iron
0.63
48.21
88.00
3/3
-
-
-
0/0
-
-
Lead
0.03
2.11
7.00
4/4
0.25
0 25
0.25
2/2
5 0
0
Magnesium
0.10
2.77
4.20
3/3
-
-
-
0/0
-
Manganese
0.02
0.04
0.06
212
-
-
-
0/0
-
-
Mercury
0.0001
0.0001
0.0001
1/1
0.10
0.10
0 10
212
0.2
0
Molybdenum
0.72
1.76
2.80
2/2
-
-
-
0/0
-
-
Nickel
0.10
0.97
3.00
4/4
-
-
-
0/0
-
-
Selenium
0.02
3.08
9.00
3/3
0.05
0.05
0.05
212
1 0
0
Silver
0.02
0.02
0.02
1/1
0.25
0.25
0.25
212
5.0
0
Thallium
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
Zinc
0.11
0.57
1.00
3/3
-
-
-
0/0
-
-
Sulfate
1.250.00
6.908.25
18.842.00
4/4
-
-
Fluoride
17.00
17.00
17.00
1/1
-
-
Chloride
129.00
1,573.50
2,230.00
4/4
-
-
TSS
2,230.00
11,742.50
25,470.00
4/4
-
-
pH *
1.30
6.36
10.00
9/9
212
2
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed lo be present at 1/2 the detection limit TCLP data are currently unavailable, therefore, only tP data aio presented
NJ
(£>
-------
SUMMARY OF EPA/ORD. 3007, AND RTI SAMPLING DATA - WASTEWATER TREATMENT PLANT SLUDGE - COPPER
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
ft Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenic
-
-
-
0/0
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
Cadmium
-
-
-
0/0
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
50,000
225,000
400,000
2/2
-
-
0/0
-
-
Iron
150.000
150,000
150,000
1/1
-
-
0/0
-
-
Lead
-
-
-
0/0
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
Vanadium
-
-
-
0/0
-
-
0/0
-
_
Zinc
-
-
-
0/0
-
-
0/0
_
_
Sulfate
-
-
-
0/0
-
_
Fluoride
-
-
-
0/0
_
_
Chloride
-
-
-
0/0
_
_
TSS
700,000
700,000
700,000
2/2
_
_
pH *
3.10
6.05
9.00
2/2
2 12
-
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only bP data are presented
-------
ATTACHMENT 2
MINING SITES ON THE NATIONAL PRIORITY LIST
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282
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283
Mining Sites on the National Priority List
Name of Site: Anaconda Smelter
Owner of Site: Anaconda Copper Mining Company (merged with ARCO in 1977)
Location of Site: Mill Creek, Montana (26 miles west of Butte)
Climate Data: To be determined
Commodity Mined: Copper
Facility History: 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 reverberatorv
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, an
electrolytic copper refinery had been built as well, and was located between the
two smelters. Due to shortage of smelting 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.
Waste(s) at Issue: 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.
Disposal Sites: 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 ore§ 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
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284
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. Community soils — 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 — 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.
Soil Pathway: 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.
Ground Water The water table underlying Mill Creek is 20 feet or deeper below the surface.
Pathway: 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.
Surface Water Mill Creek is the major drainage system is the area of the Anaconda Smelter and
Pathway: 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.
Air Pathway: 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/m3.
Environmental Issues: 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
environmejit] (e.g, aquatic life, drinking water).
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285
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: 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.
Waste(s) at Issue: Heavy metals (arsenic, tin, lead and nickel) found in onsite surface and ground
water, and in ambient air sampled on and off the site.
Disposal 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 Amiberi-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. "Tlie 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
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286
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.
Soil Pathway: 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 the 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).
Air Pathway: In January 1986, air-quality monitoring samples were obtained along the site
perimeter using high-volume paniculate samplers. The conclusion reached after
the sampling was that heavy metals and arsenic were being carried offsite by the
wind. TTie maximum values of the detected contaminants were: arsenic (2.34
ug/m3), cadmium (0.64 ug/m3), chromium (0.40 ug/m3), lead (4.42 ug/m3), nickel
(0.21 ug/m3), and tin (103.6 ug/m3).
Environmental Issues: 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'me site and is used primarily for recreational fishing
andJ crabbing. rA principarconcem is the potential environmental contamination
ofrsunace waters througrrtne transport of heavy metals into Chicot Aquifer, and
Ground Water
Pathway:
Surface Water
Pathway:
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287
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.
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288
Mining Sites on the National Priority List
Name of Site: Torch Lake
Owner of Site: Not applicable
Location of Site: Keweenaw Peninsula of Upper Michigan (14 miles from Lake Superior)
Climate Data: Not given
Commodity Mined: Copper
Facility History: For over 100 years, the area surrounding Torch Lake was the center of Michigan's
copper mining, smelting, and 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.
Waste(s) at Issue: 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.
Disposal Site: The Torch Lake site has three operable units (OUs). OU1 includes surface
tailings, contents of buried and submerged drums 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.
Tailings: Mine tailings are divided into two categories. The first involves tailings resulting
from crushing and gravitational separation processes. The resulting contaminants
of concern are: aresenic, 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 exanthates). 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
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289
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.
Drums: 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.
soil hattiway: 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.
Ground Water The U.S. Geological Survey sampled well water in 1968 and 1977. Analysis of the
Pathway: 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 Water enters Torch Lake from the Trap Rock River, and Hammell, Dover,
Pathway: 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.
Air Pathway: 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
-------
290
concentrations for aluminum, arsenic, barium, copper, magnesium, iron
manganese, and TSP.
Environmental Issues: 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
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.
-------
291
ELEMENTAL PHOSPHORUS
A. Commodity Summary
Phosphorus is the twelfth most abundant element. Nearly all of the naturally occurring
phosphorus compounds are salts of phosphoric acid. Apatite minerals comprise the majority of phosphate
constituents in phosphate rock. Phosphate rock deposits occur as marine phosphorites, apatite-rich
igneous rock, and modern and ancient guano. All domestic production is from marine phosphorites.
According to the U.S. Bureau of Mines, nearly 93% 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%) 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.
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 U.S. Bureau of Mines, there are only two domestic producers of elemental
phosphorus. FMC operates a facility in Pocatello, ID and Monsanto operates a facility in Soda Springs,
ID.
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.4
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 Ibid.
-------
292
2. Generalized Process Flow Diagram
White Phosphorus
Exhibit 2 presents a process flow diagram for the production of white phosphorus. The furnace
burden must be porous enough to allow gases to escape from the reaction zone near the bottom of the
furnace. To ensure this, one of several agglomeration methods must be employed. Phosphate-rock 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.5
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 arfe 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.6
Red Phosphorus
While red phosphorus is usually manufactured by a batch process, continuous methods have been
developed. 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.7
FMC Facility Process
FMC Corporation is the world's largest producer of elemental phosphorus, producing about 240
million pounds of elemental phosphorus per year. 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.
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
5 Ibid.
6 Ibid.
7 Ibid.
-------
EXHIBIT 2
ELEMENTAL PHOSPHORUS PRODUCTION
(Adapted from: Phosphorus, A Mineral Porcessing Waste Generation Profile.)
CO to
Phosphate Dust to I'hossy Water
Fertilizer Blending Mud to Disposal
NJ
10
LaJ
-------
NJ
KO
EXHIBIT 3
PROCESS AT FMC FACILITY
(Adapted from: Elemental Phosphorus Processing Waste Characterization Report For FMC Corporation, 1991, pp. 1-4.)
Shale
Shale
Slacker-
Reclaimer
Screening
Crushing
Unquoting
Calcining
P., Sumps
l\, Storage
FMC
lank
Farm
r
~
FMC Plants
Lawrence, KS
Newark, CA
(Jreen River, WV
Carteret, NJ
Nilio, WV
Dust
Slurry
T
lined
I'onds
Secondary
Primary
Precipitators
IZlectric
Condei\scrs
Condensers
Furnace
Clull
Molds
Crushing
Calcined
Phosphate
~
Nodule
Storage &
Reclaim
I I I
¦Coke
" Silica
Proportioning
i
Slag
Pit
Screening
Crushing
• Sale
Scicening
Slag
-------
295
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 screened to remove
oversized material which is 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. The briquettes are
then routed to the calciners where they are heated to burn organic material, remove water, and harden.
The calcined briquettes, called nodules, are cooled and either stockpiled for later use or fed directly to
proportioning. Calciners are fueled by carbon monoxide which is generated in the electric arc furnace
operation. Air emissions from the calciners go to one of two sets of scrubbers for removal of particulates
and radionuclides. The primary scrubbers remove particulates and the John Zink scrubber removes
polonium 210, a radionuclide. The nodules are routed from the calciners to the proportioning building
where they are mixed with silica and coke, creating a mixture called burden. The burden is sent to one of
five feed bins on each furnace. Fugitive dust from transfer points at the calciners and the proportioning
building is collected by baghouses.
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 which heat the furnaces to reduce the phosphate to
gaseous elemental phosphorus. Silica is used as a flux 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 particulate 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.9
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
8 National Enforcement Investigations Center (NEIC), Multi-Media Compliance Investigation. FMC
Corporation - Phosphorus Chemicals Division. Pocatello, Idaho.e January^ 1994-r : ,
iierorerarion of ihe Bevill Exclusion
9 Ibid.
-------
296
are also primarily phosphorus pentoxide. Emissions from slag tapping are vented to the atmosphere
through a Medusa scrubber followed bv an Anderson scrubber.10
3. Identification/Discussion of Noyel (or otherwise distinct) Process(es)
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 presented above in Section B.
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.
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.
10 Ibid.
-------
297
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Waste , rock from mining.
Fugitive dust is generated from screening and crushing. FMC collects this dust in baghouses.11
2. Mineral Processing Wastes
Surface impoundment waste solids are generated at a rate of 373 kg per kkg product.12 Existing
data and engineering judgement 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.
Slag quenchwater. Prior to treatment, raw slag quenchwater may be toxic for cadmium and lead
Before being discharged, slag quenchwater may be lime treated to precipitate phosphates and fluorides.13
We used the methodology outlined in Appendix A to estimate a low, medium, and high generation rate of
0 mt/y, 0 mt/y, and 1,000,000 mt/y. This waste may be recycled and is classified as a spent material. Waste
characterization data for treated slag quenchwater are presented in Attachment 1.
Slag, a RCRA special waste, contains trace amounts of radioactive materials in a stable, calcium
silicate matrix. For every pound of white phosphorus produced, four pounds of slag are produced. In
1991, this waste was generated at a rate of 2,867 metric tons per year. 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.15
Dust. Phosphatic dusts may be slightly enriched in radioactivity as well as volatilized, reduced
heavy metals. Phosphatic dusts are normally sold for blending with fertilizer materials16 and are
classified as byproducts. Management includes storage in a wastepile and offsite landfill disposal.17 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.
11 Ibid.
12 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals
Industry. Volume II, Chapter 8, 1980.
13 U.S. Environmental Protection Agency, Op. Cite.. Volume II, Chapter 8.
14 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.
15 NEIC, 1992, Op. Cit.
16 U.S. Environmental Protection Agency. "Phosphate Rock," from 1988 Final Draft Summary Report
¦of Mineral Industry Processing Waste. 1988, pp. 2-120 - 2-127.
17 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.
-------
298
Condenser phossy water discard may contain cyanide.18 This waste water comes from furnace
washdown, phosphorus dock' operations, condensers, and furnace building- sumps. At FMC, phossy water
is collected in a tank and then discharged to ponds for solids settling. The water may eventually be
recycled for use in the process areas. Sediments from the settling ponds are dredged and place in another
pond.19 The generation rate for this waste is 720,000'metric tons per year20 (adjusted from a reported
value to reflect recent changes in the sector). Waste characterization data are presented in Attachment 1.
This waste is not expected to be hazardous.
Furnace offgas solids. These solids may be toxic for cadmium. In addition, the waste may also
contain cyanide. The generation rate for furnace offgas solids is 24,000 metric tons per year21 (adjusted
from a reported value to reflect recent changes in the sector). FMC sends air emissions from the caiciners
to scrubbers for removal of particulates and radionuclides.22 Waste characterization data are presented
in Attachment 1. This waste may be recycled and is classified as a sludge.
Furnace offgas may contain elemental phosphorus, carbon monoxide, and particulates. At FMC,
an electrostatic precipitator removes the particulates. Dust slurry from the four ESPs is discharged to
ponds which are dredged.23 Based on existing data and engineering judgement, this waste is not
expected to be hazardous. Therefore, the Agency did not evaluate this material further.
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. 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.25 Existing data and engineering judgement 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 2
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. Waste characterization
data are presented in Attachment 1.
18 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.
19 NEIC, 1992, Op. Cit.
20 U.S. Environmental Protection Agency, Op. Cit.. 1992.
21 Ibid.
22 NEIC. 1992. Op. Cit.
23 NEIC, 1992, Op. Cit.
24 U.S. Environmental Protection Agency, Op. Cite.. Volume II, Chapter 8, 1980.
25 NEIC, 1992, Op. Cit.
26 Ibid.
-------
299
Waste filter media is generated by Anderson scrubbers. At FMC, the waste filter media is washed
to reduce radionuclide levels before off-site disposal. Filter media wash water is discharged to the
wastewater treatment tank and then to the calciner ponds.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.
Cooling water is generated from cooling of furnace domes by direct water spray. At FMC, this
water is discharged via a permitted outfall.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.
Furnace scrubber blowdown. We used the methodology outlined in Appendix A of this report to
estimate a high, medium, and low generation rate of 270,000 metric tons/yr, 0 metric tons/yr, and 0 metric
tons/yr.29 Management for this waste may include treating in a tank and sending the sludge to disposal
impoundments. This waste may exhibit the characteristics of toxicity for cadmium and corrosivitv prior
to treatment. Waste characterization data for raw furnace scrubber blowdown are presented in
Attachment 1.
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.
Spent furnace brick. 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
funher.
Non-contact cooling water is generated by cooling of the grates which transport the briquettes. At
FMC, the noncontact cooling water is discharged via a permitted outfall.31 This waste is a non-uniquely
associated waste.
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.32 Based on existing data and engineering judgement,
this waste is not expected to exhibit characteristics of a hazardous waste. Therefore, the Agency did not
evaluate this material further.
27 Ibid.
28 Ibid.
29 U.S. Environmental Protection Agency, 1992, Op. Cit.. pp. 14-45 - 14-59.
30 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.
31 NEIC, 1992, Op. Cit.
32 Ibid.
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300
Process wastewater is a RCRA special waste.
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 year33 (adjusted from a
reported value to reflect recent changes in the sector). Waste characterization data are presented in
Attachment 1.
AFM Rinsate. The generation rate for this waste stream is 2,000 metric tons per year34
(adjusted from a reported value to reflect recent changes in the sector). This waste may be toxic for
cadmium and selenium. Waste characterization data are presented in Attachment 1.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants.
33 U.S. Environmental Protection Agency, Op. Cite.. Vol. II, pp. 14-45 - 14-59.
34 FMC Corporation LDR presentation for EPA/OSW, December 1994.
-------
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. 3rd.ed. 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 Processing 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.
-------
,302
-------
ATTACHMENT 1
-------
304
-------
SI^4MAfl¥-OF-EPA/ORDr3007r^ND=RTI SAMPLING-DATA SURRAGE-IMPQUNDMENT-SOLIDS - ELEMENTAL PHOSPHOROUS
uonsiuuents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
tt Detects
TC
Level
# Values
In Excess
Aluminum
-
0/0
-
0/0
-
-
Antimony
_
0/0
-
0/0
-
-
Arsenic
_
0/0
-
0/0
5 0
0
Barium
_
0/0
-
0/0
100.0
0
Bervllium
.
0/0
-
0/0
-
-
Boron
_
0/0
-
0/0
-
-
Cadmium
_
0/0
-
0/0
1.0
0
Chromium
_
0/0
-
0/0
5.0
0
Cobalt,
_
0/0
-
0/0
-
~
Copper
-
0/0
-
0/0
-
-
Icon
_
0/0
-
0/0
-
-
Lead
_
0/0
-
0/0
5 0
0
Magnesium
-
0/0
-
0/0
-
-
Manganese
-
0/0
-
0/0
-
-
Mercury
-
0/0
-
0/0
0 2
0
Molybdenum
-
0/0
-
0/0
-
-
Nickel
_
0/0
-
0/0
-
-
Selenium
_
0/0
-
0/0
1 0
0
Silver
_
0/0
-
0/0
5.0
0
Thallium
_
0/0
-
0/0
-
-
Vanadium
_
0/0
-
0/0
-
-
Zinc
_
0/0
-
0/0
-
-
Cyanide
0/0
-
0/0
-
-
Sulfide
_
0/0
-
0/0
-
-
Sulfate
_
0/0
-
0/0
-
-
Fluoride
10,000 10,000 10,000
1/1
-
0/0
-
-
Phosphate
200,000 386,667 480,000
3/3
-
0/0
-
-
Silica
50,000 50,000 50,000
2/2
-
0/0
-
-
Chloride
_
0/0
-
0/0
-
-
TSS
_
0/0
-
0/0
-
-
pH •
5.00 5.53 5.80
3/3
212
0
Organics (TOC)
-
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
-------
fSHWMARV'OF'EPA/ORD, 3007, AND"RTrSAMPLlNG'DATA'"™SL"AG~QUENCHWATER ELEMENTAL PHOSPHOROUS'
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
# Detects
TC
Level
# Values
In Excess
Aluminum
11.60
11.60
11.60
1/1
11.50
11.50
11.50
1/1
-
-
Antimony
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
-
-
Arsenic
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
5.0
0
Barium
0.05
0.05
0.05
0/1
0.050
0.050
0.050
0/1
100.0
0
Beryllium
0.005
0.005
0.005
0/1
0.0050
0.0050
0 0050
0/1
-
-
Boron
-
-
--
0/0
-
-
-
0/0
-
-
Cadmium
0.012
0.012
0.012
1/1
0.011
0.011
0.011
1/1
1.0
0
Cnromium
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
5.0
0
CJOB'ait
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
-
-
Copper
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1.
-
-
Ifon
3.60
3.60
3.60
1/1
3.34
3.34
3.34
1/1
-
-
bead
0.35
0.35
0.35
1/1
0.17
0.17
0.17
1/1
5.0
0
Magnesium
5.72
5.72
5.72
1/1
5.72
5.72
5.72
1/1
-
-
Manganese
1.54
1.54
1.54
1/1
1.52
1.52
1.52
1/1
-
-
Mercury
0.00010
0.00010
0.00010
0/1
0.00020
0.00020
0.00020
1/1
0.2
0
Malvbdenum
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
-
-
Nickel
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
-
-
Selenium
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
1.0
0
silver
0.050
0.050
0.050
0M
0.050
0 050
0.050
0/1
5.0
0
Thallium
0.250
0.250
0.250
0/1
0.25
0.25
0.25
0/1
-
-
Vanadium
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
-
-
Zinc
3.13
3.13
3.13
1/1
2.94
2.94
2.94
1/1
-
-
cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
5.00
5.00
5.00
1/1
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
" -
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
41.30
41.30
41.30
1/1
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
5.78
8.29
10.80
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 - CONDENSER PHOSSY WATER DISCARD - ELEMENTAL PHOSPHOROUS
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
0 Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
0.424
64.39
220
5/5
5.70
11.90
16.10
3/3
-
-
Antimony
0.016
1.76
4
3/5
0.050
0.71
1.30
3/4
-
-
Arsenic
0.0024
1.27
3
3/5
0.031
0.12
0.25
3/5
5.0
0
Barium
0.120
16 09
90
5/6
0.15
0.86
3.20
5/6
100.0
0
Bervlllum
0.005
0.026
0.05
2/4
0.005
0.014
0.025
1/3
-
-
Boron
14
14.000
14
1/1
9.400
9.400
9.400
1/1
-
-
Cadmium
0.002
324
3200
11/11
0.067
0.17
0.40
6/6
1.0
0
Chromium
0.014
33.15
250
8/8
0 049
0.23
0.40
5/6
5.0
0
Cottelt
0.013
0.15
0.5
2/4
0.050
0.15
0.25
0/2
-
-
CoDDer
0.017
20.98
100
5/5
0.005
0.08
0.25
1/4
-
-
rron
1.2
20.26
53
4/4
0.87
4.02
6.49
3/3
-
-
bead
0.024
13.49
48
7/7
0.125
0.64
1.80
2/4
5.0
0
Magnesium
Manganese
6.83
32.22
64
6/6
6.4
13.23
17.00
3/3
-
-
0.23
1.77
3.8
4/4
0.25
0.95
1.85
2/4
-
-
Mercury
0.00010
0.1506
1
3/7
0.00010
0.000175
0.0002
1/4
0.2
0
Molybdenum
0.035
0.17
0.5
2/4
0.05
0.15
0.25
0/2
-
-
Nickel
0.046
6.93
45
5/7
0.02
0.09
0.25
2/5
-
-
Selenium
0.002
2.58
13.9
3/6
0.002
0.10
0.25
0/3
1.0
0
Silver
0.02
1.36
4.47
3/5
0.01
0.08
0.25
0/4
5.0
0
Thallium
0.0455
24.88
120
2/5
0.25
0.75
1.25
0/2
-
-
Vanadium
0.05
2.27
10
4/6
0.05
0.17
0.25
1/3
-
-
Zinc
0.6
5,794
53,000
10/10
6.47
71.49
167
5/5
-
-
Cyanide
36.00
36.00
36.00
1/1
-
-
-
0/0
-
-
Sulfide
1.20
1.20
1.20
1/1
-
-
-
0/0
-
-
Sulfate
2.50
363
964
6/7
41.00
74.00
107
2/2
-
-
Fluoride
80.00
3,934
25,900
7/7
155
304
453
2/2
-
-
Phosphate
25.00
1,833
9,070
6/6
591
662
732
2/2
-
-
Silica
63.00
63.00
63.00
1/1
-
-
-
0/0
-
-
Chloride
38.00
364
1,250
9/9
69
152
234
2/2
-
-
TSS
0.78
12652
50000
4/4
-
-
-
0/0
-
-
PH *
3.00
5.09
7.10
7/7
212
0
Organlcs (TOC)
20.00
39.67
76.20
3/3
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented
u>
o
-------
:St3MMARY*OF'EPA/ORD,"3007;°A'ND"RTI SAMPITING'DATA - FURNACET)FFGAS SOLIDS - ELEMENTAL" PHOSPHOROUS
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
.Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
H Detects
Level
In Excess
Aluminum
98.20
4,290
11,500
4/4
4.60
11.22
24.10
3/3
-
-
Antimony
0.43
9.68
25.50
2/3
0.050
0.76
1.32
2/3
-
-
Arsenic
0.050
12.78
25.50
0/2
0.020
0.56
1.30
5/7
5.0
0
Barium
0.84
34.18
96.70
3/3
0.050
0.14
0.25
2/4
100.0
0
Beryllium
0.022
1.29
2.55
1/2
0.005
0.015
0.025
0/2
-
-
boron
39.000
185.50
332.00
2/2
24.000
24.000
24.000
1/1
-
-
Cadmium
0.45
60.74
200
4/4
0.011
8.05
27.00
7/7
1 0
4
ChTomium
1.61
14.04
25.50
2/3
0.050
0.33
0.90
6/8
5 0
0
Cobalt
0.05
12.78
25.50
0/2
0.050
0.15
0.25
0/2
-
-
copper
0.05
37.64
116
2/4
0.050
0.15
0.25
0/2
-
irorio,
16.80
7,744
20,000
5/5
1.81
6.67
13.00
3/3
-
-
Lead>
2.57
136
368
3/3
0.45
0.90
1.40
4/4
5.0
0
Magnesium
84.00
687
1,373
4/4
3.39
5.84
7.10
3/3
-
-
Manganese
2.79
337
1,170
4/4
0.25
0.74
1.55
2/3
-
-
Mercury
0.00010
0.00010
0.00010
0/1
0.00010
0.00010
0.00010
0/1
0.2
0
Molybdenum
0.050
12.78
25.50
0/2
0.05
0.15
0.25
0/2
-
-
Nickel
0.050
14.14
29.00
2/4
0.10
0.17
0.25
2/3
-
-
Selenium
0.050
12.78
25.50
0/2
0.010
0.07
0.25
3/5
1.0
0
Silver
0.050
12.78
25.50
0/2
0.020
0.12
0.25
4/6
5.0
0
Thallium
0.25
43.65
128
1/3
0.25
0.75
1.25
0/2.
-
-
vanadium
0.64
12.71
25.50
2/3
0.05
0.30
0.60
1/3
-
-
Zinc
5.70
13,489
61,665
5/5
6.07
116
267
3/3
-
-
Cyanide
52.00
52.00
52.00
1/1
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
173
8,802
17,616
4/4
-
-
-
0/0
-
-
Fluoride
941
1,221
1,500
212
-
-
-
0/0
-
-
Phosphate
13.38
240,007
480,000
2/2
-
-
-
0/0
-
-
Silica
50,000
125,000
200,000
2/2
-
-
-
0/0
-
Chloride
510
38,564
150,000
4/4
-
-
0/0
-
-
TSS
988,200
988,200
988,200
1/1
-
-
-
0/0
-
-
pH *
5.00
5.40
5.80
2/2
2l2
0
Organics (TOC)
20.00
384,940
1,140,000
3/3
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable, therefore, only EP data are presented
-------
,(®ft"FlY"OPEPA7ORD73007/AND-RTI1SAMPLING DATAr-vPRECIPITATOR w^URRY - ELEMENTAL PHOSPHOROUS-
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
tt Values
Constituents
Minimum
Average
Maximum
tt Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
'Aluminum
-
-
-
0/0
-
-
-
0/0
-
-
wmimony
28
28
28
1/1
0 31
0.31
0 31
1/1
-
-
Arsenic
5
5
5
1/1
0.1
0.1
0 1
1/1
5.0
0
parium
18
18
18
1/1
1
1
1
1/1
100.0
0
beryllium
0.2
0.2
0.2
1/1
0.01
0.01
0.01
1/1
-
-
bor.on
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
1300
1300
1300
1/1
0.022
0.022
0.022
1/1
1.0
0
C.hr,Qn[iium
60
60
60
1/1
0.237
0.237
0.237
1/1
5 0
0
Cobalt
-
-
-
0/0
-
-
-
0/0
-
-
Cooper
-
-
-
0/0
-
-
-
0/0
-
-
Ron
-
-
-
0/0
-
-
-
0/0
-
-
bead
130
130
130
1/1
0.11
0.11
0.11
1/1
5.0
0
Magnesium
-
-
-
0/0
-
-
-
0/0
-
-
Mdhganese
-
-
-
0/0
-
-
-
0/0
-
-
Mercury
1
1
1
1/1
0.0005
0.0005
0.0005
1/1
0 2
0
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
NiCKel
11
11
11
1/1
0.08
0.08
0.08
1/1
-
-
Seienium
8
8
8
1/1
0.2
0.2
0.2
1/1
1.0
0
Silver
1
1
1
1/1
0.02
0.02
0.02
1/1
5.0
0
Thallium
650
650
650
1/1
0.2
0.2
0.2
1/1
-
-
Vanadium
60
60
60
1/1
0.3
0.3
0.3
1/1
-
-
Zinc
11000
11000
11000
1/1
69.9
69.9
69.9
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
¦ -
-
0/0
-
-
TSS
200000
200000
200000
1/1
-
-
-
0/0
-
-
PH '
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
NOn-detects were assumed (o be present at 1/2 the deletion limit. TCLP data are currently unavailable, therefore, only EP data are presented
u>
o
10
-------
SUMMARY OF EPA/ORD, 3007. AND RTI SAMPLING DATA - F-UHNAUt SUHUBBEH BLUWUUWN - ELEMENTAL PHOSPHOROUS
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum # Detects
TC # Values
Level In Excess
Aluminum
3.70
2,360
18,000
8/8
0.25
4.23
11.40
5/6
-
-
Antimony
0.016
1.31
4.80
2/8
0.05
0.53
1.60
3/7
-
-
Arsenic
0.016
1.46
8.70
4/8
0.00125
0.14
0.54
3/6
5.0
0
Barium
0.050
41.94
280.00
4/7
0.050
0.43
1.20
4/7
100.0
0
Beryllium
0.0020
0.17
0.93
3/7
0.0025
0.01
0.03
1/6
-
-
Boron
25.00
25.00
25.00
1/1
19
19.00
19.00
1/1
-
-
uaamium
0.0010
2.37
9.60
10/13
0.0050
0.40
2 07
4/7
1.0
2
Chromium
0.0005
110
940
7/10
0.005
0.34
0.90
4/7
5.0
0
Uobait
0.0030
38.81
260
3/7
0.03
0.08
0.25
0/5
-
-
Copper
0.0005
46.66
310
3/7
0.005
0.07
0.25
1/5
-
-
iron
0.030
10,382
63,000
8/8
0.0375
3.88
6.86
5/6
-
-
Lead
0.004
25.69
150
8/8
0.125
0.31
0.42
2/6
5.0
0
Maanesium
5.40
174
1,300
10/10
0.17
6.10
10.70
5/6
-
-
Manganese
0.50
3,464
26,000
7/8
0.25
2.03
6.50
5/6
-
-
Mercury
0.00010
0.019
0.10
2/8
0.0001
0.0001
0 0002
1/6
02
0
MoiyDaenum
0.029
11.06
71.00
4/7
0.010
0.074
0 25
0/5
-
-
hicxel
0.009
68.89
530
5/8
0.015
0.079
0.25
2/6
-
-
Selenium
0.003
0.12
0.50
3/7
0.0025
0.071
0.25
1/6
1.0
0
Silver
0.0010
0.48
1.60
1/7.
0.01
0.074
0.25
1/6
5.0
0
Thallium
0.040
1.52
4.50
1/8
0.25
0.53
1.25
1/6
-
-
Vanadium
0.015
83.25
710
7/9
0.015
0 25
0.79
3/7
-
-
Zinc
0.023
79.11
211
12/12
0.55
44.38
130
7/7
-
-
Cyanide
0.900
0.90
0.90
1/1
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
18.10
3,167
18,600
8/8
6.00
7.00
8.00
2/2
-
-
Fluoride
51 60
2,481
20,200
9/9
2.41
5.66
8 91
2/2
-
-
Phosphate
6.40
959
3,700
7/7
2.17
4.02
5 87
2/2
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
0.38
177
420
10/11
0.27
0.47
0.67
2/2
-
-
TSS
0.49
2,667
8,000
4/4
-
-
0/0
-
-
PH *
1 10
4 45
6 61
10/10
212
1
Organics (TOC)
-
-
-
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.
-------
S£MBWRY"0F"EPA70RD, 3007, AND RTl SAMPLING DATA - WASTEWATER* !, ._ATMENT PLANT SLUDGE/SOLlUS - ELEMENTAL"PHOSPHOROUS
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
# Detects
TC
Level
# Values
In Excess
Aluminum
54500
54,500
54,500
1/1
-
0/0
-
-
Ahtimony
-
-
0/0
-
0/0
-
-
Arsenic
233
233
233
1/1
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
1143
1,143
1,143
1/1
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
iron
17400
17,400
17,400
1/1
-
0/0
-
-
LTead
188
188
188
1/1
-
0/0
5.0
0
Magnesium
2775
2,775
2,775
1/1
-
0/0
-
-
Manaanese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
10625
10,625
10,625
1/1
-
0/0
-
-
cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
1507
1,507
1,507
1/1
-
0/0
-
-
Fluoride
150
2,575
5,000
2/2
-
0/0
-
-
Phosphate
200
200
200
1/1
-
0/0
-
-
Silica
50000
162,200
274,400
2/2
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
-
-
-
0/0
-
0/0
-
-
pR *
4
7.1
11.3
3/3
212
0
Organics (TOC)
-
-
-
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 - SURFACE IMPOUNDMENT LIQUIDS - ELEMENTAL PHOSPHOROUS
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
# Detects
TC
Level
ft Values
In Excess
Aluminum
0.424
0.42
0.42
1/1
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
--
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
0.643
0.64
0.64
1/1
-
0/0
-
-
Cadmium
2.86
2.86
2.86
1/1
-
0/0
1.0
0
Chromium
0.014
0.04
0.07
2/2
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
-
-
-
0/0
-
0/0
-
-
Lead
-
-
-
0/0
-
0/0
5.0
0
Magnesium
54.5
54.50
54.50
1/1
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
0.00012
0.00012
0.00012
1/1
-
0/0
0.2
0
Molybdenum
0.084
0.084
0.084
1/1
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
0.045
0.045
0.045
1/1
-
0/0
1.0
0
Silver
-
-
-
0/0
0/0
5.0
0
Thallium
- -
-
-
0/0
-
0/0
-
-
Vanadium
0.21
0.37
0.53
2/2
-
0/0
-
-
Zinc
0.29
2.11
3.94
2/2
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
118
118
118
1/1
_
0/0
-
-
Fluoriae
122
122
122
1/1
_
0/0
-
-
Phosphate
100
490
1,000
3/3
_
0/0
-
-
Silica
47.70
47.70
47.70
1/1
.
0/0
-
-
Chloride
38.00
111
183
212
0/0
-
-
TSS
240
240
240
1/1
.
0/0
-
-
pH *
4.00
5.33
6.80
4/4
212
0
Organics (TOC)
-
-
-
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 - WASTEWATER "I r.cATMENT PLANT LIQUID EFFLUENT - ELEMENTAL PHOSPHOROUS
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum 0 Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
# Values
In Excess
Aluminum
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
1.00
1.00
1.00
1/1
-
0/0
5 0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
177
177
177
1/1
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
-
-
-
0/0
-
0/0
-
-
Lead
-
-
-
0/0
-
0/0
5.0
0
Magnesium
190
190
190
1/1
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
Nickel.
-
-
-
0/0
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
536
536
536
1/1
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
1,533
1,533
1,533
1/1
-
0/0
-
-
Fluoride
22.80
22.80
22.80
1/1
-
0/0
-
-
Phosphate
100
100
100
1/1
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
2,308
2,308
2,308
1/1
-
0/0
-
-
TSS
-
-
-
0/0
-
0/0
-
-
PH*
4.00
4.85
5.70
2/2
212
0
Organics (TOC)
-
-
-
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 - AFM RINSATE - ELEMENTAL PHOSPHOROUS
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum tt Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum tt Detects
TC It Values
Level In Excess
Aluminum
-
-
0/0
-
-
-
0/0
-
-
Antimony
-
-
0/0
0.2
0.2
0.2
1/1
-
-
Arsenic
1
1 1
1/1
0.14
0 14
0.14
1/1
5.0
0
Barium
-
-
0/0
1
1
1
1/1
100.0
0
Beryllium
-
-
0/0
0 01
0.01
0.01
1/1
-
-
Boron
-
-
0/0
T
-
-
0/0
-
-
Cadmium
4
4 4
1/1
4.12
4.12
4.12
1/1
1.0
1
Chromium
1
1 1
1/1
0.278
0.278
0.278
1/1
5.0
0
Cobalt
-
-
0/0
-
-
-
0/0
-
-
Copper
-
-
0/0
-
-
-
0/0
-
-
Iron
-
-
0/0
-
-
-
0/0
-
-
Lead
-
-
0/0
0.19
0.19
0.19
1/1
5.0
0
Magnesium
-
-
0/0
-
-
-
0/0
-
-
Manganese
-
-
0/0
--
-
-
0/0
-
-
Mercury
-
-
0/0
0.0005
0.0005
0.0005
1/1
0 2
0
Molybdenum
-
-
0/0
-
-
-
0/0
-
¦-
Nickel
-
-
0/0
0.08
0.08
0.08
1/1
-
-
Selenium
1
1 1
1/1
1.03
1.03
1.03
1/1
1 0
1
Silver
-
-
0/0
0.02
0.02
0.02
1/1
5.0
0
Thallium
-
-
0/0
0.03
0.03
0.03
1/1
-
-
Vanadium
-
-
0/0
0.19
0.19
0.19
1/1
-
-
Zinc
-
-
0/0
37.2
37.2
37.2
1/1
-
-
Cyanide
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
0/0
-
-
-
0/0
-
-
Fluoride
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
0/0
-
-
-
0/0
-
-
TSS
20000
20000 20000
1/1
-
-
-
0/0
-
-
PH *
-
-
0/0
212
0
Organics (TOC)
-
-
0/0
-
-
NOn-detecls were assumed to be present at 1/2 the detection limit TCLP data are currently unavailable; therefore, only EP data are presented
-------
FLUORSPAR AND HYDROFLUORIC ACID
A. Commodity Summary
In 1994, approximately 73 percent of the reported fluorspar (CaF2) 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 industrv.
The names and locations of the three hydrofluoric acid production facilities are shown in Exhibit 1.
EXHIBIT 1
Summary of Hydrofluoric Acid Producers (in 1989)
Facility Name
Location
Allied Signal
Geismar, LA
E.I. duPont
La Porte, TX
Attochemical, N.A
Calvert City, KY
B. General Process Description
I. 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.
4 M.M. Miller, 1994, Op. Cit.. p. 58.
-------
316
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 concentration.5
Hydrofluoric acid is produced from acid-grade fluorspar (CaF,) 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 (S03) 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) Process (es)
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 hexafluonde
(CaSiF6) produced by the reaction of fluorosilicic acid and phosphate rock.9
5 M.M. 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.
-------
317
EXHIBIT 2
HYDROFLUORIC ACID PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1994, p. 367
and Development Document, Section 12, Hydrofluoric Acid Industry .)
Aqueous Hydrogen
Fluoride Product
Anhydrous Hydrogen
Fluoride Product
Wastewater
to
Treatment
I
I
Packaging
~
To Sales
Packaging
t
To Sales
LEGEND:
Common Practice
Intermittent Process
(or process at oniv
some plants)
-------
318
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.,
pelletLzing 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 Section B.
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, Quorogypsum 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.
-------
319
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, ignitabilitv, and
extraction procedure (EP) toxicity. Based on analyses of four samples from two facilities (Geismar and
Calvert City) and professional judgment, the Agency 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.11
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 tonsfyr, 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.
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, Newlv 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.
14 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-5.
-------
320
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. Ancillary 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, 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.
-------
321
BIBLIOGRAPHY
"Fluorspar." Kirk Othmer Encyclopedia of Chemical Technology. 4th ed. Vol. XI. 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.
-------
322
-------
323
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 S51.6
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.
1 Gordon Austin, "Gemstones," from Mineral Commodity Summaries. U.S. Bureau of Mines, January
1995, pp. 64-65.
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324
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 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) Process (es)
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. Extraction/Beneficiation 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.
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.
-------
325
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. Mineral Processing Wastes
No wastes are identified.
D. Ancillary Hazardous Wastes
Ancillary wastes may include used chemicals, tires from trucks and large machinery, sanitary
sewage, waste oil (may or may not be hazardous), and other lubricants. Small operations may have fewer
ancillary wastes.
4 Ibid.
-------
326
BIBLIOGRAPHY
Austin, Gordon. "Gemstones." From Mineral Commodity Sumntan'es1.- '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. SOS-
SIS.
-------
ill
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 recover}'
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
Location
Type of Operations
Atomergic Chem
Plainview, NY
Refining
Cabot
Revere, PA
Refining
Eagle-Picher
Quapaw, OK
Refining
Jersey Miniere
Clarksville, TN
Mining
Musto Exploration
St. George, UT
Mining and Refining
Germanium is available commercially as a tetrachloride and a high purity oxide, and is commonh
found in the form of zone-refined ingots, single crystal bars, castings, doped semiconductors, and optical
materials.5 Some of the major end uses for germanium include infrared optics, fiber-optics systems,
detectors, and semiconductors.6
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.
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328
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
T
Fumes from Zinc Sintering
Containing Germanium Oxide
Leaching
Reagents
Precipitation
Reagents —
Leaching
Waste
Wastewater
~
Crude Germanium Oxide
-------
329
B. Generalized Process Description
L. 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. 2.
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.'
Most germanium, regardless of the process by which it was recovered from ore, is refined using
chlonnation. As shown in Exhibit 3, germanium concentrates are chlorinated with concentrated
hydrochloric acid or chlorine gas to produce germanium tetrachloride (GeCl4) 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.10
The resultant purified germanium tetrachloride is then hydrolyzed with deionized water to produce
a solid germanium dioxide (Ge02). 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.11
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
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.
11 "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.
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330
EXHIBIT 3
PRIMARY AND SECONDARY GERiMANIUM PRODUCTION PROCESS
' (Adapted from: Development Document for Effluent Limitations Guidelines and Standards for Nonferrous
Metals Manufacturing Point Source Category, 1989, pp. 5231 - 5352.)
High Purity
Ge Product
-------
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
I'enous Sulfate /.,„o Sulfate
Solution Solution
-------
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
None Identified.
4. Beneficiation/Processing Boundary
Since germanium is recovered as a by-product of other metals, all of the wastes generated during
germanium recover)' 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.
C. Process Waste Streams
1. Extraction/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/vr, 210 metric tons/tyr, 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/Vr, 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.
13 U.S. Environmental Protection Agency, 1989, Op. Cit., p. 5273.
-------
333
Hydrolysis Filtrate. As shown in Exhibit 3, germanium tetrachloride is hvdrolyzed 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.
Low, medium, and high annual waste generation rates were estimated as 10 metric tons/vr, 210
metric tons/vr, and 400 metric tons/vr 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-HNO-
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.10 Low.
medium, and high annual waste generation rates were estimated as 400 metric tons/yr. 2,200 metric
tons/vr, 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.
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 the 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 the
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, the Agency did not evaluate this material further.
15 Ibid.
16 Ibid.
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334
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.1'
D. Ancillary 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
naphtha), acidic tank cleaning wastes, and polvchlorinated 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.
17 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-96.
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335
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-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol XI. 1994. p. 796.
-------
336
-------
337
ATTACHMENT 1
-------
338
-------
?tJMMARY-0F-EPA/ORDr3OO7; AND RTI SAMPLING DATA—WASTE-AGIP-WASH AND RINSE WATER—GERMANIUM
1
Total Constituent Analysis
- PPM
EP Toxicity Analysis - PPM
TC
tt Values
Constituents
Minimum
Average
Maximum
# Detects
Min. Avg. Max. H Detects
Level
In Excess
Aluminum
350
350
350
1/1
0/0
-
_
Antimony
0.04
0.04
0.04
1/1
0/0
-
-
Arsenic
0.39
0.39
0.39
1/1
0/0
50
0
Barium
-
-
-
0/0
0/0
100.0
0
Beryllium
005
0.05
0.05
1/1
0/0
-
-
Boron
-
-
-
0/0
0/0
-
-
Cadmium
0.05
0.05
0.05
1/1
0/0
1.0
0
Chromium
0.50
0.50
0.50
1/1
0/0
5.0
0
Cobalt,
0.50
0.50
0 50
1/1
0/0
-
-
Copper
0.10
0.10
0.10
1/1
0/0
-
-
iron
2.90
2.9
2.9
1/1
0/0
-
-
bead
0.78
0.78
0 78
1/1
0/0
5.0
.0
Magnesium
-
-
-
0/0
0/0
-
-
Manganese
0.09
0.09
0.09
1/1
0/0
-
-
Mercury
-
-
-
0/0
0/0
0.2
0
Molybdenum
0.50
0.50
0.50
1/1
0/0
-
-
Nickel
0.20
0 20
0.20
1/1
0/0
_
-
Selenium
0.01
0.01
0.01
1/1
0/0
1.0
0
Silver
0.07
0.07
0.07
1/1
0/0
5 0
0
OialUum
0.01
0.01
0.01
1/1
0/0
-
-
Vanadium
1.00
1.00
1.00
1/1
0/0
_
_
Zinc
0.06
0.06
0.06
1/1
0/0
-
-
Cyanide
-
-
-
0/0
0/0
-
-
SuHlde
-
-
-
0/0
0/0
-
-
Sulfate
-
-
-
0/0
0/0
-
-
Fluoride
-
-
-
0/0
0/0
_
-
Phosphate
-
-
-
0/0
0/0
-
-
Silica
-
-
-
0/0
0/0
_
_
Chloride
-
-
-
0/0
0/0
_
-
TSS
-
-
-
0/0
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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.
UJ
UJ
-------
SUMMARY OF EPA/ORD. 3007, AND RTI SAMPLING DATA - HYDROLYSIS FILTRATE - GERMANIUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis - PPM
TC
H Values
Constituents
Minimum
Average
Maximum
# Detects
Min. Avg. Max. N Detects
Level
In Excess
Aluminum
0.78
0.78
0.78
1/1
0/0
-
-
Ahflmony
0.01
0.01
0.01
1/1
0/0
-
-
Arsenic
0.20
0.20
0.20
1/1
0/0
5.0
0
nanum
-
-
-
0/0
0/0
100.0
0
Beryllium
0.05
0.05
0.05
1/1
0/0
-
-
BOron
-
-
-
0/0
0/0
-
-
Cadmium
0.05
0.05
0.05
1/1
0/0
1 0
0
tmromium
0.50
0.50
0.50
1/1
0/0
5.0
0
uooait
0.50
0.50
0.50
1/1
0/0
-
-
t'OODer
0.10
0.10
0.10
1/1
0/0
-
-
iron
0.37
0.4
0.4
1/1
0/0
-
-
Leaa
0.20
0.20
0.20
1/1
0/0
5.0
0
Magnesium
-
-
-
0/0
0/0
-
-
Manganese
0.05
0.05
0.05
1/1
0/0
-
-
Mercury
-
-
-
0/0
0/0
0.2
0
Molybdenum
0.52
0.52
0.52
1/1
0/0
-
-
Nickel
1.00
1.00
1.00
1/1
0/0
-
-
Stfehlum
0.12
0.12
0.12
1/1
0/0
1.0
0
stiver
0.00
0.00
0.00
1/1
0/0
5.0
0
TftWIIum
0.02
0.02
0.02
1/1
0/0
-
-
^inadium
1.00
1.00
1.00
1/1
0/0
-
-
ZltVc
0.05
0.05
0.05
1/1
0/0
-
-
cyanide
-
-
-
0/0
0/0
-
SCilflde
-
-
-
0/0
0/0
-
-
Sulfate
-
-
-
0/0
0/0
-
-
Fluoride
-
-
-
0/0
0/0
-
-
Phosphate
-
-
-
0/0
0/0
-
-
Silica
-
-
-
0/0
0/0
-
-
Chloride
-
-
-
0/0
0/0
-
-
TSS
-
-
-
0/0
0/0
-
-
pH *
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detacts 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 STILL LIQUOR - GERMANIUM
Total Constituent Analysis
-PPM
EP Toxicity Analysis - PPM
TC
H Values
Constituents
Minimum
Average
Maximum
n Detects
Mln. Avg. Max. # Detects
Level
In Excess
Aluminum
1.50
1.50
1.50
l/l
0/0
-
-
Antimony
0.03
0.03
0.03
l/i
- . - 0/0
-
-
Arsenic
1.70
1.70
1.70
l/l
0/0
5.0
0
Barium
-
-
-
0/0
0/0
100.0
0
Beryllium
0.05
0.05
0.05
1/1
0/0
-
-
Boron
-
-
-
0/0
0/0
-
-
Cadmium
0.23
0.23
0.23
1/1
0/0
1.0
0
Chromium
0.50
0.50
0.50
1/1
0/0
5.0
0
Cobalt
0.50
0.50
0.50
1/1
0/0
-
-
Copper
0.16
0.16
0.16
1/1
0/0
-
-
Iron
1.80
1.8
1.8
1/1
0/0
-
-
Lead
0.20
0.20
0.20
1/1
0/0
5.0
0
Magnesium
-
-
-
0/0
0/0
-
-
Manganese
2.20
2.20
2.20
1/1
0/0
-
-
Mercury
-
-
-
0/0
0/0
0.2
0
Molybdenum
0.50
0.50
0.50
1/1
0/0
-
-
Nickel
2.00
2.00
2.00
1/1
0/0
-
-
Selenium
0.09
0.09
0.09
1/1
0/0
1.0
0
Silver
0.00
0.00
0.00
1/1
0/0
5.0
0
Thallium
0.01
0.01
0.01
1/1
0/0
-
-
Vanadium
1.00
1 00
1.00
1/1
0/0
-
-
fclnc
150.00
150.00
150.00
1/1
0/0
-
-
Cyanide
-
-
-
0/0
0/0
-
-
Sulfide
-
-
-
0/0
0/0
-
-
Sulfate
-
-
-
0/0
0/0
-
-
Fluoride
-
-
-
0/0
0/0
-
-
Phosphate
-
-
-
0/0
0/0
-
-
Silica
-
-
-
0/0
- - - 0/0
-
-
Chloride
-
-
-
0/0
0/0
-
-
TSS
-
-
-
0/0
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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 - CHLORINATOR WET APC - GERMANIUM
Total Constituent Analysis
-PPM
EP Toxicity Analysis - PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Min. Avg. Max. # Detects
Level
In Excess
Aluminum
4.10
4.10
4.10
1/1
0/0
-
-
Antimony
0.02
0.02
0.02
l/l
0/0
-
-
Arsenic
0.10
0.10
0.10
i/l
0/0
5.0
0
Barium
-
-
-
0/0
0/0
100 0
0
Beryllium
0.05
0.05
0.05
1/1
0/0
-
-
Boron
-
-
-
0/0
0/0
-
-
Cadmium
0.46
0.46
0.46
1/1
0/0
1.0
0
Chromium
0.50
0.50
0.50
1/1
0/0
5.0
0
Cobalt
0.50
0.50
0.50
1/1
0/0
-
-
Copper
0.20
0.20
0.20
1/1
0/0
-
-
Iron
11.00
11.0
11.0
1/1
0/0
-
-
Lead
0.45
0.45
0.45
1/1
0/0
50
0
Magnesium
-
-
-
0/0
0/0
-
-
Manganese
0.25
0.25
0.25
1/1
0/0
-
-
Mercury
-
-
-
0/0
0/0
0.2
0
Molybdenum
0.50
0.50
0.50
1/1
0/0
-
-
Nickel
1.B0
1.80
1.80
1/1
0/0
-
-
Selenium
0.04
0.04
0.04
1/1
0/0
1.0
0
Silver
0.00
0.00
0.00
1/1
0/0
5.0
0
Thallium
0.02
0.02
0.02
1/1
- - 0/0
-
-
Vanadium
1.00
1.00
1.00
1/1
0/0
-
-
Zinc
0.17
0.17
0.17
1/1
0/0
-
-
Cyanide
-
-
-
0/0
0/0
-
-
Sulllde
-¦
-
-
0/0
0/0
-
-
Sulfate
-
-
-
0/0
0/0
-
-
Fluoride
-
-
-
0/0
0/0
-
-
Phosphate
-
-
-
0/0
0/0
-
-
Silica
-
-
-
0/0
0/0
- -
-
Chloride
-
-
-
0/0
0/0
-
-
TSS
-
-
-
0/0
0/0
-
-
pH*
-
-
-
0/0
2l2
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detects ware assumed to be present at 1/2 the detection limit. TCLP data ate currently unavailable; therefore, only EP data are presented.
-------
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 particular
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 twenty-five leading gold
producing mines in the United States.
EXHIBIT I
Summary Of Known Gold And Silver Smelters And Refineries
Facility Name
Facility Location
ASARCO, Inc.
Amarillo, TX
Omaha, NE
AURIC-CHLOR, Inc.
Rapid City, SD
David Fell & Company, Inc.
City of Commerce, CA
Drew Resources Corp.
Berkeley, CA
Eastern Smelting & Refining Corp.
Lynn, MA
Englehard Industries West, Inc.
Anaheim, CA
GD Resources, Inc.
Sparks, NV
Handy & Harman
Attleboro, MA
South Windsor, CT
Johnson Matthey
Salt Lake City, UT
Metalor USA Refining Corp.
North Attleboro, MA
Multimetco, Inc.
Anniston, AL
Nevada Gold Refining Corp.
Reno, NV
Sunshine Mining Co.
Kellogg, ID
Williams Advanced Materials
Buffalo, NY
Source: Randol Mining Directory. 1994, pp. 741-743.
-------
EXHIBIT 2
Twenty-Five Leading Gold-Producing Mines in the United States (In Order of Output)
Mine
Location
Source of Gold
Nevada Mines Operations, Newmont Gold Company
Elko and Eureka, NV
Gold ore
Gold Strike, Barrick Mercur Gold Mines, Inc.
Eureka, NV
Gold ore
Bingham Canyon, Kennecott-Utah Copper Corp.
Salt Lake, UT
Copper ore
Jerritt Canyon (Enfield Bell), Freeport-McMoran Gold
Company
Elko, NV
Gold ore
Smoky Valley Common Operation, Round Mountain Gold
Corp.
Nye, NV
Gold ore
Homestake, Homestake Mining Company
Lawrence, SD
Gold ore
McCoy and Cove, Echo Bay Mining Company
Lander, NV
Gold ore
McLaughlin, Homestake Mining Company
Napa, CA
Gold ore
Chimney Creek, Gold Fields Mining Company
Humboldt, NV
Gold ore
Fortitude and Surprise, Battle Mountain Gold Company
Lander, NV
Gold ore
Bulldog, Bond Gold, Bullfrog, Inc.
Nye, NV
Gold ore
Mesquite, Goldfields Mining Company
Imperial, CA
Gold ore
Getchell, FMG, Inc.
Humboldt, NV
Gold ore
Sleeper, Amax Gold, Inc.
Humboldt, NV
Gold ore
Cannon, Asamera Minerals (U.S.), Inc.
Chelan, WA
Gold ore
Ridgeway, Ridgeway Mining Company
Fairfield, SC
Gold ore
Jamestown, Sonora Mining Corp.
Tuolumne, CA
Gold ore
Paradise Peak, FMC Gold Company
Nye, NV
Gold ore
Rabbit Creek, Rabbit Creek Mining, Inc.
Humboldt, NV
Gold ore
Barney's Canyon, Kennecott Corp.
Salt Lake City, UT
Copper ore
Continental, Montana Resources
Silver Bow,MT
Gold ore
Zortman-Landusky, Pegasus Gold, Inc.
Phillips, MT
Gold ore
Golden Sunlight, Golden Sunlight Mines, Inc.
Jefferson, MT
Gold ore
Wind Mountain, Amax Gold, Inc.
Washoe, NV
Gold ore
Foley Ridge & Amie Creek, Wharf Resources
Lawrence, SD
Gold ore
Source: Mining Industry Profile Gold, 1993, pp. 5.
-------
345
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% of domestic production. The 1994 mine production value was over S4.1 billion. Uses of gold
include jewelry and arts, 71%; industrial (electronic), 22%; and dental, 7% 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% of the refined silver consumed domestically during 1993 was
used in the manufacture of photographic products; 20% in electrical and electronic products; 10% in
electroplated ware, sterlingware, and jewelry; and 20% in other uses.2
Silver occurs as native metal, but is usually found combined with sulfur. 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, ceragyTite, 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 the ore while 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
I. 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.
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.
-------
346
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
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
The 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. This technique is currently used on an
experimental basis at the Homestake Tonkin Springs property in Nevada. 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. In effect, roasting oxidizes the sulfur in the ore,
generating sulfur dioxide that can be captured and convened 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 and reduced 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
4 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.
5 Ibid.
6 U.S. Environmental Protection Agency, Technical Resource Document. Extraction and Beneficiation
of Ores and Minerals. Vol. II, July 1994.
-------
347
Mine in Utah are currently using pressure oxidation (autoclave) technology, totally or in part, to
beneficiate sulfide or carbonaceous gold ores.'
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.
Cyanidation - Leaching
Cvanidation 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 have
required extensive preparation prior to leaching. Gold and silver are dissolved by cyanide in solutions of
high pH in the presence of 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
vat leaching account for most gold and silver recovery.8 These leaching methods are discussed in detail
below.
(1) Cyanidation - Heap Leaching
Heap leaching, shown in Exhibit 3, is the least expensive process and therefore, low value ores are
most often treated by heap leaching. In 1993, heap leaching accounted for 39 percent of gold
production.9 In many cases, heaps are constructed on lined pads with ore 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 the heap to increase permeability of the heap and maintain the high
pH (optimally 10.5) needed for leaching to occur.
Two common types of pads used in gold heap leaching include 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
following the leach cycle and fresh ore to be placed on the pad. Permanent heaps are typically built in
lifts. Each lift is composed of a 5 to 30 foot layer of ore. On-off pads are not commonly used in the
industry and are constructed to allow spent ore to be removed after the leaching cycle and re-use of the
pad.
After the ore is piled on a leaching pad, the leaching solution is applied to the top of the pile by
sprinklers. The solution generally has a concentration of 0.5 to 1 pound of sodium cyanide per ton of
solution.10 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, the solution returns for reuse once the metals are removed. The leaching process will
continue until no more precious metal is extracted. Typical operations will involve leaching for several
7 Ibid.
8 Personal communication between ICF Incorporated and Robert G. Reese, U.S. Bureau of Mines,
September 23, 1994.
9 Personal communication between ICF Incorporated and John M. Lucas, U.S. Bureau of Mines,
September 15, 1994.
10 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.
-------
uu
00
EXHIBIT 3
GOLD-SILVER LEACHING
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-100 - 3-1 IS.)
I leap or Vat
Ore
\
-------
349
months 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 the
leach liquor never contacts the precious metal or because the metal bearing solution is trapped in blind
channels. Waste streams from this process include spent ore and leaching solutions as well as residual
leach liquor in the pile.11
(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 1993, vat leaching accounted for 53 percent of gold recovery.12 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.13
(3) Cyanidation - Agitation Leaching
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 any
exhibit hazardous characteristics. 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 to the process.14
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 several ways: (1) the Merrill-Crowe process, (2)
activated carbon loading, and (3) activated carbon stripping. The primary difference between recovery
methods is whether the metal is removed by precipitation with zinc or by absorption 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.15 The different recovery
methods are described below.
11 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-100 - 30-115.
12 Personal communication, September 15, 1994.
13 U.S. Environmental Protection Agency, 1988, Op. Cit., 3-100 - 3-115.
14 Ibid.
15 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-100 - 3-115.
-------
350
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
T
-------
351
(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 dor6. 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.16
(2) Cyanidation - Metal Recovery - Activated Carbon Loading
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 surfaces of the 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.17
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 the 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.18 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 the carbon than in
the 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. A process flow diagram of
carbon-in-leach metal recovery is presented in Exhibit 5.
(3) Cyanidation - Metal Recovery - Activated Carbon Stripping
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
16 Ibid.
17 Ibid.
18 Ibid.
19 Ibid.
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Ln
NJ
EXHIBITS
CARBON-IN-PULP AND CARBON-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
I
Ground
Ore
Slurry
*
do
CARBON-IN-LEACH
Ground
Ore —
Slurry
Cyanide
do
Leach Tanks
Cyanide.
~
1
CO
i
~
Loaded Carbon
to Stripping
*
do
*
CO
I
t
do
I
Carbon Tanks
~
Loaded Carbon
lo Snipping
*
do
i
do
T
lo
Waste
Caibon
1
do
i
To
Waste
• Cai boil
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353
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 refining. Some operations refine the steel wool on site to make dor6 while
others ship it directly to commercial refineries. The primary waste from carbon stripping is the spent
stripping solution.20
Carbon Regeneration
After stripping, the caroon 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.21
The acid used for carbon washing depends on what 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 is also 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 wash solution reaches a stable
pH of 10, it is sent to a tailing impoundment. Metallic elements may also be precipitated with sodium
sulfide.22
The carbon is screened to remove fines and thermally reactivated in a rotary kiln at about 730°C
for 20 minutes. The reactivate carbon is subsequently rescreened and reintroduced into the recovery
system. Generally, about 10 percent of the carbon is lost during the process because of particle abrasion.
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.23
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
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
20 Ibid.
21 U.S. Environmental Protection Agency, July 1994, Op. Cit.. pp. 1-12.
22 Ibid.
23 Ibid.
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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 Section B.
EPA determined that for this specific mineral commodity, the beneficiation/processing line occurs
between cyanidation metal recovery and refining because this is where significant physical/chemical changes
occur. 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: PRECIOUS METAL RECOVERY FROM REFINERY SLIMES
1. Discussion of Typical Production Processes
Gold and silver are also 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. 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 dor6 in the furnace is removed and sent to
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355
refining to recover the precious metals.24 See the selenium and tellurium chapters 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 dor6 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 dor6 is then sent to refining.25
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
None identified.
4. Beneflciation/Processing Boundaries
Since gold is recovered as a by-product of other metals, all of the wastes generated during gold
recovery are mineral processing wastes. For a description of where the beneficiation/processing boundary
occurs for this mineral commodity, see the reports for lead and copper presented elsewhere in this
document.
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.26
2. Generalized Process Flow Diagram
Like several other gold refineries, at the Newmont facility in Nevada the gold cyanide solution is
electrowon 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 residue. The
waste sulfuric acid and steel wool solution is discharged to the tailings slurry. The gold solids are filtered
under vacuum through diatomaceous earth. The gold 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 is
smelted in an induction furnace. It is from this induction furnace that gold dor6 bars are poured. The
slag generated from this smelting is sent to a ball mill for crushing, grinding, and gold recovery. Some of
24 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-100 - 3-115.
25 Ibid.
26 Ibid.
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356
the slag is immediately recycled back to the smelting process to recover its gold content. The gold slag
may have between 3 and 4 ounces per ton of recoverable-gold.27
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 sluny precipitates the solubilized mercury and also some silver.28 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 6 presents an overall process flow sheet for gold production.
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
None identified.
4. Beneficiation/Processing Boundaries
As discussed above, 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.
EPA determined that for recovering gold and silver from precious metal refining, the
beneficiation/processing line occurs between retorting and smelting because this is where a significant
chemical change ocurrs. 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.
27 U.S. Environmental Protection Agency, Trip report for Newmont Gold Corporation, South
Operations Facilities, Carlin Nevada, May 17, 1995.
28 Simpson, W.W., W.L. Staker, and R.G. Sandberg, Calcium Sulfide Precipitation of Mercury From
Gold-Silver Cvanide-Leach Slurries. U.S. Department of Interior, 1986
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357
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Mining
Mine water is a waste stream generated from gold and silver production. This waste consists of all
water that 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.29
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 convened to sulfuric acid. This may be sold to
other mines or used on-site for carbon washing and regeneration. At least two facilities generate sulfuric
acid, the Goldstrike Mine operated by American Barrick and Newmont's facility in Nevada.
29 U.S. Environmental Protection Agency, Mining Industry Profile. Gold. Office of Solid Waste,
Special Waste Branch, 1993, pp. 41-45.
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358
EXHIBIT 6
OVERVIEW OF GOLD PRODUCTION
(Adapted from: Technical Resource Document, Extraction and Beneficiation of Ores and Minerals,
July 1994, pp. 1-12.)
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359
Cvanidation
Spent carbon.
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
placed on on-off heap pads is periodically removed for ultimate disposal at an alternative site, such as
waste rock 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 cvanide-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.30
Spent leaching solution. During the leaching operations, most of the barren cyanide solution is
recycled to leaching activities; 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 or land-applied after treatment to detoxify cyanide.31
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. TTie 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 leaching process.
Activated Carbon Stripping
Spent stripping solution.
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 oh
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.32
Waste sulfuric acid may be corrosive.
Waste steel wool solution may be corrosive.
30 U.S. Environmental Protection Agency, 1994, Op. Cit.. pp. 1-12.
31 Ibid.
32 Ibid.
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360
Carbon Regeneration
Carbon fines and acid wash solution are wastes from the reactivation circuit. The carbon may
contain small amounts of residual base metals and cyanide. The acid wash residues may contain metals,
cyanide, and the acid (typically hydrochloric or nitric). The acid is usually neutralized in a totally enclosed
system prior to release to a tailings impoundment. Most operations capture less-than-optimum-size
carbon particles and, prior to disposal, extract additional gold values. This may involve either incinerating
the carbon/gold that could not be desorbed chemically during the normal course of operations or
subjecting the material to an extended period of concentrated cyanide leaching. Any liquids used to wash
or transport carbon material are recirculated.33 These wastes are non-uniquely associated with mineral
processing operations.
2. Mineral Processing Wastes
Smelting and Refining
Slag. This waste may be recycled to leaching and smelting operations. 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 judgement to determine that this waste may exhibit the characteristic of toxicity for silver.
This waste is classified as a byproduct.
WWTP sludge. This waste may be recycled. 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/tyr, and 720,000 metric tons/yr, respectively. We used best engineering judgement to determine
that this waste may exhibit the characteristic of toxicity for silver. This waste is classified as a sludge.
Spent furnace dust 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 judgement to determine that this waste may
exhibit the characteristic of toxicity for silver. This waste is recycled and is classified as a byproduct.
Wastewater is generated from numerous sources, including the smelter APC, silver chloride
reduction, electrolytic cell wet APC, and electrolyte preparation wet APC. 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.34 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 judgement to
determine that this waste may exhibit the characteristic of toxicity for arsenic, silver, cadmium, chromium,
and lead. This waste is classified as a sludge.
33 Ibid.
34 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.
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361
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/yT, 360,000
metric tons/yr, and 720,000 metric tons/yr, respectively. We used best engineering judgement to determine
that this waste may exhibit the characteristic of toxicity for silver and corrosivity. This waste is recycled to
extraction/beneficiation units.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants.
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362
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 1CF 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 Sulfide 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.
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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
Location
Asahi Glass Company of Japan
Woodward, OK
Iochem Corporation of Japan
Vici, OK
North American Brine Resources (miniplant)
Dover, OK
North American Brine Resources (major plant)
Woodward, OK
B. Generalized Process Description
1. Discussion of Typical Production Processes
All three facilities (Asahi Glass Company of Japan, Iochem 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 Iochem 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.
Brines are separated from hydrocarbons by using the blowing-out process. Iochem Corporation
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.
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364
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) Process (es)
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.
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365
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
I
Sulfur Dioxide.
Treatment
Iodine Product
I
Waste Bleed Liquor
¦Filtrate Waste
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366
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. Extraction/Beneflciation 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/Beneflciation 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.
7 Ibid.
8 U.S. Environmental Protection Agency, Multi-Media Assessment of the Inorganic Chemicals
Industry. Volume II, 1980, Chapter 9.
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367
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous) and other lubricants.
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368
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 Lydav, 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.
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369
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 thai 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 S55 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 1993.2 Exhibit
1 presents the names and locations of facilities involved in the primary production of iron and steel.
EXHIBIT I
Summary of Primary Iron and Steel Producers in 1989
Facility Name
Location
Type of Operations
Acme
Riverdale, IL
Iron; BOF Steel
Alleghany Ludlum
Brackenridge
Iron; BOF Steel
Armco Steel Co., L.P.
Middletown, OH
Iron; BOF Steel
Armco Steel Co., L.P.
Ashland, KY
Iron; BOF Steel
Bethlehem Steel
Sparrows Point, MD
Iron; BOF Steel
Bethlehem Steel
Bethlehem, PA
Iron; BOF Steel
Bethlehem Steel
Chesterton, IN
Iron; BOF,OHF Steel
1 Gerald Houck, "Iron and Steel," from Mineral Commodity Summaries, U.S. Bureau of Mines,
January 1995, p. 86.
2 Ibid.
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EXHIBIT I (continued)
Summary of Primary Iron and Steel Producers in L989
Facility Name
Location
Type of Operations
Geneva Steel
Orem. UT
Iron; OHF Steel
Gulf States Steel
Gadsden. AL
Iron; BOF Steel
Inland Steel
E. Chicago, IN
Iron; BOF Steel
LTV
E. Cleveland. OH
Iron; BOF Steel
LTV
W Cleveland. OH
Iron; BOF Steel
LTV
Indiana Harbor, IN
Iron, BOF Steel
McLouth Steel
Trenton. Ml
Iron; BOF Steel
National Steel
Granite City, IL
Iron; BOF Steel
National Steel
Escore, MI
Iron; BOF Steel
Rouge Steel
Dearborn, MI
Iron; BOF Steel
Sharon Steel
Farrell, PA
Iron; BOF Steel
(shut down in November
1992)a
Shenango
Pittsburgh, PA
Iron
US Steel
Braddock, PA.
Iron; BOF Steel
US Steel
Gary. IN
Iron; BOF Steel
US Steel
Fairless Hills, PA
Iron; OHF Steel
US Steel
Fairfield, AL
Iron; BOF Steel
US Steel/Kobe
Lorain, OH
Iron; BOF Steel
Warren Steel
Warren, OH
Iron; BOF Steel
Weirton Steel
Weirton, WV
Iron; BOF Steel
Wheeling-Pittsburgh Steel
Steubenville, OH
Iron; BOF Steel
Wheeling-Pittsburgh Steel
Mingo Junction, OH
Iron; BOF Steel
a Gerald Houck. "Iron and Steel" from Minerals Yearbook Volume 1. Metals and Minerals. U.S Bureau of Mines. 1992. p. 649
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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%; 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
3 Gerald Houck, "Iron and Steel," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p.
412.
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.
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372
EXHIBIT 2
IRONMAKING AND STEELMAKING PROCESSES
(Adapted from: USS Lorain flow diagram.)
APC Dust
'on-site disposal)
Alternate Process
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373
Steelmaking
Ail 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 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
1987.7
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 washin'g 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
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.
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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'.
Pelletizing. 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 - ai
less than 1000 °C.U 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.
10 Ibid.
11 J. Astier, "Present Status of Direct Reduction and Smelting Reduction," from Steel Times. October
1992, pp. 453-458.
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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 (CaC03)
and/or dolomite [(Ca,Mg)C03] 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
((Ca0+Mg0)/(Si02+AJ203)) 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.
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
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376
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, took 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) Process(es)
• Dezincing 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 amount of manganese recovered. Results indicated that the method cannot be
applied satisfactorily to all steelmaking slags.15
• Classification16 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.
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.
15 S.N. Mcintosh 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.
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known as Classification, utilizes'electric arc furnace dust from both the steel and nonferrous
metals industries to produce glass products.1'
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, chlonnation). 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 agglomeration (sintering, pelletizing, and briquetting) and reduction of iron ore 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 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 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
17 R.B. Ek and J.E. Schlobohm, "Classification of Electric Arc Furnace Dust," from Iron ana 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.
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378
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 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 wastes.19
2. Mineral Processing Wastes
Ferrous metal production operations generate four RCRA special mineral processing wastes: 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 methods used to cool the
molten slag. In the surveys, all facilities characterized their slags as solid, though slag is molten ai
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
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379
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
22 Ibid.
23 Ibid.
24 Ibid.
-------
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 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polvchlorinated 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 unrip.r RTR a Snhntip
C requirements.
-------
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, J.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
IndustA' 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.
Kjrk, 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.
Mcintosh, S.N. and Baglin. E.G. "Recovery of Manganese from Steel Plant Slag by Carbamate Leaching." U.S.
Bureau of Mines. 1992.
Nvirenda 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.
-------
382
-------
383
LEAD
A. Commodity Summary
Lead 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 totalled 330.000 mt and 30,000
mt, respectively, in 1994. In addition, domestic secondary production from lead scrap totalled 880,000 mt
in 1993, up from 842,000 mt in 1989. United States lead reserves totalled 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.
Treatment of lead ores begins with crushing, grinding, and concentrating. Pelletized concentrates are fed
with other materials (e.g., smelter 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 (S02). The exit gas stream from the sinter 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. (SA1C, 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 other 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 drossing 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 other
-------
KXIIIHIT I
Summary c»i-- Lkad Mining, Smki.tinc;, and Ugkininu Faciutiks
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 the special waste
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 special waste management units has
exceeded national ambient surface water quality
criteria for lead
• Ambient air monitored near the special waste
management units has exceeded^the NAAQS for
lead (arithmetic 3-month average, 1.5/jg/m3)
-------
EXHIBIT 33-1 (Cont.)
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 special waste
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 special waste management units have
shown exceedances 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 special waste
management units has exceeded the NAAQS for
lead (arithmetic 3-month average, 1.5/jg/m3)
ASARCO Leadviile Unit
Leadviile, CO
Mining
UJ
00
Ln
-------
EXHIBIT 33-1 (Cont.)
Facility Name
Location
Type of Operations
Potential Factors Related to Sensitive Environments
Doe Run Co.
Herculaneum, MO
Smelting and
Refining
• 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.
Fourth of July Mine
Yellow Pine, ID
Extraction
Galena Mine
Mullan, ID
Extraction
Glass Mine
Pend Oreille County,
WA
Extraction
Greens Creek Mine
Admiralty Island, AK
Extraction
Lucky Friday Mine
Mullan, ID
Extraction
Magmont Mine
Bixby, MO
Extraction
Montana Tunnels Mine
Jefferson County,
MT
Extraction
Red Dog Mine
Kotzebue, AK
Extraction
-------
EXHIBIT 33-1 (Cont.)
Facility Name
Location
Type of Operations
Potential Factors Related to Sensitive Environments
Sunnyside Mine
Silverton, CO
Extraction
Sweetwater Mine
Bunker, MO
Extraction
Viburnum Mines (6 mines):
Brushy Creek
Casteel
Fletcher
Viburnum 28
Viburnum 29
Buick
Iron, Reynolds, and
Washington
Counties, MO
Extraction and
Beneficiation
West Fork Mine
Bunker, MO
Extraction
-------
388
precious metals. The lead bullion may then be decopperized before being sent to the refining stages.
(U.S. EPA. 1990. p. 10-2)
Lead refining operations generally consist of several steps, including (in sequence) softening,
desilverizing, dezincing, bismuth removal, and final refining. Various other saleable materials may also 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; the 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 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, materials 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, although 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-staged 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 crushing 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 also 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 flotation (collectors, frothers.
activators, and depressants). Flotation typically occurs in a series of steps, and multiple floats may be
required to remove several 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)
-------
Exhibit 2. Process Flow Diagram of Primary Lead Production in the U.S.
Acid
Mining
Plant
Lead Ores
SO.
Gases
and Oust
Lead
Concentrates
Dusl
Sintering
( Sullunc\
Vv
Biowdown
Concentrating .
BaghoutM A
ESPs
Impoundments
&
WWTP
Cadmium
Roasting
Unit
Roaster Residue
To Sinter Plant
^ Solids ^ ^ Effluent
Baghousas &
ESPs
Dusl
Sinter
Gas and Oust
Blast
Furnace
Bullion
I
I
J
Slag
'vVv-^
J ( IMatte j Bpeissj
Crossing
Kettles
r
_L
y Slag ^
Zinc
Fuming
Furnace
I
Slag [
A L
Granulalor
^ Slag ^
Dross
Rough-
Drossed
Bullion
Decop peri zing
Dross
Raverbeiatory
Furnace
Copper
Sulfide
Slag
Matte I (Speiss)
Slag and Lead
Recycled to
Blast Furnace
Bullion to
Soltening
Water
Thickener
\ * / y~*~7
j Waler ( i Sludge (
-------
u>
o
Exhibit 2 (Continued).
Rovartoeratoiy
Softening
Vacuum
De zincing
Zinc
Drossed.
Dec opperlzed
BuUtoo
Kent*
Soltenlng
Softened
Bullion
Harris
Softening
^ Slag ^
Slag lo
Sinter Feed .
or
Blast Furnace
_ytv
Zlnc
Parties
Desilverizing
Zinc
Reverberalory
Softening
Slag,
Sodium
Antimonate
Desilverized
Bullion
Chlorine
Oezinclng
Precious
Metal
Cnra is
Harris
Oezinclng
Relorllng
Recovery
Furnace
Gold-Silver Alloy
(Dore)
Cupelling
Flue Ousls
' Recycled to
Sinter Feed
Lead Oxide
¦ Slag lo
Softening Process
¦ Flue Dusts and
Slag lo
Blast Furnace
Dezinced
Bullion
Deblsmuthlng
Bullion
Dross
Bismuth
Helming
Cooling
Water
Slag
I
To Slag
Gianulation
Final
Refining &
Casting
Slag lo
' Blasl
Furnace
)s"° (
L^^Lead^
Contaminated
Cooling
Walei
To Tailings
Pond
^ Sludge ^
-------
EXHIBIT 3
MATERIALS PLOW TO AND FROM ASARCO, GLOVER, MISSOURI
-------
EXHIBIT 4
MATERIALS FLOW TO AND FROM ASARCO, HELENA, MONTANA
I'lCCIOII.^ Mclill.S
((ioLl)
Keci 01 cd I'ii>lJiicIs
-------
393
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. unrecovered lead materials, chemical reagents, and
wastewater) is pumped to a tailing pond. Clarified water from the tailings pond may be recycled to the
mill. (U.S. EPA, 1993b, p. 20)
Sintering
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 the 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 (SO-,). Product sinter is sized for use in the blast furnace, and fine sinter particles are recycled to
the feed mixture. (PEL 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 either baghouses or electrostatic
precipitators (ESPs) and recycled. (PEL 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 S02 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 with 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 either dumped while hot onto a slag pile, or granulated with cooling water and then
dumped. Some plants dewater the slag; the granulating water may be cleaned in thickeners and recycled to
the granulation unit. The granulation water may also 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, the dust is roasted to
recover cadmium. Fume emissions from the roasting operation are cooled and recovered as product
(cadmium concentrate), and the residue is recycled to the sinter feed. Blast furnace off-gases also contain
small quantities of S02 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)
-------
394
Dressing
Lead bullion recovered from the blast furnace is fed to a drossing kettle, agitated with air, and
cooled to just above its freezing point. Oxides of lead, copper, and other impurities form a dross on the
surface that is skimmed. Sulfur may be added to the drossing kettle to enhance copper removal, forming
copper sulfide (Cu2S) that is skimmed off with the dross. Skimmed dross is sent to the dross reverberator,'
furnace for additional processing; off gases and particulates from the drossing 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."l980, 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 drossing 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 drossing 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 (NaN03) are added as fluxes. The
fluxes react with impurities to form salts such as sodium antimonate (NaSb03), 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 jeached with hot
water to dissolve the sodium salts. The solution is cooled to precipitate sodium antimonate (NaSb03),
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 (Sb203), the sodium antimonate is heated to volatilize antimonial
trioxide and arsenic trioxide (As203), 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)
-------
395
Parkes Desilverizing
This process is used to recover gold and silver from softened lead bullion. Gold and silver
removal are usually done in two steps. First, a small amount of zinc is added to the molten bullion to
generate a skim with high gold content, since 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 (Dord). The zinc can be
recycled to the process. Flue dusts from the-furnaces can 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.
One 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
hydrolvzes 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., Cafy^Bi^ 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 particulate lead and lead
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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) Process(es)
Hvdrometallurgical Beneficiation
The U.S. Bureau of Mines has 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 (HnSiF6). using hydrogen
peroxide (H202) and lead dioxide as oxidants. After filtration to separate the lead fluosilicate (PbSiFJ
leach solution and the sulfur-containing residue, the PbSiF^ 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)
Since H20, 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 (O,) in place of
H202. This method also utilizes H2SiF6 as the leach solution and electrowinning to recover lead metal.
The researchers conducted several experiments, varying 02 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 has 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 H202 or pure oxygen (02) as an oxidant. Lead was selectively leached
and zinc remained in the solid residue. All experiments were performed on a bench-scale level. (Bevke,
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 H?SiF6 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. (Bevke, 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.
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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 in this
section.
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 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) 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
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.
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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 byproduct of
mineral extraction in underground mines. The quantity and composition of waste rock generated at lead
mines varies greatly between 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 may also 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 sulfide minerals and moisture are present. There is 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. There is no information on the quantities of mine
water generated annually at all lead mining/milling locations. 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 may also be contaminated with small quantities of oil and grease from mining equipment and
nitrates from blasting operations. 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 are also 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)
There is no information on the quantities of tailings generated annually at all lead mining/milling
locations.
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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, BDAT 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. (PELA, 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, drossing kettles, dross reverberatory furnace,
refinery, baghouses, and pavement are sent directly to WWTP-1 for treatment. (Doe Run Company,
1989b) This waste is classified as a spent material and may be partially recycled based on best engineering
judgment.
Surface Impoundment Waste Solids
In past years, surface impoundments at primary lead facilities received various types of
wastewaters, including slag granulation water, acid plant blowdown, plant runoff, and plant washdown
waters. Solids dredged from these impoundments were typically either recycled to the sinter feed
preparation or disposed of at the slag dump. (PEIA, 1984, pp. 3-6 to 3-7, 3-12 to 3-15) However, EPA
published a final rule on September 13, 1988 that relisted as hazardous certain wastes generated by metal
smelting operations. These wastes include K065 wastes, defined as "surface impoundment solids contained
in and" dredged from surface impoundments at primary lead smelting facilities." (SAIC, 1991b, p. 1)
The American Mining Congress and other plaintiffs filed suit with the U.S. Court of Appeals
challenging the basis for the listings. In July 1990, the court remanded several listings, including K065, to
EPA. The Agency is deciding whether to respond to the remand in order to relist the wastes or to manage
the wastes as characteristically hazardous. (U.S. EPA, 1994, pp. 8-9) Nonetheless, the relisting of surface
impoundment solids resulted in altered waste management practices at primary lead production facilities.
For example, at the ASARCO facility in Glover, MO, existing unlined surface impoundments are no
longer used and are in the process of clean closure. Plant wastewaters (e.g., slag granulation water) are
now clarified in two rubber-lined concrete 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. When sufficient quantities of settled solids have accumulated in the concrete settling
tanks, the plant will remove these materials recycle them to the process. (SAIC 1991b, pp. 8-10)
In addition, the Doe Run plant in Herculaneum, MO now continuously treats wastewaters that
were formerly routed to unlined surface impoundments. Plant washdown water, blast and dross furnace
slag granulation water, and neutralized acid plant blowdown are treated with lime and charged to a
clarifier (WWTP-1). The slag granulation waters receive some initial settling treatment in a concrete-lined
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impoundment, before they are combined with washdown waters and neutralized blowdown. Clarifier
underflow is treated in a thickener along with sinter plant scrubber blowdown. The clarifier overflow is
sent to gravity filters; backwash from the gravity filters is routed to the clarifier and the filtrate is
discharged through an outfall. The thickener underflow is dewatered by a filter press and returned to the
sinter plant. The filter"press liquids are recycled to the thickener, and the thickener overflow is recycled to
the sinter plant. (SAIC. 1991b, pp. 9-12;,ICF. 1989. pp. 2-3)
The remaining operational primary lead smelting facility, Asarco, East Helena, MT, is
reconstructing its wastewater management system. The reconstructed system will allow the facility to
completely recycle wastewater treatment solids from the treatment of acid plant blowdown and other
process wastewaters. The modified system will allow the plant to discontinue its use of surface
impoundments. When the modified system is complete, wastewater treatment solids will be blended with
lead ore concentrates and recycled to the process. (U.S. EPA, 1994. pp. 22-23)
A 1984 study entitled Overview of Solid Waste Generation. Management, and Chemical
Characteristics. Primary Lead Smelting and Refining Industry (PEI Associates. November 1984. prepared
for the Office of Research and Development) contains results of EP toxicity tests on one sample each of
dredged and undredged surface impoundment solids. The plants from which the samples were taken were
not identified. The dredged solids came from an impoundment that received blowdown, run-off, and other
plant wastewaters; the solids had been stockpiled prior to recycling. This sample exhibited EP toxicity for
cadmium (97.5 mg/L) and lead (37.8 mg/L). The undredged solids came from the bottom of an
impoundment that received washdown, run-off, scrubber water, and some granulation water. This sample
also exhibited EP toxicity for cadmium (92.3 mg/L) and lead (308 mg/L). (PEIA. 1984, pp. 5-16 to 5-17)
The NIMPW Characterization Data Set contains additional data 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 characteristic of toxicity for arsenic, cadmium, lead, and mercury.
A 1991 study entitled Characterization Report for Surface Impoundment Solids Contained in and
Dredged from Surface Impoundments at Primary Lead Smelting Facilities CK065') for ASARCO, Glover.
Missouri, and Doe Run Company. Herculaneum. Missouri (SAIC, April 25, 1991, prepared for the Office
of Research and Development) contains results of TC tests on one sample of settled K065 material
collected from a lined retention pond at the Asarco plant. The sample exhibited the toxicity characteristic
for lead (395 mg/L) and cadmium (69.9 mg/L). The sample contained no volatile organics, semivolatile
organics, organochlorine pesticides, or PCBs, but some phenoxvacetic acid herbicides and
organophosphorus insecticides were detected. The authors suggested that the detected compounds could
be the result of a mixing of plant wastewater streams with facility run-off. When the sample was analyzed
using the SPLP, it exhibited leachable levels of lead (28.7 mg/L) and cadmium (23.2 mg/L) above the levels
specified in 40 CFR 261.24. Dioxins and furans were also detected in the ASARCO K065 sample, but all
homologs were present at levels below existing EPA treatment standards. A 2,3,7,8-TCDD equivalent of
0.0885 ppb was calculated. (SAIC, 1991b, pp. 13-23)
As described above, the three remaining active primary lead smelting facilities (Asarco's Omaha.
NE facility is a refinery only) are moving away from the use of surface impoundments for managing plant
wastewaters. All three plants have replaced, or are in the process of replacing their on-site surface
impoundments with engineered settling/retention basins or wastewater treatment systems. As a result,
surface impoundment solids may no longer be generated.
This waste stream is listed as hazardous but has been remanded. Therefore, the waste stream was
not included in our analysis.
Spent Furnace Brick
Primary lead smelters generate used refractory brick during the reconstruction of blast furnaces.
Some plants crush and recycle the brick to the blast furnace, while other plants discard the brick in on-site
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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 results 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 is 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 run-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 corrosivitv. However, since the effluent is not managed
m 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 is classified as a
sludge.
WWTP Sludges/Solids
Wastewater treatment sludges and solids consist of solid materials that settle following lime
neutralization of influent wastewaters. The sludges and solids are typically recycled to the sinter feed
preparation operation. For example, at the Doe Run Herculaneum facility, a thickener serves as the final
collection point for solids in the WWTP. Thickener solids are dewatered using a filter press and then
shipped by rail car to the sinter plant. (PEIA, 1984, pp. 3-12 to 3-15; SAJC 1991b, pp. 9-12)
Approximately 380,000 metric tons of WWTP sludges and solids are generated annually (ICF, 1992). The
waste generation rate per facility is greater than 45,000 metric tons/yr due to comingling of numerous
waste streams. The NIMPW Waste 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. We used best
engineering to determine that this waste stream may exhibit the characteristic of toxicity (cadmium and
lead). This waste stream is fully recycled and is classified as a sludge.
The April 25, 1991 SAIC study contains data on samples of clarifier underflow and filter press
solids collected from the wastewater treatment system (WWTPrl) at Doe Run's Herculaneum, MO facility.
The clarifier underflow sample, which is'derived from plant washdown and acid plant blowdown, exhibited
the toxicity characteristic for cadmium (8.51 mg/L). The filter press solids, which are derived from
thickened clarifier underflow and sinter plant blowdown, exhibited the toxicity characteristic for lead (185
mg/L) and cadmium (98.8 mg/L). The Doe Run samples were not analyzed for any organic compounds.
(SAIC, 1991b, pp. 13, 15)
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Surface Impoundment Waste Liquids
As noted above, 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 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 the 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). (PE1A, 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 the characteristic of toxicity (arsenic, cadmium, and lead). This waste is 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. (PELA. 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. (PELA, 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).
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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 sludge. The sludge sample exhibited EP toxicity for arsenic (304 mg/L) and
cadmium (155 mg/L). (PELA, 1984, pp. 5-14, 5-16. 5-17) The NIMPW Characterization Data Set contains
additional data 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 is classified as a spent material.
Slurried APC Dust
At one integrated smelter/refinerv. 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 RT1 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). (PELA. 1984, pp. 5-16, 5-17) This waste
stream is fully recycled and is 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 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 corrosivity. This waste is classified as a sludge.
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 is classified as a by-product.
Baghouse 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. (PE1, 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, it is
unclear from the survey what the dust's ultimate destination is. 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)
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). (PE1A, 1984, pp. 5-16 to 5-17) This waste stream is fully recycled and is 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. In addition, it is not known whether, or how, acid plant cooling tower
blowdown differs from acid plant blowdown.
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.
-------
405
Waste Nickel Matte
The 1989 RTI Survey for the Doe Run facility in Herculaneum. MO indicated that the dross plant
reverberatorv generates a product known as nickel matte. (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.
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 maierial 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 "baghoiise 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/vr, and 30,000
metric tons/yT, 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). (PELA, 1984, pp. 5-16, 5-17) The plant from which the sample was obtained was not
identified. 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 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 is classified as a
spent material.
-------
D. Ancillary 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). acidic tank cleaning-wastes, and polvchlorinated 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)
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-KJeen 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)
-------
407
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Buick Smelter, Boss, MO.
-------
Doe Run Company. 1989b. National Survey of Solid Wastes from Mineral Processing, Doe Run Companv
Smelting Division. Herculaneum, MO.
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91 fCobre 91). Ottawa. Ontario. Canada. 18-21 August. 1991. Elmsford, NY. Pergamon Press Inc..
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Goodwill, J.E.. 1991. "Plasma Melting and Processing - World Developments," from 48th Electric-Furnace
Conference Proceedings, New Orleans. Louisiana. USA. 11-14 December 1990. Warrendale, PA.
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Grebe, K., and H.J. Lehmkuhler, 1991. "High, Residue-Free Iron and Zinc Recovery from Integrated Steel
Plant Wastes with Less than 2% Zinc Plus Lead," from Ironmaking Conference Proceedings. Vol.
50. Washington. D.C.. USA. 14-17 April. 1991. Warrendale, PA, The Iron and Steel Society, pp.
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John Wiley & Sons.
ICF Incorporated (ICF), 1987. Draft Report to Congress on Solid Waste from Selected Metallic Ore
Processing Operations. Prepared for EPA, Office of Solid Waste, December 14.
ICF, 1989. "The Doe Run Company, Herculaneum, MO, Mineral Processing Wastes Sampling Visit -
Trip Report," from Mineral Processing Waste Sampling Survey Trip Reports. Prepared by ICF
Incorporated. August 31.
ICF, 1992. Newly Identified Mineral Processing Waste Characterization Data Set. Volume I. Aluminum
Reduction - Copper Smelting and Refining. Prepared for EPA, Office of Solid Waste, Waste
Treatment Branch, August.
Kelly. Errol G., and David J. Spottiswood, 1982. Introduction to Mineral Processing. New York, John
Wiley & Sons.
IChaidurov, V.P., et al., 1991. "The Production of Ferrite Complex Fluxes (FCF) at Novolipetsk Iron and
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Kjeldsen, P. and T.H. Christensen, 1990. "Leaching Tests to Evaluate Pollution Potential of Combustion
Residues from an Iron Recycling Industry." Waste Management and Research, Vol. 8, No. 4, pp.
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Kotraba, N.L. and M.D. Lanyi, 1991. "Inclined Rotary Reduction System for Recycling Electric Arc
Furnace Baghouse Dust." Iron and Steel Engineer. Vol. 68, No. 4, pp. 43-45. April.
Lee, A.Y. et al., 1990. "Pressure Leaching of Galena Concentrates to Recover Lead Metal and Elemental
Sulfur." U.S. Bureau of Mines Report of Investigations 9314.
-------
409
Lenchev, A., 1991. "Recovery of'Heavy Non-Ferrous Metals and Silver by a Two-Step Roasting Process."
Neue Hutte. Vol. 36, No. 4, pp. 146-149. April.
Madanv. I.M. and E. Raveendran, 1992. Teachability of Heavy Metals from Copper Blasting Grit Waste."
Waste Management and Research. Vol. 10. No. 1, pp. 87-91.
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Separation Technologies for Metals and Fuels. Palm Coast. Florida. USA. 13-18 March 1993.
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EPD Congress '91. The Minerals, Metals & Materials Society, pp. 745-760.
Ojebuoboh, Funsho K., 1992. "Bismuth-Production. Properties, and Applications." Journal of Metals, pp.
46-49. April.
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in Nonferrous Smelters. Prepared for EPA, Office of Research and Development. Industrial and
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PEI Associates, Inc., (PELA) 1984. Overview of Solid Waste Generation. Management, and Chemical
Characteristics. Primary Lead Smelting and Refining Industry. Prepared for EPA. Office of
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-------
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-------
41 1
ATTACHMENT 1
-------
412
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PROCESS WASTEWATER - LEAD
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
U Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
H Detects
Level
In Excess
Aluminum
0.043
3.75
17.90
8/8
0.050
4.85
18.80
4/4
-
-
Antimony
0.005
2.97
21.90
9/9
0.050
7.82
30.20
4/4
-
-
Arsenic
0.029
765.04
3,800.00
9/9
0.002
530.41
3,160 00
6/6
5 0
2
Barium
0.001
0.18
0.50
7/7
0.050
0.25
0 50
5/5
100.0
0
Beryllium
0.0003
0.01
0.05
6/6
0.005
0.03
0.05
4/4
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.002
8.76
31.30
13/13
0001
2.78
8.96
6/6
1.0
2
Chromium
0.001
0.13
0.50
7/7
0.001
0 19
0 50
6/6
5.0
0
Cobalt
0.006
0.49
2.10
9/9
0.050
0.28
0.50
4/4
-
-
Copper
0.009
30.20
250
10/10
0.138
0.72
1 75
4/4
-
-
Iron
0.035
26.51
77.80
9/9
0.050
1.38
5.69
5/5
-
-
Lead
0.002
1,820.30
21000
13/13
0.220
15.54
84.00
6/6
5 0
2
Magnesium
0.008
17.91
61.30
9/9
0 500
22 43
54 00
4/4
-
-
Manganese
0.010
4.97
33.60
8/8
0.030
0.93
2.86
5/5
-
-
Mercury
0.0001
12.86
90.00
7/7
0.0001
0.0032
0 0180
6/6
0.2
0
Molybdenum
0.020
1.07
4.62
6/6
0.050
1.66
4.67
4/4
-
-
Nickel
0.002
0.55
1.90
9/9
0.050
0.28
0 50
4/4
-
-
Selenium
0.004
0.23
1.66
9/9
0.001
0.94
4.96
6/6
1.0
1
Silver
0.001
0 16
050
9/9
0.005
0.19
0.50
6/6
5 0
0
Thallium
0.220
1.04
2.50
7/7
0.250
1.47
2.50
4/4
-
-
Vanadium
0.001
0.11
0.50
9/9
0.050
0.28
0 50
4/4
-
-
Zinc
0.010
99.61
690.00
11/11
0.500
20.18
83.20
5/5
-
-
Sulfide
25.00
136.33
207.00
3/3
-
-
Sulfate
270.00
1,785.88
530b
8/8
-
-
Fluoride
0.010
6.34
19.00
3/3
-
-
Chloride
5.00
1,158.09
7000
9/9
-
-
TSS
1.31
10,325.34
73700
8/8
-
-
pH *
2 22
8.41
13.30
17/17
212
0
Organics (TOC)
4 56
16.47
39.20
5/5
-
-
Non-delects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only LP data are presented.
-------
SUMMARY.OF-EPA/ORD, 3007, AND RTI SAMPLING DATA - ACID PLANT BLOWDOWN - LEAD
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum # Detects
TC «Values
Level In Excess
Aluminum
0.05
1.82
7.68
5/6
0.05
0 58
1.18
3/3
-
_
Antimony
0.05
29.57
148
6/6
0 05
30.72
91.60
3/3
-
-
Arsenic.
0.05
785.14
2370
6/6
0 05
640.18
2,520.00
3/3
5 0
1
Barium
0.05
0.14
0.50
6/6
0.05
0.35
0 50
3/3
100 0
0
uervmum
0.0005
0.02
0.05
5/5
0.005
0.035
0.050
3/3
-
-
boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.41
77.21
362.00
7/7
3 67
126 78
368 00
3/3
1 0
3
Ctuomium
0.00
0.20
0.50
5/5
0.05
0.35
0.50
3/3
5.0
0
Cobalt
0.05
0.55
2.32
6/6
0.05
0.35
0.50
3/3
-
-
Copper
0.01
2.85
17.80
7/7
0.05
0.35
0.50
3/3
-
-
iron
0.63
29.19
94.80
6/6
0.50
14.21
39.20
3/3
-
-
Lead
1.63
115.30
674.00
7/7
1.79
4 14
7 29
3/3
5.0
'l
Magnesium
2.90
23.92
78.20
6/6
7.94
25.88
54.00
3/3
-
-
Manganese
0.53
1.71
3.81
6/6
0.78
0 99
117
3/3
-
-
Mercury
0.0010
1.23
4.80
5/5
0.0001
0.0001
0.0002
3/3
0.2
0
Molybdenum
0.05
0.22
0.50
3/3
0.05
0.35
0.50
3 n
-
-
Nickel
0.05
0.61
2.81
6/6
0.05
0.35
0.50
3 i
-
-
Selenium
0.05
1.91
5.59
3/3
0.05
1.36
3 54
3/j
1 c
I
Silver
0.01
0.18
0.50
5/5
0.05
0.35
0.50
3/3
5.0
0
Thallium
0.25
47.77
142.00
3/3
0.25
36 58
107 00
3/3
-
-
Vanadium
0.00
0.21
0.50
5/5
0.05
0 35
0.50
3/3
-
-
Zinc
0.32
47.43
160
7/7
0.29
59.50
113.00
3/3
-
-
Sulfate
536
1.126.83
3150
6/6
-
-
Fluoride
57
364.50
672
212
-
Chloride
3
1,250.56
4300
9/9
-
-
TSS
21 30
7,965.06
24730
8/8
-
-
pH *
0.62
3.91
9.04
7/7
212
2
Organics (TOC)
8.81
125.90
350.00
3/3
-
-
Non-detects were assumed to be present al 1/2 Ihe detection limit. TCLP data are currently unavailable; thereloie, only EP data are presented.
-------
SUMMARY- OF EPA/ORD, 3007, AND RTI SAMPLING DATA - MISCELLANEOUS SOLIDS - LEAD
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
U Values
Constituents
Minimum
Average
Maximum
It Delects
Minimum Average
Maximum
# Delects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenic
-
-
-
0/0
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
r
-
0/0
-
-
0/0
-
-
Cadmium
-
-
-
0/0
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt,
-
-
-
0/0
-
-
0/0
-
-
Cooper
10,000
10,000
10,000
1/1
-
-
0/0
-
-
Iron
100,000
100,000
100,000
1/1
-
-
0/0
-
-
Lead
500,000
500,000
500,000
1/1
-
r
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
50,000
50.000
50,000
1/1
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-•
TSS
-
-
-
0/0
-
-
pH *
-
-
-
0/0
2l2
0
Organics (TOC)
-
-
-
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.
-------
SOMMARY'OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - LEAD
Total Constituent Analysis
-PPM
EP Toxicity Analysis
-PPM
TC
# Values
Constituents
Minimum
Average Maximum
tt Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenic
18.00
18.00
18.00
1/1
-
-
0/0
50
0
Barium
-
-
-
0/0
-
-
0/0
1000
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.05
5.52
20.70
4/4
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper-
0 01
0.23
0 50
4/4
-
-
0/0
-
-
Iron
0.25
0.52
1.00
3/3
-
-
0/0
-
-
Lead
0.95
2.28
3.18
4/4
-
-
0/0
5.0
0
Magnesium
18.00
18.00
18.00
1/1
-
-
0/0
-
-
Manganese
3.00
3.00
3.00
1/1
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0 2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
2.00
15.10
43.20
4/4
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
PH*
7.00
7.60
8.00
3/3
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed lo 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 - LEAD
Total Constituent Analysis - PPM
EP Toxicity Analysis
-PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
* Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
_
_
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenic
-
-
-
0/0
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
19.00
19.00
19.00
1/1
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
2,500
2,500
2,500
2/2
-
-
0/0
-
Iron
-
-
-
0/0
-
-
0/0
-
_
Lead
1,290
27,430
59,000
3/3
-
-
0/0
5.0
0
Magnesium
-
-
-
010
-
-
0/0
-
-
Manganese
-
-
-
010
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
010
-
-
0/0
-
-
Zinc
68
64,689
98,000
3/3
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
PH*
7.50
9.06
13.00
5/5
212
1
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed lo 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 - LEAD
Total Constituent Analysis
- PPM
EP Toxicity Analysis
- PPM
TC
tt Values
Constituents
Minimum
Average Maximum
H Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
0/0
-
-
Arsenic
-
-
-
0/0
-
-
0/0
5 0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
Cadmium
0.08
o.oa
0.08
1/1
-
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
-
-
-
0/0
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
15.00
17.50
20.00
2/2
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
-
-
-
0/0
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
0/0
-
-
Selenium
-
-
-
0/0
-
-
0/0
1.0
0
Silver
-
-
-
0/0
-
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
35.00
35.00
35.00
1/1
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
pH *
7.00
9.08
13.00
4/4
212
1
Organics (TOC)
-
-
-
0/0
-
Non-datecls 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
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
-
0/0
-
-
Anllmony
-
-
-
0/0
-
-
-
0/0
-
-
Arsenic
-
-
-
0/0
0.00
46.95
304.00
7/7
5.0
2
Barium
-
-
-
0/0
0.15
1.08
2.60
6/6
100.0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
Cadmium
640.00
670.00
700.00
2/2
0 01
54.34
155.00
7/7
1.0
6
Chromium
28.00
44.00
60.00
2/2
0.00
0.02
0.07
3/7
5.0
0
Cobalt
-
-
-
0/0
-
-
-
0/0
-
-
Copper
-
-
-
0/0
-
-
-
0/0
-
-
Iron
--
-
-
0/0
0.05
30.25
178.00
6/6
-
-
Lead
115000
127500
140000
2/2
0.22
188.01
959.00
7/7
5.0
3
Magnesium
-
-
-
0/0
-
-
-
0/0
-
-
Manganese
-
-
-
0/0
0.03
513.63
3,560.00
7/7
-
-
Mercury
-
-
-
0/0
0.0001
1.1313
7.9000
7/7
0.2
1
Molybdenum
-
-
-
0/0
-
-
-
o/n
-
-
Nickel
-
-
-
0/0
-
-
-
0.
-
-
Selenium
-
-
-
0/0
0.001
0.077
0.420
7//
1.U
0
Sliver
-
-
-
0/0
0 015
0.018
0.030
5/5
5.0
0
Thallium
-
-
-
0/0
0.02
0.02
0.02
1/1
-
-
Vanadium
-
-
0/0
-
-
-
0/0
-
-
Zinc
80000
106000
132000
2/2
0.02
65.66
' 184.00
7/7
-
-
Sulfate
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
PH'
4.80
6.29
11.20
6/6
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed (o be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
420
-------
421
ATTACHMENT 2
-------
422
-------
423
Mining Sites on the National Priority List
Name of Site:
Owner of Site:
Location of Site:
Climate Data:
Commodity Mined:
Facility History:
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'Alene River in Northern Idaho.. It ts 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, Smelteiville,
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 dowhdraft 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.
Waste(s) at Issue: 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
-------
424
impoundment at the Central Impoundment Area (CIA) began operation. After
1961, the coarse fraction of mill tailings were used as sand 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.
Disposal Site: 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.
Soil Pathway: 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 Rats 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.
Ground Water Primary sources of ground water contamination include: seepage trom the CIA
Pathway: (estimated to be 1 ft3/sec), 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
-------
425
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/dav of zinc to the ground water in 1975.
The ponds have subsequently been converted for sewage treatment. Information
on the potential of heavy-metal contamination of ground water from these ponds
remains unavailable.
Surface Water The Bunker Hill site is situated in the Coeur d'Alene River basin. The main
Pathway: 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 M-g/L), iron (1,146 Mg/L), manganese
(1.507 Atg/L), and zinc (3,270 /j.gfL).
Air Pathway: 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 lbs of
lead: 560,000 lbs of cadmium; 860,000 lbs of zinc; 29,000 lbs of mercury; and
70,000 lbs 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 jj.g/m3 (on
a quarterly basis) and ambient levels of total suspended particulates have ranged
from 30 to 70/xm/m3 (on an annual basis) with daily values ranging to 900 ^g/m3.
The NAAQS for lead is 1.5 /xg/m3 (on a quarterly basis) and the primary NAAQS
for particulate matter is 150/j.g/m3 (on a 24-hour basis, for particles <10
microns).
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426
Environmental Issues: The pathways for human exposure include household dusts, soils, and locallv
grown vegetables. EPA has (through a health intervention program)
recommended against eating the vegetables since 1985. Shown below are
concentrations of lead, cadmium, and zinc from studies performed in 1974 and
1983.
Lead (in ppm)
Cadmium (in ppm)
Zinc (in ppm)
Media
1974
L983
1974
1983
1974
1983
Household Dust
11,920
3.994
NA
67
NA
2.840
Soils
7.224
3.504
63
54
2,340
126
Garden Vegetables
231
48
28
5
NA
73
NA - not analyzed
Environmental and ecological damage has also occurred. The Bunker Hill Company, as part of a
revegetation effort beginning in the early 1970's, identified about 14,000 acres that had been damaged.
Studies conducted as part of the Remedial Investigation concluded that site vegetation has been damaged
by logging, fires, and emissions from the lead smelter, zinc plant, and phosphoric acid/fertilizer plant.
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427
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 types 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, in order to
avoid ambiguity, 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
I. 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. 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.
-------
EXHIBIT 1
Facilities Producing Lightweight Aggregates from Naturally Occurring Raw Materials
Facility Name
Location
Arkansas Lightweight Aggregate
West Memphis, AR
Big River
Livingstone, AL
Big River
Erwinville, LA
Buildex
Dearborn, MO
Buildex
Ottawa, KS
Buildex
Marquette, KS
Chandler Materials Co.
Tulsa, OK
Chandler Materials Co.
Choctaw, OK
Dakota Block Co.
Rapid City, SD
Featherlite
Strawn (Ranger), TX
HP Brick Co.
Brooklyn, IN
HP Brick Co.
Independence, OH
Jackson Concrete
Jackson, MS
Kanta
Three Forks, MT
Lehigh Portland Cement Co.
Woodsboro, MD
Lorusso Corp.
Plainville, MA
Norlite
Cohoes, NY
Parkwood Lightweight Plant
Bessemer, AL
Porta Costa
Porta Costa, CA
Ridgelite
Frazier Park, CA
Solite
Cascade, VA
Solite
Arvonia, VA
Northeast Solite
Mount Marion, NY
Carolina Solite
Norwood, NC
Kentucky Solite
Brooks, KY
Florida Solite
Green Cove, FL
Strawn
Strawn, TX
Texas Industries
Streetman, TX
Utelite
Coalville, UT
Weblite
Blue Ridge, VA
Source: Determination of Waste Volume for Twenty Conditionally Retained Bevill Mineral Processing Wastes. 1990, pp. 5-9. A10
Facilities thai bum hazardous waste fuels are shaded.
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429
EXHIBIT 2
Byproduct Lightweight Aggregate Producers
Facilities
Location
Waylite Corporation
Bethlehem, PA
Standard LaFarge Corporation
Cleveland, OH
Edward C. Levy Company
Detroit, MI
Koch Minerals
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 quany 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. Extraction/Beneficiation 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
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430
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.
EPA determined that for the production of lightweight aggregates from naturally ocurring raw
materials,, the beneficiation/processing 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/processing line, along with
associated information on waste generation rates, characteristics, and management practices for each of
these waste streams.
SECTION 2: BYPRODUCT PRODUCTION
1. Discussion of Typical Production Processes
Both expanded slag and air-cooled slag are lightweight aggregate products produced as byproducts
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 may be 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
Since lightweight aggregates are recovered as by-proaucis of other metals, all of the wastes
generated during lightweight aggregate recovery are mineral processing wastes. For a description of where
the beneficiation/processing boundary occurs for this mineral commodity, see the 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 since no thermal processes are involved. However, production of manufactured lightweight
aggregates generates both extraction/beneficiation and mineral processing wastes. Overburden and
2 Bruce Mason, 1994, Op. Cit.. pp. 343-350.
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431
screenings are generated-from the mining and extraction of lightweight aggregate minerals. These
materials are likely left in place at the original mining site.
2. Mineral Processing Wastes
The hazardous wastes generated from lightweight aggregate production are not "newly identified
mineral processing wastes" and are therefore outside the scope of this report. However, a description of
these wastes is included.
Production From Naturally Occurring Raw Materials
Hazardous waste fuels may be used 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 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 waste because
all the APC dust that is generated is returned to the operation.
Air pollution control scrubber water and solids. This waste is no longer generated since all
facilities now use dry collection systems. Kilns equipped with wet scrubbers generated 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 mtfy. 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.4 In 1989, this waste was generated at a rate of
2,420,000 mt/y.5 Attachment 1 presents waste characterization data for this waste stream. Although this
waste stream is no longer generated, 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, scrubberwater and solids would have been considered a
hazardous waste at the five facilities that used wet scrubbers and burn hazardous waste fuels in their kilns.
Although this waste is no longer generated, Exhibit 7 presents waste generation rates for these five
facilities.
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 panicles and two
consisting of lighter panicles. This waste is collected by a shovel loader and placed in a waste water
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 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
5 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.
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432
EXHIBIT 3
LIGHTWEIGHT AGGREGATE PROCESS FLOW DIAGRAM
Raw Materials (Clay, Shale, Slate)
T
Landfill
Dry'
Collection
Scrubber
Offgases
Mining
'
Drying
1
'
Kiln or Sinter
Machine
Clinker
Fuel
(Coal, Waste
Derived Fuel)
WWTP
WWTP
Effluent
T
Surface
Impoundment
Screening
& Sizing
T
Lightweight Aggregate
Product Storage
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433
EXHIBIT 4
EXPANDED SLAG PROCESS FLOW DIAGRAM
Ore, Coke, Limestone.
Oxygen, and Flux
T
Hot Water
Blast Furnace Slag
Crushing &
Screening
T
Expanded Slag Product
-------
EXHIBIT 5
AIR-COOLED SLAG PROCESS FLOW DIAGRAM
Ore, Coke, Limestone,
Oxygen, and Flux
T
Air-Cooled Slag
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435
EXHIBIT 6
APC SCRUBBERWATER AND SOLIDS AT FACILITIES NOT USING WASTE-DERIVED FUELS
Facility
RTI
ID#
1988 Generation
pH
Management Practices
Buildex, Dearborn, MO
100685
Wastewater:
8,784,000 gallons
5.8
Sent to bedrock lined
. surface impoundment for
settling
Chandler Materials, Tulsa, OK
101725
Wastewater:
17,900,000 gallons
Solids:
177 cubic yards
5.5
Sent to bedrock lined
surface impoundment for
solids precipitation
Chandler, Choctaw, OK
101766
Wastewater:
14,100,000 gallons
5.6
Sent to in-situ clay lined
surface impoundment for
solids precipitation
Featherlite, Strawn, TX
101659
Wastewater:
4,535 mtons
NA
Sent to in-situ clay lined
surface impoundment for
solids precipitation
HP Brick, Brooklyn, IN
100263
Wastewater:
9,071 mtons
5.5
Sent to in-situ shale
lined surface
impoundment for
dewatering
Texas Industries, Streetman, TX
101808
Wastewater:
250,000,000
gallons
9.94
Sent to in-situ clay lined
surface impoundment for
solids precipitation
Porta Costa, Porta Costa, CA
100792
Wastewater:
600 gallons
7.2
Sent to in-situ clay lined
surface impoundment for
water evaporation and
solids recycling
Parkwood, Bessemer, AL
100180
Wastewater:
8,981 mtons
NA
Sent to bedrock lined
surface impoundment for
solids precipitation and
pH adjustment with
caustic soda
Jackson Ready Mix Concrete,
Jackson, MS
100438
Wastewater:
104 mtons
NA
Sent to recompacted
local clay lined surface
impoundment for solids
precipitation
Big River, Livingston, AL
NA
NA
NA
NA
Big River, Erwinville, LA
NA
NA
NA
NA
Arkansas Lightweight
Aggregate; West Memphis, AR
' NA
NA
NA
NA
NE Solite, Mt. Marion, NY
NA
NA
NA
NA
SOURCE: 1988 RTI Surveys.
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436
EXHIBIT 7
APC SCRUBBERWATER AND SOLIDS AT FACILITIES USING WASTE-DERIVED FUELS
Facility
Location
APC
Scrubberwater
and Solids
(mt/y)
Percent Solids
APC
Dust/Sludge
(mt/y)
Carolina Solite
Norwood, NC
923,902
40
369,561
Florida Solite
Green Cove, FL
478,751
40
191,500
Kentucky Solite
Brooks, KY
224,541
40
89,816
Norlite
Cohoes, NY
NA
NA
. NA
Solite
Arvonia, VA
NA
NA-
NA
SOURCE: Determination of Waste Volumes for Twenty Conditionally Retained Bevill Mineral Processing Wastes, EPA.
Office of Solid Waste, January, 1990.
pond/lagoon area onsite. The wet scrubber at the Arkansas facility operates for particulate removal only;
no chemical treatment of water occurs.6
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 since all APC dust is returned to the process. Exhibit 7
presents waste generation rates for these five facilities.
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.7 At the Carolina Solite facility in Norwood, NC., WWTP liquid effluent is
discharged under an NPDES.8 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 year9 (adjusted from a
reported value to reflect recent changes in the sector). This waste is discharged under an NPDES at the
Carolina Solite in Norwood, NC and the Norlite Corporation in Cohoes, NY.10 This waste is not
expected to be hazardous.
6 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
7 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
8 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.
9 U.S. Environmental Protection Agency, 1990, Op. Cit.. pp. 5-9, A10.
10 U.S. Environmental Protection Agency, 1992, Op. Cit.. Vol. II, pp. 22-1 - 22-19.
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437
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. Ancillary 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), acidic tank cleaning wastes, and polychlorinated biphenvls 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.
-------
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. 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.
-------
ATTACHMENT 1
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440
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - APC SCRUBBER WATER AND SOLIDS - LIGHTWEIGHT AGGREGATE
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum It Detects
EP Toxicity Analysis
Minimum Average
PPM
Maximum
H Detects
TC
Level
tt Values
In Excess
Aluminum
11.50
171
330
2/2
18.90
18.90
18.90
1/1
-
-
Antimony
0.030
0.14
0.25
0/3
0.050
0.050
0.050
0/1
-
-
Arsenic
0.0040
0.28
0.81
2/3
0.050
0.050
0.050
0/1
5 0
0
Barium
0.21
1.92
3.62
2/2
0.21
0.21
0.21
1/1
100.0
0
Beryllium
0.0050
0.016
0.025
1/3
0.0050
0.0050
0.0050
0/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.025
0.39
1.08
2/3
0.0050
0.0050
0.0050
0/1
1.0
0
Chromium
0.0025
0.44
1.08
1/3
0.050
0.050
0.050
0/1
5.0
0
Cobalt
0.25
0.31
0.36
1/2
0.050
0.050
0.050
0/1
-
-
Copper
0.025
0.21
0.34
1/3
0.050
0.050
0.050
0/1
-
-
Iron
1.16
145
289
2/2
2.07
2.07
2.07
1/1
-
-
Lead
0.013
0.13
0.35
3/3
0.025
0.025
0.025
0/1
5.0
0
Magnesium
90.60
212
334
2/2
21.60
21.60
21.60
1/1
-
-
Manganese
13.50
30.20
46.90
2/2
4.55
4.55
4.55
1/1
-
-
Mercury
0.0017
0.0018
0.0020
2/3
0.00010
0.00010
0.00010
0/1
0 2
0
Molybdenum
0.250
0.250
0.250
0/1
0.050
0.050
0.050
0/1
-
-
Nickel
0.050
0.30
0.53
3/3
0.050
0 050
0.050
0/1
-
-
Selenium
0.001
0.092
0.25
0/3
0.050
0.050
0.050
0/1
1.0
0
Silver
0.01
0.090
0.25
1/3
0.050
0.050
0.050
0/1
5.0
0
Thallium
0.074
0.52
1.25
1/3
0.25
0.25
0.25
0/1
-
-
Vanadium
0.050
0.31
0.56
2/2
0.050
0.050
0.050
0/1
-
-
Zinc
0.23
1.33
2.51
3/3
0.34
0.34
0.34
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
653
653
653
1/1
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
23.70
25.35
27.00
2/2
-
-
-
0/0
-
-
TSS
1,650
4,525
7,400
212
-
-
-
0/0
-
-
pH *
5.50
5.50
5.50
1/1
212
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detects were assumed lo 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
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
n Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
16.900
20.050
23.200
212
-
-
-
0/0
-
-
Antimony
0.70
0.75
0.79
1/2
-
-
-
0/0
-
-
Arsenic
17.00
26.50
36.00
2/2
0.00050
0.038
0.25
8/13
5.0
0
Barium
193
470
746
2/2
0.10
1.12
8.10
7/13
100.0
0
Beryllium
0.81
1.26
1.70
2/2
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
9.40
9.40
9.40
1/1
0.0025
0.18
0.78
9/13
1.0
0
Chromium
9.90
74.95
140
2/2
0.0050
0.071
0.12
3/13
5.0
0
Cobalt
-
-
-
0/0
-
-
-
0/0
-
-
Cooper
29.70
84.85
140
2/2
-
-
-
0/0
-
-
Iron,
28,200
34,050
39,900
2/2
-
-
-
0/0
-
-
Lead
8.91
274
539
2/2
0.05
0.46
2.55
7/13
5.0
0
Magnesium
10,900
11,550
12,200
2/2
-
-
-
0/0
-
-
Manganese
611
816
1,020
2/2
-
-
-
0/0
-
-
Mercury
0.40
0.67
0.93
2/2
0.00020
0.0012
0.0050
3/12
0.2
0
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
Nickel
14.70
26.85
39.00
2/2
-
-
-
0/0
-
-
Selenium
0.49
2.85
5.20
2/2
0.00050
0.031
0.15
6/13
1.0
0
Silver
1.70
1.70
1.70
1/1
0.0050
0.029
0.25
1/13
5.0
0
Thallium
0.55
5.08
9.60
1/2
-
-
-
0/0
-
-
Vanadium
31.00
41.50
52.00
212
-
-
-
0/0
-
-
Zinc
9.90
240
470
212
-
-
-
0/0
-
-
Cyanide
0.105
0.15
0.19
012
0.50
0.50
0.50
0/2
-
-
Sulfide
-
-
-
0/0
0.50
4.75
9.00
1/2
-
-
Sulfate
-
-
-
0/0
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
-
0/0
-
-
TSS
710,000
767,667
830,000
3/3
550,000
673.440
756,400
5/5
-
-
PH *
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detecls were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
_ JMMARY OF EPA/ORD. 3007. AND RTI SAMPLING DATA - WASTEWATt rtEATMENT PLANT LIQUID EFFLUENT - LIGHTWEIGHT AGGREGATE
Total Constituent Analysis - PPM
EP Toxicity Analysis - PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
10.00
10.00
10.00
2/2
-
0/0
5.0
0
Barium
57.00
57.00
57.00
2/2
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
8.00
-
-
0/0
-
0/0
1.0
0
Chromium
12.00
12.00
12.00
2/2
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
-
-
-
0/0
-
0/0
-
-
Lead
11.00
11.00
11.00
2/2
-
0/0
5 0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
--
-
Mercury
0.100
0.100
0.100
2/2
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
0.700
0.700
0.700
2/2
-
0/0
1.0
0
Silver
0.400
0.400
0.400
2/2
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
-
-
-
0/0
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
-
-
-
0/0
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therelore, only EP data are presented
£
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - LIGHTWEIGHT AGGREGATE
-t.
Total Constituent Analysis - PPM
EP Toxicity Analysis - PPM
TC
tt Values
Constituents
Minimum Average Maximum
ft Detects
Minimum Average Maximum
# Detects
Level
In Excess
Aluminum
.
o/u
-
0/0
-
-
Antimony
-
0/0
-
0/0
-
-
Arsenic
-
0/0
-
0/0
5.0
0
Barium
_
0/0
-
0/0
100.0
0
Beryllium
-
0/0
-
0/0
-
-
Boron
-
0/0
-
0/0
-
-
Cadmium
_
0/0
-
0/0
1.0
0
Chromium
_
0/0
-
0/0
5.0
0
Cobalt
_
0/0
-
0/0
-
-
Copper
-
0/0
-
0/0
-
-
Iron
_
0/0
-
0/0
-
-
Lead
_
0/0
-
0/0
5.0
0
Magnesium
_
0/0
-
0/0
-
-
Manganese
-
0/0
-
0/0
-
-
Mercury
-
0/0
-
0/0
0.2
0
Molybdenum
-
0/0
-
0/0
-
-
Nickel
.
0/0
-
0/0
-
-
Selenium
_
0/0
-
0/0
1.0
0
Silver
_
0/0
-
0/0
5.0
0
Thallium
_
0/0
-
0/0
-
-
Vanadium
_
0/0
-
0/0
-
-
Zinc
_
0/0
-
0/0
-
-
Cyanide
-
0/0
-
0/0
-
-
Sulfide
_
0/0
-
0/0
-
-
Sulfate
500 500 500
2/2
-
0/0
-
-
Fluoride
-
0/0
-
0/0
-
-
Phosphate
-
0/0
-
0/0
-
-
Silica
_
0/0
-
0/0
-
-
Chloride
100 100 100
2/2
-
0/0
-
-
TSS
400 400 400
2/2
-
0/0
-
-
PH *
6 6.00 6.00
2/2
212
0
Organlcs (TOC)
-
0/0
-
-
Non-delecls were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therelore, only EP data are presented.
-------
445
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.1
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
Location
Cyprus-Foote
New Johnsonville, TN
Cyprus-Foote
Sunbright, VA
Cyprus-Foote
Kings Mountain, NC
FMC Corp
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.
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.
-------
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.
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) Process(es)
None Identified.
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.
-------
EXHIBIT 2
LITHIUM CARBONATE FROM SPODUMENE
(Adapted from: Technical Background Document, 1989.)
OfTgases
1
h2so4
OiTgases
1
Limestone
I
Concentrate ^
Roasting/
~
Acid
Leach,
Filtration,
Cooling
Roasting
Neutralization
Washing
Gangiie to Disposal
Na2CO,
i
1120 Process
Wasli
Na-,SO,, to ^
Drying,
Cooling/
I.i2C03
Sale
Dehydration
Filtration
Precipitate
Reduction/
Conversion
t
T
I.i2C03 to
Sale
Lime/Soda
Treatment
Mg, Ca
Removal
i
Mg/Ca
Sludge
to Disposal
livaporator
£
-------
EXHIBIT 3
LITHIUM CARBONATE FROM BRINES
(Adapted from: Technical Background Document, 1989.)
£
00
Lime
Raw
Brine
Solar Evaporation
Sludge Settling
Lime/Soda
Treatment
t
Mg/Ca
Sludge
to Disposal
Mg, Ca
Removal
Evaporatoi s
I
1120 Process
Wash
Na2C03
t
Salt Solutes
to Disposal
Li2C03
Precipitation
u2co,
to Sale
-------
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.
Roaster Off-gases. Sources indicate the following generation rates: 600 ACF/lb, containing 0.01
lb dust/lb. The generated dusts are concentrate fines.11
Acid roaster gases. Sources indicate the following generation rates: 60 ACF/lb, containing 0.001
lb dust/lb. The off-gases contain trace amounts of sulfuric acid and sulfur dioxide.12
Gangue. Sources indicate the following generation rates for gangue: 35 lb/lb, aluminosilicate
residues of concentrate gangue. The solids generated contain 25 lb/lb water with trace amounts of
lithium and other salts."
Magnesium/Calcium sludge. Sources indicate the following generation rates for Mg/Ca sludge:
0.1 lb/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.
11 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.
12 Ibid.
13 Ibid.
14 Ibid.
15 Versar, Inc., "Lithium Derivatives," Multi-media Assessment of the Inorganics Chemical Industry'.
1980, p. 25-7.
-------
450
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.
D. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenvls from electrical transformers and
capacitors.
16 Versar, Inc., 1980, Op. Cit., p. 25-8.
17 Ibid.
-------
BIBLIOGRAPHY
Kunasz, Ihor 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 BeviH 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.
-------
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.
-------
453
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.1
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 machinabilitv,
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 Ibjd.
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.
-------
EXHIBIT I
Summary Of Magnesium Processing Facilities
Facility Name
Location
Type of Operations
Barcroft Co.
Lewes, DE
MgO from seawater
Dow Chemical Co.
Freeport, TX
MgCl from seawater
Great Salt Lake
Ogden, UT
MgCl from lake brine
Marine Magnesium Co.
South San Francisco, CA
MgO from seawater
Martin Marietta Chemicals
Manistee, MI
MgCl from brine
Morton Chemical Co.
Manistee, MI
MgCl from brine
National Refractories & Minerals Corp.
Moss Landing, CA
MgO from seawater
Premier Services Inc.
Port St. Joe, FL
MgO from seawater
Premier Services Inc.
Gabbs, NV
Mine magnesium
carbonate and calcine
to MgO
Reilly Ind.
Wendover, UT
Brine Extraction
EXHIBIT 2
Summary Of Magnesium Metal Processing Facilities
• Facility
Location
Dow Chemical Co.
Freeport, TX
Magnesium Corp. of America
Rowley, UT
Northwest Alloys Inc.
Addy, WA
EXHIBIT 3
Summary Of Magnesia (MgO) Processing Facilities
Facility Name
Location
Type of Operations
Basic Incorporated
Gabbs, NV
Uncertain
Dow Chemical Co.
Freeport, TX
Brine Extraction
Magnesia Operations
San Francisco, CA
Uncertain
-------
455
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 MgCl2 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 MgCI2 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.
4 Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. XIV, 1981, pp. 576-586, 631-635.
5 Ibid.
6 Ibid.
-------
456
EXHIBIT 4
ELECTROLYTIC PRODUCTION USING HYDROUS MAGNESIUM CHLORIDE FEED
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 578.)
-------
457
EXHIBIT 5
ELECTROLYTIC PRODUCTION USING SURFACE AND UNDERGROUND BRINES AS FEED
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 582.)
Subterranean Bnne
11% MgCl,
Surface Brine
1 6% MgCl,
J
Dehydration II
(Thermal)
V
Purification I
J
Dehydration III
(Thermal)
J
Purification II
T
Electrolysis
1
Chlorine
Dehvdration I
NaCI
NaCl
(Solar)
Salt for Sale
Punfication and
Liquefaction
Liquid Chlorine
for Sale
Mg
Refining, Alloying
and Casting
J
Pure Mg Ingots
Alloy Mg Ingots
-------
458
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.
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
fenosilicon 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
7 Ibid.
8 Ibid.
9 Ifeid.
10 Ibid.
-------
459
EXHIBIT 6
THE PIDGEON PROCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 584.)
Raw Materials
Magnesium Crystals
-------
EXXHIBIT 7
MAGNESIA RECOVERY FROM SEAWATER
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 634.)
Waste
Spent Seawater
Washwater
To Sea
-------
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.
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 S02 from flue gas. The flue gas is treated with a magnesium hydroxide slurry in a venturi
scrubber to form MgS03 and some MgS04, 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 the 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 then 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
11 Ibid.
12 Ibid.
13 Ibid.
14 ]bid.
15 Ibid.
-------
462
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 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) Process (es)
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 in Section B.
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
16 Ibid.
17 Ml-
18 Ibid.
-------
463
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 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.
-------
464
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
1991.19 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 have a low pH. This waste is may be discharged to a waste pond.23 Process
wastewater is a RCRA special waste.
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.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 Dust/Sludge is a possible waste stream from magnesium production.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.
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.
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 BeviH 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.
23 U.S. Environmental Protection Agency. Mineral Processing Waste Sampling Survey Trip Reports.
AMAX Magnesium Company, Rowley, Utah. August 30, 1989.
24 Ibid.
25 U.S. Environmental Protection Agency, 1992, Op. Cit., pp. 1-2 - 1-8.
-------
465
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, arid high annual waste
generation rate of 76 metric tons/yr, 760 metric tons/vr, 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. Ancillary 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), 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
waste oil (which may or not be hazardous) and other lubricants.
-------
466
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.
-------
ATTACHMENT 1
-------
468
-------
NUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SMUT (SLUDGE AND DROSS) - MAGNESIUM
Total Constituent
Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
Constituents
Minimum Average
Maximum # Detects
Minimum
Average
Maximum
If Detects
Level
In Excess
Aluminum
-
0/0
-
-
-
0/0
-
-
Antimony
-
0/0
-
-
-
0/0
-
-
Arsenic
-
0/0
0.1
0.375
0.65
2/2
5.0
0
Barium
-
0/0
14.9
81.95
149
2/2
100.0
1
Beryllium
-
0/0
-
-
-
0/0
-
-
Boron
-
0/0
-
-
-
0/0
-
-
Cadmium
-
0/0
0.01
0.0185
0 027
2/2
1.0
0
Chromium
-
0/0
0.023
0.0385
0.054
2/2
5.0
0
Cobalt
-
0/0
-
-
-
0/0
-
-
Copper
-
0/0
0.025
1.2325
2.44
1/2
-
-
Iron
-
0/0
0.22
0.29
0.36
212
-
-
Lead
-
0/0
0.043
1.8415
3.64
2/2
5.0
0
Magnesium
-
0/0
-
-
-
0/0
-
-
Manganese
-
0/0
0.03
0.1
0.17
1/2
-
-
Mercury
-
0/0-
0.0008
0.0009
0.001
2/2
0.2
0
Molybdenum
-
0/0
-
-
-
0/0
-
-
Nickel
-
0/0
-
-
-
0/0
-
-
Selenium
-
0/0
0.013
0.0145
0.016
2/2
1.0
0
Silver
-
0/0
0.05
0.095
0.14
2/2
5.0
0
Thallium
-
0/0
-
-
-
0/0
-
-
Vanadium
-
0/0
-
-
-
0/0
-
-
Zinc
-
0/0
0.02
0.355
0 69
1/2
-
-
Cyanide
-
0/0
-
-
0/0
-
-
Sulfide
-
0/0
-
-
-
0/0
-
-
Sulfate
-
0/0
4
4
4
0/2
-
-
Fluoride
-
0/0
0.2
1.3
24
2/2
-
-
Phosphate
-
0/0
-
-
-
0/0
-
-
Silica
-
0/0
-
-
-
0/0
-
-
Chloride
-
0/0
25600
27150
28700
212
-
-
TSS
-
0/0
-
-
-
0/0
-
-
PH '
-
0/0
212
0
Organics (TOC)
-
-
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.
cn
-------
470
-------
471
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.-5
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.
-------
EXHIBIT 1
Summary of Manganese, Manganese Dioxide, Ferromanganese, and Silicomanganese Producers3
Facility Name
Location
Products
Type of Process
Chemetals Inc.
Baltimore, MD
Mn02
Chemical
Chemetals Inc.
New Johnsonville, TN
Mn02
Electrolytic
Elkem Metals Co.
Marietta, OH
FeMn, SiMn, Mn
Electric Furnace and Electrolytic
Kerr McGee Chemical Corp.
Hamilton, MS
Mn
Electrolytic
Kerr McGee Chemical Corp.
Henderson, NV
MnO,
Electrolytic
Everready Battery Co.
Marietta, OH
MnO:
Electrolytic
3 - 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. 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 C02- 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 C02 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 Ibii, p. 832.
-------
EXHIBIT 2
FERROMANGANESE AND SILICOMANGANESE PRODUCTION
Gas
Ore,
Coke, and
Limestone
Furnace
Ore
and
Coke
T
Slag
la
~ t
Slag Gas
Standard
Ferromanganese
Quartz
Furnace
Standard
Silicomanganese
Standard
Silicomanganese,
quartz, Coke or Coal
Gas
A
Furnace
Low Carbon
Silicomanganese
-------
474
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 3-5 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. 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 MnC03 or Mn(N03)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 MnS04. This treatment removes the excessive quantities of
adherent and bound alkali. KMn04 is added to convert the ion exchanged divalent Mn into Mn02. The
product is washed and dried at low temperature, so as to avoid the undesirable loss of water of
hydration.14
10 Ibid., pp. 834-837.
11 Ibid., pp. 835-836.
12 Ibid., p. 837.
13 Ibid., p. 863.
14 Thirl
-------
475
EXHIBIT 3
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE RAW ORE PRACTICE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
Slag
Discard
-------
EXHIBIT 4
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE FUSED ORE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
Coal
Lime
Mn Ore
I
}
f
I
Molten
Solid
I
I
SiMn
T
I
J
Tilting Furnace
Mn Ore-Lime
Melt
7
Ladle
Medium-Carbon
Ferromanganese
Mn Ore
Quartz
Coal
Slag
I
I
I
Silicomanganese
Smelting Furnace
T
Slag Discard
-------
477
EXHIBIT 5
REFINED FERROMANGANESE PRODUCTION
MEDIUM-CARBON FERROMANGANESE FUSED ORE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1981, pp. 835 - 837.)
-------
478
EXHIBIT 6
MANGANESE METAL PRODUCTION
Manganese Ore
*
Manganese Metal
-------
EXHIBIT 7
PRODUCTION OF ELECTROLYTIC MANGANESE DIOXIDE
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-14.)
20 l'cS (iiapliite Anodes 1,000 I'roilucl
Waste Solids (Solid Waste) Manganese Dioxide
I .andllllcd
lO
-------
480
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)9C03 is
added to precipitate manganese carbonate. The MnCO, is filtered, dried, and roasted in air to produce
manganese dioxide (Mn02) and carbon dioxide (C02).
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 tnanganese 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.18
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.
-------
EXHIBIT 8
PRODUCTION OF CHEMICAL MANGANESE DIOXIDE (TYPE II)
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-16.)
Vent
0-20 1,000 1'roduel
lion Sulfides Manganese. Dioxide
-------
oo
IVJ
EXHIBIT 9
PRODUCTION OF MANGANESE SULFATE (HYDROQUINONE PROCESS)
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-5.)
879 - 1,749
Manganese Dioxide Ore
(Contains 50 - 85% Mn02)
936 Quinone
to Hydroquinone
Manufacture
806
Ajiiiinc
Steam
1,265 .Sulfuric
Acid
~
Solid Waste
130 - 1,000 Oie
Ciangue
1-liter
Vent
livaporator
and
Centiifuge
1,000
MiiS()4
1'iodiict
W.ilci Inline Wastes
10 - 600 (NI1J2S()4 (Aveiage 570)
60 - 500 MiiSO, (Average 300)
23 - 190 I.line
63 - 660 Solid
Waste MnG2
CaSO.
KlTlueiil
30 - 500
(Nl l4)2S04
-------
EXHIBIT 10
PRODUCTION OF MANGANESE SULFATE (ORE-COKE PROCESS)
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, |i|t. 6-7.)
Pmilucl
1,000 MnSO'l
(in 10% Piodticl
which includes
130 - 1,000 of ore
residues )
-------
EXHIBIT II
PRODUCTION OF MANGANESE CARBONATE
(Adapted from: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, pp. 6-9.)
jReaclion MnSO^ + Na3C03 —> M11CO3 + NajSO^
oo
946
Soda Ash
1,000 MnCO,
Pi oducl
Wastewater Containing
1,268 Na2SO^
-------
485
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
Researchers are investigating how to increase recovery of manganese from refractory ores and steel
slag.1920-21
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 in Section B.
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. Carnahan, "CaF2-Enhanced Leaching of a Manganese-Bearing
Silicate Ore," U.S. Bureau of Mines, Report of Investigations 9372, 1991.
20 S.N. Mcintosh, 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;, 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
-------
486
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 beneficiaiion/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. 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/Beneflciation 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. 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.
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.
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488
Iron Sulfide 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 particulate 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 this 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 this material further.
Wastewater. This waste is generated by slurrying the ore residues to the treatment lagoons. After
treatment the slurry water is discharged.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.
24 Ibid.
25 Ibid,, p. 6-13.
26 Ibid.
27 Ibii, p. 6-17.
28 IbicL, p. 6-17.
29 Ibid, p. 6-17.
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489
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.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.
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.
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.
-------
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.
D. Ancillary 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, tank cleaning wastes,
and polychlorinated biphenyls from electrical transformers and capacitors.
36 Ibid.
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491
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. "CaF2-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.
Mcintosh, 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.
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492
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493
MERCURY
A. Commodity Summary
Mercury, also known as quicksilver, is a liquid metal at room temperature, and is used in baiii~n<.o,
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 is
also 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. None of these minerals are currently mined in the United States. Mercury is recovered in
small quantities as a byproduct of gold mining.1 According to the U.S. Bureau of Mines, nine gold
mining operations in California, Nevada, and Utah recovered mercury as a by-product in 1994. as shown in.
Exhibit l.2
EXHIBIT I
Summary of Mines Producing Mercury as a By-Product in I994a b
Company Name
Mine
Location
Barrick Mercur Gold Mines Inc.
Mercur
Toole, UT
FMC Gold Co.
Getchell
Humboldt, NV
FMC Gold Co.
Paradise Peak
Nye, NV
Homestake Mining Co.
McLaughlin
Napa, CA
Independence Mining Co. Inc.
Enfield Bell
Elko, NV
Newmont Gold Co.
Carlin Mines Complex
Eureka, NV
Pinson Mining Co.
Pinson and Kramer Hill
Humboldt, NV
Placer Dome U.S.
Alligator Ridge
White Pine, NV
Western Hog Ranch Go.
Hog Ranch
Washoe, NV
a - "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. Discussion of 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 Repon of
Mineral Industrial Processing Wastes. 1988, pp. 1-2.
2 Jasinski, S.M., "Mercury," from Mineral Commodity Summaries. U.S. Bureau of Mines, January 1995,
p. 108.
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494
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.3-4 The sulfur in the ore is oxidized to sulfur dioxide (S02). Some water
may condense with the mercury and is discharged as a waste stream (labelled 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 S02 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).5
Recovering mercury from gold ore is shown in Exhibit 3, and is similar to recovery from cinnabar
ore. If the gold ore is a sulfide ore, it is typically 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.6
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.7 The exhaust gas from the retort, containing mercury, S02, 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.8
3 Personal communication between ICF Incorporated and Steve Jasinski, U.S. Bureau of Mines, March
1994.
4 Carrico, L.C., "Mercury," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, p. 501.
5 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.
6 Personal Communication between ICF Incorporated and Steven M. Jasinski, November 1994.
7 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.
| UsgJ—~
6 Personal Communication oetween ICF Incorporated ana Steven jM. Jasinski, November 1994.
-------
495
EXHIBIT 2
PRODUCTION OF METALLIC MERCURY FROM PRIMARY MERCURY ORES
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 217S.)
H,0
To Atmosphere
Stack
Gas
Cooling
H,0
Beneficiation
Product —
H,0
Calcmer Wet Air
Pollution Control
(Multistage)
Calcining or
Roasting
Furnace
Calcine
T
Calcined Ore
Waste Product
H,0
Stack
Gas
Liquid Mercury
Product
Condenser
- A
i
i Hg Vapor
Cleaning
Bath
Clean
¦ Mercury
Product
Condenser
Blowdown
-------
EXHIBIT 3
PRODUCTION OF METALLIC MERCURY FROM GOLD ORES
(Source: Personal Communication Between 1CF Incorporated anil Steven M. Jasinski, November 1994.)
to
CTl
Cyclone
. i3
Pretreatinenl
Koa&tkT
•c
Carbon
Condensers
J
$
I
II.O
Wet F.SPs
t
A(|UCOUS
Stream
Mercury
Recovery
Oversow
Storage
IIjU
jS
Cuiblicd
Oie
ir*
Classifier
Concentrator
Atmosphere
Lime S02
Scrubber
Cyanide Solution
1
1 nne SO,
Scmbbei
Impingei
lower
\ endin
Mercury
"g
Condensei
I'utiticalion
Tubes,
Launders
Stoiage
•
' Ik
Agtlaiois
liber
1.lectio-
Heton
Multiple
winning
'
Filler Cake
to
Disposal
Ciudo
Gold
Kceoven
1 mnace
Bullion
Potential Meieuiv Lnmston Souices
-------
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.9 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) Process(es)
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.10 Research is continuing
on the best way to recover mercury from gold and silver solutions for byproduct mercury
production.11,1213
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
9 "Mercury," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd Ed., Vol. XV, 1981, pp. 147-48.
10 Carrico, L.C., 1985, Op. Cit.. p. 501.
11 "Mercury," 1981, Op. Cit.. p. 148.
12 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.
13 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. p. 1.
-------
498
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.
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
Sincemercury is being recovered as a byproduct of other metals, all of the wastes generated during
mercury recovery are mineral processing wastes. For a description of where the beneficiation/processing
boundary occurs for this mineral, see the report for gold presented elsewhere in this document.
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.14
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 waste associated with primary retorting are not included in the tables
summarizing waste stream generation rates and waste characteristics. These waste streams, however, 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.15
No other information on waste characteristics, waste generation, or waste management was available in the
sources listed in the bibliography.
14 Harty, D.M., and P.M. Terlecky, Characterization of Wastewater and Solid Wastes generated in
Selected Ore Mining Subcategories. CSb. He. Al. V. W. Ni. TiV U.S. Environmental Protection Agency,
August 21, 1981, pp. 11-36 - 11-40.
15 U.S. Environmental Protection Agency, Newlv Identified Mineral Processing Waste Characterization
Data Set. Volume I, Office of Solid Waste, August 1992, p. 1-6.
-------
S02 Scrubber Effluent. Approximately 3,000 metric tons of S02 scrubber effluent 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.
Particulate 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.17 No other information on waste characteristics, waste generation, or waste
management was available in the sources listed in the bibliography.
Lastly, no information on waste characteristics, waste generation, or waste management was
available in the sources listed in the bibliography for the wastes listed below.
Cleaning Bath Water
Condenser Slowdown
Stack Gas Cooling Water
Calciiier Quench Water
Byproduct Retorting. The wastes produced in byproduct retorting will vary greatly depending on the input
materials. It is possible that the wastes may contain other metals.
Dust Approximately 10 metric tons of dust are produced annually in the U.S..18 Although no
published information regarding waste characteristics was found, we used best engineering judgement to
determine that this waste may exhibit the characteristics of toxicity for mercury. We also used best
engineering judgement to determine that this waste stream may be partially recycled. This waste stream is
classified as a sludge.
Furnace Residues. Approximately 100 metric tons of furnace residues are produced annually in
the United States.19 Although no published information regarding waste characteristics was found, we
used best engineering judgement 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 quench water 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 81,000 mt/y, 99,000 mt/y, and 540,000 mt/y, respectively.
This waste may be toxic for lead and mercury. This waste stream is classified as a spent material.
16 Ibid.
17 Ibid.
18 Ibid.
19 Ibid.
-------
500
D. Ancillary 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, 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.
-------
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 Subcategories, ("Sb. Hg, Al, V, W. Ni. TiY 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 arid 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 arid 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.
-------
502
-------
MOLYBDENUM, FERROMOLYBDENUM, AND AMMONIUM MOLYBDATE
A. Commodity Summary
Almost all molybdenum is recovered from low-grade deposits of the mineral molybdenite, which, is
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 molvbdic 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 Producers3
Facility Name
Location
Cyprus-Climax - Henderson
Empire, CO
Cyprus-Climax
Fort Madison, LA
Cyprus-Climax
Clear Water, MI
Cyprus-Climax - Green Valley
Tucson, AZ
Cyprus-Climax
Bagdad, AZ
Kennecott
Bingham Canyon, UT
Kennecott
Salt Lake City, UT
Montana Resources Inc.
Butte, MT
Phelps Dodge i
Chino, NM
San Manuel
San Manuel, AZ
San Manuel
Morenci, AZ
Thompson Creek
Chalis, ID
Thompson Creek
Langeloth, PA
Personal 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 pf 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
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.
-------
504
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.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Molybdenum and molybdenum products, including ammonium molvbdate, 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 reductant. These processes are described in greater detail below.
2. Generalized Process Flow Diagram
Molybdenum Metal and Ammonium Molvbdate
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 the
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 - 95 percent Mo03, 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 the
concentrates.8 The roasting process removes sulfur and converts the sulfide to oxide. The flue gas
contains products of combustion, S02, and may contain rhenium or selenium. The S02 in the flue gas is
converted to sulfuric acid (H2S04).9 More information on the processing of the flue gas, and the
production of sulfuric acid can be found in the 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
4 Ibidy p. 850.
5 "Molybdenum and Molybdenum Alloys," from Kirk-Othmer Encyclopedia of Chemical Technology.
3rd ed., Vol. XV, 1981, p. 670.
6 Blossom, J. W„ 1992, Op. Cit.. p. 850.
' 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.
-------
Gas
i
Rhenium
Recovery
Scrubber
Molybdenum
Sulfide
Concentrate _
Molybdenum
Sulfide
Concerilrale
Wastewater
S02 Scmhbei
or Acul Mailt
i
Gas
EXHIBIT 2
MOLYBDENUM PRODUCTION
(Source: Development Document for Effluent Limitation!* Guidelines, 1989, p. 3370.)
- Wastewater
Wastewater
I'urc Molvhdic
Sublimation
0\ide
Reduction
I'urnace
Mol\l>dciHiiii
Metal
Powder
Acid •
Water
Ammonium
Molvbdatc
Wastewatei
n
i
i'uie MoKIhIk- W'.ilei
()\ide Nil,Oil
n
\l IIII loilllll 11
MoKhil.ilc
Solvent
l\ti action oi
Ion l-Achaiiye
Wiiblcwalci
Dissaving,
CrYslnfliznUnn
Cnidc
Ammonium
I'ciilieuale
I'm ilication,
Reduction
1.caching
I'iiic Molvhdic
(Kide ^
Dissolution,
Ammonium
Molybdale
Calcining
Rhenium Meta
Crystallization
l\iic
Mol\ hdu
( Hide
Ln
O
LD
-------
506
cooling ducts and the condensed oxide particles are collected in a fabric filter. The purified oxide contains
greater than 99.5 percent M0O3. 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.11
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
Ferromolvbdenum
Exhibit 3 illustrates the production of low carbon and high carbon ferromolybdenum. Low carbon
ferromolvbdenum 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 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.14
Low carbon ferromolybdenum produced by the thermite process is more common than the high carbon
alloy.
3. Identification of Novel or Distinct Process(es)
One researcher has investigated the separation and recovery of critical metals (including
molybdenum) from mixed and contaminated superalloy scrap.15
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 IbicL, p. 3-154. •
15 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.
-------
EXHIBIT 3
FERROMOLYBDENUM PRODUCTION
Aluminum, Technical Grade Molvbdic Oxide,
FeiTosilicon, Iron Oxide, Limestone. Lime and Fluorspar
Slag
Low Carbon Ferromolvbdenum
Technical Grade Oxide, Iron, Calcium or
Sodium Molybdate, Carbon
High Carbon Ferromolvbdenum
-------
4. Extraction/Beneficiation 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 meiting 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 Section B.
Molybdenum Powder
EPA determined that for the production of molybdenum powder, the beneficiation/processing line
occurs between the roasting and sublimation steps since leaching does not follow and because the molybdic
sulfate is chemically roasted to pure molybdic oxide. 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 Molvbdate and Pure Molvbdic 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.
Ferromolvbdenum
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 ferromolybdenum.
-------
509
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.16,17 The tailings from molybdenite
concentration are not eroected to exhibit any hazardous characteristics, but metal leaching and acid
formation are possible.
2. Mineral Processing Wastes
Ammonium Molvbdate Refining
Refining Wastes. Available data do not indicate that ammonium molybdate refining wastes exhibit
any hazardous characteristics.19 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.20 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.21 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.22 Silicon was found at a concentration of 10 percent in solids from the quench and
scrubber towers/thickener.23 Therefore, the Agency did not evaluate this material further.
16 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.
17 Weiss, Norman L., Ed. "Molybdenum," SME Mineral Processing Handbook, Volume II, Society of
Mining Engineers, 1985, pp. 16-1 - 16-36.
18 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-152.
19 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste Characterization
Data Set, Volume I, Office of Solid Waste, August 1992, p. 1-2.
20 Ibjda p. 1-6.
21 Ibid,, Vol. II, p. 28-11.
22 Ibid^ Vol. I, p. 1-6.
?3 Ibid.; Vol. II, p. 28-8.
-------
510
Solid Residues. Available data do not indicate that solid residues exhibit any hazardous
characteristics (see Attachment l).24 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.25 Therefore, the Agency did not evaluate this material further.
Molybdic Oxide Refining Wastes. Approximately 2,000 metric tons of molybdie oxide refining
wastes are generated annually in the United States.26 This waste may exhibit the characteristic of toxicity
for mercury,2' and is not recycled.
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 S02. These metals may include lead, zinc, tin
and others.28 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 1,200 metric tons/yr, 270,000 metric tons/yr, and 540,000 metric tons/yr, respectively.
We used best engineering judgement to determine that this waste may exhibit the characteristic of toxicity
for lead. This waste is not recycled.
Metal Refining
Refining Wastes. Available data do not indicate that metal refining wastes exhibit any hazardous
characteristics. Therefore, the Agency did not evaluate this material further.
H2 Reduction Furnace Scrubber Water. Existing data and engineering judgement suggest that this
material does not exhibit any characteristics of hazardous waste (see Attachment 1). Therefore, the
Agency did not evaluate this material further.
Ferromolvbdenum 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.30 Therefore, the Agency did not evaluate this material further.
24 Ibidy Vol. II, p. 1-6.
25 Ibid.
26 Ibid.
27 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.
28 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-153.
y?s> tnvaronmental Rrotection-Asencv. 4992, Op. Cit. Vol. I, p. 1-6.
w Ibid., p. 1-4.
-------
Slag. This waste, formed in either the production of low carbon ferromolybdenum or high carbon
ferromolybdenum, is not expected to exhibit any hazardous characteristics. The slag is usually
discarded.31 Therefore, the Agency did not evaluate this material further.
D. Ancillary 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, 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.
31 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-154.
-------
BIBLIOGRAPHY
Blossom, J. W. "Molybdenum." From Mineral Commodity Summaries. U.S. Bureau of Mines. January'
1995. pp. 114-115.
Blossom, J. W. "Molybdenum." From1 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. Am ax Incorporated. Fort Madison. LA: 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, LA. 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. Newlv 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.
-------
513
Weiss. Norman L., Ed. "Molybdenum." SME Mineral Processing Handbook. Vol. [I Snne.rv nf Mining
Engineers. 1985. pp. 16-1 - 16-36.
-------
514
-------
515
ATTACHMENT 1
-------
516
-------
SOKiiwrtflY'OF'EPAyORD* 3007. AND RTI SAMPLING DATA - LIQUID RESIDOEbMOLYBDENUM OXIDE
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum tt Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
# Detects
TC
Level
U Values
In Excess
Aluminum
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
60.00
60.00
60.00
1/1
-
0/0
5.0
0
uarium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
1.20
1.20
1.20
1/1
-
0/0
1.0
0
Chromium
1.80
1.80
1.80
1/1
-
0/0
50
0
Gooan
-
-
-
0/0
-
0/0
-
-
'Copper
-
-
-
0/0
-
0/0
-
-
tfon
-
-
-
0/0
-
0/0
-
-
L'ead
5.80
5.80
5.80
1/1
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
100
100
100
1/1
-
0/0
-
-
Nickel,
-
-
-
0/0
-
0/0
-
-
Selenium
32.00
32.00
32.00
1/1
-
0/0
1 0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
vanadium
-
-
-
0/0
-
0/0
-
-
zinc
-
-
-
0/0
-
0/0
-
-
eyaniae
--
-
-
0/0
-
0/0
-
-
Suinae
-
-
-
0/0
-
0/0
-
-
SUItate
-
-
-
0/0
-
0/0
-
-
FiUbride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
-
-
-
0/0
-
0/0
-
-
pH •
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects ware assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; thamiore, only EP data are presented.
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SOLID RESIDUES - MOLYBDENUM OXIDE
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
# Values
In Excess
Aluminum
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
_
_
Copper
-
-
-
0/0
-
0/0
-
-
Iron
-
-
-
0/0
-
0/0
-
-
Lead
-
-
-
0/0
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
—
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
_
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
_
_
Vanadium
-¦
-
-
0/0
-
0/0
-
-
Zinc
-
-
-
0/0
_
0/0
-
_
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
_
Sulfate
-
-
-
0/0
_
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
_
0/0
-
-
Silica
100,000
100,000
100.000
1/1
_
0/0
_
_
Chloride
-
-
-
0/0
_
0/0
_
_
TSS
-
-
-
0/0
_
0/0
-
-
PH*
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit TCLP data are currently unavailable; therelore, only EP data are presented.
-------
SUN.. MY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - H2 REDUCTION I-_ JACE SCRUBBER WATER - MOLYBDENUM
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
# Values
Constituents
Minimum
Average
Maximum
§ Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.001
0.0090
0.024
3/3
-
-
0/0
-
-
Arsenic
0.002
0.0107
0.024
3/3
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.001
0.0023
0.005
3/3
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.001
0.0010
0.001
3/3
-
-
0/0
1.0
0
Chromium
0.001
0.0040
0.006
3/3
-
-
0/0
5.0
0
Cooait
-
-
-
0/0
-
-
0/0
-
-
Copper
0.004
0.3947
0.64
3/3
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.001
0.0657
0.17
3/3
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0002
0.0002
3/3
-
-
0/f1
0.2
0
Molybdenum
-
-
-
0/0
-
-
0
-
-
Nickel
0.024
1.1613
2.8
3/3
-
-
01J
-
Selenium
0.001
0.0010
0.001
3/3
-
-
0/0
1.0
0
Silver
0.001
0.0053
0.014
3/3
-
-
0/0
5.0
0
Thallium
0.001
0.0010
0.001
3/3
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.51
0.5733
0.63
3/3
-
-
0/0
-
-
Cyanide
0.01
0.0100
0.01
3/3
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoriae
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
pH*
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed lo be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
520
-------
521
PHOSPHORIC ACID
A. Commodity Summary
About 95 percent of the commercial grade wet-process phosphoric acid is used to produce
fertilizers and animal feed, with a small portion used as a feedstock in chemical processing operations.
Typically, the fertilizer and feed plants are co-located with the phosphoric acid facilities.1 Phosphoric
acid producing facilities are listed in Exhibit 1.
EXHIBIT 1
Summary Of Phosphoric Acid Producing Facilities
Facility Name
Locations
Type of
Operations
Potential Factors Related to
Sensitive Environments
Agrico Chem
Pierce, FL
Uncle Sam, LA
Donaldsonville, LA
' Wet Process
Wet Process
Wet Process
Uncertain
Uncertain
Uncertain
Albright & Wilson
Fernald, OH
Charleston, SC
Furnace
Furnace
Uncertain
Uncertain
Arcadian
Geismar, LA
Wet Process
Located in 100-year
floodplain, within 1 mile of
wetland
Cargill
Riverview (Tampa), FL
Wet Process
Located in 100-year
floodplain, located in
wetland
Central Phosphates
Plant City, FL
Wet Process
Within 1 mile of wetland,
located in area,of karst
terrain
CF Ind.
Bartow, FL
Wet Process
Uncertain
Chevron
Rock Springs, WY
Wet Process
Uncertain
Conserv
Nichols, FL
Wet Process
Within 1 mile of wetland
Farmland
Pierce (Bartow), FL
Wet Process
Within 1 mile of wetland
FMC
Carteret, NJ
Lawrence, KS
Newark, CA
Furnace
Furnace
Furnace
Uncertain
Uncertain
Uncertain
Gardinier, Inc.
Riverview, FL
Wet Process
Uncertain
Hydrate
Milwaukee, WI
Furnace
Uncertain
IMC
Mulberry, FL
Wet Process
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.
-------
EXHIBIT 1 (continued)
Facility Name
Locations
Type of
Operations
Potential Factors Related to
Sensitive Environments
JR Simplot
Pocatello, ID
Wet Process
Located in 100-year
floodplain, located in fault
zone
Mobil
Pasadena, TX
Wet Process
Located in 100-year
floodplain
Monsanto
Trenton* MI
Augusta, GA
Carondelet, MO
Long Beach, CA
Furnace
Furnace
Furnace
Furnace
Uncertain
Uncertain
Uncertain
Uncertain
Nu West
Soda Springs (Conda), ID
Wet Process
Uncertain
Nu South
Pascagoula, MS
Wet Process
Occidental
Jeffersonville, IN
Columbia, TN
White Springs, FL
Dallas, TX
Furnace
Furnace
Wet Process
Furnace
Uncertain
Uncertain
Located within 1 mile of
wetland
Uncertain
Royster
Palmetto (Piney Pt.), FL
Wet Process
Located within 6.5 miles of
endangered species habitat,
within 1 mile of wetland,
located in area of karst
terrain
Mulberry, FL
Wet Process
Located within 1 mile of
wetland
Seminole
Bartow, FL
Wet Process
Located in endangered
species habitat, located in
100-year floodplain, within 1
mile of wetland
Stauffer
Morrisville, PA
Nashville, TN
Richmond, CA
Chicago Heights, IL
Chicago, IL
- Furnace
Furnace
Furnace
Furnace
Furnace
Uncertain
Uncertain
Uncertain
Uncertain
Uncertain
Texasgulf
Aurora, NC
Wet Process
Located in 100-year
floodplain, located in
wetland
US Agri-Chemicals Corp
(USAC)
Ft. Meade, FL
Wet Process
Within 1 mile of wetland
Uncertain
-------
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, and a -brief discussion of the
furnace process is provided in Section 2. (The furnace process uses a refined mineral commodity 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
L. Discussion of the Typical Production Processes
The wet process methods include digestion, filtration, and concentration. Phosphate rock is
dissolved in phosphoric acid, to which sulfuric acid is added. The sluny 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
The wet process for phosphoric acid production consists of three operations: digestion, filtration,
and concentration. As shown in Exhibit 2, 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, 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.
-------
EXHIBIT 2
PHOSPHORIC ACID TREATMENT
(Adapted from: Report to Congress on Special Wastes from Mineral Processing, July 1990, pp. 12-1 - 12-61.)
Beneficiated
Phosphate
Sulfuric Acid Rock (BPR)
I -
Phosphoric Acid
Production
Digestion
Filtration
Uranium
Extraction
(Optional)
Defluorination
(Options)
Concentration
BPR
Super
Phosphate
Acid
Production
(Optional)
Super
Phosphoric
Acid
Merchant Grade
Phosphoric Acid
Process
Process Wastewater
Phosphogypsum
Process
Wastewater
Hydrofluosilicic Acid
(Optional)
Phosphoric
Acid
1
Non-Ammoniated
Animal Feed
(Optional)
1
Special Waste
Management
BPR
Limestone
and/or
Soda Ash
Animal Feed
Process
Wastewater
l~ G\psum |
| Stack j
I
Process
Wastewater
Storage
Surface I
| Impoundment |
?
Return
to
Production
N'PDES
Discharge
Production Operation
Special Waste
I ' Waste Management Unit
-------
525
EXHIBIT 3
SOLVENT EXTRACTION PURIFICATION OF WET-PROCESS PHOSPHORIC ACID
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1982, pp. 426 - 442.)
Solvent
Fertilizer Product
-------
526
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 since 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. They are mostly based 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 H3P04 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 P205 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
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
None identified.
4. Extraction/Beneficiation 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.,
6 Ibid.
7 Ibid.
8 Ibid.
9 Ibid.
10 Ibid.
-------
527
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 Section B.
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 refined mineral commodity
(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 principle processes 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-cooled, (3) air-cooled; depending on the method used to protect the
combustion chamber wall. 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
11 Ibid.
-------
528
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.12
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.13
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.14
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 P205 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 H3P04 leaves the hydrator
through a heat exchanger.15
The P2Os initially is hydrated and absorbed in the hot gas stream by direct contact with relatively
strong acid. Tliis is often followed by successive stages of scrubbing with progressively more dilute acid
and finally, with incoming make-up water.16
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) Process(es)
None identified.
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.
12 Ibid.
13 Ibid.
14 Ibid.
15 Ibid.
16 Ibid.
-------
EXHIBIT 4
FURNACE-GRADE PHOSPHORIC ACID PROCESSES
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1982, pp. 426 - 442.)
Atomizing
Air
Phosphorous
Combustion
Aii-
Product
Acid
Phosphorous
A"
A
Combustion
Air
Exit Gas
¦ to
Hvdrator
(a) Wetted-Wall Combustion Chamber
(b) Air-Cooled Combustion Chamber
Cooling
Water
Overflow
Phosphorous
Atomizing
Air
To
Hvdrator
Phosphorous
Combustion
Gas
A A
A A"
A—A
To Nlist Collector
.Weak Acid from
Mist Collector
Product Acid
Cooling
Water
Heat
Exchanger
(c) Water-Cooled Combustion Chamber
,(d) Hvdrator/Absorber
-------
SECTION 3. ANCILLARY PROCESSES
Feed and fertilizer plants as well as sulfuric acid plants are often 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. These ancillary
processes use a refined mineral commodity and are therefore, 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.17
Animal Feed Production
Ammonia is reacted with defluorinated P205 to produce the defluorinated ammonium phosphates
Monofos and Duofos. Limestone is reacted with defluorinated P2Os to produce the defluorinated calcium
phosphates Dynafos and Biofos. IMC in Mulberry, FL produces up to 2,500 tons per day of these
products.18
Superphosphoric Acid Operations
Superphosphoric acid is produced from concentrated (54 percent) acid by heating it in a shell and
tube exchanger, routing 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.19
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.20
Silicofluoride Recovery
In order to produce low-fluorine animal feed supplements, P205 must be defluorinated. IMC in
Mulberry, Florida defluorinates 600 tons per day of 54 percent P2Os in a batch tank using silica to remove
fluoride. IMC uses 16,000 gallons per minute of cooling pond water to condense vapors, which contain
SiF4 and P2Os, 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
17 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.
18 Ibid., pp. A2-6.
19 Ibid.
20 Ibid.
-------
531
EXHIBIT 5
OVERVIEW OF PHOSPHORIC ACID PRODUCTION AND RELATED PRODUCTS MANUFACTURE
(Adapted from: Supplemental Information on Phosphoric Acid Production, 1990, pp. A2 - 11.)
H,0
H,0
H.O
-------
532
is returned to the cooling pond.21 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.22 Gardinier
in Riverview, Florida also recovers FSA and in 1992 supplied 70 percent of the domestic market for
drinking water fluoridation.23 Agrico in Uncle Sam, Louisiana collects FSA and either sells it or
processes it in an on-site plant to produce silicon tetrafluoride.24 Agrico in Donaldsonville, LA sells the
recovered FSA
Multifos Plant
IMC reacts non-defluorinated 54 percent P205, 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.25
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, freshwater 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.26 IMC in Mulberry, Florida produces 13,000 tons per day of
98.5 percent sulfuric acid.27 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.28 Gardinier in Riverview, Florida also manufactures sulfuric
acid for the wet process.29
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
None identified.
21
Ibid., pp. A2-6.
22
Ibid., pp. A3-4.
23
Ibid., pp. A4-3.
24
Ibid., pp. A5-4.
25
Ibid.
26
Ibid., pp. Al-3.
27
Ibid., pp. A2-3.
28
Ibid., pp. A3-2.
29
Ibid., pp. A4-2.
-------
4. Extraction/Beneficiation Boundaries
These processes use a refined mineral commodity and as such, are completely outside the scope of
the Mining Waste Exclusion.
C. Process Waste Streams
1. Extraction/Beneficiation 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.
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.30 This waste is not expected to be hazardous.
3. Other Related Wastes
Based on existing data and engineering judgement, none of the wastes listed below are expected to
be hazardous mineral processing wastes. Therefore the Agency did not evaluate these wastes further.
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 sulfide sludge. Approximately 0.28 kg per kkg of product of arsenic sulfide is formed
during product purification.31
Spent filter cake is a possible waste stream generated from the production of phosphoric acid by
the furnace process.
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.32 This wastewater may be discharged to a cooling pond and may have a low pH.
30 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.
31 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.
32 Ibid.
-------
534
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.33
Superphosphoric Acid Production
Sludge is a likely waste stream from superphosphoric acid production.
Silicofluoride Recovery
Filter cake.
Process wastewater.
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.34 IMC in Mulberry, Florida and USAC in Ft. Meade, Florida create a cooling tower blowdown of
pH 7 and a boiler blowdown of pH 11-12. USAC 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.35
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous) and other lubricants.
33 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.
34 U.S. Environmental Protection Agency, Op. Cit„ 1990, pp. Al-3.
35 Ibid., pp. A2-3.
-------
535
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. I. 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. III. 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. Chapter 8.
-------
536
-------
537
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." 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 reduction4, and platinum is used in both automobile oxygen
sensors and spark plugs.5
EXHIBIT 1
Summary of Platinum-Group Metals Processing Facilities
Facility Name
Location
Type of Operations (source)
Stillwater Mine
Nye, MT
Mining and Beneficiation3
Allied Signal
Tulsa, OK
Secondary (spent automotive catalysts)
Allied Precious Metals
Tucson, AZ
Secondary (solutions and sludges)
ASARCO
Amarillo, TX
Secondary
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.
-------
538
EXHIBIT 1
Summary of Platinum-Group Metals Processing Facilities (continued)
Facility Name
Location
Type of Operations (source)
AT & T Metals
Staten Island, NY
Secondary (electronic scrap)
Colonial Metals
MD
Secondary (spent industrial catalysts)
Degussa Corp.
South Plainfield, NJ
Secondary (solutions, electronic scrap, catalysts)
Eastern Smelting and
Refining Corp.
Lynn, MA
Secondary (solutions, sludges, catalysts)
Engelhard Corp
Iselin, NJ
Secondary (spent industrial catalysts, electronic
scrap)
Gemini Industries
. Santa Ana, CA
Secondary (spent industrial catalysts, petroleum
catalysts)
Handy and Harman
Fairfield, CT
Secondary
Handy and.Harman
South Windsor, CT
Secondary (filter cake, metallic scrap, spent
automotive catalysts)
Hauser & Miller
St. Louis, MO
Secondary
JM Ney Co
Bloomfield, CT
Secondary
Johnson Matthey
West Deptford, NJ
Secondary (filter cake, spent automotive catalysts,
solutions, unrefined ingot)
Kinsbursky Brothers
Anaheim, CA
Secondary (solutions, electronic scrap, spent
automotive catalysts)
Kennecott Copper
Salt Lake City, UT
Secondary
Leach and Garner
Attleboro, MA
Secondary
Leytess Metal and
Chemical
New York, NY
Secondary
LG Balfour CO
Attleboro, MA
Secondary
Martin Metals
Los Angeles, CA
Secondary (electronic scrap, solid scrap)
McRilley Mark Co.
CA
Secondary
Multimetco, Inc.
Anniston, AL
Secondary (spent automotive catalysts)
Noranda/Micrometallics
Corp.
San Jose, CA
Secondary (electronic scrap, filter cakes, sludges,
solutions, catalysts, filter media)
Noranda Sampling
Providence, RI
Secondary (electronic scrap, solid scrap)
-------
539
EXHIBIT 1
Summary of Platinum-Group Metals Processing Facilities (continued)
Facility Name
Location
Type of Operations (source)
PGP Industries, Inc.
Santa Fe, CA
Secondary (spent industrial catalysts, sludges,
electronic scrap)
Sabin Metals
Rochester , NY
Secondary (electronic scrap, filter cakes, solid
scrap)
Sipi Metals
Chicago, IL
Secondary (electronic scrap)
Southwest Smelter &
Refining
Dallas, TX
Secondary
Stern Metals
Attleboro, MA
Secondary
Techamet, Inc.
Houston, TX
Secondary (spent automotive catalysts, petroleum
catalysts)
Technic, Inc.
Providence, RI
Secondary
Texas Instruments
•MA
Secondary
Trifari, Krussmari
Providence, RI
Secondary
William Gold Refining
Buffalo, NY
Secondary
a Stillwater Mines sends the ore to their smelter facility in Columbus. MT."
After the ores have been smeltered, 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.7
B. Generalized Process Description
1. Discussion or Typical Production Processes
Platinum-group metals can be recovered from a variety of different sources, including electrolytic
slimes from copper refineries or metal ore. 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, smelting, and refining. In the
concentrating step, platinum ore is crushed and treated by froth flotation. The concentrates are dried.
6 Personal Communication between Jocelyn Spielman, ICF Incorporated and J. Roger Loebenstein,
U.S. Bureau of Mines. October 17, 1994.
7 Ibid.
-------
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.8 Secondary platinum group metals recovered from scrap and spent catalysts are
refined and used in the fiber glass industry and various catalytic applications.
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.9
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.10
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 panicles by conventional gravity methods. The remainder is further
concentrated by smelting, oxygen blowing, magnetic separation, and pressure leaching.
8 J. Roger Loebenstein, 1992, Op. Cit.. pp. 995-996.
9 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-159.
10 Personal Communication between Jocelyn Spielman, ICF Incorporated and J. Roger Loebenstein
U.S. Bureau of Mines, October 17, 1994.
-------
541
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
Heireshoff Furnace
H,S04
Scrubber Mud
1
TT
Dried Slime
Acid Digesters
Gas
Scrubber and Cottrell
^Solution ^rude Se
To Selenium Plant
Fume
I
SO,
Waste
Chain Roaster
T
Scrap Copper
I
Leach
Leach Tanks
Liquor
T
Cementation Tanks
NaOH
H,0
Holding Tanks
TT
Cement Silver
Leach Liquor to
CuS04 Plant or
Luberator Cells
I
h:so4
Gas
t
Caustic
Caustic Leach Tanks
Solution
Fluxes
Scrubber and Cottrell
^Solution
To Selenium Plant
Gases
Neutralization Tanks
Caustic
Slimes
Dore' Furnace
To Anode
Furnace ^
Slag
Soda Slag
^Te-Pb Mud
H.O
Slag Leaching Tank
Dore' Anodes
Solution^
Residue
"Anode Plant
— H;S04
*
Neutralization Tank
Parting Plant
~
^Solution
Neutralized
Mud
To Se Plant To Te Plant
Platinum Group Metals
-------
542
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
fnade 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 treatment.11
Refining
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.12 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 orsulfur dioxide. Solvent extraction is used as an alternative method for
separating gold at some refineries.13 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, osmitim, 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.1'4
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.
11 "Platinum-Group Metals," Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. XVIII,
1982, p. 234.
12 Personal Communication between Jocelyn Spielman, ICF Incorporated and J. Roger Loebenstein,
U.S. Bureau of Mines, October 17, 1994.
13 "Platinum-Group Metals," 1982, Op. Cit.. p. 238.
14 Ibid.
15 Ibid.
-------
EXHIBIT 3
PLATINUM GROUP METAL REFINING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology', 1982, pp. 228 - 239.)
Platinum Metal
Concentrates
j^Aqua Regia
-------
544
EXHIBIT 3 (Continued)
I
-------
545
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.16
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(N02)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.17
Ruthenium
The ruthenium, osmium, and iridium 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.18
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 iridium 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 iridium 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.19
16 Ibid.
17 Ibid.
18 Ibid.
19 Ibid.
-------
546
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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 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 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.
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547
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.
S02 Waste. As shown in Exhibit 2, waste sulfur dioxide is produced from acid digestion.
Smelting
Slag. The slag generated during smelting is likely to contain metallic panicles 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 tonstyr, 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.
Refining
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. TTie resultant wastes from
these processes would most likely be spent acids which might contain residual metals21
Although no published information regarding waste generation rate or characteristics was found,
20 Gregg J. Hodges, et. al., "Stillwater Mining Co.'s precious metals smelter: From pilot to production,
Mining Engineering, July 1991.
21 U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-162.
-------
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 thiswaste may exhibit
the characteristics of toxicity (lead and silver), conosivity, and reactivity.
D. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
-------
549
BIBLIOGRAPHY
Hodges, G., G. Roset, 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, 1CF 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.
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.
-------
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.1 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
Pyrobitumens
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 pyrobituinens 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
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.
-------
(Adapted from:
EXHIBIT I
PYROBITUMEN PROCESSING
1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988.)
Pyrobi turn ens
Cracking
Still
(1) Waste Catalyst
(2) Still Bottoms
Pyrobitumen
Products
-------
553
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
-------
EXHIBIT 3
NATURAL ASPHALT PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988.)
Rock
Asphalt
T
-------
555
known as "Montan Wax." Extraction solvents used in the production of mineral waxes may be listed in 40
Cre 261 Subpart D.3
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 binsv 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 panicle 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
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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, processinjg activities often destroy the physical and
chemical structure of the incoming ore or mineral feedstock such that the materials leaving the operation
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.
4 Harry D. Lewis, "Gilsonite," from Industrial Minerals and Rocks. Society of Mining, Metallurgy, and
Exploration, 1994, pp. 535-541.
-------
556
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 Section B.
Pvrobitumens
EPA determined that for pvrobitumens, 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
Pvrobitumens
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
Pvrobitumens
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.
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557
Waste catalyst. 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, 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
None identified.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants.
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558
BIBLIOGRAPHY
"Asphalt." Kirk-Qthmer 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-Qthmer 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.
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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. Since 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 which 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. 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.
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 fractional crystallization and precipitation, solvent extraction, ion exchange, and reduction.
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.2
2. Generalized Process Flow
Mining
Because rare earth elements are often associated with the radioactive elements uranium and
thorium, many rare-earth deposits are discovered during exploration for these elements.
At Mountain Pass, Molycorp mines rare earth ore in an open pit approximately 100 m deep. Blast
holes drilled at 3 to 4 m spacing are routinely assayed for total rare earth oxides and other elements by
X-ray 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 kt and fed to a mill located less than
1 James Hedrick, "Rare Earths," from Mineral Commodity Summaries. U.S. Bureau of Mines, January
1995, pp. 134-135.
2 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.
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560
EXHIBIT 1
Summary Of Rare Earths Processing Facilities
Facility Name
Location
Products
Associate Minerals
Green Cove Springs, FL
Uncertain
Crucible Materials
Elizabethtown, KY
Rare earth magnets
Delco Remy
Division of General Motors
Anderson, IN
Rare earth magnets, neodymium-iron-
boron magnet alloys
Hitachi Magnetics
Edmore, MI
Rare earth magnets
IG Technologies
Valparaiso, IN
Rare earth magnets
Molycorp
York, PA
Louviers, CO
Washington, PA
Mountain Pass, CA
Canton, OH
Neodymium-iron-boron magnet alloys
Uncertain
Uncertain
Bastnasite mine
Uncertain
Mountain Pass Mine & Mill
Mountain Pass, CA
Uncertain
Neomet
West Pittsburgh, PA
Neodymium-iron-boron magnet alloys
Nord Resources
Jackson, NJ
Uncertain
Reactive Metals & Alloys Corp.
West Pittsburgh, PA
Mischmetal
/
Research
Phoenix, AZ
Uncertain
RGC (USA) Mineral Inc.
Green Cove Springs, FL
Byproduct monazite
Rhone-Poulenc Chemicals Co.
Phoenix, AZ
Mineville, NY
Freeport, TX
Neodymium-iron-boron magnet alloys
Uncertain
Uncertain
W.R. Grace
Chattanooga, TN
Uncertain
100 m from the pit.3 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.4
3 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.
4 U.S. Bureau of Mines, Rare Earths Annual Report, 1993.
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561
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 a series of wet gravity equipment that includes 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.
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
As Exhibit 2 shows, rare earth metals are recovered as oxides from monazite ore by sulfuric acid
digestion. The ore undergoes grinding, spiraling, or other similar operations for the initial coarse
purification of the ore. Magnetic separation removes the 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 then 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.6
Bastnasite Ore Processing
As shown in Exhibit 3, to recover rare earth chlorides from bastnasite ore, the ore is crushed,
ground, classified, and concentrated to increase the rare earth concentrations. Tailings produced during
these operations are discarded as waste. The concentrated bastnasite undergoes an acid digestion to
produce several rare earth chlorides; hydrochloric acid is used to digest the bastnasite. The resulting slurry
is filtered, and the filter cake is further digested with sodium hydroxide to produce rare earth hydroxides.
This rare earth hydroxide cake is chlorinated, converting the hydroxide to chlorides. Final filtration and
evaporation yields the solid rare earth chloride products. The wastes produced include a sodium fluoride
filtrate, which can be recovered for further processing, and filter cake which is discarded.7
5 Stephen B. Castor, "Rare Earth Minerals," from Industrial Minerals and Rocks. 6th ed., Society for
Mining, Metallurgy, and Exploration, 1994, pp. 827-837.
6 U.S. Environmental Protection Agency, "Rare Earths," from 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. 1988, pp. 3-164 - 3-174.
Ibid
-------
562
EXHIBIT 2
RECOVERY OF RARE EARTHS FROM MONAZITE BY THE SULFURIC ACID PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
h,so4
Cold Water -
Moazamte Ore
j
Spirals
T
T
Slurry
Dissolution of
Rare Earths and
Thorium Sulfates
J
Filtration
^Filtrate
Double Sulphate
Precipitation
J
Filtration
• Waste Tailings
Magnetic
Magnetic
Separation
Fractions
1
Grinding
1
Digestion
200-220 °C
Waste Monazite
Solids
NaOH and Water
I
Cake
^Filtrate
Caustic
Digestion
^Slurrry
Recovery of
Thorium and Minor
Rare Earth Fractions
Filtration
T
Rare Earth
Hydroxide Cake
Waste
Fihraxe
-------
563
EXHIBIT 3
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.)
Bastnaesiw Ore
HC1
*
Crushing
1
Grinding
T
- Waste Tailings
Classifier
I
Waste Tailings
Acid
Digestion
T
Slurry
Cake
Rare Earth
NaOH
J
Rare Earth
Chloride Product
-------
564
Purification/Concentration
Flotation
Flotation is used at Mountain Pass to make a bastnasite concentrate containing about 60% rare
earth oxides. This concentrate is either used on site as feed for chemical separation of rare earth
elements, leached to produce a 70% rare earth oxide concentrate, or shipped as is.
Extraction
Extraction of rare earth elements from monazite and xenotime is accomplished by dissolution 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 calcined to
drive off C02 and fluorine, and leached with hydrochloric acid to dissolve most of the trivalent rare earth
elements. The residue is sold as a polishing abrasive.8
The rare earth hydroxides and chlorides recovered from sulfuric and hydrochloric acid digestion
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
fractional crystallization, fractional precipitation, solvent extraction, ion exchange, and reduction.
Fractional Crystallization and Precipitation
In fractional crystallization, one or more rare earths in a mixture are precipitated by changing the
salt concentrations in solution through evaporation or temperature control. Fractional precipitation
involves adding a precipitating agent to selectively remove a metal from solution. These two processes
generally produce waste salts and salt solutions requiring treatment and disposal. If organic precipitation
is used, then organic containing waste fractions may be produced as well.9
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. Since all of the products are aqueous solutions, the spent solvents leave the process as wastes.10
Exhibit 4 presents a process flow diagram for solvent extraction.
Ion Exchange
Ion exchange produces highly pure rare earths in small quantities. For separating a lanthanide
mixture, a cation exchange resin is flushed with a solution such as cupric sulfate to prepare the resin for
ion exchange. A solution containing the lanthanides is then passed over the ion exchange resin. The
lanthanides displace the cation on the resin surface. This step produces an aqueous waste containing the
cation which was exchanged, and small amounts of rare earths. At this stage, the lanthanides have been
8 Stephen Castor, 1994, Op. Cit.l pp. 827-837.
9 U.S. Environmental Protection Agency, 1988, Op. Cit„ pp. 3-164 - 3-174.
10 Ibid.
-------
565
EXHIBIT 4
RARE EARTH SEPARATION BY SOLVENT EXTRACTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
Rare Earth Nitrate Solution
(La. Pr. Nd. Sm)
*
Aqueous Sm Aqueous Nd Aqueous La Aqueous Pr
-------
deported on the resin as a mixture. To separate individual rare earth elements, ,a chemical solution
containing a complexing agent, such as NH4+EDTA, is passed over the resin. The EDTA has a high
affinity for rare earths, and the lanthanides are complexed with the EDTA and displaced by NH4+ on the
resin. Each lanthanide has a different affinity for EDTA, and individual lanthanides can be separated and
recovered as a result of these varying affinities. Relative to the amount of product generated, large
quantities of waste solutions are generated during the process. The waste solutions may be acidic, basic, or
neutral, and will contain the metals displaced from the resin during ion.exchange, as well as the
complexing agents used.11 Exhibit 5 presents a process flow diagram for ion exchange.
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% 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.12
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. A process flow diagram for
calcium reduction is presented in Exhibit 6.
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 run the dehydration furnaces.13
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.14
Exhibits 7 and 8 present process flow diagrams for mischmetal production.
11 Ibid.
12 Ibid.
13 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.
14 Ibid.
-------
'567
EXHIBIT 5
LANTHANIDE SEPARATION BY ION EXCHANGE
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
Rare Earth
Lantharude Solution
Resin
Flushing
Solution
Eluant with
Completing Agent
ft?
Flushing
Wash
Ion
Exchange
Resin
Waste
Eluant
T
Rare Earths
Product Solutions
-------
568
EXHIBIT 6
CALCIUM REDUCTION PROCESS
(Adapted from: 19NN Fin;il Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
Rare Earth Calc[um
Muondes
Non-Contact
I noline
Calcium
Reduction
Reduced Metal
M
Noil-Contact
Cooling
~
Melting
and
Casting
Impurities
i'uie Rare Earth
Metal Ingot
t
Calcium
Fluoride
-------
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 crushed into
powder or melted and cast if a solid product form is desired.
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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 bnquetting) 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 Section B.
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. 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.
-------
570
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. Extraction/Beneficiation Wastes
Tailings and magnetic fractions are possible waste streams from the extraction and beneficiation
of rare earths.
2. Mineral Processing Wastes
Existing data and engineering judgement suggest that the materials listed below do not exhibit any
characteristics of hazardous waste. Therefore, the Agency did not evaluate these materials further.
Off-gases from dehydration from the furnaces are treated by water or alkaline scrubbers to remove
particulates and acid. The treated gases are vented.15 Existing data and engineering judgement indicate
that this waste does not exhibit any characteristics of a hazardous waste. Therefore, the Agency did not
evaluate this material further.
Spent hydroxide cake. Existing data and engineering judgement indicate that this waste does not
exhibit any characteristics of a hazardous waste. Therefore, the Agency did not evaluate this material
further.
Spent monazite solids. Existing data and engineering judgement indicate that this waste does not
exhibit ajiy 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.16 Existing data and engineering judgement indicate
that this waste does not exhibit any characteristics of .a hazardous waste. Therefore, the Agency did not
evaluate this material further.
Spent sodium fluoride. Existing data and engineering judgement 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 judgement 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 judgement to determine that this waste
15 U.S. Environmental Protection Agency, 1989, Op. Cit. pp. 5376-5446.
16 Ibid.
-------
571
may exhibit the characteristic of ignitability. This waste may be recycled and is classified as a spent
material.
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: This
waste may be recycled to extraction/beneficiation units and is classified as a byproduct. 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 3,300 metric tons/yr, 4,200 metric tons/yr, and 5,000 metric tons/yr, respectively.
Lead Backwash Sludge. Existing data and engineering judgement indicate that this waste does not
exhibit characteristics of a hazardous waste. Therefore, the Agency did not evaluate the material further.
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 judgement to determine
that this waste may exhibit the characteristic of toxicity for mercury. This waste may be recycled and is
classified as a byproduct.
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. We used best engineering judgement to determine that this waste may
exhibit the characteristic ignitability. This waste may be recycled and is 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 1991.17 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.18 This waste is not expected to be hazardous. Waste
characterization data are presented in Attachment 1.
Lanthanide 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.19 Attachment 1 presents waste characterization data.
17 U.S. Environmental Protection Agency, 1992, Op. Cit.. Vol. I, pp. 1-2 -1-8.
18 Ibid.
19 Ibid.
-------
EXHIBIT 7
MISCHMETAL REDUCTION PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-164 - 3-174.)
Rare Earth
Metal Oxide
Misch
Metal
Rare Earth
Metal Product
-------
EXHIBIT 8
MISCIIMETAL PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, l'J89, pp. 5376 - 54-16.)
To Atmosphere
Chloi idc
-------
574
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.20 Waste characterization data are presented in Attachment 1. This waste
may be recycled and is classified as a spent material.
Mischmetal Production
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 judgement to determine that this waste may exhibit the characteristic of
corrosivitv. This water may be recycled or discharged to wastewater treatment. This waste is classified as a
spent material.
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 judgement to
determine that this waste may exhibit the characteristics of toxicity for chromium and lead and corrosivitv.
Scrubber liquor is recycled and the bleed stream is discharged to treatment. This waste is 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 judgement 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% sodium hypochlorite concentration is attained, the solution is drawn off and sold for
industrial use. This waste is not expected to be hazardous.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants. Pinion gear grease is an ancillary
waste. At Molycorp, this waste contains 50% aromatic oils, 35% petroleum asphalts, and 0-10% 1,1,1
trichloroethane.
20 Ibid.
-------
575
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. Newlv 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. Newlv Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. Vol. I. 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.
-------
576
-------
577
ATTACHMENT 1
-------
578
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT LIQUIDS - CERIUM/LANTHANIDES/RARE EARTHS
l'*"1
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average
Maximum # Detects
Minimum Average
Maximum
H Detects
Level
In Excess
Aluminum
-
-
-
0/0
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1 0
0
Chromium
0.008
0.008
0.008
1/1
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
-
-
-
0/0
-
0/0
-
-
Lead
0.03
0.03
0.03
1/1
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1 0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Ztnc^
-
-
-
0/0
-
0/0
-
-
Cyanide
-
-
-
0/0
..
0/0
-
-
Sulfide.
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
-
-
-•
0/0
-
0/0
-
-
PH*
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
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 EP/VORD, 3007, AND RTI SAMPLING DATA - SPENT SURFACE IMPOUNDMENT SOLIDS - CERIUM/LANTHANIDES/RARE EARTHS
Total Constituent Analysis - PPM
EP Toxicity Analysis
-PPM
TC
# Values
Constituents
Minimum
Average
Maximum 0 Detects
Minimum Average
Maximum
ti Delects
Level
In Excess
Aluminum
20000
20000
200.00
1/1
-
0/0
_
_
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
_
Boron
-
-
-
0/0
-
0/0
-
_
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cdbalt
-
-
-
0/0
-
0/0
_
_
copper
-
-
-
0/0
-
0/0
-
-
Iron'
20000
20000
20000
1/1
-
0/0
_
_
liead
7500
7500
7500
1/1
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
_
Manganese
2000
2000
2000
1/1
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
_
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
thallium
-
-
-
0/0
-
0/0
-
_
Vanadium
-
-
-
0/0
-
0/0
_
_
Zinc
-
-
-
0/0
-
0/0
-
_
cyanide
-
-
-
0/0
-
0/0
-
-
sulfide
-
-
-
0/0
-
0/0
_
_
Stiffate
-
-
-
0/0
-
0/0
_
_
Fluoride
-
-
-
0/0
-
0/0
_
Phosphate
-
-
-
0/0
-
0/0
-
_
Silica
-
-
0/0
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
110000
110000
110000
1/1
-
0/0
_
PH*
-
-
-
0/0
212
0
Organics (TOC)
33
33
33
1/1
-
-
Non-detects were assumed to be present at 1/2 the detection limit TCLP data are currently unavailable, therefore, only EP data are Dresented
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT AMMONIUM NITRATE PROCESSING SOLUTION - CERIUM\LANTHANIDES\RARE EAK
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
H Values
Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
H Detects
Level
In Excess
Aluminum
0.046
0.38
0.97
3/3
-
-
-
0/0
-
-
Antimony
0.229
10.11
20
2/2
-
-
-
0/0
-
-
Arsenic
0.0025
0.01
0.025
4/5
0.002
0.049
0.132
3/3
5.0
0
Barium
0.038
0.07
0.11
5/5
0.006
6.99
20
3/3
100 0
0
Beryllium
0.009
0.01
0.009
1/1
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.0025
0.03
0.095
4/5
0.003
0.013
0.03
3/3
1.0
0
Chromium
0.009
0.06
0.24
3/5
0.027
0.048
0.079
3/3-
5.0
0
Cobalt
0.054
4.93
9.8
2/2
0.0005
0.065
0.15
2/3
-
-
Copper
0.005
0.04
0.085
2/3
-
-
-
0/0
-
-
Iron
0.053
0.05
0.053
1/1
-
-
-
0/0
-
-
Lead
0.001
0.02
0.03
4/4
0.005
0.014
0.02
2/3
5 0
0
Magnesium
0.005
56.08
221
6/6
-
-
-
0/0
-
-
Manganese
0.005
0.02
0.045
3/4
-
-
-
0/0
-
-
Mercury
0.0001
0.00
0.0005
2/3
0.0065
0.06
0.094
2/3
0.2
0
Molybdenum
-
-
" -
0/0
0.009
0.07
0.124
3/3
-
-
Nickel
-
-
-
0/0
0.004
3.28
9.8
3/3
-
-
Selenium
0.0025
0.01
0.016
1/3
0.023
0.05
0.095
3/3
1 0
0
Silver
0.005
0.04
0.097
3/5
0.009
0.02
0.038
3/3
5.0
0
Thallium
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
Zinc
0.001
0.02
0.046
3/4
-
-
-
0/0
-
-
Cyanide
0.005
0.09
0.25
0/3
-
-
-
0/0
-
-
Sulfide
0.025
0.34
0.5
0/3
-
-
-
0/0
-
-
Sulfate
69
595
1,494
3/3
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
--
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
1,126
11,108
21,300
3/3
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
PH *
0.1
7.07
9.59
9/9
212
1
Organics (TOC)
107.13
109.17
111.2
2/2
-
-
Non-detecls 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
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum H Detects
TC # Values
Level In Excess
Aluminum
27.9
35.7
43.5
2/2
23.2
25.6
28
2/2
-
_
Antimony
0.50
0.50.
0.50
0/2
0.50
0.50
0.50
0/2
-
_
Arsenic
0.50
0.50
0.50
0/2
0.50
0.50
0.50
0/2
5.0
0
Barium
0.50
0.50
0.50
0/2
0.50
0.85
1.20
1/2
100.0
0
Beryllium
0.05
0.05
0.05
0/2
0.05
0.05
0.05
0/2
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
Cadmium
0.00050
0.039
0.054
1/4
0.05
0.05
0.05
0/2
1.0
0
Chromium
0.00050
0.26
0.50
1/4
0.50
0.50
0.50
0/2
5.0
0
Cobalt
0.5
0.50
0.50
0/2
0.50
0.50
0.50
0/2
_
_
Copper
0.5
1.08
1.65
1/2
0.50
1.56
2.62
1/2
-
_
Iron
8.57
10.19
11.80
2/2
7.55
7.76
7.97
2/2
_
_
Lead
0.0005
2.50
8.45
3/4
0.63
5.31
10.0
2/2
5.0
1
Magnesium
154
2.117
4,080
2/2
1,020
4,955
8,890
2/2
-
-
Manganese
3.68
104
204
2/2
2.52
10.4
18.3
2/2
-
-
Mercury
0.00010
0.00010
0.00010
0/2
0.0001
0.0001
0.0001
0/2
0.2
0
Molybdenum
0.50
0.50
0.50
0/2
0.50
0.50
0.50
0/2
-
-
Nickel
0.008
1.25
4.00
2/4
0.50
0.50
0.50
0/2
-
_
Selenium
0.50
0.50
0.50
0/2
0.50
0.50-
0.50
0/2
1.0
0
Silver
0.50
0.50
0.50
0/2
0.50
0.50
0.50
0/2
5.0
0
Thallium
2.50
2.50
2.50
0/2
2.50
2.50
2 50
0/2
_
Vanadium
0.50
0.50
0.50
0/2
0.50
0.50
0.50
0/2
_
_
Zinc
1.98
8.09
14.20
2/2
1.98
7.24
12.5
2/2
_
_
Cyanide
-
-
-
0/0
-
-
0/0
-
_
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
152
786
1,420
2/2
-
-
-
0/0
_
_
Fluoride
0.20
15.10
30.0
2/2
-
-
-
0/0
_
_
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
0.034
1,675
6,490
4/4
-
-
-
0/0
_
_
TSS
0.030
4,740
9,480
2/2
-
-
-
0/0
_
pH *
0.056
0.6215
1.1
4/4
212
4
Organics (TOC)
-
-
-
0/0
-
-
Non-detecls 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 ELECTROLYTIC CELL QUENCH WATER - CERIUM/LANTHANIDES/RARE EARTHS
Total Constituent Analysis
- PPM
EP Toxicity Analysis
PPM
TC
H Values
Constituents
Minimum
Average Maximum
H Detects
Minimum Average
Maximum
H Delects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.005
0.0067
0.01
3/3
-
-
0/0
-
-
Arsenic
0.006
0.0177
0.025
3/3
-
-
0/0
5 0
0
Barium
-
-
-
0/0
-
-
0/0
100 0
0
Beryllium
0.001
0.0010
0.001
3/3
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.001
0.0073
0.02
3/3
-
-
0/0
1.0
0
Chromium
0.001
0.0173
0.033
3/3
-
-
0/0
5 0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.01
0.0230
0.033
3/3
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.14
0.2733
0.4
3/3
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
--
-
0/0
-
-
Mercury
0.0002
0.0008
0.002
3/3
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.013
0.0380
0.051
3/3
-
-
0/0
-
-
Selenium
0 005
0.0110
0.023
3/3
-
-
0/0
1 0
0
Silver
0.001
0.0010
0.001
3/3
-
-
0/0
5.0
0
Thallium
0.001
0.0057
0.015
3/3
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.06
0.1167
0.19
3/3
-
-
0/0
-
-
Cyanide
0.0003
0.0075
0.022
3/3
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
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.
«_n
00
uJ
-------
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. perhennic 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
the 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 bv eight
companies. Exhibit 1 presents the names and location of those companies generating molybdenum
concentrates that contain rhenium.,
EXHIBIT 1
Summary of Rhenium Facilities
Facility Name
Location
Type of Operation
Chino Mines Co.
Hurley NM
Molybdenum concentrates
Cyprus-Climax
Sierrita, AZ
Molybdenum concentrates
Cyprus-Climax
Bagdad, AZ
Molybdenum concentrates
Kennecott Minerals Co.
Bingham Canyon, UT
Molybdenum concentrates
Magna Copper Corp.
San Manuel, AZ
Molybdenum concentrates
Magna Copper Co.
Miami, AZ
Molybdenum concentrates
Phillips Dodge Corporation
Morenci, AZ
Molybdenum concentrates
Sheilds Resources Inc. (Continental Pit)
Butte, MT
Molybdenum concentrates
Although most of these 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 Mines, October 17, 1994.
-------
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
(NH4Re04).8 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.
4 Blossom, J. W., 1995, Op. Cit.. p. 136.
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.
-------
EXHIBIT 2
MOLYBDENUM AND RHENIUM PRODUCTION PROCESSES
Molybdenum
Sulfide
Concentrate
Molybdenum
Sulfide
Concentrate
(Adapted from
Development Document for Effluent Limitation Guidelines and Standards for Nonferrous Metals Manufacturing
Point Source Category, 1989, pp. 3341 - 3483.)
Wastcwatci
Rhenium
Metal
ui
00
-------
Oxidation and Evaporation
The next stage of the process following filtration involves oxidation and neutralization. These
steps are achieved with the addition of H202 (hydrogen peroxide) and NH4OH. The resulting NH4Re04
is then evaporated to yield dry rhenium salt (also known as ammonia perrhenate). NH4Re04.
Reduction
The dryammonium 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.10
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
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/Beneflciation 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
, 9 U.S. Environmental Protection Agency, "Rhenium," from 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. Office of Solid Waste, 1988, p. 3-175.
10 J.W. Blossom, 1985, Op. Cit.. p. 667.
-------
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 Slack or
Metal
-------
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.11 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 be recycled and may exhibit the characteristic of
toxicity for selenium. This waste is 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.12 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
11 U.S. Environmental Protection Agency, 1989. Op. Cit. p. 3430
12 U.S. Environmental Protection Agency, 1989. Op. Cit. p. 3381
-------
591
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.
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592
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SYNTHETIC RUTILE
A. Commodity Summary
Synthetic rutile (TiO-,) 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.-
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 Ti02 product using rutile as a feedstock. In
comparison, direct chlorination of ilmenite generates approximately 1.2 tons of waste (primarily ferric
chloride) per ton of Ti02 4
B. Generalized Process Description
1. Discussion of Typical Production Processes
Several processes using oxidation, reduction, leaching, and/or chlorination have been developed to
remove iron from low-grade, beach sand ilmenite and produce synthetic rutile having 90 to 97% Ti02 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 chlorination is used to remove the iron.5
1 J. Gambogi, Annual Report: Titanium-1992, U.S. Bureau of Mines, December 1993, p. I.
2 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, p. B-39.
J 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.
-------
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 Dlant 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% TiOz 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:'
The reduced ilmenite is then batch-digested in rotaTy-ball digesters with 18-20% HC1 at 140° C.(
Ferrous oxide in the ilmenite is converted to soluble ferrous chloride, and the Ti02 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 TiOz solids are washed with water and filtered and calcined at 870° C, yielding
synthetic rutile with approximately 94% Ti02. 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 sluny.
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
High-grade synthetic rutile (98% Ti02) 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. CarT, 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, et al.. "On Extraction of High Grade Synthetic Rutile from Indian Ilmenite," The
Minerals, Metals & Materials Society, 1992, p. 1079.
-------
595
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
L. 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 cvcloned to remove entrained solids,
10 U.S. Environmental Protection Agency, "Titanium," from 1988 Final Draft Summary Report of
Mineral Industry Processing Wastes. 1988. p. 3-219.
-------
EXHIBIT 1
BENELITE CYCLIC PROCESS FOR SYNTHETIC RUTILE PRODUCTION
(Adapted from: Kerr-McGee Corp., Comments oo Notice of Proposed Rulemaking, 1989.)
Illmenite Ore
(54 - 65% TiO,)
t
Synthetic Rutile
(94% TiOj)
-------
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.11 This
waste stream has a reported waste generation rate of 30,000 mt/vr. 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).1213 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 tne 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. Ancillary 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), 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
waste oil and other lubricants.
11 D. Carr, ed., 1994, Op. Cit., p. 1085.
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.
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598
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.
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599
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 one 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
Location
Type of Operation
Baldwin Metals
Processing Co.
Phoenix, AZ
Ingot and distilled scandium metal production.
Boulder Scientific Co.
Mead, CO
Refining. Processed scandium concentrates derived
from thortveitite-bearing tailings from the mined-out
Crystal Mountain fluorite mine near Darby, Montana.
Interpro (subsidiary of
Concord Trading Corp.)
Golden, CO
Refining. Processed stocks of scandium concentrates
previously generated by the Energy Fuels Nuclear
uranium plant at Bingham Canyon, Utah.
Materials Preparation
Center
Ames, IA
Scandium Oxide and Ingot Production (research
organization).
Rhone Poulenc, Inc.
Phoenix, AZ
Ingot and distilled scandium metal production.
Kennecott
Garfield, UT
Scandium is available for refining in the form of a
byproduct generated during processing of uranium at
the copper mine:
Climax Mine
Climax, CO
Scandium is available for refining from the tungsten
byproduct generated during the molybdenum
operation.
APL Engineered
Materials
Urbana, IL
Refining. Ingot and distilled scandium metal
production.
Sausville Chemical Co.
Garfield, NJ
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.
-------
600
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 sofuble. 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 sulfuric 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. Cii..*pp. 148-149.
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601
EXHIBIT 2
SCANDIUM FROM THORTVEITITE #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 H,S04
*
Dissolution
7
Silica Residue
Containing Scandium
I
Leaching
Process
t
Leaching Solution
I
Precipitation
T
Scandium Precipitate
*
Spent Acid
Waste Sulfuric Acid
Waste Solution
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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
I
Scandium Chloride
Scandium Precipitate
-------
603
EXHIBIT 4
SCANDIUM FROM THORTVEITITE #3
(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
Chlonnation
850 °C
T
Scandium Chloride
I
Leaching
J
Leaching Solution
I
Precipitation
T
Scandium Precipitate
I
Scandium Oxide
I
Waste Chlorme
Solution
Waste Sulfuric Acid
Waste Solution
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EXHIBIT 4 (Continued)
SCANDIUM FROM THORTVEITITE #3
Scandium Oxide
Hydrochloric
Acid
Wash
Waste Acid
Scandium Chloride
Ion Exchange
t
Scandium Metal
Solvent Extraction
T
Scandium Metal
-------
605
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.'
Recovery From Uranium ("no longer usedl
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) Process(es)
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
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.
-------
606
EXHIBIT 5
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 ppm SC
Hvdrofluonc Acid ¦
Hydrochloric Acid ¦
Oxalic Acid
Counter Current
Solvent Extraction
Stage 1
Stage 2
7
Filter
T
Filter Cake
10% Scandium
*
Digester
J
Digestion Solution
I
Filter
J
Scandium, Iron, Uranium Filtrate
I
J
Scandium Oxalate
Precipitate
I
Waste -Solvent
Waste Acid
Thorium, Titanium,
Zirconium, Iron, and
Silica (ppt)
Waste Acid
-------
607
EXHIBIT 5 (Continued)
SCANDIUM FROM URANIUM
Hydrochloric
Acid
t
Scandium Metal
-------
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, chlonnation) 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
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/Beneflciation 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
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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 thai
this material does not exhibit any characteristic 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, 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 Alters 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.
9 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-20.
-------
610
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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenvls from electrical transformers and
capacitors.
-------
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%;
• chemicals and pigments, 20%;
• glass manufacturing, 30%; and
• other, including agriculture and metallurgy, 15%. 1
Exhibit 1 lists the names and locations of the facilities involved in the production of selenium.
EXHIBIT 1
Summary Of Selenium Processing Facilities
Facility Name
Location
ASARCO
Amarillo, TX
Kennecott (RTZ)
Garfield, UT
Phelps Dodge
•EI Paso, TX
B. Generalized Process Description
1. Discussion of Typical Production Processes
Generally, 30-80% 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. Exhibits 2 through 4 present process flow
diagrams for selenium production. 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
1 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.
-------
<71
rvj
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
-------
613
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
I
Selenium
-------
614
EXHIBIT 4
SELENIUM PURIFICATION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-187 - 3-193.)
Crude Selemum
Sodium
Sulfite
Sulfuric
Acid
I
Purified Selenium
-------
615
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 S02 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 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 Copper Corp.
Kennecott Copper Corp., recovers selenium from anode slimes at its Garfield facility through
fusion with sodium bisulfate to oxidize copper-silver selenide compounds and other slime constituents.
Both S02 and Se02 are evolved during the fusion, and are absorbed in water in the gas scrubbing and
Cottrell system as H2Se03 and H2S03. The H2Se03 slowly oxidizes the H2S03 to H2S04 and red
amorphous selenium is precipitated. Periodically, elemental selenium is harvested from the settling tanks
and other pans of the scrubber and Cottrell circuit. The red amorphous selenium, harvested from the
scrubber system, is coked with hot water and steam to convert it to a gray crystalline form. Coked
selenium is used for preparation of commercial grade selenium without further purification. Commercial
selenium is produced by drying coked selenium, grinding, and sizing by screening. The material is
packaged and sold.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
H2S04. The solutions are kept cool during acidification to obtain red amorphous selenium. After
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 Arnold M. Lansche, "Selenium and Tellurium - A Materials Survey," U.S. Bureau of Mines.
Information Circular 8340, 1967, pp. 32-34.
-------
616
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 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) Process(es)
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 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.
6 Ibid.
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617
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 ejected to have a pH of 0.8
to 1.9. The 1991 generation rate for the sector was 66,000 metric tons per year. Waste characterization
data are presented in Attachment 1. This waste may be recycled and is 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
judgement to determine that this waste may exhibit the characteristic of toxicity for selenium. 'Slag may be
recycled and is 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 judgement to determine that this waste may exhibit
the characteristic of toxicity for selenium. This waste may be recycled and is classified as a byproduct.
Tellurium slime waste 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 judgement to
determine that this waste may exhibit the characteristic of toxicity for selenium. This waste is 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 judgement to determine that this waste may exhibit
the characteristic of toxicity for selenium.
D. Ancillary 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), 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,
waste oil (which may or may not be hazardous), and other lubricants.
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.
-------
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.
-------
ATTACHMENT 1
-------
620
-------
SUfaiviARY OF EPA/ORD, 3007, AND RTI SAMPLING DAtA - PLANT PROCESS WASTEWATER (ACID PLANT BLOWDOWN) - SELENIUM
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
H Values
Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
0.50
0.50
0.50
0/1
0.32
0.32
0.32
1/1
-
-
Antimony
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
-
-
Arsenic
0.50
1.45
2.40
1/2
0.95
0.95
0.95
1/1
5.0
0
Barium
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
100.0
0
Beryllium
2.000
0.050
0.050
0/1
0.0050
0.0050
0.0050
0/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.017
0.034
0.050
1/2
0.043
0.043
0.043
1/1
1.0
0
Chromium
0.50
0.50
0.50
0/1
0.11
0.11
0.11
1/1
5.0
0
Cobalt
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
-
-
Copper
0.090
0.30
0.50
1/2
0.050
0.050
0.050
0/1
-
-
Iron
1.63
1.63
1.63
1/1
1.50
1.50
1.50
1/1
-
-
Lead
1,42
9.16
16.90
2/2
12.00
12.00
12.00
1/1
5.0
1
Magnesium
14.90
14.90
14.90
1/1
14.10
14 10
14.10
1/1
-
-
Manganese
1.06
1.06
1.06
1/1
0.98
0.98
0.98
1/1
-
-
Mercury
0.00072
0.00072
0.00072
1/1
0.00088
0.00088
0.00088
1/1
0.2
0
Molybdenum
23.30
88.43
130
3/3
20.90
20.90
20.90
1/1
-
-
Nickel
0.10
0.30
0.50
1/2
0.050
0.050
0.050
0/1
-
-
Selenium
0.50
2.05
3.60
1/2
0.90
0.90
0.90
1/1
1.0
0
Silver
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
5.0
0
Thallium
2.50
2.50
2.50
0/1
0.25
0.25
0.25
0/1
-
-
Vanadium
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
-
-
Zinc.
0.50
0.50
0.50
0/1
0.21
0.21
0.21
1/1
-
-
Cyaniae
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate.
27,000
27,400
27,800
2/2
-
-
-
0/0
-
-
Fluorlde
40.00
80.00
120
2/2
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
¦-
-
0/0
-
-
Chloride
158
158
158
1/1
-
-
-
0/0
-
-
TSS
25
20,313
40,600
2/2
-
-
-
0/0
-
-
pH *
0.80
1.35
1.90
2/2
212
2
Organlcs (TOC)
25.20
26.35
27.50
2/2
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
622
-------
623
SILICON AMD FERROSILICON
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 L992)a
Facility Name
Location
Products
American Alloys Inc.
New Haven, WA
FeSi and Si
Applied Industrial Minerals Corp.
Bridgeport, AL
FeSi
Dow Corning Corp.
Springfield, OR
Si
Elkem Metals Co.
Alloy, WV
Si
Elkem Metals Co.
Ashtabula, OH
FeSi
Globe Metallurgical Inc.
Beverly, OH
FeSi and Si
Globe Metallurgical Inc.
Selma, AL
Si
Keokuk Ferro-Sil Inc
Keokuk, LA
FeSi
Silicon Metaltech Inc.
Wenatchee, WA
Si
Simetco Inc.
Montgomery, AL
Si
SKW Alloys Inc
Calvert City, KY
FeSi
SKW Alloys Inc
Niagara Falls, NY
FeSi and Si
3 - 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 ofrMines. 1992 p 1183.
-------
624
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 (Si02) 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/
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 halide or halosilane
which is then reduced with a high purity reagent.5
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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..
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 ll-14th 1990, p. 280.
7 J.E. Goodwill, "Developing Plasma Applications for Metal Production in the USA," Ironmaking and
Steelmaking. Vol. XVII, No. 5, 1990, pp. 350-354.
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625
pelleuzing 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 Section B.
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 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
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.
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.
-------
EXHIBIT 2
SILICON PRODUCTION
Silica
Coul, Coke, or
Charcoal
Wood
Chips
1-urnace
Fume
Dust
cn
ro
cn
Silicon
-------
EXHIBIT 3
FERROSILICON PRODUCTION
Silica
I
Coal, Coke, or
Charcoal
Wood
Chips
Iron and
Sleel —
!• urnace
Fume
Dust
Fenosilicon
cn
KJ
-¦j
-------
628
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, 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. Ancillary 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, 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.
10 "Silicon and Ferrosilicon," Op. Cit.. p. 3-195.
11 L.D. Cunningham, 1992, Op. Cit.. p. 1184.
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629
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 9237. 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.
-------
630
-------
631
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% • chemicals, 23%
• soap and detergents, 13% » distributors, 5%
• flue gas desulfurization, 3% • pulp and paper, 2%l
Soda ash is the common name tor 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
Summary Of Soda Ash Processing Facilities
Facility Name
Location
FMC Corporation
Green River, WY
General Chemical Partners
Green River, WY
North American Chemical Company
Argus,CA
Westend, CA
Rhone-Poulenc Mine
Green River, WY
Tenneco
Green River, WY
TG Soda Ash Mine
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.
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632
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 raining 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:
2Na2C03 • NaHC03 • 2H20 (trona) + heat -* 3Na2C03 + C02 + 5HzO
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.
4 Md.
5 Ibid.
6 Ibid.
-------
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 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.'
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 crashed, 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. 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 + Na2C03 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.
-------
EXHIBIT 2
THE MONOHYDRATE PROCESS
(Adapted from: Soda Ash: Mineral Processing Waste Generation Profile.)
OITgases
-------
EXHIBIT 3
THE SESQUICARBONATE PROCESS
(Adapted from: Soda Ash: Mineral Processing Waste Generation Profile.)
-------
636
EXHIBIT 4
THE SEARLES LAKE PROCESS
(Adapted from: 1988 Final Draft Summan Report of Mineral Industry Processing Wastes, 1988, pp. 2-43 - 2-46.)
Brine
f
Light Soda Ash
Dense Soda Ash
-------
637
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. 11
Sodium Sesquicarbonate
Sodium sesquicarbonate is a hydrated compound containing soda ash and sodium bicarbonate.
Troria 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) Process(es)
None identified.
4. Extraction/Beneflciation Boundaries
Based on a review of this 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
Particulates from crushing and calcination are generated. The calciner offgases contain carbon
dioxide. Airborne particulate 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
11 Ibid.
12 Ibid.
13 Ibid.
14 Ibjd.
15 Ibid.
-------
638
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 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.
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
16 Ibid.
17 U.S. Environmental Protection Agency, Mineral Processing Waste Sampling Survey Trip Reports.
Tenneco Corporation, Green River, WY, August 1989.
18 Ibid.
19 Ibid.
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639
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.
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 particulates 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. Particulate
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
Ore residues. About 110 to 150 kg per kkg or ore residues, chiefly shale, are generated in the
initial steps.24
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.
20 RTI survey for General Chemical Partners, Green River, WY, 1988, ID# 100388.
21 RTI Survey for Tg Soda Ash, Green River, WY, 1988, ID# 100206.
^ 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.
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640
Searles Lake Process Waste Streams
Calciner offgases. 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
Particulate emissions from driers. These emissions are controlled by dry collectors, and the
recovered solids are recycled to the process. Residual airborne particulate 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. Ancillary 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), 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,
waste oil (which may or may not be hazardous) and other lubricants.
27 Ibid.
28 Ibid.
29 Ibid.
30 Ibid.
-------
641
BIBLIOGRAPHY
"Alkali and Chlorine Products." Kirk-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.
Tenneco 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.
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642
-------
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 S50 million in 1994. End uses of sodium sulfate are soap and detergents
(40%), pulp and paper (25%), textiles (19%), glass (5%), and other uses (l^).1
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 plavas, are found in arid to semiarid 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
Location
Great Salt Lake Minerals and Chemicals Corp.
Great Salt Lake, UT
North American Chemical, Inc.
Searles Lake, CA
Ozark-Mahoning Co.
Western Texas
B. Generalized Process Description
I. 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
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.
-------
these three processes are all 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 Laket
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 American'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. "TTie final product is
99.5% pure.6
3. Identification/Discussion of Novel (or otherwise distinct) Process (es)
None identified.
4. Extraction/Beneficiation 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.
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645
EXHIBIT 2
OZARK-MAHONING PROCESS
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-47 - 2-51.)
Brine
I
-------
646
EXHIBIT 3
THE SEARLES LAKE PROCESS
(Adapted from: 198S Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 2-47-2-51.)
Brine
~
-------
647
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. Extraction/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. Ancillary 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), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors. Non-hazardous wastes may include sanitary sewage, waste oil (which may or may not be
hazardous), and other lubricants.
-------
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.
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.
-------
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%)1. 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.J 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 method 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 (SrC03) 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.
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.
-------
650
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.
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
4 "Strontium-Uses, Supply, and Technology," U.S. Bureau of Mines Information Circular, 1989, p. 6.
-------
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
3
"8
Na,SO.
Celcstite
(SrSO„)
1,100 C
J
co2
SrS
J
SrS i
HjO
OR
n,o
98% SrCOj
OK
Na,S
T
Coal
CO,
Na,COj
PiL'iipjl.itcs liom Solution
Celestile
(SrSOj)
Na,CO,
11,0
100 °c
Na2S04
95°,o SiCOj
Precipitates from Solulion
(Ti
-------
652
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) Process (es)
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. -
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 HN03. 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. Extraction/Beneficiation Boundaries
Based on a review of this 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.
6 Ibid.
7 John E. FerrelV "Strontium," from Mineral Facts and Problems. U.S. Bureau of Mines, 1985, pp.777-
782.
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.
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653
Vacuum drum filtrate.-
Waste solution.
Soda Ash Method
Waste sodium sulfate solutions.
2. Mineral Processing Wastes
None identified.
D. Ancillary 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), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
-------
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 Laboratorv.
1991. pg. 1.
Ober, Joyce A. "Strontium." From Mineral Yearbook Volume 1. Metals and Minerals. U.S. Bureau of
Mines. 1992. 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.
-------
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 $500 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 gypsum.
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. Penzoil 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.
4 Gregory R. Wessel, 1994, Op. Cit., pp. 1011-1046.
5 Ibid.
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656
EXHIBIT 1
Summary Of Major Primary Sulfur Processing Facilities
Facility Name
Location
Freeport Sulphur Co.
Caminada, offshore LA
Penzoil Sulphur Co.
Culberson, W. TX
Texasgulf Inc.
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 f 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
convened 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 convened 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 acid, liquid sulfur dioxide,
and elemental sulfur, all of which can be used if a local market exists. If no local markets exist, large
-------
EXHIBIT 2
FRASCH PROCESS
(Adapted from: Multi-Medial Assessment of the Inorganic Chemicals Industry, 1980, Chapter 14.)
Water
T
Bleed Water l ,000 Sulfur
(Contains 600 - 1,000 ppm Product
Dissolved Sulfides)
-------
EXHIBIT 3
CLAUS PROCESS
(Adapted from: Multi-Medial Assessment of the Inorganic Chemicals Industry, 1980, Chapter 14.)
Sulfide Containing
Refinery Gas
(1.094 - 1,126 Hydrogen Sulfide)
-------
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 drums, 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 the belt, the sheet breaks into smaller pieces. Sulfur prilling can be
accomplished with air or water. In air prilling, molten sulfur is sprayedfrom 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 graniilator until the particle size reaches the required
diameter. In the Procor GX granulation process, liquid sulfur is sprayed into a rotating drum in which
small seed panicles of sulfur are recycled from the end of the process. Pastilles are individual droplets of
molten sulftir that have been dropped on a steel belt and cooled by conduction. The Sandvik Rotoform
process uses a patented 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 acid9
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 conveners.' The process proceeds from this point as it does
with pure sulfur as the feed.10
6 Ibid.
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.
-------
EXHIBIT 4
SULFURIC ACID PRODUCTION
(Adapted front: Multi-Media Assessment of the Inorganic Chemicals Industry, 1980, Chapter 14.)
Wastewater (Condensate)
1,000 Sulfuric Acid
I'roduct
-------
661
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 particulate matter.
The gas is cooled to remove water vapor before it can be used in the process.11
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 sulfuric 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) Process(es)
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.1-3
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/Beneflciation 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
11 Ibid.
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.
-------
662
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.
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 oxvsulfide are
produced by side reactions of organic compounds presem-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
14 U.S. Environmental Protection Agency, 1980, Op. Cit. Chapter 14.
15 Ibid.
16 Ibid.
17 Ibid.
-------
663
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 Weilman 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.*5
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 Weilman Lord
process, (4) molecular sieves to absorb sulfur dioxide, and (5) no control.21
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. Ancillary 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), 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,
waste oil (which may or may not be hazardous) and other lubricants.
18 Ibid.
19 Ibid.
20 Ibid.
21 Ibid.
22 Ibid.
23 Ibid.
-------
Bibliography
Ober, Joyce. "Sulfur." From Mineral Commodity Summaries. U.S. Bureau of Mines. January 1995. ]
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.
-------
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 pvrochlore 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. 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. 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.
5 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.
-------
EXHIBIT 1
Summary of Tantalum, Columbium, and Ferrocolumbium Producers (in L992)a
Facility Name
Location
Type of Products
Cabot Corp.
Boyertown, PA
Cb and Ta pentoxide/metal, FeCb, Ta
capacitor powder
Kennametals, Inc.
Latrobe, PA
Cb and Ta carbide
Herman C. Stark Inc. (NRC, Inc.)
Newtown, MA
Cb and Ta metal, Ta capacitor powder
Reading Alloys, Inc.
Robesonia, PA
FeCb
Shieldalloy Metallurgical Corp.
Newfield, NJ
FeCb
Teledyne Wah Chang Albany
Albany, OR
Cb pentoxide/metal, FeCb
Thai Tantalum Inc.
Gernee, IL
Ta metal
a - 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 Coiumbium 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
The concentrate or slag is digested with aqueous hydrofluoric acid (sometimes in conjunction with
sulfuric 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
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.
-------
EXHIBIT 2
PRIMARY COLUMBIUM-TANTALUM PROCESS
(Adapted from: U.S. Environmental Protection Agency, 1989, p. 4359.)
IIP
Ore
Mill
1
Digestion
1
| II2<) as
¦ Needed
MIRK
(Recycle)
Cangue
(Waste)
Nb, Ta
Impurities
Extraction
IIF
Nb Impurities
(IITBK)
la
I
Fresh MIBK
MIBK
Extraction
Impurities
(Waste)
n
(MIBK)Nb
4_i
Deionized
Water
^Nll,
(ll20) Nb
Extraction
Fresli
MIBK
FUl rate
(Waste)
t
Extraction
ll2()
+
Ta
Nllj
Deionized
Water
Or
Precipitation
I'recipltution
1
1
'
Filtrate
Kilter
Filter
(Waste)
1
'
Calclner
Calcincr
1
Nb (Oxide)
l a (Oxide)
'
Nb Reduction
Nb Reduction
. ( 'ollllllllilllll
' M.lul
i
. 1:1111 :iltini
' Met.il
KF
I
Precipitation
Filter
(or Central
litigation)
Dryer
Ta (Salt)
I n Reduction
T
I iintiiliiin Metal
Filtrate
(Waste)
o»
¦vj
-------
668
generates an acid mist that may be controlled by wet scrubbers. The scrubber liquor is a source of
wastewater.11
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 (Ta2Os) 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 the 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
the mixture. Columbium and tantalum are reduced to metal while aluminum is oxidized.1'
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.
12 Ibid.
13 L.D. Cunningham, 1992, Op. Cit., pp. 438-39.
14 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 4352.
15 Ibid-- p. 4353.
16 Ibid.
17 Ibid.
-------
669
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.18
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. "Hie 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).19
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 wav 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 pyTochlore concentrates, usually by an aluminothermic process with
an iron-iron oxide mixture. Exhibit 5 illustrates this process. Pyrochlore, 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.
19 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.
a*
23 U.S. Environmental Protection Agency, 1989, Op. Cit.. p. 4354.
-------
670
EXHIBIT 3
ELECTRON BEAM MELTING
rom: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 552.)
High Voltage Power Lead
Tantalum
Feedstock
Molten Pool
Ingot Puller
-------
671
EXHIBIT 4
VACUUM ARC MELTING
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 551.)
Electrode
Dnve
Vacuum
Tantalum
Ingot
Cooled
Mold ¦
r
~L
m
Power Terminal
-•""E
Vacuum
Seal
Electrode
Holder
Tantalum
Feedstock
, Molten
Pool
Power
Terminal
-------
672
EXHIBIT 5
FERROCOLUMBIUM PRODUCTION
Pyrochlore (Ore)
Aluminum
Iron Scrap or Oxide ¦
Lime
or
Fluorspar
Furnace
FeCb
Slag
Crushing
T
Sizing
~
Ferrocolumbium
-------
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.25
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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/Beneficiation 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 withinahis 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.
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.
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.
26 I. Gaballah, 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.
-------
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.
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.2'
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.
-------
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 characteristics 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 characteristics 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. 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 is classified as 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 ferrocolumbium. 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.
-------
D. Ancillary 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, tank cleaning wastes,
and polychlorinated biphenyls from electrical transformers and capacitors. Non-hazardous wastes may
include sanitary sewage, and waste oil and other lubricants.
-------
677
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.
-------
ATTACHMENT 1
-------
SUMK
OF EPA/ORD, 3007. AND RTI SAMPLING DATA - PROCESS WASTB
:R - TANTALUM/COLUMBIUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis - PPM
TC
# Values
Constituents
Minimum
Average
Maximum
K Detects
Min. Avg. Max. # Detects
Level
In Excess
Aluminum
50000
50000
50000
1/1
- _ 0/0
-
-
Antimony
0 010
6.461
30.00
10/10
0/0
-
-
Arsenic
0.003
6.256
45.00
13/13
0/0
5.0
0
Barium
-
-
-
0/0
0/0
100.0
0
Beryllium
0.001
0.126
0.500
13/13
0/0
-
-
Boron
-
-
-
0/0
0/0
-
-
Cadmium
0.008
6.392
40.00
13/13
0/0
1.0
0
Chromium
0.006
232.846
1000
13/13
0/0
5.0
0
Cobalt
-
-
-
0/0
0/0
-
-
Copper
0.200
56.553
300
13/13
0/0
-
-
Iron
25000
25000
25000
1/1
0/0
-
-
Lead
0.020
255.869
1000
13/13
0/0
5.-0
0
Magnesium
-
-
-
0/0
0/0
-
-
Manganese
-
-
-
0/0
0/0
-
-
Mercury
0.000
0.013
0.063
13/13
0/0
0.2
0
Molybdenum
-
-
-
0/0
0/0
-
-
Nickel
0.500
2.460
10
10/10
0/0
-
-
Selenium
0.002
13.507
70
10/10
0/0
1.0
0
Silver
0.020
0.050
0.070
4/4
0/0
5.0
0
Thallium
0.050
0.406
1.180
9/9
0/0
-
-
Vanadium
7800
7800
7800
1/1
0/0
-
-
Zinc
0.600
331.960
1000
10/10
0/0
-
-
Cyanide
0.001
0.006
0.033
17/17
0/0
-
-
Sulfide
2650
14037.50
45000
4/4
0/0
-
-
Sulfate
-
-
-
0/0
0/0
-
-
Fluoride
10000
45750
130000
4/4
0/0
-
-
Phosphate
-
-
-
0/0
0/0
-
-
Silica
40000
40000
40000
1/1
0/0
-
-
Chloride
900
9450
18000
2/2
0/0
-
-
TSS
-
-
-
0/0
0/0
-
-
pH *
3.0
8.4
12.0
5/5
212
2
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable, theretore. only EP data are presented.
-------
682
-------
683
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 refiner}' in the United States (ASARCO -
Amarillo. TX). Selenium is also recovered from the copper anode slimes during this process (see
Selenium). 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
L. Discussion of Typical Production Processes
Nearly all tellurium is obtained as a 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.4
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.
4 "Tellurium," 1983, Op. Cit.. p. 663.
-------
684
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
Sullunc
Acid
Sodium
Hvdroxide
Sodium
Sulfide
I
Telluruus Acid Precipitate
-------
685
EXHIBIT 2
PURIFICATION OF TELLURIUM BY ACID PRECIPITATION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 204 - 210.)
Crude Tellurous Acid Solids
Hydrochloric or
Suliiinc Acid
Sulfur
Dioxide
Water
*
Wastewater
Wastewater
Tellurium Metal
-------
686
EXHIBIT 3
ELECTROLYTIC PURIFICATION OF TELLURIUM
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 204 - 210.)
Crude Telluruus-Acid Solids
Sodium
Hvdroude
Water
*
Tellurium Metal
-------
687
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.' 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.s
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
5 Ibid., p. 662.
6 Ibid.
7 Ibid.
8 Ibid.
9 Ibid.
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688
a strong nitric acid, hvdrolvzed to white 2Te02N03 and precipitated by diluting and boiling, and
separating. The resultant precipitate is washed (redissolving and rehvdrolvzing. if desired), dissolved in
hydrochloric acid, and reduced with sulfur dioxide. Ultra high-puritv tellurium is prepared by zone
refining in a hydrogen or inert-gas atmosphere.10
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.11
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
None Identified.
4. Beneficiation/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.12 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/vr. 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 is
classified as a by-product.
Solid waste residues. Solids, likely containing sulfur, are generated from precipitation as
impurities and are discarded as waste.13 Although no published information regarding waste
generation rate or characteristics was found, we used the methodology outlined in Appendix A of.
10 Ibid.
11 Ibid.
12 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.
13 U.S. Environmental Protection Agency, 1988, Op. Cit, pp. 204 - 210.
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this report to estimate a low, medium, and high annual waste generation rate of 100 metric
tons/vr. 1.000 metric tons/vr. 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.
Wastewater. There is wastewater associated with the neutralization steps that follow both the
addition of sulfuric 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/yri 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 is 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenyls from electrical transformers and
capacitors.
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690
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.
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TIN
A. "* Commodity Summary
The primary source of tin is the mineral cassiterite, Sn02, 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 reverberatorv 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 cassiterite
(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 cassiterite (tin oxide concentrate) to produce tin and carbon dioxide. The silica
flux reacts with cassiterite 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
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.
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692
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
Smelting
Furnace
Offgas to Scrubber
Slag
Cell Slimes to Recycle
Waste Acid
Casting
T
Tin Product
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fluxes to create a liquid slag. Unreacted carbon in the fuel reduces the stannous silicate to tin and the
ferrous silicate to iron.7,8 In addition to molten tin and slag, an off-gas is 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) Process(es)
A research program is being conducted at the Colorado School of Mines for developing a
pvTOchemical 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.
' U.S. Environmental Protection Agency, "Tin," from 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988, pp. 3-214.
8 Carr, D., ed., 1994, Op. Cit., p. 672.
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,
MaVch 13-18, 1993, sponsored by the Minerals, Metals, & Materials Society, Warrendale, PA.
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694
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 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.'
13 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-211.
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695
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 Newlv 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 Texas City smelter generated 22,000 liters of wastewater per metric ton
of tin produced.16 Process wastewater 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).17 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 electrolvtically, generate solid and
liquid wastes, as described below.
14 U.S. Environmental Protection Agency, Newlv Identified Mineral Processing Waste
Characterization Data Set. Office of Solid Waste. August 1992, p. 1-7.
15 Ibid.
16 U.S. Environmental Protection Agency, 1988, Op. Cit., p. 3-214.
17 U.S. Environmental Protection Agency, 1992, Op. Cit., pp. 34-2.
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696
Dross
Dross forms during pvrometallurgical 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 tonsfyr, respectively. We used best engineering judgment to
determine that this waste may exhibit the characteristic of toxicity (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/Vr, 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. 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, respecti%ely.
We used best engineering judgment to determine that this waste may exhibit the characteristics of
toxicity (lead) and corrosivity.
D. Ancillary 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), 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
waste oil and other lubricants.
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.
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697
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. 3rd ed. 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. Newlv Identified Mineral Processing Waste Characterization Data
Set. Office of Solid Waste. August 1992.
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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% 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
llmenite (FeTi03) is the most abundant titanium-bearing mineral and is comprised of about 43%
to 65% titanium dioxide (Ti02). A second major mineral form of titanium is rutile, a crystalline, high-
temperature polymorph of Ti02, containing about 95% Ti02. Another crystalline form of TiO,, 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.4 Other sources of titanium
include titaniferous slags (70-85% Ti02) made by electric furnace smelting of ilmenite with carbon.
B. Generalized Process Description
1. Discussion of Typical Production Processes
Titanium dioxiae pigment is manufactured through either the sulfate, chloride, or chloride-
ilmenite process. The sulfate process, used at only two U.S. plants, employs digestion of ilmenite ore or
Ti02-rich slag with sulfuric acid to produce a cake, which is purified and calcined to produce TiO,
pigment. The sulfate process generates sulfuric acid wastes in as much as two times the product weight,
resulting in expensive 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 purified to form Ti02 pigment. A third 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 Johnsonviile, 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. Each of these processes is described in more detail below.
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.
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700
EXHIBIT 1
U.S. Titanium Dioxide Production Facilities3
Facility Name
Location
Process
Ore Type
E.I. Du Pont de Nemours & Co.,
Inc. (Du Pont)
Antioch, CA
Chloride
Rutile
Du Pont
Edgemoor, DE
Chloride-Ilmenite
Ilmenite
Du Pont
New Johnsonville, TN
Chloride-Ilmenite
Ilmenite
Du Pont
Pass Christian, MS
Chloride-Ilmenite
Ilmenite
Kemira, Inc.
Savannah, GA
Chloride
Rutile
Sulfate
Slag
Kerr-McGee Chemical Corp.
Hamilton, MS
Chloride
Synthetic Rutile
[Cronos, Inc.
Lake Charles, LA
Chloride
Unknown
SCM Chemicals, Inc.
Ashtabula, OH
Chloride
Rutile
S. African Slag
SCM Chemicals, Inc.
Baltimore, MD
Chloride
Rutile
Sulfate
S. African Slag
0 J. Gambogi. 1993, Op. Cil. 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 Ti02 content
is digested with sulfuric acid, forming a porous cake; this cake is further dissolved by dilute acid to form
titanyl sulfate (Ti0S04). Scrap iron is added to the digestion process to ensure that iron impurities
remain in the ferrous (Fe2+) state so that the eventual TiOz product can be easily washed. The titanyl
sulfate solution is clarified, yielding a waste sludge, and then concentrated through vacuum evaporation,
which promotes crystallization of copperas (ferrous sulfate heptahydrate, FeS04 - 7H20) to remove iron.
(If low-iron, high-Ti02 slag is used as feed, it is not necessary to crystallize copperas.) Copperas by-
product is separated by filtration, which also removes a second 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 Ti02 product.5
Chloride Process
In the chloride process, presented in Exhibit 4, rutile or high-grade ilmenite is converted to
titanium tetrachloride (TiCl4). TTie conversion takes place in a chlorinator (i.e., fluidized bed reactor) in
5 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-221 - 3-222.
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701
EXHIBIT 2
U.S. Titanium Sponge and Ingot Production Facilities13
Facility Name
Location
Product
Howmet Corp., Titanium Ingot Div.
Whitehall, MI
Ingot
A Johnson Metals Corp.
Lionville, PA
Ingot
Lawrence Aviation Industries, Inc.
Port Jefferson. NY
Ingot
Oregon Metallurgical Corp. (Oremet)
Albany, OR
Sponge & Ingot
RMI Co.
Niles, OH
Ingot
Teledvne Allvac
Monroe, NC
Ingot
Teledvne Wah Chang Albany
Albany, OR
Ingot
Titanium Hearth Technologies of America
Lionville, PA
Ingot
Titanium Metals Corp. of America (Timet)
Henderson, NV
Sponge & Ingot
Viking Metallurgical Corp.
Verdi, NV
Ingot
Wyman-Gordon Co.
Worcester, MA
Ingot
b J. Gambogi. 1993. Op Cil., p. 11.
the presence of chlorine gas at 850° C to 950° C, with petroleum coke added as a reductant. All U.S.
producers of TiCl4 use fluid-bed chlorinators; static-bed systems can also 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.'"
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 (VOCl3), 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 VOCl2, or by complexing with copper
(not shown in Exhibit 4). The purified TiCl4 is then oxidized to Ti02 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 TiOz product.8
Chloride-Ilmenite Process
In the chloride-ilmenite process, presented in Exhibit 5, low-grade ilmenite (approximately 65
percent Ti02) is converted to TiCl4. The ilmenite ore used in the process contains a much larger amount
6 J. Gambogi, 1993, Op. Cit.. p. 3.
' U.S. Environmental Protection Agency, "Titanium Tetrachlorid 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.
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EXHIBIT 3
SULFATE PROCESS FOR TITANIUM DIOXIDE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-221.)
Ilmemte Ore or
High Ti02 Slag
4 Ti02 Product
I -2
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EXHIBIT 4
CHLORIDE PROCESS FOR TITANIUM DIOXIDE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-223.)
| Rutile or High Grade/
X Processed Ilmemte
Ti02 Product
-------
o
-t*
EXHIBIT 5
CHLORIDE-ILMENITE PROCESS SCHEMATIC ; DELISLE PLANT
(Adapted from: U.S. EPA National Survey of Solid Wastes from mineral Processing Facilities: Questionnaire # 102013, 198'J.)
^Ore
-------
705
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% Ti02 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
TiC14 to Ti02 is similar to that used in the chloride process, as described above.
Titanium Sponge CKroll 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.
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 (MgCI2), which is tapped
from the bottom of the reactor. The MgCl2 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, MgCl2, and unreacted TiCl4, 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 (HN03) 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 MgCl2 stream
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 Allovs," Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol.
XXIII, 1981, p. 114.
12 J. Gambogi, 1993, Op. Cit.. p. 4.
13 "Titanium and Titanium Alloys," 1981, Op. Cit., p. 116.
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706
EXHIBIT 6
KROLL PROCESS FOR TITANIUM SPONGE PRODUCTION
(Adapted from: U.S. Environmental Protection Agency, 1988, p. 3-223.)
| Ti'CI4
-------
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.15,16 After drying, crushing, and screening, the
sponge is packaged in air-tight 23-kg drums before further processing into ingots. Sponge can also be
crushed to create titanium powder.
Titanium Ingot
Titanium ingots are formed from sponge using two or more successive vacuum-arc melting
operations.1' 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) Process(es)
The United States Bureau of Mines is actively researching new processes to produce titanium
alloys, with a focus on developing a continuous process to produce titanium powder for metallurgical
applications. The Bureau is also conducting research on improving 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 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
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.t
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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 Ti02 in the ore undergoes a significant chemical change through
conversion by H2S04 to Ti0S04. In both the chloride and chloride-ilmenite processes, the
beneficiation/processing line occurs just before the chlorination step. Similarly, beneficiation ends and
mineral processing begins at this point because Ti02 is chemically converted to TiCl4 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/Beneflciation 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 ceils and, based on EPA data, 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 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.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.
Waste Solids
Waste solids are generated at two points in the sulfate process. The first point occurs when titanvl
sulfate (TiOS04), which is generated by digesting ilmenite or slag with sulfuric acid, is clarified. Waste
sludge is also generated when copperas by-product (FeS04 ¦ 7H20) 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 1 million metric tons per facility annually. (Volume data are unavailable for this
waste stream due to confidential business information [CBI] designation.) The waste did pass the low
hazard criterion for special waste status.20
io ^
U.S. Environmental Protection Agency, 1988, Op. Cit.. p. 3-219.
20 55 FR 2341-2342.
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Waste Acids
Waste acids are generated when titania hydrate, generated by vacuum-evaporation and hydrolysis
of titania sulfate, is filtered prior to washing. At 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 The volume of this
waste stream generated annually is unavailable due to CB1 designation, but it did pass the high volume
criterion for special waste status of 1 million metric tons per facility annually. 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 slurry and 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
disposed in a landfill. In addition, the chloride and chloride-ilmenite processes generate several other
waste streams, ferric chloride and ferric chloride sludge, scrubber water and solids, and vanadium
oxychloride.
Waste Acids
Waste acids from the chloride and the chloride-ilmenite processes are generated in the
chlorination 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 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 are generated annually. We used best engineering judgement to
determine that this waste may be partially recycled and may exhibit the characteristics of toxicity
(chromium, selenium, and lead) and corrosivity. This waste is classified as a spent material. Data for this
wastestream are presented in Attachment 1.
Waste Solids
Waste solids from the chloride ana tne cnionae-ilmenite processes are generated in the
chlorination step as a combined acids/solids slurry and are classified as a mineral processing special waste.
The combined waste acids and solids are treated by a solids/liquids separation process, and the resulting
chloride process waste solids (a special waste) are landfilled. while the chloride process waste acids are
21 ICF 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.
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deep-well injected. Approximately 414.000 metric tons of waste solids are generated annually.24
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 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 for waste ferric chloride of 22,000 metric tons/yr, 29,000 metric tons/vr,
and 35,000 metric tons/yr, respectively. We used best engineering judgement 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 is classified as a by-product. Data for this
wastestream 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 24,000 metric tons/yr, 30,000 metric tons/yr,
and 36,000 metric tons/yr, respectively.. 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.
Two scrubber water wastestreams are generated in the chloride process, as described below. Data
describing these wastestream 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.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 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^r] is due to commingling of numerous
wastestreams.) We used best engineering judgement 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.26 We used the methodology outlined in Appendix A of this report to estimate a low,
24 Ibid.
25 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.
26 Ibid.
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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
judgement 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 (VOCl2), 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 judgement 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 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
wastestreams.) Existing data (Attachment 1) 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 Plant Sludge/Solids
Wastewater treatment plant sludge/solids, also a post-mineral processing waste, consists of sludges
and solids resulting from the treatment of the wastewaters described above. Sludge/solids are disposed in
on- or off-site landfills. Approximately 420,000 metric tons are generated annually.27 We used best
engineering judgement to determine that this waste may exhibit the characteristics of toxicity (chromium).
Data describing this wastestream 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 has 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/yT, and 6,700 metric tons/yr, respectively. We used best engineering judgement to determine
that this waste may be recycled and may exhibit the characteristics of toxicity (chromium and lead). This
waste is classified as a spent material. Data describing this wastestream are presented in Attachment 1.
27 U.S. Environmental Protection Agency, 1992, Op. Cit., p.1-7!
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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.28 We used best engineering judgement to determine that this waste
may exhibit the characteristic of toxicity (chromium and lead). Data describing this wastestream 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 judgement suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material
further.
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.29 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
wastestreams.) 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.
Melt Cell Scrubber Water
If the reduction process is conducted rapidly, excess MgCl2 can be generated and is collected in a
nielt 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.30 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 judgement
suggest that this material does not exhibit any characteristics of hazardous waste. Therefore, the Agency
did not evaluate this material further.
28 Ibid.
29 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 4862.
30 Ibid.
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713
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.31 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 wastestreams.) 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.
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 convened to titanium metal through sodium* reduction.32 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/Vr, 8,600
metric tons/yr, and 10,000 metric tons/yr, respectively. 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.
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.33 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 judgement 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 MgCl2 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.34 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/fyT,
and 580,000 metric tons/yr, respectively. We used best engineering judgement to determine that this waste
31 Ibid.
32 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 4863.
33 Ibid.
34 ICF Incorporated, Timet Corporation: Mineral Processing Waste Sampling Visit — Trip Report,
August 1989, p. 3.,
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may be partially recycled and may exhibit the characteristics of corrosivity and toxicity (chromium and
lead). This waste is classified 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
wastestreams 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/vr,
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 wastestreams.) 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.
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 judgement to determine that this waste may be recycled and may
exhibit the characteristic of reactivity with water. This waste is 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 judgement suggest that this material does not
exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this material
further.
Ingot production generates six 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.35 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 judgement 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 is classified as a spent material. Data describing
this wastestream are presented in Attachment 1.
35 U.S. Environmental Protection Agency, 1989, Op. Cit., pp. 4843, 4864, 4945.
-------
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.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
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 judgement 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, supended solids, and
metals.37 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 judgement 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
judgement 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.38
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 judgement suggest that this material
does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate this
material further.
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.39 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 judgement suggest that this
material does not exhibit any characteristics of hazardous waste. Therefore, the Agency did not evaluate
this material further.
36 Ibid.
37 Ibid.
38 U.S. Environmental Protection Agency, 1989, Op. Cit., pp. 4946.
39 Ibid.
-------
716
D. Ancillary Hazardous 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), 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 waste oil and other lubricants.
-------
717
BIBLIOGRAPHY
Derktcs, 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. Kemira. 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.
-------
718
-------
ATTACHMENT 1
-------
720
-------
'SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - PICKLE LIQUOR AND WASH WATER FROM INGOT PRODUCTION - TITANIUM
Total Constituent Analysis
- PPM
EP Toxicity Analysis
PPM
TC
H Values
Constituents
Minimum
Average Maximum
tt Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.027
0.579
0.88
3/3
-
-
0/0
-
-
Arsenic
0.06
0.3167
0.62
3/3
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.0002
0.0011
0.002
3/3
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.19
0.227
0.28
3/3
-
-
0/0
1.0
0
Chromium
0.21
0.26
0.3
3/3
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.54
0.94
1.7
3/3
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
2.6
3.17
4
3/3
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0011
0.002
3/3
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
1.3
1.83
2.6
3/3
-
-
0/0
-
-
Selenium
0.009
0,14
0.22
3/3
-
--
0/0
1 0
0
Silver
0.0014
0.50
1.2
3/3
-
-
0/0
5.0
0
Thallium
1.7
2.83
3.8
3/3
-
-
0/0
-
-
Vanadium
-
. -
-
0/0
-
-
0/0
-
-
Zinc
0.43
0.53
0.67
3/3
-
-
0/0
-
-
Cyanide
0.01
3333.67
10000
3/3
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
- -
0/0
-
-
0/0
-
-
pH '
-
-
-
0/0
212
0
Organlcs (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the deletion limit. TCLP data are currently unavailable, therefore, only EP data are presented
-------
SEKtRrHFTrOFEPA/ORD, 3007, AND RTI SAMPLING DATA - SPENT BRINE TREATMENT FILTER CAKE - TITANIUM
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
tt Detects
TC
Level
# Values
In Excess
AMrtiinum
-
-
-
0/0
-
0/0
-
_
Aftwwony
-
-
-
0/0
-
0/0
-
-
Arsanic
-
-
-
0/0
-
0/0
5.0
0
Barttim
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
_
Cadmium
-
-
-
0/0
-
0/0
1 0
0
Ghrtftftium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron'
-
-
-
0/0
-
0/0
-
-
Lead
-
-
-
0/0
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
--
-
0/0
-
0/0
-
_
Zinc
-
-
-
0/0
-
0/0
_
Cyanide
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
_
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
40000
40,000
40,000
1/1
_
0/0
-
_
TSS
-
-
-
0/0
_
0/0
-
-
pH '
10.1
10.1
10.1
1/1
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non.-rdetects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
fjb.«r(.i.itf*ARY"OF EPA/ORD, 3007. AND RTI SAMPLING DATA - WASTEWATER i ..cATMENT PLANT LIQUID EFFLUENT - TITANIUM DIOXIDE
Total Constituent Analysis - PPM
EP Toxicity Analysis - PPM
TC
It Values
Constituents
Minimum
Average
Maximum
ft Detects
Minimum Average Maximum
It Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chromium
0.01
0.01
0.01
1/1
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
1.10
1.10
1.10
1/1
-
0/0
-
-
Lead
0.01
0.01
0.01
1/1
-
0/0
5.0
0
Magnesium
-
-
-
0/0
- -
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
0.02
0.02
0.02
1/1
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
-
-
-
0/0
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
160,000
160,000
160,000
1/1
-
0/0
-
-
TSS
70,000
70,000
70,000
1/1
-
0/0
-
-
PH '
7
7.15
7.3
2/2
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detection limit. IULP data are currently unavailable; therefore, only EP data are presented
-------
OTW0amyWEPA/ORD, 3007, and resampling data - surface impoundment-liquids—titanium dioxide-
Baflum
QftOStituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
# Values
In Excess
Aluminum
3900
12,543
16,000
7/7
-
0/0
-
Antimony
-
-
-
0/0
-
0/0
-
-
AKssnioui
-
-
-
0/0
-
0/0
5 0
0
Baiium
60
60.00
60.00
2/2
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chromium
203
338
524
9/9
-
0/0
5.0
0
Gbbalt
20
20.00
20.00
2/2
-
0/0
-
-
Copper
9
9.00
9.00
2/2
-
0/0
-
-
frony
0.2
67,194
97,000
10/10
-
0/0
-
-
Lead
0.005
74.60
139
10/10
-
0/0
5.0
0
Magnesium
100000
100,000
100,000
1/1
-
0/0
-
-
Manganese
200
1,629
5,200
7/7
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
02
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
13.00
13.00
13.00
2/2
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
553
553
553
2/2
-
0/0
-
-
Zinc
-
-
-
0/0
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
0.2
0
0
1/1
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
6,100
108,773
200,000
13/13
-
0/0
-
-
TSS
0.60
592
2,000
11/11
-
0/0
-
-
pH *
4.00
6.25
7.00
4/4
212
0
Organics (TOC)
32.00
32.00
32.00
2/2
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therelore, only EP data are presented
-------
fSMKSMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - TITANIUM DIOXIDE
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
tt Values
In Excess
Aluminum
2,822
11,502
14,395
4/4
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
43.00
138
169
4/4
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chrpmium
10.00
497
887
6/6
-
0/0
5.0
0
Cobalt
20.00
20.00
20.00
1/1
-
0/0
-
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
17,000
51,509
70,000
5/5
-
0/0
-
-
Lead
a. oo
113
167
5/5
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
730
2,200
3,700
5/5
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
6.00
60.75
79.00
4/4
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
10.00
628
893
5/5
-
0/0
-
-
Zinc
62.00
62.00
62.00
1/1
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
290
290
290
1/1
-
0/0
-
-
Silica
57,369
57,369
57,369
3/3
-
0/0
-
-
Chloride
1,500
26,175
100,000
4/4
-
0/0
-
-
TSS
98,000
512,000
800,000
4/4
-
0/0
-
-
PH *
3.9
5.9
7.0
7/7
212
0
Organics (TOC)
19.00
318,755
425,000
4/4
-
-
Non-delects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable, therefore, only EP data are presented
-------
jStPMA'RY'OF'EPA/ORD. 3007, AND RTI SAMPLING DATA - LEACH LIQUOR AND SPONGE WASH WATER - TITANIUM AND TITANIUM DIOXIDE
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
G9!)stituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
H Detects
Level
In Excess
Aluminum
2.50
2.50
2.50
1/1
0.05
0.28
0.50
2/2
-
-
flftllmony
0.07
1.29
2.50
2/2
0.50
0.50
0.50
2/2
-
-
'Arsenic
0.10
1.30
2.50
2/2
0.01
0.26
0.50
2/2
5.0
0
Bafl'um
2.50
2.50
2.50
1/1
0.50
0.72
0.93
2/2
100.0
0
Beryllium
0.00
0.13
0.25
2/2
0.025
0.038
0.050
2/2
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Qsklmium
0.16
0.21
0.25
2/2
0.025
0.038
0.050
2/2
1.0
0
(Mrromium
1.20
1.85
2.50
2/2
0.080
0.29
0.50
212
5 0
0
©ctoalt
2.50
2.50
2.50
1/1
0.050
0.28
0.50
2/2
-
-
©opper
2.50
2.70
2.90
2/2
0.50
1.05
1.60
2/2
-
-
Iron
9.42
9.42
9.42
1/1
0.020
3.28
6.55
2/2
-
-
Lead
1.25
2.03
2.80
2/2
0.010
0.13
0.25
212
5.0
0
Magnesium
5,000
25,667
40,000
3/3
25,700
43,800
61,900
2/2
-
-
Manganese
2.50
2.50
2.50
1/1
0.50
3.24
5.98
212
-
-
Mercury
0.0002
0.0009
0.0016
2/2
0.00010
0.00055
0.0010
212
0.2
0
Molybdenum
2.50
2.50
2.50
1/1
0.50
0.50
0.50
1/1
-
-
Nickel
2.50
4.75
7.00
2/2
0.17
0.34
0.50
212
-
-
Selenium
0.01
1.26
2.50
2/2
0.010
0.26
0.50
212
1.0
0
Silver
0.03
1.27
2.50
2/2
0.03
0.26
0.50
212
5.0
0
Thallium
2.40
7.45
12.50
1/2
0.55
1.53
2.50
212
-
-
Vanadium
2.50
2.50
2.50
1/1
0.50
1.10
1.70
2/2
-
-
Zinc
0.54
1.52
2.50
212
0.50
0.52
0.54
212
-
-
Cyanide
0.01
0.01
0.01
1/1
¦-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
-
0/0
-
-
Fluoride
198
198
198
1/1
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
115
43,023
80,000
5/5
-
-
-
0/0
-
-
TSS
50,000
50,000
50,000
1/1
-
-
-
0/0
-
-
pH*
0
0.50
1
2/2
212
2
Organics (TOC)
1,670
1,670
1,670
1/1
-
-
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 - SCRUBBER WATER - TITANIUM (CHLORIDE PROCESS)
Constituents
Total Constituent.Analysis - PPM
Minimum Average Maximum H Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum tt Detects
TC # Values
Level In Excess
Aluminum
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
-
-
Antimony
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
-
-
Arsenic
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
5.0
0
Barium
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
100.0
0
Bervilium
0.15
0.15
0.15
1/1
0.10
0.10
0.10
1/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.050
0.050
0.050
0/1
0.050
0.050
0.050
0/1
1 0
0
Chromium
0.50
0.50
0.50
0/1
6.45
6.45
6.45
1/1
5.0
1
Cobalt
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
-
-
Copper
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
-
-
Iron
0.50
0.50
0.50
0/1
25.70
25.70
25 70
1/1
-
-
Lead
0.25
0.25
0.25
0/1
0.25
0.25
0.25
0/1
5.0
0
Magnesium
5.87
5.87
5.87
1/1
6.56
6.56
6.56
1/1
-
-
Manganese
0.50
0.50
0.50
0/1
0.50
0 50
0.50
0/1
-
-
Mercury
0.00010
0.00010
0.00010
0/1
0.00028
0.00028
0.00028
1/1
0.2
0
Molybdenum
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
-
-
Nickel
0.50
0.50
0.50
0/1
2.79
2 79
2.79
1/1
-
-
Selenium
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
1 0
0
Silver
0.50
0.50
0.50
0/1
0.50
0.50
0.50
0/1
5 0
0
Thallium
2.50
2.50
2.50
0/1
2.50
2.50
2.50
0/1
-
-
Vanadium
1.51
1.51
1.51
1/1
1.82
1.82
1.82
1/1
-
-
Zinc
0.50
0.50
0.50
0/1
0.50
0.50
0 50
0/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
15.40
15.40
15.40
1/1
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
235,000
235,000
235,000
1/1
-
-
-
0/0
-
-
TSS
3,740
3,740
3,740
1/1
-
-
-
0/0
-
-
pH '
0.5
1.2
1.9
212
212
2
Organics (TOC)
-
-
-
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 - WASTEWATER TREATMENT PLANT SLUDGE/SOLIDS - TITANIUM DIOXIDE
(TftristitimntS
Total Constituent Analysis - PPM
Minimum Average Maximum tt Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
tt Detects
TC
Level
tt Values
In Excess
Aluminum
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
-
-
-
0/0
-
0/0
1.0
0
Chromium
58
679
1,300
2/2
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Coooar
-
-
-
0/0
-
0/0
-
-
Iron.
17000
27,000
37,000
2/2
-
0/0
-
ILead
8
8.00
8.00
1/1
-
0/0
5.0
0
Maanesium
9000
9,000
9,000
1/1
-
0/0
-
-
Manaanese
730
1,865
3,000
2/2
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
fsllcKei
6
6.00
6.00
1/1
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
--
-
Vanadium
600
600
600
1/1
-
0/0
-
-
Zinc
-
-
-
0/0
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide.
-
-
-
0/0
-
0/0
-
-
Sulfate
11000
11,000
11,000
1/1
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
40000
40,000
40,000
1/1
-
0/0
-
-
Chloride
1500
40,750
80,000
2/2
-
0/0
-
-
TSS
98000
98,000
98,000
1/1
-
0/0
-
-
pH'
7.8
9.4
11
2/2
212
0
Organics (TOC)
-
-
-
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 - FERRIC CHLORIDE - TITANIUM
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
# Detects
TC # Values
Level In Excess
Aluminum
-
0/0
930
930
930
1/1
-
-
Antimony
-
0/0
25
25
25
1/1
-
-
Arsenic
_
0/0
0.083
0.083
0.083
1/1
5.0
0
Barium
_
0/0
23
23
23
1/1
100 0
0
Beryllium
-
0/0
1.8
1.8
1.8
1/1
-
Boron
_
0/0
18
18
18
1/1
-
-
Cadmium
_
0/0
1.5
1.5
1.5
1/1
1.0
1
Chromium
_
0/0
310
310
310
1/1
5.0
1
Cobalt
_
0/0
9.9
9.9
9.9
1/1
-
-
Copper
-
0/0
18
18
18
1/1
-
-
Iron
_
0/0
48000
48000
48000
1/1
-
-
Lead
_
0/0
58
58
58
1/1
5.0
1
Magnesium
- - -
0/0
970
970
970
1/1
-
-
Manganese
-
0/0
2200
2200
2200
1/1
-
-
Mercury
-
0/0
0.02
0.02
0.02
1/1
0.2
0
Molybdenum
-
0/0
8.8
8.8
8 8
1/1
-
-
Nickel
_
0/0
30
30
30
1/1
-
-
Selenium
_
0/0
0.02
0.02
0.02
1/1
1.0
0
Silver
0/0
6.2
6.2
62
1/1
5.0
1
Thallium
_
0/0
0 004
0.004
0.004
1/1
-
-
Vanadium
_
0/0
320
320
320
1/1
-
-
Zinc
_
0/0
52
52
52
1/1
-
-
Cyanide
-
0/0
-
-
-
0/0
-
-
Sulfide
_
0/0
-
-
-
0/0
-
-
Sulfate
_
0/0
326
326
326
1/1
-
-
Fluoride
_
0/0
2
2
2
1/1
-
-
Phosphate
-
0/0
-
-
-
0/0
-
-
Silica
_
0/0
-
-
-
0/0
-
-
Chloride
_
0/0
104160
104160
104160
1/1
-
-
TSS
_
0/0
-
-
-
0/0
-
-
pH *
-
0/0
212
0
Organics (TOC)
-
0/0
-
-
Non-detects were assumed lo 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
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
# Values
In Excess
Aluminum
447
10,612
16,000'
4/4
-
0/0
-
-
Antimony
1.73
1.73
1.73
1/1
-
0/0
-
-
Arsenic
0.0050
0.0050
0.0050
0/1
-
0/0
5.0
0
Barium
0.50
0.50
0.50
0/1
-
0/0
100.0
0
Beryllium
0.05
0.05
0.05
0/1
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
0.11
0.11
0.11
1/1
-
0/0
1.0
0
Chromium
35.80
637
3,300
6/6
-
0/0
5.0
0
Cobalt
0.78
0.78
0.78
1/1
-
0/0
-
-
Copper
0.050
0.050
0.050
0/1
-
0/0
-
-
Iron
12.00
27,552
72,000
8/8
-
0/0
-
-
Lead
0.0025
38.67
58.00
2/3
-
0/0
5.0
0
Magnesium
7.60
1,916
4,800
3/3
-
0/0
-
-
Manganese
46.00
2,087
7,900
4/4
-
0/0
-
-
Mercury
0.00020
0.00020
0.00020
1/1
-
0/0
0.2
0
Molybdenum
0.25
0.25
0.25
0/1
-
0/0
-
-
Nickel
0.61
0.61
0.61
1/1
-
0/0
-
-
Selenium
0.0050
0.0050
0.0050
0/1
-
0/0
1.0
0
Silver
0.0050
0.0050
0.0050
0/1
-
0/0
5.0
0
Thallium
0.0050
0.0050
0.0050
0/1
-
0/0
-
-
Vanadium
13.00
331
1,500
5/5
-
0/0
-
-
Zinc
27.00
27.00
27.00
1/1
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
44.00
1,022
2,000
2/2
-
0/0
-
-
Chloride
76,000
124,500
210,000
4/4
-
0/0
-
-
TSS
10,000
47,000
200,000
6/6
-
0/0
-
-
pH *
2.00
2.00
2.00
1/1
212
1
Organlcs (TOC)
40.00
40.00
40.00
1/1
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SI ARY OF EPA/ORD, 3007. AND RTI SAMPLING DATA - WASTE ACIDS -
tNIUM (SULFATE PROCESS)
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
tt Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
2.50
253
480
3/4
0.05
363
1,030
2/4
T
-
Antimony
0.50
1.15
2.50
1/4
0.50
2.25
5^00
1/4
-
-
Arsenic
0.0050
0.88
2.50
0/4
0.01
1.33
5.00
1/5
5.0
1
Barium
0.50
1.00
250
0/4
0.05
1.31
5.00
2/5
100.0
0
Beryllium
0.050
0.10
0.25
0/4
0.0050
0.15
0.50
0/4
-
-
Boron
0.025
0.025
0.025
0/1
-
-
-
0/0
-
-
Cadmium
0.050
0.12
0.25
1/4
0.0050
0.12
0.50
1/5
1.0
0
Chromium
2.50
21.63
40.00
3/4
0.080
31.12
83.00
4/5
5.0
3
Cobalt
0.50
1.28
2.50
1/4
0.050
1.64
5.00
1/4
-
-
Copper
0.05
0.89
2.50
0/4
0.050
1.79
5.00
1/4
-
-
Iron
9.42
1544
3000
4/4
0.020
2,174
5,910
4/4
-
-
Lead
0.0025
0.44
1.25
0/4
0.010
0.77
2.50
1/5
5.0
0
Magnesium
223
13.195
40,000
6/6
941
22,685
61,900
4/4
-
-
Manganese
2.50
28.13
51.00
3/4
0.50
39.12
111
3/4
-
-
Mercury
0.00010
0.00048
0.0016
1/4
0.00010
0.00028
0.0010
0/5
0.2
0
Molybdenum
0.25
0.94
2.50
0/4
0.50
2 75
5.00
0/2
-
-
Nickel
0.50
1.03
2.50
1/4
0.17
1.89
5.00
1/3
-
-
Selenium
0.0050
0.88
2.50
0/4
0.010
1 21
5.00
0/5
1.0
1
Silver
0.0050
0.88
2.50
0/4
) 005
1.12
5.00
0/5
5.0
1
Thallium
0.0050
5.00
12.50
1/4
0.55
9.76
25.00
2/4
-
-
Vanadium
2.50
54.63
100
3/4
0.50
77.55
225
3/4
-
-
Zinc
0.50
13.75
27.00
2/4
0.50
7.51
24.00
2/4
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
0/0
-
-
-
0/0
-
-
Sulfate
0
99
198
2/2
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
2.50
30,735
80,000
6/7
-
-
-
0/0
-
-
TSS
50000
65,450
80,900
2/2
-
-
-
0/0
-
-
PH '
0.
0.33
1
3/3
212
3
Organics (TOC)
20.00
845
1,670
2/2
-
-
Non-detects were assumed to be present at 1/2 the detection limit TCLP data are currently unavailable, therefore, only EP data are presented.
-------
733
TUNGSTEN
A. Commodity Summary
More than 20 tungsien-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 metalworking, 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 S180 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.,
crushing, 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 Fallon, 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 stan 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.
-------
734
EXHIBIT 1
Summary of Tungsten Facilities
Facility Name
Location
Products
Buffalo Tungsten
Depew. NY
APT, Tungsten (carbide)
Curtis Tungsten, Incorporated
Upland, CA
Tungsten (concentrate)
General Electric
Euclid, OH
APT, Tungsten (carbide)
OSRAM Sylvania, Inc.
Towanda, PA
APT, Tungsten (carbide)
Kennametal
Fallon; NV
LaTrobe, PA
Tungsten (carbide)
Teledyne Firth Sterling
La Vergne, TN
APT
Teledyne Advance Materials
Huntsville, AL
APT, Tungsten (carbide)
U.S. Tungsten
Bishop, CA
APT
B. Generalized Process Description
1. Discussion of Typical Production Processes
Tungsten is found primarily in quartz veins and contact-metamorphic 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 flotation usually are sent through a reprocessing and scavenger froth
4 Phillip T. Stafford, 1985, Op. Cit.. pp. 881-891.
-------
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 CaW04. 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.
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.
-------
736
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 countercurTently 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. N?, H2, etc.) and
temperature. Blue, brown, or yellow tungsten oxides are possible products. 4
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.15
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.
13 ]bid.
14 Ibid.
15 Ibid.
16 Ibid.
-------
737
EXHIBIT 2
TUNGSTEN PRODUCTION
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, pp. 2963 - 3037.)
Jigging and Tabling to Separate Minerals from Gangues
-------
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
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. 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 in Section B.
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.
17 Phillip T. Stafford, 1985, Op. Cit., pp. 881-891.
-------
C. Process Waste Streams
1. Extraction/Beneficiation Wastes
Mining and Concentrating Ore
Waste fines are generated from handling tungsten ore. The tailings are sent to tailings ponds.18
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
18 U.S. Environmental Protection Agency, 1988, Op. Cit., pp. 2963-3037.
19 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.
-------
740
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 amourtts 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
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
22 U.S. Environmental Protection Agency, 1989, Op. Cit., pp. 2963-3037.
23 Ibid.
24 ]bid.
25 Ibid.
26 Ibid.
27 Ibid.
-------
741
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 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
28 IWd.
29 Ibid.
30 Ibid.
31 Ibid.
32 Ibid.
-------
presents additional waste characterization data for this waste stream. This waste is not expected to be
hazardous.
D. Ancillary 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), acidic tank cleaning wastes, and polychlonnated biphenyls from electrical transformers and
capacitors. Non-hazardous wastes may include tires from trucks and large machinery, sanitary sewage,
waste oil (which may or not be hazardous) and other lubricants.
-------
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. Newlv 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
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. VI. Office of
Water Regulations Standards. May 1989. pp. 2963-3037.
U.S. Environmental Protection Agency. Technical Support for the Development of Hazardous Waste
Disposal Regulations & Guidance, Technical Proposal, Part 4: Technical Approach. September
1989. pp. 4.b.3-6--13.
U.S. Environmental Protection Agency. "Tungsten." From 1988 Final Draft Summary Report of Mineral
Industry Processing Wastes. 1988. pp. 3-228 - 3-244.
-------
744
-------
ATTACHMENT 1
-------
746
-------
.AMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SCRUBBER V.
. EWATER - TUNGSTEN
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
# Values
Constituents
Minimum
Average
Maximum
H Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.1
0.1
0.1
2/2
-
-
0/0
-
-
Arsenic
0.1
0.1
0.1
2/2
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
-
-
-
0/0
-
-
0/0
1.0
0
Chromium
0.04
0.04
0.04
1/1
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
-
-
-
0/0
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.02
0.02
0 02
1/1
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0003
0.0004
212
-
-
0/0
0.2
0
Molybdenum
. -
-
-
0/0
-
-
0/0
-
-
Nickel
0.005
0.005
0.005
1/1
-
-
0/0
-
-
Selenium
0.01
0.01
0.01
2/2
-
-
0/0
1.0
0
Silver
0.02
0.02
0.02
2/2
-
-
0/0
5.0
0
Thallium
0.1
0.1
0.1
2/2
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.06
0.06
0.06
2/2
-
-
0/0
-
-
Cyanide
-
-
-
0/0
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
pH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
010
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
SGHUIMARY*OPEPA/ORD,-3007, AND RTI SAMPLING DATA - TUNGSTIC'ACID RINSE WATER - TUNGSTEN
11 '
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
0 Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.1
0.1
0.1
1/1
-
-
0/0
-
-
Arsenic
0.13
3.665
7.2
2/2
-
-
0/0
5.0
0
Barium
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.03
0.03
0.03
1/1
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.03
0.115
0.2
2/2
-
-
0/0
1.0
0
Chromium
0.1
1.05
2
2/2
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.2
2.6
5
2/2
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.2
10.1
20
2/2
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0005
0.0008
0.0011
2/2
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.05
0.525
1
2/2
-
-
0/0
-
-
Selenium
0.01
0.01
0.01
1/1
-
-
0/0
1.0
0
Silver
0.02
0.155
0.29
2/2
-
-
0/0
5.0
0
Thallium
0.1
0.4
0.7
2/2
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.6
1.3
2
2/2
-
-
0/0
-
-
Cyanide
0.001
0.00975
0.02
4/4
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detction limit TCLP data are currently unavailable; therefore, only EP data are presented.
-------
MMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - TREATMENT
NT EFFLUENT - TUNGSTEN
Total Constituent Analysis
- PPM
EP Toxicity Analysis
- PPM
TC
# Values
Constituents
Minimum
Average Maximum
# Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.002
0.116
0.8
7/7
-
-
0/0
-
-
Arsenic
0.018
0.118
0.446
9/9
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.002
0.009
0.01
7/7
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.02
0.044
0.08
10/10
-
-
0/0
1.0
0
Chromium
0.024
0.087
0.22
7/7
-
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
-
0/0
-
-
Copper
0.01
0.047
0.148
10/10
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.1
0.140
0.242
10/10
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.001
0.003
9/9
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
-
-
Nickel
0.05
0.110
0.202
10/10
-
-
0/0
-
-
Selenium
0.016
0.234
1
8/8
-
-
0/0
1.0
0
Silver
0.03
0.030
0.03
1/1
-
-
0/0
5.0
0
Thallium
0.005
0.150
0.9
9/9
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.05
0.191
0.6
10/10
-
-
0/0
-
-
Cyanide
0.001
0.157
0.6
14/14
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
-
Sulfate
-
-
-
0/0
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
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.
vO
-------
SUMMARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - WATER OF FORMATION - TUNGSTEN
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average
Maximum
# Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
0/0
-
-
Antimony
0.01
0.01
0.01
1/1
-
-
0/0
-
-
Arsenic
0.02
0.02
0.02
1/1
-
-
0/0
5.0
0
Barium
-
-
-
0/0
-
-
0/0
100.0
0
Beryllium
0.005
0.005
0.005
1/1
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
0/0
-
-
Cadmium
0.02
0.02
0.02
1/1
-
-
0/0
1.0
0
Chromium
0.02
0.02
0.02
1/1
-
-
0/0
5.0
0
Cobalt
• -
-
0/0
-
-
0/0
-
-
Copper
0.25
0.25
0.25
1/1
-
-
0/0
-
-
Iron
-
-
-
0/0
-
-
0/0
-
-
Lead
0.05
0.05
0.05
1/1
-
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
-
0/0
-
-
Manganese
-
-
-
0/0
-
-
0/0
-
-
Mercury
0.0002
0.0002
0.0002
1/1
-
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
-
0/0
- -
-
Nickel
0.05
0.05
0.05
1/1
-
-
0/0
-
-
Selenium
0.01
0.01
0 01
1/1
-
-
0/0
1.0
0
Silver
0.01
0.01
0.01
1/1
-
-
0/0
5.0
0
Thallium
0.01
0.01
0.01
1/1
-
-
0/0
-
_
Vanadium
-
-
-
0/0
-
-
0/0
-
-
Zinc
0.14
0.14
0.14
1/1
-
-
0/0
-
Cyanide
-
-
-
0/0
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
0/0
-
Sulfate
-
-
-
0/0
-
-
0/0
_
Fluoride
-
-
-
0/0
-
-
0/0
-
-
Phosphate
-
-
-
0/0
--
-
0/0
-
-
Silica
-
-
-
0/0
-
-
0/0
-
_
Chloride
-
-
-
0/0
-
-
0/0
-
_
TSS
-
-
-
0/0
-
-
0/0
-
-
PH *
-
-
-
0/0
212
0
Organlcs (TOC)
-
,
-
0/0
-
-
Non-detects were assumed to be present at 1/2 the detction limit. TCLP data are currently unavailable; therefore, only EP data are presented
-------
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, the domestic production of uranium declined from almost 44 million pounds
U3Os 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 Federal facility for processing. 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.-'
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 fluoride (UF6), which is enriched and further refined to produce the
fuel rods used in nuclear reactors.4 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% 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
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 U.S. Environmental Protection Agency, "Uranium," from Technical Resource Document. Extraction
and Beneficiation of Ores and Minerals. Vol. 5, January 1995, pp. 3-5.
4 |U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 13-16.
-------
752
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.3 Exhibits 1 and 2 show process flow
diagrams for open pit and underground acid-leach mills. A process flow diagram for an underground
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).6,7 Leaching involves bringing a solvent (lixiviant) in contact with the crushed ore slurry.
Uranvl 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.8
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.9 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
vellowcake.10 After the uranium is removed, the barren solutions are reconditioned and recycled. A
typical in situ leach process is shown in Exhibit 4.
Solvent' Extraction
Solvent extraction is typically employed by conventional milling operations since solvent extraction can be
used in the presence of fine solids (slimes). 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 recycled to the leaching circuit. 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 m 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 the
5 Werthman, P., and K. Bainbridge, "An Investigation of Uranium Mill Wastewater Treatability,"
Proceedings of the 35th Purdue Industrial Waste Conference, 1980, p. 248.
6 "Uranium and Uranium Compounds," 1983, Op. Cit.. pp. 516-517.
' "Uranium," in SME Mineral Processing Handbook, Vol. 2, 1985, p. 24-3.
8 U.S. Environmental Protection Agency, January 1995, Op. Cit., pp. 18, 21.
9 Department of Energy, February 1995, Op Cit., p. 30.
¦ .U.-S. Environmental 'Protection Agency, January 1995, Op. Cit.. p. 27.
-------
EXHIBIT 1
PROCESS FLOW CHART FOR AN OPEN PIT ACID-LEACH MILL
(Adapted from: Assessment of Environmental Aspects of Uranium Mining and Milling, U.S. EPA, 1976, p. 36.)
Organic Vapors
U1
UJ
-------
un
EXHIBIT 2
ACID LEACH PROCESS FLOW CHART FOR AN UNDERGROUND MILL
(Adapted from: Assessment of Environmental Aspects of Uranium Mining and Milling, U.S. EPA, 1976, p. 38.)
-------
EXHIBIT 3
ALKALINE LEACH PROCESS FLOW CHART FOR AN UNDERGROUND MINE
(Adapted from: Assessment of Environmental Aspectsof Uranium Mining and Milling, U.S. EPA, 1976, p. 41.)
-------
EXHIBIT4
URANIUM IN SITU LEACH PROCESS
(Adapted from: DOE, Decommissionim; of U.S. Uranium Production Facilities. 1995, p. 31.)
LT1
(Tt
h2o2
NaOlI
Precipitation
Ion Exchange
Resin Columns
Loaded Resin
I'd Kvapoiation
Pond
Stripped Resin
To Evaporation
Pond
Elution
Columns
NaCI
Nal ICO,
Oxidant
ll202
Filtering and
Drying
U308
-------
757
pregnant 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.11
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.12 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 uranvl 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.13
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 (U02) as shown in Exhibit 5. UC>2 is
then converted to uranium tetrafluoride (UF4) based on the following reaction:
The process used to convert U02 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:
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
11 U.S. Environmental Protection Agency, January 1995, Op. Cit.. pp. 22-23.
12 "Uranium and Uranium Compounds," 1983, Op. Cit., p. 522.
U02(s) + 4HF(g) -> UF4(s) + 2H20(g)
UF4(s) + F2(g) -> UF6(g)
13 U.S. Environme rotection Agency, January 1995, Op. Cit., p. 23.
-------
758
EXHIBIT 5
PRODUCTION OF URANIUM DIOXIDE
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 523.)
Yellowcake
I
Waste Nitric
Acid
Waste Nitric
Acid
Evaporation
I
Dehydration and Denization
U03
I
Reduction with Hydrogen
t
-------
EXHIBIT 6
FLOW SHEET FOR UF4 PRODUCTION
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 527.)
Steam Condensate Steam Condensate
LTI
VD
-------
CTi
O
EXHIBIT 7
THE AMES PROCESS
(Adapted from: Kirk-Othmer Encyclopedia of Chemical Technology, 1983, p. 530.)
-------
761
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.14
Uranium-235 Enrichment.
Most nuclear reactors built for the generation of electric power are based on uranium fuel
enriched in 235U. 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 (es)
An improved Eulex process for uranium extraction has been developed. 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.
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.
Nuclear explosives have been used to increase the recovery of underground resources. The process
may be useful in combination with solution mining of uranium ore bodies. However, the problem of
radioactive contaminated waste would increase due to the production of artificial radionuclides.15
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 berieficiation 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
14 "Uranium and Uranium Compounds," 1983, Op. Cit.. pp. 523-528.
15 Clark, D., State-of-the-Art: Uranium Mining. Milling, and Refining Industry. Prepared for EPA,
Office of Water Resources Research, Washington D.C., pp. 102-105.
-------
762
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.16
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 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.1'
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).18 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
16 U.S. Environmental Protection Agency, Assessment of Environmental Aspects of Uranium Mining
and Milling. December 1976, pp. 36-43.
17 U.S. Environmental Protection Agency, January 1995, Op. Cit., pp. 30-37.
18 Werthman P., and K. Bainbridge, 1980, Op. Cit., pp. 249-250.
-------
generation rate of 17,000 mt/yr, 3,833.500 mt/yr, and 7,650,000 mt/yT, 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.
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.19 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 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.20 The supernatant generated from
precipitation and dewatering circuits can be recycled to the respective solvent extraction or ion exchange
stripping solutions:
Solvent extraction generates the non-uniquely associated wastes listed below. 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 8).
Waste Acids from Solvent Extraction. We used best engineering judgment to determine that this
waste may exhibit the characteristics of toxicity (arsenic, chromium, lead, and selenium) and
corrosivity.
Barren Lixiviant. We used best engineering judgment to determine that this waste may exhibit the
characteristics of toxicity (arsenic, chromium, lead, and selenium) and corrosivity.
Slimes from Solvent Extraction. We used best engineering judgment to determine that this waste
may exhibit the characteristic of toxicity (arsenic, chromium, lead, and selenium).
Waste Solvents. We used best engineering judgment to determine that this waste may exhibit the
characteristic of ignitability.
19 U.S. Environmental Protection Agency, January 1995, Op. Cit., pp. 30-37.
20 Clark, D., Op. Cit. pp. 50 - 51.
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764
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 8).
Production of UP2
Waste Nitric Acid from the Production of UO,. Waste
of vellowcake in nitric acid and during back-extraction,
determine that this waste may be partially recycled and
corrosivity. This waste is classified as a spent material.
Production of UF,
Waste Calcium Fluoride. Waste calcium fluoride is discharged to sewers. 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.
Superheater Condensate. We used best engineering judgment to determine that this waste may
exhibit the characteristic of corrosivity.
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 is 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 is classified as
a by-product.
D. Ancillary Hazardous Wastes.
nitric acid is produced during dissolution
We used best engineering judgment to
may exhibit the characteristic of
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.
-------
EXHIBIT 8
Estimated Waste Generation Rates
Waste
Waste Generation Rate (metric tons/yr)
Stream
Low
Medium
High
Waste Acids from Solvent Extraction
1.700
9,350
17,000
Barren Lixiviant
0
1,700
17,000
Slimes from Solvent Extraction
1,700
9,350
17,000
Waste Solvents
0
0
1.700
Waste Nitric Acid from Production of U02
1,700
2,550
3,400
Vaporizer Condensate
1,700
9,350
17,000
Superheater Condensate
1,700
9,350
17,000
Slag
0
8,500
17,000
Uranium Chips from Ingot Production
1,700
2,550
3,400
-------
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 Treatability," Proceedings
of the 35th Purdue Industrial Waste Conference, 1980.
-------
767
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
Facility Name
Location
Type of Operations
Akzo Chemical Company
Weston, Ml
Vanadium catalysts
AMAX Metals Recovery Corp
Braithwaite, LA
Vanadium Pentoxide
Bear Metallurgical Corp.
Butler, PA
Ferrovanadium
Cotter Corp.
Canon City, CO
Vanadium pentoxide from uranium
byproducts (inactive)
Gulf Chemical & Metallurgical Corp.
Freeport, TX
Vanadium pentoxide
Kerr-McGee Chemical Corp
Soda Springs, ID
Vanadium pentoxide
Reading Alloys
Robesonia, PA
Aluminum-vanadium master alloy
Shieldalloy Metallurgical Corp
Cambridge, OH
Ferrovanadium, ammonium
metavanadate, and aluminum-
vanadium
Stratcor
Niagara Falls,, NY
Ferrovanadium, aluminum-
vanadium alloy, and Nitrovan
(inactive)
Teledyne Wah Chang
Albany, OR
Vanadium metal and vanadium-
zirconium alloy
Umetco Minerals
Blanding, UT
Vanadium pentoxide from uranium
byproducts (inactive)
Stratcor
Hot Springs, AR
Vanadium pentoxide
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.
-------
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 bearing-slag with aluminum, carbon, or ferrosilicon.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.3
B. Generalized Process Description
1. Discussion of Typical Production Processes
Vanadium is usually produced as the byproduct or coproduct of another element, such as iron,
uranium, molybdenum, or phosphorus. In the United States, vanadium is recovered. (1) as a principal
mine product, (2) as a coproduct from carnotite 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.6 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 coproduct 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, the 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 the 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 the production of an oxide concentrate. The second stage involves the production
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.
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769
of vanadium pentoxide either by fusion or dissolution. Production of vanadium metal or ingot is the third
stage in the operation.
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., NaCl or Na2C03. 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.l1
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.
11 Ibid.
-------
EXHIBIT 2
GENERALIZED FLOWSHEET FOR PROCESSING VANADIFEROUS RAW MATERIALS
(Adapted from: Mineral Facts and Problems, 1985, pp. 895 - 914.)
•vj
o
SOURCE VANADIUM PRODUCT
FROM PRIMARY PROCESS
VANADIUM RECOVERY
PROCESS
VANADIUM PRODUCT
RECOVERED
REDUCTION
PROCESS
VANADIUM
ADDITIVES
-------
771
EXHIBIT 3
SODIUM HEXAVANDATE PRODUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
Sodium Salt
Water
V anadium-beanng
Material
Leaching/
Separation
Solution
Solid Residues
Sulfuric Acid
Precipitation
Wash Water •
Filtration
t
Sodium hexavandate
Filtrate
-------
EXHIBIT 4
VANADIUM PENTOXIDE PRODUCTS
(Adapted from: 1988 Final Draft Sutqmary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
OPTION 1 Sodium Hexavandate
I
Fusion
T
Vanadium Pentoxide
OPTION 2
Sodium Hexavandate
Sodium
Bicarbonate
Solution
Ammonium
Chloride ~
I
Calcination
I
Vanadium Pentoxide
-------
773
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.12
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. 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. 14 Neither
calcium reduction nor carbon reduction are currently used.15
EXHIBIT 5
CALCIUM REDUCTION
(Adapted from: 1988 Final Draft Summary Report of Mineral Industry Processing Wastes, 1988, pp. 3-245 - 3-253.)
Vanadium Pentoxide
I
Calcium ^
Iodine ^
Metallic Vanadium
Vacuum
Heating
• Slag
12 Henry E. Hillard, 1992, Op. Cit. p. 1449.
13 Ibid.
14 U.S. Environmental Protection Agency, "Vanadium," from 1988 Final Draft Summary Report
Mineral Industry Processing Wastes. Office of Solid Waste, 1988, p. 3-245 - 3-253.
i ^ 11 Li k ra h o
Personal cornmunication between Jocelyn Spielman, ICF and Henry E. Hillard, Vanadium Specialist.
U.S. Bureau of Mines, October 20, 1994.
-------
774
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 Pentoxide
Aluminum
I
Bomb
Reduction
Vanadium-Aluminum
Alloy
Slag
Vanadium Sponge
Vanadium Ingot
-------
775
Aluminothermic Process. As shown in Exhibit 6, in the aluminothermic process for preparing
ferrovanadium, a mixture of technical grade vanadium pentoxide, aluminum, iron scrap, and a flux are
charged into an electric furnace, and the reaction between aluminum and pentoxide is initiated. The
reaction is highly exothermic, producing very high temperatures. The temperature can be controlled by
reducing the particle size of the reactants and the feed rate of the charge and by using partially reduced
pentoxide or by replacing some of the aluminum with a milder reducing agent. Ferrovanadium containing
up to 80 weight-percent vanadium can be produced by this method.16
Thermit Reaction. Ferrovanadium can also be prepared by the thermit reaction, a variation on
the aluminothermic reduction, in which vanadium and iron oxides are coreduced by aluminum granules in
a magnesia-lined steel vessel or in a water-cooled crucible. The reaction is initiated by a barium peroxide-
aluminum ignition charge. This method is also used to prepare aluminum master alloys for the titanium
industry.1'
3. Identification/Discussion of Novel (or otherwise distinct) Process(es)
Recent literature lists several new procedures for recovery of vanadium from industrial wastes, including:
• Extraction of vanadium from coke using microwave wet acid digestion.
"Certified coal standards and Venezuelan petroleum coke samples were submitted to
microwave acid digestion to evaluate the convenience of this procedure for the extraction
of their vanadium content. The solution and the solid'residue remaining after microwave
treatment were separated by filtration and analyzed for vanadium."18
Recovery of vanadium from titaniferous slags by sulphiding.19
• Recovery of vanadium from process residues.20
Extraction of vanadium from industrial waste.21
• Recovery of pure vanadium oxide from Bayer sludge.22
16 Henry E. Hillard, 1992, Op. Cit.. p. 1450.
17 Ibid.
18 Alvarado, Jose, et al. "Extraction of vanadium from petroleum coke samples by means of microwave
wet acid digestion," FUEL, 69, January 1990, pp. 128-130.
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," JOM, 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.
-------
776
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 thai 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 the production of sodium hexavandate and the production of vanadium pentoxide and
metallic vanadium. 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 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 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
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 and iron phosphates per kkg of product.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.
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.
25 Versar, Inc., "Vanadium Derivatives," from Assessment of the Inorganic Chemical Industry. Vol. IV.
1980, p. 32-7. '
-------
778
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.2' 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. Ancillary 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
naphtha), acidic tank cleaning wastes, and polychlorinated biphenvls from electrical transformers and
capacitors.
26 Ibid.
27 U.S. Environmental Protection Agency, 1988, Op. Cit.. pp. 3-245 - 3-253.
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779
BIBLIOGRAPHY
Battels. 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.
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780
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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% of
zinc produced today; zinc can also be recovered from six additional minerals, including hemimorphite,
smithsonite, zincite, hydrozincite, willemite, and franklinite.1 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 paints.2e
Canada and Australia were the world's largest producers of zinc in 1994, accounting for 31% of
mine production, followed by China, Peru, the United States, and Mexico.3 Canada, Australia, and the
U.S. also possess 39% of the world's zinc reserves. In the U.S., mines in Alaska, Missouri, New York, and
Tennessee produced more than 90% 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
Operator
Location
Red Dog
Cominco Alaska, Inc.
Northwest Arctic, AK
Elmwood-Gordonsville
Jersey Miniere Zinc Co.
Smith, TN
Greens Creek
Greens Creek Mining Co.
Admiralty Island, AK
Balmat
Zinc Corp. of America (ZCA)
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
the 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 their 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.
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782
Facility Name
Location
Process
Big River Zinc Corp.
Sauget, IL
electrolytic
Jersey Miniere Zinc Co.
Clarksville, TN
electrolytic
Zinc Corp. of America
Bartlesville, OK
electrolytic
Zinc Corp. of America
Monaca, PA
pyrometallurgical
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).6 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 1994.7
B. Generalized Process Description
1. Discussion of Typical Production Processes
Zinc minerals are generally 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% to
60% zinc.8
Zinc is processed through either of two primary processing methods, electrolytic or
pyrometallurgical. However, before 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% of world capacity. There
are no ISF-process plants in the U.S.9
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, which is burned in a combustion chamber. In the American process, zinc oxide is
6 Jolly, J., 1992, Op. Cit.. p. 1472.
' U.S. Bureau of Mines, 1995, Op. Cit., p. 190.
8 "Zinc and Zinc Alloys," 1983._Op._Cit.. pp. 809, 812.
9 U.S. Bureau of Mines, 19«s. up.j-Cit.. pp. 927-928.
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783
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 Bartlesviile, 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.
Electrolytic Process
The ZCA electrolytic zinc refinery in Bartlesviile, Oklahoma produces several zinc products and
associated by-products from zinc ore concentrates. Zinc products include zinc metal, roofing granules, and
zinc sulfate solution. By-products include cadmium metal, sulfuric acid, lead/silver residue, copper residue,
nickel/cobalt residue, lead scrap, and aluminum scrap. ZCA utilizes zinc sulfide concentrates containing
50-55 percent zinc as feed for its Bartlesviile plant.
Production of zinc products from ore concentrates at this facility involves roasting, leaching
(digestion), purification, and electrowinning. Roasting takes place at the Zinc Ore Roaster (ZOR), and
the remaining three processes take place at the Zinc Refinery (ZRF), as shown in the process flow
diagram in Exhibit 1. Both the ZOR and the ZRF are located at the Bartlesviile plant.
Zinc ore concentrates are 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% sulfur dioxide. Calcine dusts are
recovered from the off-gas by two cyclone separators and added to the calcine. The off-gas is humidified
and passed through a wet electrostatic precipitator in a hot tower to remove remaining solids from the
sulfur dioxide gas so that it may 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, are
pumped directly to the facility's wastewater treatment plant, and the remaining third is recycled to the hot
tower. Total acid plant blowdown flow is approximately 50 gallons per minute. Process wastewater
generated by the ZOR consists of non-contact cooling water used to cool the calcine as it exits the roaster
and slurry water that leaks from a pump that directs the slurried ore concentrates to the roaster. These
waters collect in a clay-lined sump outside the roaster and are pumped to the wastewater treatment plant.
A process wastewater stream generated at the ZAP, consisting of cooling tower blowdown, is pumped
directly to the treatment plant.
The leaching (digestion) process dissolves the zinc in the calcine, creating a zinc sulfate solution
from which the zinc can be removed through electrowinning. By mixing the calcine from the roaster with
150-170 g/L sulfuric acid in a step called neutral leaching, about 90% of the zinc in the calcine dissolves.
The insoluble zinc calcine is separated from the leaching solution in a settling tank. Neutral leach zinc
sulfate solution is sent to a purification system, and the solids containing the insoluble zinc are pumped to
a residue treatment circuit, where additional sulfuric acid is added to the solids in a series of three hot acid
leach tanks to dissolve another 6-7 percent of the zinc from the calcine. Remaining solids in the resulting
slurry are separated in a second settling tank and filtered into a cake that is dried and sold for its lead and
silver content (20% lead and up to 70 ounces of silver per ton).
When the calcine is leached with sulfuric acid in the hot acid leach tanks, iron in the calcine
dissolves along with zinc. Because this solution still contains recoverable zinc, ZCA recycles the solution
to the original 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
10 "Zinc and Zinc Alloys," 1983, Op. Cit.. pp. 855.
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EXHIBIT 1
ELECTROLYTIC ZINC PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 479.)
Blocks
-------
utilizes the goethite process.11 Zinc sulfide concentrates are added to the hot acid leach solution to
reduce the dissolved iron to its ferrous or divalent state. Zinc calcine is added to neutralize remnant
sulfuric acid from the hot acid leach step. Zinc oxide and air are 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 settles in a tank; the clarified solution containing recoverable zinc is recycled to the neutral leach
step, and the iron oxide slurry (goethite) solids are washed and filtered.
Goethite removed from the filter contains 30-40% iron, but recovery of the iron is currently not
economical.12 Moist goethite cake is stored in an uncovered, unlined waste pile on-site that dates from
1978, when the electrolytic process began at the facility. Runoff from the pile flows to a clay-lined sump
pond and then to the wastewater treatment plant.
In the purification step, trace impurities from the zinc oxide calcine that dissolved in the leaching
steps are removed from the neutral leach solution. Like iron, these impurities must be removed so that
zinc can be converted to metal. Zinc dust is added to the solution to chemically replace copper and
cadmium, which precipitate out of solution as a sludge. Cadmium metal and copper residue are recovered
for sale. Zinc dust is again added, along with antimony as a catalyst, to replace nickel and cobalt, which
are also recovered for sale. 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.
Purified, zinc-rich solution is cooled in evaporative cooling towers and stored in tanks before the
zinc is electrowon from the solution at the cell house. The cell house consists 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 are removed from their cells each day so that the metallic zinc
layer can be scraped off each cathode and so that zinc can continue to be removed from solution with the
other cathodes. Spent solution containing dilute sulfuric acid is recycled to the neutral'leach step of the
leaching process. Because heat builds in the cells, the zinc sulfate solution continuously passes through
the cooling towers. Non-contact cooling water along with boiler blowdown, condensate, and brushing
water used to wash cathodes make up a process wastewater stream from the ZRF. This stream flows
through a feeder ditch to a clay-lined sump pond, then to a large, clay-lined surface impoundment, and is
finally pumped to the wastewater treatment plant.
Zinc removed from cathodes is melted in a furnace and cast into 55-pound, 600-pound, or 2,400-
pound ingots. Some zinc is converted to dust used in the purification system. Zinc fume collected in the
furnace baghouse is recycled.
ZCA also converts 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 are made up of small streams from the roasting, purification,
electrowinning, and zinc secondaries processes. Acid plant blowdown is generated when sulfur dioxide off-
gas from the ZOR passes through a wet electrostatic precipitator in the hot tower to remove solids.
Process wastewater from the ZSP consists primarily of water from Venturi scrubbers used to collect dusts
from rotary drying of calcine. Process wastewater from the ZRF consists primarily of brushing water used
to wash the aluminum cathodes that serve as a depositional surface for zinc ions during electrowinning.
11 Additional methods to precipitate iron include the hematite and jarosite processes.
12 As of July 1989, ZCA was studying a pilot system to recover iron from goethite; the status of this,
project is unknown.
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786
The ZAP, which converts sulfur dioxide gas generated in the ZOR to commercial-grade sulfuric acid,
generates process wastewater consisting of non-contact cooling tower blowdown. Smaller streams of boiler
blowdown, non-contact cooling water from cooling towers, and condensate also make up the wastewater
flow.
Process wastewater and plant runoff that collect in the two large, clay-lined surface impoundments
are pumped to the wastewater treatment plant. Following a two-stage neutralization process and
clarification, sludge is recycled to the roaster and treated water is pumped to two synthetically-lined
holding ponds before it is injected in a Class I industrial well.
PvrometaHurgical Process
The primaiy 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 furnacing. Dust which is removed from sintering off-gases in baghouses is returned to the
sintering operation or used as a feed to the zinc sulfate circuit.1 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.
13 Eeed to the zinc sulfate circuit .also corisists.of zinc .carbonate that.was generated before the zinc
sulfate circuit became operational ana mat is stocKpuea onsite.,
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787
EXHIBIT 2
PYROMETALLURGICAL ZINC PRODUCTION PROCESS
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, p. 480.)
Zinc Concentrates
t
T
Ferrosilicon
Lead-Silver
Concentrate to
Lead Plant
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788
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 ferro-silicates are stockpiled onsite 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.
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) Process(es)
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
less than 1,000°C. The technology reportedly generates little waste.14
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.15
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% and 99% were achieved for
zinc and copper, respectively.16
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% of both zinc (as
14 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.
15 U.S. Bureau of Mines, 1985, Op. Cit.. p. 927
16 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. '' ^
-------
zinc sulfate) and sulfuric acid in the bleed stream was recovered at concentrations high enough for direct
recycle to the process.17
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.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 in this
section.
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 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.
17 Eyal, A, et. al.. 1990, Op. Cit.. pp. 209-222.
18 Beckstead, L., et al.. 1993, Op. Cit.. pp. 862-875.
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C. Process Waste Streams
1. Extraction/Beneficiation 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 onsite or offsite, 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
onsite construction for road or other purposes. Surface mines usually generate large volumes of
overburden and waste rock that are usually 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 1/4 and 1/2 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 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.19
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 onsite 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 (N03) from blasting activities. EPA20 and the Bureau of Mines21 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.22
19 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.
20 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.
21 Coppa, L., 1984, Op. Cit..
22 National Institute for Occupational Safety and Health, 1990.
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Acetylene
Calcium Oxide
Hexone
Hydrogen Chloride
Methyl Chloroform
Methyl Isobutvl Carbinol
Nitric Acid
Propane
Sodium Cyanide
Sulfur Dioxide
Sulfuric Acid
Diesel Fuel No. 1
Diesel Fuel No. 2
Chromic Acid, Disodium Salt
Copper Solution
Kerosene
Methane, Chlorodifuoro-
Sodium Aerofloat
Sulfuric Acid Copper (2 + )
Salt (1:1)
Zinc Solution
Zinc Sulfate
Mineral Processing Wastes
Electrolytic refining operations generate two mineral processing wastes: goethite and leach cake
residues, and saleable residues. These are described below.
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 by the three
electrolytic refineries in the U.S. Site-specific information on management practices for goethite were
available for only one facility, ZCA's Bartlesville, OK refinery. Moist goethite cake is stored in an
uncovered, unlined waste pile on-site that dates from 1978, when the electrolytic process began at the
facility. Runoff from the pile flows 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 is classified as a by-product. Data for this wastestream
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.24 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. 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.25
23 U.S. Environmental Protection Agency, Newly Identified Mineral Processing Waste
Characterization Data Set. Office of Solid Waste, August 1992, pp. 1-8.
24 Ibid.
25 Ibid.
-------
792
Production of primary zinc metal at both electrolytic and pyrometallurgical zinc processing plants
generate several wastestreams common to both processes, as described below.
Process Wastewater
Process wastewater is generated at all four of the operating zinc processing plants. At ZCA's
electrolytic refinery in Bartlesville, OK process wastewaters consist of small streams from the roasting,
purification, electrowinning, and zinc secondaries processes, as described above. Process wastewater and
plant runoff collect in two large, clay-lined surface impoundments and are 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 treated in a two-stage neutralization process.
Approximately 6.6 million metric tons of process wastewater are generated annually at the four U.S.
primary zinc facilities.26 (The excessive generation rate for this wastewater [i.e., greater than one million
metric tons/yr] is due to commingling of numerous wastestreams.) 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 is classified as a spent material. Data for this wastestream are presented in Attachment 1.
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 are pumped directly to the facility's wastewater treatment plant, and the remaining
third is 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 130,000 metric tons of acid plant blowdown
are generated annually at the four U.S. primary zinc facilities.27 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 wastestream
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 has been remanded. 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 four zinc facilities and may
become contaminated with potentially hazardous constituents. Approximately 200 metric tons of these
waste materials are generated annually.28 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 is classified as a spent material.
26 Ibid.
27 Ibid.
28 Ibid.
-------
793
TCA Tower Blowdown
Approximately 1,000 metric tons of TCA tower blowdown are generated annually.29 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 21,000 metric tons are generated annually.30 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 wastestream 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 3.5 million metric tons of effluent are
generated annually by the four operating U.S. plants. Effluent generated at ZCA's Bartlesville plant is
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. "TTiis waste stream is classified as a spent material. Data for this
wastestream are presented in Attachment 1.
Wastewater Treatment Plant Sludge
Wastewater treatment plant sludge also results from the treatment of process wastewaters, acid
plant blowdown, and plant runoff. Approximately 45,000 metric tons of sludge are generated annually by
the four operating U.S. plants.32 Wastewater treatment plant sludge from primary zinc processing is a
RCRA-listed hazardous waste and must be managed and disposed accordingly. At ZCA's Bartlesville and
Monaca plant, these solids are recycled to the zinc ore roaster. We used best engineering judgment to
determine that wastewater treatment plant sludge may exhibit the characteristic of toxicity for cadmium.
Data for this wastestream 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 2.5 million
metric tons of liquid are generated annually by the four operating plants.33 (The excessive generation
rate for this wastewater [i.e., greater than one million metric tons/yr] is due to commingling of numerous
wastestreams.) We used best engineering judgment to determine that spent surface impoundment liquid
29 ]bld.
30 Ibid.
31 Ibid.
32 Ibid.
33 Ibid.
-------
794
may exhibit the characteristics of corrosivity and toxicity (cadmium). This waste stream may be partiallv
recycled and is classified as a spent material. Data for this wastestream are presented in Attachment 1.
Spent Surface Impoundment Solids
Surface impoundment solids consists of solids that settle out of process wastewaters, acid plant
blowdown, and plant runoff discharged to the surface impoundment. Approximately 1,000 metric tons of
solids are generated annually by the four operating plants.34 We used best engineering judgment to
determine that surface impoundment solids may exhibit the characteristic of toxicity for arsenic, cadmium,
lead, mercury, selenium, and silver. Data for this wastestream 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.35 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 level36 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.3' 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 is classified as a by-
product. Data for this wastestream 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. We used best engineering judgment to determine that
waste ferrosilicon may be recycled and may exhibit the characteristic of toxicity for lead. This waste is
classified as a by-product. Data for this wastestream are presented in Attachment 1.
34 Ibid.
35 U.S. Environmental Protection Agency, 1992, Op. Cit.; p. 1-8.
36 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.
37 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-8.
38 Ibid.
-------
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.39 We
used best engineering judgment to determine that refractory brick may exhibit the characteristic of toxicity
for arsenic, cadmium, chromium, and lead.
D. Ancillary 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), 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
waste oil and other lubricants.
39 U.S. Environmental Protection Agency, 1992, Op. Cit.. p. 1-8.
-------
796
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.
Eval, 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.
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.
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. II. 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.
-------
797
ATTACHMENT 1
-------
798
-------
4MARY OF EPA/ORD, 3007, AND RTI SAMPLING DATA - GOETHITE AND lEACH CAKE RESIDUES (ELECTROLYTIC) - ZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM.
TC
# Values
Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
3,130
3,130
3,130
1/1
5.00
5.00
5.00
0/1
-
-
Antimony
100
175
249
2/2
5.00
5.00
5.00
0/1
-
-
Arsenic
953
1,977
3,000
2/2
0.014
2.51
5.00
1/2
5.0
1
Barium
25.00
25.00
25.00
0/1
0.50
2.75
5.00
1/2
100.0
0
Beryllium
2.50
2.50
2.50
0/1
0.50
0.50
0.50
0/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
•-
-
Cadmium
128
926
2,600
5/5
6.68
7.82
8.96
2/2
1.0
2
Chromium
25.00
37.50
50.00
1/2
0.001
2 50
5.00
0/2
5.0
1
bonaft
25.00
113
200
1/2
5.00
5.00
5.00
0/1
-
-
eo'DDer
3,400
11,456
24,000
5/5
3.62
14.26
24.90
2/2
-
-
Iron
150,000
273,500
400,000
4/4
0.050
2.53
5:00
0/2
-
-
Lvea"d
2,530
11,606
20,000
5/5
1.43
1.97
2.50
1/2
5.0
0
Magnesium
1,470
1,470
1,470
1/1
70.90
70.90
70.90
1/1
-
-
Manganese
860
860
860
1/1
0.27
15.99
31.70
2/2
-
-
Mercury
0.050
0.050
0.050
0/1
0 0001
0.00345
0.0068
1/2
0.2
0
Molybdenum
25.00
25.00
25.00
0/1
5.00
5.00
5.00
0/1
-
-
NicKel
25.00
62.50
100
1/2
5.00
5.00
5.00
0/1
-
-
Selenium
25.00
25.00
25.00
0/1
0.0010
2.50
5.00
0/2
1.0
1
Sliver
0.94
12.08
25.00
2/3
0.015
2.51
5.00
0/2
5.0
1
1 nanium
125
125
125
0/1
25.00
25". 00
25.00
0/1
-
-
Vanadium
25.00
25.00
25.00
0/1
5.00
5.00
5.00
0/1
-
-
Zinc
38,900
110,780
150,000
5/5
334
737
1,140
2/2
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
35,000
35,000
35,000
1/1
-
-
-
0/0
-
-
Sulfate
33,600
36,800
40,000
2/2
2,278
2,278
2,278
1/1
-
-
Fluoride
-
-
-
0/0
0.30
0.30
0.30
1/1
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
25.60
1,013
2,000
2/2
2.20
2.20
2.20
1/1
-
-
TSS
610,000
610,000
610,000
1/1
-
-
-
0/0
-
-
pH *
-
-
-
0/0
212
0
Organlcs (TOC)
890
890
890
1/1
-
-
Non-detects were assumed to be present at 1/2 the detection limit. TCLP data are currently unavailable; therefore, only EP data are presented.
-------
3tPftWAfiY™OF"EPA7ORD~ 30071 AND RTI SAMPLING DATA'- PROCESS WASTEWATERZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
0 Values
Constituents
Minimum
Average
Maximum
# Delects
Minimum
Average
Maximum
If Detects
Level
In Excess
Aluminum
0.050
15.28
123
7/10
0.050
18.27
133
3/8
-
-
Antimony
0.050
0.30
0.93
2/11
0.050
1.53
10.00
2/8
--
-
Arsenic
0.0020
0.52
2.54
4/11
0.020
1.59
10.00
2/10
5.0
1
Barilim
0.050
0.20
0.50
3/11
0.050
1.25
10.00
2/10
100.0
0
Beryllium
0.005
0.02
0.05
2/10
0.005
0.14
1.00
0/8
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.0030
93.09
555
17/17
0.023
123
589
10/10
1.0
6
Chromium
0.0010
0.16
0.50
4/11
0.0050
1.13
10.00
1/10
5.0
1
Cobalt
0.050
1.21
6.60
3/10
0.050
2.19
10.00
1/8
-
-
Copper
0.025
19.83
205
7/11
0.050
37.61
289
4/8
-
-
Iron
0.030
373
3,500
12/13
0.050
174
737
3/8
-
-
Lead
0.00050
29.84
300
9/12
0.025
1.27
5.00
6/10
5.0
1
Magnesium
3.02
914
7,160
13/13
2.81
288
2,110
8/8
-
-
Manganese
0.025
311
2,500
9/11
0.050
108
722
6/8
-
-
Mercury
0.00010
0.038
0.348
8/11
0.00010
0.0020
0.014
4/10
0.2
0
Molybdenum
0.050
0.22
0.50
2/8
0.050
1.52
10.00
2/8
-
-
Nickel
0.030
2.48
10.50
4/11
0.050
2.93
12.70
1/8
-
-
Selenium
0.0025
8.333
100,000
2/12
0.0025
1.13
10.00
0/10
1.0
1
Silver
0.0015
0.12
0.50
1/11
0.0015
1.13
10.00
0/10
5.0
1
Thallium
0.024
0.92
3.59
3/11
0.25
7.03
50.00
0/8
-
-
Vanadium
0.005
0.12
0.50
1/11
0.050
1.41
10.00
0/8
-
-
Zinc
3.00
5,872
60,000
25/25
0.37
7,919
40,500
8/8
-
-
Cyanide
0.0050
0.0050
0.0050
0/1
-
-
-
0/0
-
-
Sulfide
4.60
4.60
4.60
1/1
-
-
-
0/0
-
-
Sulfate
155
7,902
60,500
14/14
-
-
-
0/0
-
-
Fluoride
0.30
18.67
56.00
6/6
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
1,300
1,300
1,300
1/1
-
-
-
0/0
-
-
Chloride
1.00
1,277
10,000
16/16
-
-
-
0/0
-
TSS
4.40
12,905
99,500
13/13
-
-
-
0/0
-
-
PH*
1.00
5.64
10.50
24/24
212
4
Organics (TOC)
4.00
8.25
19.80
9/9
-
-
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 BLOWDOWN - ZINC
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
tt Detects
TC
Level
# Values
In Excess
Aluminum
2.67
19.99
37.30
2/2
5.00
20.20
35 40
1/2
-
-
anilmony
0.48
0.49
0.50
1/3
0.50
2.75
5 00
0/2
-
-
Arsenic
0.99
1.11
1.20
3/3
1.10
2.12
5 00
3/4
5.0
1
barium
0.21
0.40
0.50
1/3
0.14
1.45
5.00
1/4
100.0
0
Beryllium
0.050
1,475
4,400
1/3
0.050
0.28
0.50
0/2
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
3.71
155
840
6/6
0.83
8.58
19.00
4/4
1.0
2
Chromium
0.049
0.35
0.50
1/3
0.03
1.81
5.00
2/4
5.0
1
Cobalt
0.50
0.50
0.50
0/2
0.50
2.75
5.00
0/2
-
-
Copper
1.95
12.63
29.00
3/3
0.17
1.89
5.00
1/3
-
-
Iron
87.10
107
127
212
2.39
53.90
79.70
3/3
-
-
Lead
4.11
13.64
23.80
3/3
1.87
2.54
3.70
3/4
5.0
0
Magnesium
9.42
11.21
13.00
212
8.52
10.41
12.30
2/2
-
-
Manganese
1.37
4.12
6.87
2/2
0.10
2.20
5.00
2/3
-
-
Mdrcury
0.26
23,246
162,400
7/7
0.0064
0.079
0 13
4/4
0 2
0
Molybdenum
0.50
0.50
0.50
0/2
0.50
2.75
5.00
0/2
-
-
Nickel
0.50
0.67
1.00
1/3
0.50
2.75
5.00
0/2
-
-
Selenium
2.00
7.87
16.60
3/3
0.055
1.69
5.00
2/4
1.0
2
Silver
0.50
0.66
0.98
1/3
0.015
1.53
5.00
1/4
5.0
.1
Thallium
0.0090
1.67
2.50
1/3
2.50
13.75
25.00
0/2
-
-
Vanadium
0.0010
0.33
0.50
1/3
0.50
2.75
5.00
0/2
-
-
Zinc
180
2,992
13,200
13/13
21.30
588
1,570
3/3
-
-
Cyanide
0.085
0.085
0.085
1/1
-
-
-
0/0
-
-
Sulfide
330
330
330
1/1
-
-
0/0
-
Sulfate
1,860
12,340
43,193
6/6
7,330
7,330
7,330
1/1
-
-
Fluoride
11.00
1,317
11,400
12/12
23.00
23.00
23.00
1/1
-
-
Phosphate
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
1.00
1,343
5,100
11/11
547
547
547
1/1
-
-
TSS
5,490
14,395
23,300
2/2
-
-
0/0
-
-
pH *
0.50
1.67
3.40
8/8
212
6
Organlcs (TOC)
3.30
3.71
4.00
3/3
-
-
Non-detects were assumed to be present at 1/2 the detection limit TCLP data are currently unavailable: therefore, only EP data are presented
-------
SHWMARY'OF EPA/ORD, 3007/AND'RTrSAMPi:iNG DATA - SYNTHETIC'GYPSUM - ZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
# Values
.Constituents
Minimum
Average
Maximum # Detects
Minimum
Average
Maximum
tt Detects
Level
In Excess
A'ltiminum
-
-
-
0/0
-
-
-
0/0
-
-
'Antimony
-
-
-
0/0
-
-
-
0/0
-
-
Arsenic
1,954
2,945
3,935
2/2
0.0030
0.0040
0.0050
1/2
5.0
0
Barium
-
-
-
0/0
0.80
2.25
3.70
2/2
100.0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Gadmium
665
779
893
2/2
0.52
5.81
11.10
2/2
1.0
1
Chromium
-
-
-
0/0
0.0010
0.0010
0.0010
0/2
5.0
0
Cobalt
-
-
-
0/0
-
-
-
0/0
-
-
Copper
-
-
-
0/0
0.51
0.51
0.51
2/2
-
-
Iron
-
-
-
0/0
0.15
0.23
0.30
2/2
-
-
Head
290
296
302
2/2
2.36
3.00
3.63
2/2
5 0
0
Magnesium
-
-
-
0/0
-
-
-
0/0
-
-
Manganese
-
-
-
0/0
0.57
23.24
45.90
2/2
-
-
Mercury
-
-
-
0/0
0.0029
0.016
0.029
2/2
0.2
0
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
Nickel
-
-
-
0/0
-
-
-
0/0
-
-
Selenium
-
-
-
0/0
0.0010
0.0010
0:0010
0/2
1.0
0
Silver
-
-
-
0/0
0.015
0.018
0.020
0/2
5.0
0
Thallium
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
Zinc
-
-
-
0/0
10.70
417
824
2/2
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
--
-
-
0/0
-
-
-
0/0
-
_
Sulfate
-
-
-
0/0
1,160
1,795
2,430
2/2
-
-
Fluoride
-
-
-
0/0
0.40
0.45
0 50
2/2
-
_
Phosphate
-
-
-
0/0
-
-
-
0/0
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
0.15
1.43
2.70
1/2
-
_
TSS
-
-
-
0/0
-
-
0/0
-
_
pH *
5.01
5.08
5.15
2/2
212
0
Organlcs (TOC)
-
-
-
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 - WATER TREATMENT PLANT LIQUID EFFLUENT - ZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis -
PPM
TC
tt Values
Constituents
Minimum
Average
Maximum ft Detects
Minimum
Average
Maximum
# Detects
Level
In Excess
Aluminum
-
-
-
0/0
-
-
-
0/0
-
-
Antimony
-
-
-
0/0
-
-
-
0/0
-
-
Arsenic
-
-
-
0/0
0.027
0.039
0.050
1/2
5.0
0
Barium
-
-
-
0/0
0.50
3.25
6.00
1/2
100.0
0
Beryllium
-
-
-
0/0
-
-
-
0/0
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
1.00
12,101
24,200
2/2
0.070
0.125
0.180
2/2
1.0
0
Cnromium
-
-
-
0/0
0.012
0.019
0.025
1/2
5.0
0
Cobalt
3.100
3,100
3,100
1/1
-
-
'
0/0
-
-
Copper
1,300
1,300
1,300
1/1
0.030
0.030
0.030
0/1
-
-
Iron
17,200
17,200
17,200
1/1
53.90
53.90
53.90
1/1
-
-
Lead
6,100
6,100
6,100
1/1
1.00
1.82
2.64
2/2
5.0
0
Magnesium
50.00
5,225
10,400
2/2
-
-
-
0/0
-
-
Manganese
-
-
-
0/0
49.50
49.50
49.50
1/1
-
-
Mercury
-
-
-
0/0
0.000050
0.0012
0.0023
1/2
0.2
0
Molybdenum
-
-
-
0/0
-
-
-
0/0
-
-
Nickel
410
410
410
1/1
-
-
-
0/0
-
-
Selenium
-
-
-
0/0
0 0030
0.102
0.20
2/2
1.0
0
Silver
58.29
58.29
58.29
1/1
0.020
0.045
0.070
1/2
5.0
0
Thallium
-
-
-
0/0
-
-
-
0/0
-
-
Vanadium
-
-
-
0/0
-
-
-
0/0
-
-
Zinc
20.00
150,673
450,000
3/3
1,320
1,320
1,320
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
545,000
545,000
545,000
1/1
1,340
1,340
1,340
1/1
-
-
Fluoride
-
-
-
0/0
18.50
18.50
18.50
1/1
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
-
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
102
102
102
1/1
-
-
TSS
-
-
-
0/0
-
-
0/0
-
-
pH '
4.88
6.73
8.80
3/3
212
0
Organlcs (TOC)
-
-
-
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
00
o
LO
-------
B6^W3Y*OPEPA7ORDr3007,-AND RTI-SAMPLING DATA-^-WASTEWATER TREATMENT PLANT SLUDGE" ZINC
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
# Detects
TC
Level
# Values
In Excess
Aluminum
23.80
1,887
3,750
2/2
0.13
2.40
4.67
212
-
-
Antimony
0.60
24.10
47.60
1/2
0.00080
0.035
0.070
0/2
-
-
Arsenic
0.46
57.23
114
1/2
0.0055
0.063
0.12
0/2
5.0
0
Barium
0.30
33.65
67.00
2/2
0.11
0.31
0.48
3/3
100.0
0
Beryllium
0.042
0.87
1.70
1/2
0.0050
0.0055
0.0059
1/2
-
-
.B.oron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
44.40
11,415
24,200
3/3
0.19
0.88
2.13
3/3
1.0
1
Chromium
1.20
17.65
34.10
2/2
0.0015
0.049
0.099
2/3
5.0
0
.Cobalt
3.30
1,171
3,100
3/3
0.82
1.50
2.18
212
-
-
.Copper
8.20
1,159
2,170
3/3
0.020
0.68
1.35
1/2
-
-
Iron
407
12,736
20,600
3/3
13.83
25.06
36.30
2/2
-
-
Lead
55.50
4,862
8,430
3/3
0.42
1.85
4.56
3/3
5.0
0
Magnesium
1,980
6,740
10,400
3/3
74.70
267
460
2/2
-
-
Manganese
189
4,465
8,740
212
31.68
50.09
68.50
2/2
-
-
Mercury
4.10
12.20
20.30
2/2
0.00010
0.0075
0.022
1/3
0.2
0
Molybdenum
0.25
1.40
2.55
1/2
0.0088
0.012
0.015
1/2
-
-
Nickel
4.50
256
410
3/3
1.21
1.40
1.58
2/2
-
-
Selenium
5.60
113
220
2/2
0.0015
0.018
0.044
1/3
1.0
0
Silver
0.55
43.25
70.90
3/3
0.0051
0.017
0.024
3/3
5.0
0
Thallium
2.40
25.70
49.00
0/2
0.57
0.58
0.58
2/2
-
-
Vanadium
0.13
1.34
2.55
1/2
0.0036
0.009
0.015
1/2
-
-
Zinc
2,000
249,250
526,000
4/4
571
1,540
2,510
2/2
-
-
Cyanide
0.51
0.51
0.51
0/1
0.0050
0.0050
0.0050
0/1
-
-
Sulfide
3,120
3,120
3,120
1/1
143
143
143
1/1
-
-
Sulfate
545,000
545,000
545,000
1/1
-
-
0/0
-
-
Fluoride
173
173
173
1/1
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
-
-
~
0/0
-
-
-
0/0
-
-
Chloride
-
-
-
0/0
-
-
-
0/0
-
-
TSS
430,000
430,000
430,000
1/1
-
-
-
0/0
-
-
PH *
8.80
9.38
9.96
2/2
212
0
Organics (TOC)
-
-
-
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 EPA70RD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT LIQUIDS - ZINC
Constituents
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis - PPM
Minimum Average Maximum
H Detects
TC
Level
ft Values
In Excess
Aluminum
990
990
990
1/1
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
214
214
214
1/1
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
0.20
3,011
40,000
16/16
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
Copper
3358
3,358
3,358
1/1
-
0/0
-
-
iron
200
7,905
19,420
4/4
-
0/0
-
-
Lead
0.70
38,075
200,000
6/6
-
0/0
5.0
0
Magnesium
800
14,580
53,000
4/4
-
0/0
-
-
Manganese
22.90
162
302
2/2
-
0/0
-
-
Mercury
0.17
7.13
23.80
4/4
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
257
257
257
1/1
-
0/0
-
-
Selenium
11.00
11.00
11.00
1/1
-
0/0
1.0
0
Silver
185
185
185
1/1
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
0.80
132,673
800,000
22/22
-
0/0
-
-
Cyanide
-
-
-
0/0
-
0/0
-
-
sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
4,400
14,606
35,000
3/3
-
0/0
-
-
Fluoride
1.80
234
2,300
12/12
-
0/0
-
-
Phosphate
-
-
-
0/0
-
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
Chloride
200
1,174
2,800
8/8
-
0/0
-
-
TSS
41.00
41.20
41.40
2/2
-
0/0
-
-
PH *
2
6.02
10
23/23
212
3
Organics (TOC)
-
-
-
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
00
o
LH
-------
SUMMARY'OF EPA/ORD, 3007, AND RTI SAMPLING DATA - SURFACE IMPOUNDMENT SOLIDS - ZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis
- PPM
TC
0 Values
Constituents
Minimum
Average
Maximum # Detects
Minimum Average
Maximum
# Detects
Level
In Excess
'Airiminijm
-
-
-
0/0
-
0/0
-
-
Antimony
-
-
-
0/0
-
0/0
-
-
'Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
-
-
Boron
-
-
-
0/0
-
0/0
-
-
Cadmium
1.00
1.00
1.00
1/1
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
-
-
CoDDer
-
-
-
0/0
-
0/0
-
-
iron
-
-
-
0/0
-
0/0
-
-
ITead
-
-
-
0/0
-
0/0
5.0
0
Magnesium
50.00
50.00
50.00
1/1
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercury
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
-
-
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
-
-
Zinc
20.00
20.00
20.00
1/1
-
0/0
-
-
Cyanide
-
-
-
0/0
-T
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
-
-
Sulfate
-
-
-
0/0
-
0/0
-
-
Fluoride
-
-
-
0/0
-
0/0
-
-
Phosphate
-
-
0/0
0/0
-
-
Silica
-
-
-
0/0
-
0/0
-
-
Chloride
-
-
-
0/0
-
0/0
-
-
TSS
-
-
-
0/0
-
0/0
-
-
pH *
6.50
6.50
6.50
1/1
212
0
Organics (TOC)
-
-
-
0/0
-
-
Non-detecls 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
Total Constituent Analysis - PPM
Minimum Average Maximum # Detects
EP Toxicity Analysis -
Minimum Average
PPM
Maximum
# Detects
TC
Level
tt Values
In Excess
Aluminum
8,120
24,060
40,000
2/2
1.45
1.45
1.45
1/1
-
-
Antimony
33.50
33.50
33.50
1/1
0.50
0.50
0.50
0/1
-
-
Arsenic
5.00
5.00
5.00
0/1
0.50
0.50
0.50
0/1
5.0
0
Barium
129
129
129
1/1
0.50
0.50
0.50
0/1
100.0
0
Beryllium
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
-
-
Boron
-
-
-
0/0
-
-
-
0/0
-
-
Cadmium
0.50
0.50
0.50
0/1
0.050
0.050
0.050
0/1
1.0
0
Chromium
22.70
22.70
22.70
1/1
0.50
0.50
0.50
0/1
5 0
0
Cobalt
5.00
5.00
5.00
0/1
0.50
0.50
0.50
0/1
-
-
Copper
650
650
650
1/1
0.50
0.50
0.50
0/1
-
-
Iron
7,240
73,620
140,000
2/2
27.20
27.20
27.20
1/1
-
-
Lead
1,720
2,860
4,000
2/2
59.40
59.40
59.40
1/1
5.0
1
Magnesium
1,100
1,100
1,100
1/1
8.16
8.16
8.16
1/1
-
-
Manaanese
1,670
1,670
1,670
1/1
25.60
25.60
25.60
1/1
-
-
Mercury
0.050
0.050
0.050
0/1
0.00010
0.00010
0.00010
o/i
0.2
0
MoiyDdenum
10.60
10.60
10.60
1/1
0.50
0.50
0.50
0/1
-
-
Nickel
86.10
86.10
86.10
1/1
4.82
4.82
4.82
0/1
-
-
Selenium
5.00
5.00
5.00
0/1
0.50
0.50
0.50
0/1
1.0
0
Silver
5.00
5.00
5.00
0/1
0.50
0.50
0.50
0/1
5.0
0
Thallium
25.00
25.00
25.00
0/1
2 50
2.50
2.50
0/1
-
Vanadium
10.50
10.50
10.50
1/1
0.50
0.50
0.50
0/1
-
-
Zinc
6,710
58,355
110,000
2/2
325
325
325
1/1
-
-
Cyanide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfide
-
-
-
0/0
-
-
-
0/0
-
-
Sulfate
943
943
943
1/1
-
-
-
0/0
-
-
Fluoride
-
-
-
0/0
-
-
-
0/0
-
-
Phosphate
-
-
-
0/0
-
-
-
0/0
-
-
Silica
100,000
100,000
100,000
1/1
-
-
-
0/0
-
-
Chloride
24.80
24.80
24 80
1/1
-
-
-
0/0
-
-
TSS
-
-
-
0/0
-
-
-
0/0
-
-
pH '
-
-
-
0/0
212
0
Organlcs (TOC)
2,940
2,940
2,940
1/1
-
-
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 - FERROSIUCON (SMELTING) - ZINC
Total Constituent Analysis - PPM
EP Toxicity Analysis
PPM
TC
# Values
Constituents
Minimum
Average
Maximum # Detects
Minimum Average
Maximum
# Detects
Level
In Excess
Aluminum
40,000
40,000
40,000
1/1
-
0/0
-
_
Antimony
-
-
-
0/0
-
0/0
-
-
Arsenic
-
-
-
0/0
-
0/0
5.0
0
Barium
-
-
-
0/0
-
0/0
100.0
0
Beryllium
-
-
-
0/0
-
0/0
_
-
BoiyO
-
-
-
0/0
-
0/0
-
_
Caamium
-
-
-
0/0
-
0/0
1.0
0
Chromium
-
-
-
0/0
-
0/0
5.0
0
Cobalt
-
-
-
0/0
-
0/0
_
-
Copper
-
-
-
0/0
-
0/0
-
-
Iron
300,000
300,000
300,000
1/1
-
0/0
-
-
Lead
5,000
•5,000
5,000
1/1
-
0/0
5.0
0
Magnesium
-
-
-
0/0
-
0/0
-
-
Manganese
-
-
-
0/0
-
0/0
-
-
Mercurv
-
-
-
0/0
-
0/0
0.2
0
Molybdenum
-
-
-
0/0
-
0/0
-
-
Nickel
-
-
-
0/0
-
0/0
_
_
Selenium
-
-
-
0/0
-
0/0
1.0
0
Silver
-
-
-
0/0'
-
0/0
5.0
0
Thallium
-
-
-
0/0
-
0/0
-
-
Vanadium
-
-
-
0/0
-
0/0
_
Zinc
40,000
40,000
40,000
1/1
-
0/0
_
_
Cyanide
-
-
-
0/0
-
0/0
-
-
Sulfide
-
-
-
0/0
-
0/0
_
_
Sulfate
-
-
-
0/0
-
0/0
_
_
Fluoride
-
-
-
0/0
-
0/0
Phosphate
-
-
-
0/0
-
0/0
_
_
Silica
120,000
120,000
120,000
1/1
-
0/0
_
_
Chloride
-
-
-
0/0
-
0/0
_
_
TSS
-
-
-
0/0
-
0/0
_
_
PH *
-
-
-
0/0
212
0
Organics (TOC)
-
-
-
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.
-------
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 50:1.1
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.
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 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 practice reduction and purification only. 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:
ZrSi04 + 2C + 4CI2 -* ZrCl4 + SiCl4 + 2CO2
1 Thomas E. Garner, "Zirconium and Hafnium Minerals," from Industrial Minerals and Rocks. 6th
ed., Society for Mining, Metallurgy, and Exploration, 1994, pp. 1159-1164.
2 Ibid.
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.
-------
810
EXHIBIT I
Summary Of Zirconium/Hafnium Mining And Processing Facilities
Facility Name
Location
Operations/Products
Du Pont
Trail Ridge, FL
Mining, extraction
RGC
NE Florida
Mining, extraction
Teledyne
Albany, OR
Metals, and alloys
Western Zirconium
Ogden, UT
Metals, and alloys
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:
ZrCI4 + 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 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
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 ICF 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.
-------
811
EXHIBIT 2
PRIMARY ZIRCONIUM AND HAFNIUM PRODUCTION
(Adapted from: Development Document for Effluent Limitations Guidelines, 1989, pp. 5081 - 5106.)
Atmosphere ^ Atmosphere ^ Atmosphere ^ Atmosphere
f
Sand Drying
Scrubber
r~k
Sand
Driving
H,0
Caustic
f
f
Sand Chlonnation
Off-Gas Scrubbers
~ i
H,0
Caustic
Sand Chlonnation
Area-Vent Scrubbers
M
H,0
Caustic
f
Feed Makeup
Scrubbers
t
Sand
Condensation
Chlonnation
~ ^
CI, Coke
I
ZrCI4
H£CI4
H;0^
SiC14
Purification
T
SiCI4
H;0
Caustic
SiC14
Punfication
Scrubbers
J
Atmosphere
2rOCI2
HtOC12
Makeup
NH40H
MIBK
Thiocyanate
Recovery
Recovery
KM
Extraction
J
MIBK
i
1
^ Reuse
MIBK
Steam
Stnpper
HF Precipitation
and Filtration
Zn Precipitation
and Filtration
r~r
H2S04
(NH4)2S04
NH40H
Bottoms
-------
EXHIBIT 2 (CONTINUED)
Atmosphere,
1
Calcining
Caustic
Scrubber
Atmosphere
I12()
1
Magnesium
Recovery
Scmbhcrb
Atmosphere
Calcining
Water
Scrubbers
Caustic,
H2Q
1
i
Pure
Chlorinalion
Scrubbers
Recycle to
Separations
Uf
Calcination
Ilf02
Zr02
Zr
Calcination
CI2, Coke
Ilf Pure
Clilorination
Zr Pure
Chlorination
t
CI2, Coke
II20
Mg
IIICI4
~ ,
ZrCI4
t
Mg
Atmosphere
1
Reduction
Area-Veil!
Scrubbers
I
II2G
Reduction
Oil-gas
Scrubber
+
b
Magnesium
Recovery
System
Ilf
Reduction
III
Zr
Zr
Reduction
III
Distillation
and Crushing
Zr
Distillation
and Crushing
Rec>cle to
Separations
Alniosphcic
-------
EXHIBIT 2
1 Iydrogen
Reduction
Ni
MCI H2(3
i I
Leaching
1120
\
Kmse
I
Zi oi
ZrNi
Alloys
-------
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.11
. 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, the reaction becomes self-sustaining.
Zirconium metal sponge and magnesium oxide are produced.12
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.
-------
815
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) Process(es)
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/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 (elg.,
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 Section B.
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.
-------
816
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.17
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 8,524 1/kkg of zirconium dioxide and hafnium dioxide
produced.20
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.
-------
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. 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 39,900 1/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.
21 Ibid.
22 Ibid.
23 Ibid.
24 Ibid.
-------
818
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 the water
scrubbers in the 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.
Pure Chlorination
Wet APC wastewater. Pure chlorination is similar to sand chlorination except that the
chlorination of arconium oxide and hafnium oxide is earned 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
2Q0 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 corrosivity prior to
treatment. This waste is classified as a spent material.
25 Ibid.
26 U.S. Environmental Protection Agency, 1989, Op. Cit.. pp. 5081-5106.
27 Ibid.
28 Ibid.
-------
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 tliis 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/yT, and 1,600,000 metric tons/yr, respectively. We used best engineering judgement to
determine that this waste may exhibit the characteristic of corrosivity.
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.^1 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/tyr, 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
29 Ibid.
30 Ibid-
31 Ibid.
32 Ibid.
33 Ibid.
-------
820
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. Ancillary 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), 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
waste oil and other lubricants.
34 Ibid.
-------
821
BIBLIOGRAPHY
Adams, Timothy. "Zirconium and Hafnium." 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 anu
Standards for the Nonferrous Metals Manufacturing Point Source Category. Vol. IX. Office of
Water Regulations and Standards. May 1989. pp. 5081-5106.
-------
822
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PHHA-5o6oi.tr
-------
PHMA-So&sl. E.
823
V. Summary of Findings
As shown in Exhibit 5-1, EPA determined that 48 commodity sectors generated a total of 527 waste
streams that could be classified as either extraction/beneficiation or mineral processing wastes. After careful
review, EPA determined that 41 commodity sectors generated a total of 354 waste streams that could be
designated as mineral processing wastes.
Exhibit 5-2 presents the 354 mineral processing wastes by commodity sector. Of these 354 waste
streams, EPA has sufficient information (based on either analytical test data or engineering judgment) to
determine that 148 waste streams are potentially RCRA hazardous wastes because they may exhibit one or
more of the RCRA hazardous characteristics: toxicity, ignitability, corrosivity, or reactivity.
Exhibit 5-3 presents the 148 RCRA hazardous mineral processing-wastes that will be subject to the
Land Disposal Restrictions. Exhibit 5-4 identifies the mineral processing commodity sectors that generate
RCRA hazardous mineral processing wastes that are likely to be subject to the Land Disposal Restrictions.
Exhibit 5-4 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 nine
sectors also generate wastes that could be classified as mineral processing wastes: Bromine, Gemstones.
Iodine, Lithium, Lithium Carbonate, Soda Ash, Sodium Sulfate, and Strontium.
-------
824
EXHIBIT 5-1
Summary of Extraction/Beneficiation and Mineral Processing Waste Streams
by Commodity
Commodity
Waste Stream
Nature of Operation
Alumina and Aluminum
Water softener sludge
Extraction/Beneficiation
Anode prep waste
Mineral Processing
APC dust/sludge
Mineral Processing
Baghouse bags and spent plant filters
Mineral Processing
Bauxite residue
Mineral Processing
Cast house dust
Mineral Processing
Cryolite recovery residue
Mineral Processing
Wastewater
Mineral Processing
Discarded Dross
Mineral Processing
Rue Dust
Mineral Processing
Electrolysis waste
Mineral Processing
Evaporator salt wastes
Mineral Processing
Miscellaneous wastewater
Mineral Processing
Pisolites
Mineral Processing
Scrap furnace brick
Mineral Processing
Skims
Mineral Processing
Sludge
Mineral Processing
Spent cleaning residue
Mineral Processing
Sweepings
Mineral Processing
Treatment Plant Effluent
Mineral Processing
Waste alumina
Mineral Processing
Antimony
Gangue
Mineral Processing
Wastewater
Mineral Processing
APC Dust/Sludge
Mineral Processing
Autoclave Filtrate
Mineral Processing
Spent Barren Solution
Mineral Processing
Gangue (Filter Cake)
Mineral Processing
Leach Residue
Mineral Processing
Refining Dross
Mineral Processing
Slag and Furnace Residue
Mineral Processing
Sludge from Treating Process Waste Water
Mineral Processing
Stripped Anolyte Solids
Mineral Processing
Beryllium
Gangue
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Acid Conversion Stream
Mineral Processing
-------
825
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Beryllium (continued)
Spent Barren filtrate streams
Mineral Processing
Bertrandite thickener slurry
Mineral Processing
Beryl thickener slurry
Mineral Processing
Beryllium hydroxide supernatant
Mineral Processing
Chip Treatment Wastewater
Mineral Processing
Dross discard
Mineral Processing
Filtration discard
Mineral Processing
Leaching discard
Mineral Processing
Neutralization discard
Mineral Processing
Pebble Plant Area Vent Scrubber Water
Mineral Processing
Precipitation discard
Mineral Processing
Process wastewater
Mineral Processing
Spent Raffinate
Mineral Processing
Scrubber Liquor
Mineral Processing
Separation slurry
Mineral Processing
Sump Water
Mineral Processing
Waste Solids
Mineral Processing
Bismuth
Alloy residues
Mineral Processing
Spent Caustic Soda
Mineral Processing
Electrolytic Slimes
Mineral Processing
Excess chlorine
Mineral Processing
Lead and Zinc chlorides
Mineral Processing
Metal Chloride Residues
Mineral Processing
Slag
Mineral Processing
Spent Electrolyte
Mineral Processing
Spent Material
Mineral Processing
Spent soda solution
Mineral Processing
Waste acid solutions
Mineral Processing
Waste Acids
Mineral Processing
Wastewater
Mineral Processing
Boron
Crud
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Spent Solvents
Extraction/Beneficiation
Waste Bnne
Extraction/Beneficiation
Wastewater.
Extraction/Beneficiation
Spent Sodium Sulfate
Mineral Processing
Waste liquor
Mineral Processing
Underflow Mud
Mineral Processing
-------
826
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Bromine
Slimes
Extraction/Beneficiation
Waste Brine
Extraction/Beneficiation
Water Vapor
Extraction/Beneficiation
Cadmium
Caustic washwater
Mineral Processing
Copper and Lead Sulfate Filter Cakes
Mineral Processing
Copper Removal Filler Cake
Mineral Processing
Iron containing impurities
Mineral Processing
Spent Leach solution
Mineral Processing
Lead Sulfate waste
Mineral Processing
Post-leach Filter Cakes
Mineral Processing
Spent Purification solution
Mineral Processing
Scrubber wastewater
Mineral Processing
Spent elecirolyte
Mineral Processing
Zinc Precipitates
Mineral Processing -
Calcium Meial
Off-gases
Extraction/Beneficiation
Overburden
Extraction/Beneficiation
Calcium Aluminate wastes
Mineral Processing
Dust with Quicklime
Mineral Processing
Cesium/Rubidium
Alkali Alums
Extraction/Beneficiation
Calciner Residues
Extraction/Beneficiation
Cesium Chlorosonnate
Extraction/Beneficiation
Non-Pollucite Mineral Waste
Extraction/Beneficiation
Precipitated Aluminum
Extraction/Beneficiation
Precipitated Barium Sulfate
Extraction/Beneficiation
Spent Chlorine solution
Extraction/Beneficiation
Spent Ion-exchange solution
Extraction/Beneficiation
Spent Metal
Extraction/Beneficiation
Spent Ore
Extraction/Beneficiation
Spent Solvent
Extraction/Beneficiation
Waste Gangue
Extraction/Beneficiation
Chemical Residues
Mineral Processing
Digester waste
Mineral Processing
Electrolytic Slimes
Mineral Processing
Pyrotync Residue
Mineral Processing
Slag
Mineral Processing
Chromium. Ferrochrome, and
Ferrochromium-Silicon
Gangue and tailings
Extraction/Beneficiation
Dust or Sludge from ferrochromium production
Mineral Processing
Dust or Sludge from ferrochromium-silicon production
Mineral Processing
Slag and Residues
Mineral Processing
-------
827
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Coal Gas
Baghouse Coal Dust
Extraction/Beneficiation
Coal Pile Runoff
Extraction/Beneficiation
Fines
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
API Oil/Water Separator Sludge
Mineral Processing
API Water
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Dissolved Air Flotation (DAF) Sludge
Mineral Processing
Flue Dust Residues
Mineral Processing
Liquid Waste Incinerator Blowdown
Mineral Processing
Liquid Waste Incinerator Pond Sludge
Mineral Processing
Multiple Effects Evaporator Concentrate
Mineral Processing
Multiple Effects Evaporator Pond Sludge
Mineral Processing
Sludge and Filter Cake
Mineral Processing
Spent Methanol Catalyst
Mineral Processing
Stretford Solution Purge Stream
Mineral Processing
Surface Impoundment Solids
Mineral Processing
Vacuum Filter Sludge
Mineral Processing
Zeolite Softening PWW
Mineral Processing
Copper
Crud
Extraction/Beneficiation
Spent Kerosene
Extraction/Beneficiation
Raffinate
Extraction/Beneficiation
Slime
Extraction/Beneficiation
Slimes or "Muds"
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste Rock
Extraction/Beneficiation
Acid plant blowdown
Mineral Processing
Acid plant thickener sludge
Mineral Processing
APC dusts/sludges
Mineral Processing
Spent bleed electrolyte
Mineral Processing
Chamber solids/scrubber sludge
Mineral Processing
Waste contact cooling water
Mineral Processing
Discarded furnace brick
Mineral Processing
Non-recyclable APC dusts
Mineral Processing
Process wastewaters
Mineral Processing
Scrubber blowdown
Mineral Processing
Spent black sulfunc acid sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
Tankhouse slimes
Mineral Processing
-------
828
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Copper (continued)
WWTP liquid effluent
Mineral Processing
WWTP sludge
Mineral Processing
Elemental Phosphorous
Waste rock from mining
Extraction/Beneficiation
Condenser phossy water discard
Mineral Processing
Cooling water
Mineral Processing
AFM nnsate
Mineral Processing
Dust
Mineral Processing
Waste ferrophosphorus
Mineral Processing
Furnace offgas solids
¦ Mineral Processing
Furnace scrubber blowdown
Mineral Processing
Precipitator slurry scrubber water
Mineral Processing
Slag quenchwater
Mineral Processing
Sludge
Mineral Processing
Spent furnace brick
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
Surface impoundment waste solids
Mineral Processing
Waste filter media
Mineral Processing
WWTP liquid effluent
Mineral Processing
WWTP Sludge/Solids
Mineral Processing
Fluorspar and Hydrofluoric Acid
Gaague
Extraction/Beneficiation
Lead and Zinc sulfides
Extraction/Beneficiation
Spent flotation reagents
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
APC Dusts
Mineral Processing
Off-spec fluosilicic acid
Mineral Processing
Sludges
Mineral Processing
Gem Stones
Overburden
Extraction/Beneficiation
Spent chemical agents
Extraction/Beneficiation
Spent polishing media
Extraction/Beneficiation
Waste minerals
Extraction/Beneficiation
Germanium
Waste Acid Wash and Rinse Water
Mineral Processing
Chlonnator Wet Air Pollution Control Sludge
Mineral Processing
Hydrolysis Filtrate
Mineral Processing
Leach Residues
Mineral Processing
Spent Acid/Leachate
Mineral Processing
Waste Still Liquor
Mineral Processing
Wastewater
Mineral Processing
-------
829
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature or Operation
Gold and Silver
Black sand
Extraction/Beneficiation
Filter cake
Extraction/Beneficiation
Mercury bearing solution
Extraction/Beneficiation
Mine water
Extraction/Beneficiation
Spent carbon
Extraction/Beneficiation
Spent leaching solution
Extraction/Beneficiation
Spent ore
Extraction/Beneficiation
Spent stripping solution
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste rock, clay and sand
Extraction/Beneficiation
Zinc cyanide solution
Extraction/Beneficiation
Spent Furnace Dust
Mineral Processing
Refining wastes
Mineral Processing
Slag
Mineral Processing
Wastewater treatment sludge
Mineral Processing
Wastewater
Mineral Processing
Iodine
Filtrate waste
Extraction/Beneficiation
Sludge1
Extraction/Beneficiation
Sulfur compounds
Extraction/Beneficiation
Waste acid
Extraction/Beneficiation
Waste bleed liquor
Extraction/Beneficiation
Waste bleed liquor and filtrate wastes
Extraction/Beneficiation
Waste brine
Extraction/Beneficiation
Iron and Steel
Tailings
Exlraclion/Beneficianon
Wastewater and Waste Solids
Extraction/Beneficiation
Wastewater
Mineral Processing
Lead
Concentration Wastes
Extraction/Beneficiation
Mine water
Extraction/Beneficiation
Waste Rock
Extraction/Beneficiation
Acid Plant Blowdown
Mineral Processing
Acid Plant Sludge
Mineral Processing
Baghouse Dust
Mineral Processing
Baghouse Incinerator Ash
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Waste Nickel Matte
Mineral Processing
Process Wastewater
Mineral Processing
Slurried APC Dust
Mineral Processing
Solid Residues
Mineral Processing
Solids in Plant Washdown
Mineral Processing
-------
830
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Lead (continued)
Spent Furnace Brick
Mineral Processing
Stockpiled Miscellaneous Plant Waste
Mineral Processing
Surface Impoundment Waste Liquids
Mineral Processing
Surface Impoundment Waste Solids
Mineral Processing
SVG Backwash
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludges/Solids
Mineral Processing
Lightweight
Aggregate
Overburden
Extraction/Beneficiation
Screenings
Extraction/Beneficiation
APC control scrubber water and solids
Mineral Processing
APC Dust/Sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
WWTP liquid effluent
Mineral Processing
Lithium and
Lithium Carbonate
Acid roaster gases
Extraction/Beneficiation
Flotation Tailings
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Magnesium/Calcium Sludge*
Extraction/Beneficiation
Roaster Off-gases
Extraction/Beneficiation
Salt solutions
Extraction/Beneficiation
Wastewater from Wet Scrubber
Extraction/Beneficiation
Magnesium and Magnesia
from Brines
Calcium sludge
Extraction/Beneficiation
Offgases
Extraction/Beneficiation
Spent seawater
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
Calciner offgases
Mineral Processing
Calcium sludge
Mineral Processing
Casthouse Oust
Mineral Processing
Casting plant slag
Mineral Processing
Cathode Scrubber Liquor
Mineral Processing
Slag
Mineral Processing
Smut
Mineral Processing
Spent Brines
Mineral Processing
Manganese. Manganese
Dioxide, Ferromanganese
and Silicomanganese
Flotation tailings
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Spent Flotation Reagents
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
APC Water
Mineral Processing
-------
831
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Manganese. Manganese
Electrolyte Purification Waste
Mineral Processing
Dioxide, Ferromanganese
and Silicomanganese (continued)
Iron Sulfide Sludge
Mineral Processing
Ore Residues
Mineral Processing
Slag
Mineral Processing
Spent Graphite Anode
Mineral Processing
Spent Process Liquor
Mineral Processing
Waste Electrolyte
Mineral Processing
Wastewater (CMD)
Mineral Processing
Wastewater (EMD)
Mineral Processing
Wastewater Treatment Solids
Mineral Processing
Mercury
Concentrator Wastewater
Mineral Processing
Dust
Mineral Processing
Mercury Quench Water
Mineral Processing
Filter Cake Waste
Mineral Processing
Furnace Residue
Mineral Processing
Molybdenum.
Ferromolvbdenum, and
Ammonium Molvbdate
Rotation tailings
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Spent Flotation Reagents
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
Flue Dust/Gases
Mineral Processing
Liquid Residues
Mineral Processing
H2 Reduction Furnace Scrubber Water
Mineral Processing
Molybdic Oxide Refining Wastes
Mineral Processing
Refining Wastes
Mineral Processing
Roaster Gas Blowdown Solids
Mineral Processing
Slag
Mineral Processing
Solid Residues
Mineral Processing
Treatment Solids
Mineral Processing
Phosphoric Acid
Waste Scale
Mineral Processing
Platinum Group
Filtrate
Extraction/Beneficiation
Metals
Tailings
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Slag
Mineral Processing
Spent Acids
Mineral Processing
Spent Solvents
Mineral Processing
Pvrobitumens,
Mineral Waxes,
and Nature! Asphalts
Spent coal
Extraction/Beneficiation
Spent solvents
Extraction/Beneficiation
Still bottoms
Mineral Processing
-------
832
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Pyrobitumens.
Mineral Waxes,
¦and Naturel Asphalts (continued)
Waste catalysis
Mineral Processing
Rare Earths
Magnetic fractions
Extracnon/Beneficiation
Tailings
Extraction/Beneficiation
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 hydroxide cake
Mineral Processing
Spent iron/lead filter cake
Mineral Processing
Lead backwash sludge
Mineral Processing
Monazite solids
Mineral Processing
Process wastewater
Mineral Processing
Spent scrubber liquor
Mineral Processing
Spent sodium fluoride
Mineral Processing
Spent sodium hypochlorite filter backwash
Mineral Processing
Solvent extraction crud
Mineral Processing
Spent surface impoundment solids
Mineral Processing
Spent surface impoundment liquids
Mineral Processing
Waste filtrate
Mineral Processing
Waste solvent
Mineral Processing
Wastewater from caustic wet APC
Mineral Processing
Waste zinc contaminated with mercury
Mineral Processing
Rhenium
APC Dust/Sludge
Mineral Processing
Spent Barren Scrubber Liquor
Mineral Processing
Spent Rhenium Raffinate
Mineral Processing
Roaster Dust
Mineral Processing
Spent Ion Exchange/SX Solutions
Mineral Processing
Spent Salt Solutions
Mineral Processing
Slag
Mineral Processing
Scandium
Crud from the bottom of the solvent extraction unit
Mineral Processing
Dusts and spent filters from decomposition
Mineral Processing
Spent acids
Mineral Processing
Spent ion exchange resins and backwash
Mineral Processing
Spent solvents from solvent extraction
Mineral Processing
Spent wash water
Mineral Processing
Waste chlorine solution
Mineral Processing
Waste solutions/solids from leaching and precipitation
Mineral Processing
-------
833
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
.Nature of Operation
Selenium
Spent filter cake
Mineral Processing
Plant process wastewater
Mineral Processing
Slag
Mineral Processing
Tellurium slime wastes
Mineral Processing
Waste Solids
Mineral Processing
Silicon and
Ferrosilicon
Gangue
Extraction/Beneficiauon
Spent Wash Water
Extraction/Beneficiation
Tailings
Extraction/Beneficiauon
APC Dust Sludge
Mineral Processing
Dross discard
Mineral Processing
Slag
Mineral Processing
Soda Ash
Airborne emissions
Extraction/Beneficiation
Calciner offgases
Extraction/Beneficialion
Filter aid and carbon absorbent
Extraction/Beneficiauon
Mother liquor
Extraction/Beneficiauon
Ore. insolubles
Extraction/Beneficialion
Ore residues
Extracuon/Beneficiation
Overburden
Extraction/Beneficiation
Particulate emissions from driers
Extraction/Beneficiauon
Particulates
Extraction/Beneficiauon
Purge liquor
Extraction/Beneficiauon
Scrubber water
Extraction/Beneficiauon
Spent brine
Extraction/Beneficiauon
Spent carbon and filter wastes
Extraction/Beneficiation
Spent dissolution wastes
Extraction/Beneficiation
Suspended particulate matter
Extraction/Beneficiation
Tailings
Extraction/Beneficiauon
Trona ore particulates
Extraction/Beneficiation
Trona ore processing waste
Extraction/Beneficiauon
Waste mother liquor
Extraction/Beneficiauon
Sodium Sulfate
Waste Brine
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Strontium
Calciner offgas
Extraction/Beneficiation
Dilute sodium sulfide solution
Extraction/Beneficiation
Filter muds
Extraction/Beneficiation
Spent Ore
Extraction/Beneficiation
Vacuum drum filtrate
Extraction/Beneficiation
Waste solution
Extraction/Beneficiation
-------
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Sulfur
Air emissions
Extraction/Beneficiation
Filter cake
Extraction/Beneficiation
Frasch process residues •
Extraction/Beneficiation
Sludge
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Spent catalysts (Claus process)
Mineral Processing
¦ Spent vanadium pentoade catalysts from sulfuric acid production
Mineral Processing
Spilled product (Claus process)
Mineral Processing
Wastewater from wet-scrubbing, spilled product and condensates
Mineral Processing
Synthetic Rutile
APC Dust/Sludges
Mineral Processing
Spent Iron Oxide Slurry
Mineral Processing
Spent Acid Solution
Mineral Processing
Tantalum, Columbium
and Ferrocolumbium
APC Dust Sludge
Mineral Processing
Digester Sludge
Mineral Processing
Spent Potassium Titanium Chloride
Mineral Processing
Process Wastewater
Mineral Processing
Spent Raffmate Solids
Mineral Processing
Scrubber Overflow
Mineral Processing
Slag
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge
Mineral Processing
Tellurium
Slag
Mineral Processing
Solid waste residues
Mineral Processing
Waste Electrolyte and Wastewater
Mineral Processing
Wastewater
Mineral Processing
Tin
Process Wastewater
Extraction/Beneficiation
Tailings Sluriv
Extraction/Beneficiation
Brick Lining and Fabnc Filters
Mineral Processing
Dross
Mineral Processing
Process Wastewater and Treatment Sludge
Mineral Processing
Reactor slurry - acid and sludges
Extraction/Beneficiation
Slag
Mineral Processing
Slimes
Mineral Processing
Waste acids
Extraction/Beneficiation
Waste Acid and Alkaline baths
Mineral Processing
Waste liquids
Extraction/Beneficiation
-------
835
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Titanium and
Flotation Cells
Extraction/Beneficiation
Titanium Oxide
Tailings
Extraction/Beneficiauon
Spent Brine Treatment Filter Cake
Mineral Processing
FeCl Treatment Sludge
Mineral Processing
Waste Feme Chloride
Mineral Processing
Finishing Scrap
Mineral Processing
Leach Liquor and Sponge Wash Water
Mineral Processing
Waste Non-Contact Cooling Water
Mineral Processing
Pickling Liquor and Wash Water
Mineral Processing
Scrap Detergent Wash Water
Mineral Processing
Scrap Milling Scrubber Water
Mineral Processing
Reduction Area Scrubber Water
Mineral Processing
Chlonnation Off gas Scrubber Water
Mineral Processing
Chlorination Area - Vent Scrubber Water
Mineral Processing
Melt Cell Scrubber Water
Mineral Processing
Chlorine Liquefaction Scrubber Water
Mineral Processing
Chip Crushing Scrubber Water
Mineral Processing
Casting Crucible Contact Cooling Water
Mineral Processing
Smut from Mg Recovery
Mineral Processing
Spent Surface Impoundment Liquids
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
TiC14 Purification Effluent
Mineral Processing
Spent Vanadium Oxychlonde
Mineral Processing
Sodium Reduction Container Reconditioning Wash Water
Mineral Processing
Casting Crucible Wash Water
Mineral Processing
Waste Acids (Chloride process)
Mineral Processing
Waste Acids (Sulfate process)
Mineral Processing
Waste Solids (Sulfate process)
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge/Solids
Mineral Processing
Tungsten
Alkali leach wash
Extraction/Beneficiation
Calcium tungstate precipitate wash
Extraction/Beneficiauon
Ion exchange raffinate
Extraction/Beneficiation
Ion exchange resins
Extraction/Beneficiation
Leach filter cake residues and impurities
Extraction/Beneficiation
Molybdenum sulfide precipitation wet air pollution control
Extraction/Beneficiauon
Scrubber wastewater
Extraction/Beneficiation
Spent mother liquor
Extraction/Beneficiation
Tungstic acid rinse water
Extraction/Beneficiation
-------
836
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Tungsten (continued)
Waste fines
Extraction/Beneficiation
Waste rock and tailings
Extra ction/Beneficiation
Wastewater
Extra ction/Beneficiation
Wet scrubber wastewater
Extraction/Beneficiation
Spent Acid and Rinse water
Mineral Processing
Scrubber wastewater
Mineral Processing
Process wastewater treatment plant effluent
Mineral Processing
Water of formation
Mineral Processing
Uranium
Waste Rock
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Spent Extraction/Leaching Solutions
Extraction/Beneficiation
Particulate Emissions
Extraction/Beneficiation
Miscellaneous Sludges
Extraction/Beneficiation
Spent Ion Exchange Resins
Exiraction/Beneficiation
Tailing Pond Seepage
Extraction/Beneficiation
Waste Acids from Solvent Extraction
Extraction/Beneficiation
Barren Lixiviani
Extraction/Beneficiation
Slimes from Solvent Extraction
Extraction/Beneficiation
Waste Solvents
Extraction/Beneficiation
Waste Nitric Acid from Production of UO,
Mineral Processing
Vaporizer Condensate
Mineral Processing
Superheater Condensate
Mineral Processing
Slag
Mineral Processing
Uranium Chips from Ingot Production
Mineral Processing
Waste Calcium Fluonde
Mineral Processing
Vanadium
Roaster Off-gases
Extraction/Beneficiation
Solid residues
Extraction/Beneficiation
Spent Filtrate
Extraction/Beneficiation
Spent Solvent
Extraction/Beneficiation
Filtrate and Process Wastewaters
Mineral Processing
Solid Waste
Mineral Processing
Spent Precipitate
Mineral Processing
Slag
Mineral Processing
Wet scrubber wastewater
Mineral Processing
Zinc
Refuse
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste rock
Extraction/Beneficiation
Acid Plant Blowdown
Mineral Processing
Spent Cloths. Bags, and Filters
Mineral Processing
-------
837
EXHIBIT 5-1 (Continued)
Commodity
Waste Stream
Nature of Operation
Zinc (continued)
Waste Ferrosilicon
Mineral. Processing
Spent Goethile and Leach Cake Residues
Mineral Processing
Process Wastewater
Mineral Processing
Discarded Refractory Brick
Mineral Processing
Spent Surface Impoundment Liquid
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
Spent Synthetic Gypsum
Mineral Processing
TCA Tower Blowdown (ZCA Bartlesville. OK - Electrolytic Plant)
Mineral Processing
Wastewater Treatment Plant Liquid EfQuent
Mineral Processing
Wastewater Treatment Plant Sludge
Mineral Processing
Zinc-lean Slag
Mineral Processing
.Zirconium and
Hafnium
Monazite
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Spent Acid leachate from zirconium alloy production
Mineral Processing
Acid leachate from zirconium metal production
Mineral Processing
Ammonium Thiocyanate Bleed Stream
Mineral Processing
Reduction area-vent wet APC wastewater
Mineral Processing
Caustic wet APC wastewater
Mineral Processing
Feed makeup wet APC wastewater
Mineral Processing
Filter cake/sludge
Mineral Processing
Furnace residue
Mineral Processing
Hafnium filtrate wastewater
Mineral Processing
Iron extraction stream stripper bottoms
Mineral Processing
Leaching rinse water from zirconium alloy production
Mineral Processing
Leaching nnse water from zirconium metal production
Mineral Processing
Magnesium recovery area vent wet APC wastewater
Mineral Processing
Magnesium recovery off-gas wet APC wastewater
Mineral Processing
Sand Chlonnation Off-Gas Wet APC wastewater
Mineral Processing
Sand Chlonnation Area Vent Wet APC wastewater
Mineral Processing
Silicon Tetrachloride Purification Wet APC wastewater
Mineral Processing
Wet APC wastewater
Mineral Processing
Zirconium chip crushing wet APC wastewater
Mineral Processing
Zirconium filtrate wastewater
Mineral Processing
-------
EXHIBIT 5-2
Summary of Mineral Processing Waste Streams by Commodity
Commodity
Waste Stream
Nature of Operation
Aluminum and Alumina
Anode prep waste
Mineral Processing
APC dust/sludge
Mineral Processing
Baghouse bags and spent plant filters
Mineral Processing
Bauxite residue
Mineral Processing
Cast house dust
Mineral Processing
Cryolite recovery residue
Mineral Processing
Wastewater
Mineral Processing
Discarded Dross
Mineral Processing
Flue Dust
Mineral Processing
Electrolysis waste
Mineral Processing
Evaporator salt wastes
Mineral Processing
Miscellaneous wastewater
Mineral Processing
Pisolites
Mineral Processing
Scrap furnace brick
Mineral Processing
Skims
Mineral Processing
Sludge
Mineral Processing
Spent cleaning residue
Mineral Processing
Sweepings
Mineral Processing
Treatment Plant Effluent
Mineral Processing
Waste alumina
Mineral Processing
Antimony
Gangue
Mineral Processing
Wastewater
Mineral Processing
APC Dust/Sludge
Mineral Processing
Autoclave Filtrate
Mineral Processing
Spent Barren Solution
Mineral Processing
Gangue (Filter Cake)
Mineral Processing
Leach Residue
Mineral Processing
Refining Dross
Mineral Processing
Slag and Furnace Residue
Mineral Processing
Sludge from Treating Process Waste Water
Mineral Processing
Stripped Anolyte Solids
Mineral Processing
Beryllium
Acid Conversion Stream
Mineral Processing
Spent Barren filtrate streams
Mineral Processing
Benrandite thickener slurry
Mineral Processing
Beryl thickener slurry
Mineral Processing
Beryllium hydroxide supernatant
Mineral Processing
Chip Treatment Wastewater
Mineral Processing
Dross discard
Mineral Processing
Filtration discard
Mineral Processing
-------
839
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Beryllium (continued)
Leaching discard
Mineral Processing
Neutralization discard
Mineral Processing
Pebble Plant Area Vent Scrubber Water
Mineral Processing
Precipitation discard
Mineral Processing
Process wastewater
Mineral Processing
Spent Raffinate
Mineral Processing
Scrubber Liquor
Mineral Processing
Separation slurry
Mineral Processing
Sump Water
Mineral Processing
Waste Solids
Mineral Processing
Bismuth
Alloy residues
Mineral Processing
Spent Caustic Soda
Mineral Processing
Electrolytic Slimes
Mineral Processing
Excess chlorine
Mineral Processing
Lead and Zinc chlorides
Mineral Processing
Metal Chloride Residues
Mineral Processing
Slag
Mineral Processing
Spent Electrolyte
Mineral Processing
Spent Material
Mineral Processing
Spent soda solution
Mineral Processing
Waste acid solutions
Mineral Processing
Waste Acids
Mineral Processing
Wastewater
Mineral Processing
Boron
Spent Sodium Sulfate
Mineral Processing
Waste liquor
Mineral Processing
Underflow Mud
Mineral Processing
Cadmium
Caustic washwater
Mineral Processing
Copper and Lead Sulfate Filter Cakes
Mineral Processing
Copper Removal Filter Cake
Mineral Processing
Iron containing impurities
Mineral Processing
Spent Leach solution
Mineral Processing
Lead Sulfate waste
Mineral Processing
Post-leach Filter Cakes
Mineral Processing
Spent Purification solution
Mineral Processing
Scrubber wastewater
Mineral Processing
Spent electrolyte
Mineral Processing
Zinc Precipitates
Mineral Processing
Calcium Metal
Calcium Aluminate wastes
Mineral Processing
Dust with Quicklime
Mineral Processing
-------
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Cesium/Rubidium
Chemical Residues
Mineral Processing
Digester waste
Mineral Processing
Electrolytic Slimes
Mineral Processing
Pvrolytic Residue
Mineral Processing
Slag
Mineral Processing
Chromium. Ferrochromium. and
Dust or Sludge from ferrochromium production
Mineral Processing
Ferrochromium-Silicon
Dust or Sludge from ferrochromium-silicon production
Mineral Processing
Slag and Residues
Mineral Processing
Coal Gas
API Oil/Water Separator Sludge
Mineral Processing
API Water
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Dissolved Air Flotation (DAF) Sludge
Mineral Processing
Flue Dusi Residues
Mineral Processing
Liquid Waste Incinerator Blowdown
Mineral Processing
Liquid Waste Incinerator Pond Sludge
Mineral Processing
Multiple Effects Evaporator Concentrate
Mineral Processing
Multiple Effects Evaporator Pond Sludge
Mineral Processing
Sludge and Filter Cake
Mineral Processing
Spent Methanol Catalyst
Mineral Processing
Stretford Solution Purge Stream
Mineral Processing
Surface Impoundment Solids
Mineral Processing
Vacuum Filter Sludge
Mineral Processing
Zeolite Softening PWW
Mineral Processing
Copper
Acid plant blowdown
Mineral Processing
Acid plant thickener sludge
Mineral Processing
APC dusts/sludges
Mineral Processing
Spent bleed electrolyte
Mineral Processing
Chamber solids/scrubber sludge
Mineral Processing
Waste contact cooling water
Mineral Processing
Discarded furnace brick
Mineral Processing
Non-recyclable APC dusts
Mineral Processing
Process wastewaters
Mineral Processing
Scrubber blowdown
Mineral Processing
Spent black sulfuric acid sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
Tankhouse slimes
Mineral Processing
WWTP liquid effluent
Mineral' Processing
WWTP sludge
Mineral Processing
-------
841
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Elemental Phosphorous
Condenser phossv water discard
Mineral Processing
Cooling water
Mineral Processing
AFM nnsate
Mineral Processing
Dust
Mineral Processing
Waste ferrophosphorus
Mineral Processing
Furnace offgas solids
Mineral Processing
Furnace scrubber blowdown
Mineral Processing
Precipitator slurry scrubber water
Mineral Processing
Slag quenchwater
Mineral Processing
Sludge
Mineral Processing
Spent furnace bnck
Mineral .Processing
Surface impoundment waste liquids
Mineral Processing
Surface impoundment waste solids
Mirteral Processing
Waste filter media
Mineral Processing
WWTP liquid effluent
Mineral' Processing
WWTP Sludge/Solids
Mineral Processing
Fluorspar and Hydrofluoric Acid
APC Dusts
Mineral Processing
Off-spec fluosilicic acid
Mineral Processing
Sludges
Mineral Processing
Germanium
Waste Acid Wash and Rinse Water
Mineral Processing
Chlonnator Wet Air Pollution Control Sludge
Mineral Processing
Hydrolysis Filtrate
Mineral Processing
Leach Residues
Mineral Processing
Spent Acid/Leachale
Mineral Processing
Waste Still Liquor
Mineral Processing
Wastewater
Mineral Processing
Gold and Silver
Spent Furnace Dust
Mineral Processing
Refining wastes
Mineral Processing
Slag. ,
Mineral Processing
Wastewater treatment sludge
Mineral Processing
Wastewater
Mineral Processing
Iron and Steel
Wastewater
Mineral Processing
Lead
Acid Plant Blowdown
Mineral Processing
Acid Plant Sludge
Mineral Processing
Baghouse Dust
Mineral Processing
Baghouse Incinerator Ash
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Waste Nickel Matte
Mineral Processing
Process Wastewater
Mineral Processing
Slurried APC Dust
Mineral Processing
Solid Residues
Mineral Processing
-------
842
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Lead (continued)
Solids in Plani Washdown
Mineral Processing'
Spent Furnace Bnck
Mineral Processing
Stockpiled Miscellaneous Plant Waste
Mineral Processing
Surface Impoundment Waste Liquids
Mineral Processing
Surface Impoundment Waste Solids
Mineral Processing
SVG Backwash
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludges/Solids
Mineral Processing
Lightweight Aggregate
APC control scrubber water and solids
Mineral Processing
APC Dust/Sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
WWTP liquid effluent
Mineral Processing
Magnesium and Magnesia from
Brines
APC Dust/Sludge
Mineral Processing
Calciner offgases
Mineral Processing
Calcium sludge
Mineral Processing
Casthouse Dust
Mineral Processing
Casting plant slag
Mineral Processing,
Cathode Scrubber Liquor
Mineral Processing
Slag
Mineral Processing
Smut
Mineral Processing
Spent Brines
Mineral Processing
Manganese, Manganese Dioxide,
Ferromanganese, and
Siiicomanganese
APC Dust/Sludge
Mineral Processing
APC Water
Mineral Processing
Electrolyte Purification Waste
Mineral Processing
Iron Sulfide Sludge
Mineral Processing
Ore Residues
Mineral Processing
Slag
Mineral Processing
Spent Graphite Anode
Mineral Processing
Spent Process Liquor
Mineral Processing
Waste Electrolyte
Mineral Processing
Wastewater (CMD)
Mineral Processing
Wastewater (EMD)
Mineral Processing
Wastewater Treatment Solids
Mineral Processing
Mercury
Concentrator Wastewater
Mineral Processing
Dust
Mineral Processing
Mercury Quench Water
Mineral Processing
Filter Cake Waste
Mineral Processing
Furnace Residue
Mineral Processing
Molybdenum, Ferromolybdenum,
and Ammonium Molybdate
APC Dust/Sludge
Mineral Processing
Flue Dust/Gases
Mineral Processing
-------
843
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Molybdenum. FerTomolybdenum,
and Ammonium Molybdale
(continued)
Liquid Residues
Mineral Processing
H2 Reduction Furnace Scrubber Water
Mineral Processing
Molybdic Oxide Refining Wastes
Mineral Processing
Refining Wastes
Mineral Processing
Roaster Gas Blowdown Solids
Mineral Processing
Slag
Mineral Processing
Solid Residues
Mineral Processing
Treatment Solids
Mineral Processing
Phosphoric Acid
Waste Scale
Mineral Processing
Platinum Group Metals
Slag
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 hydroxide cake
Mineral Processing
Spent iron/lead filter cake
Mineral Processing
Lead backwash sludge
Mineral Processing
Monazite solids
Mineral Processing
Process wastewater
Mineral Processing
Spent scrubber liquor
Mineral Processing
Spent sodium fluoride
Mineral Processing
Spent sodium hypochlorite filter backwash
Mineral Processing
Solvent extraction crud
Mineral Processing
Spent surface impoundment solids
Mineral Processing
Spent surface impoundment liquids
Mineral Processing
Waste filtrate
Mineral Processing
Waste solvent
Mineral Processing
Wastewater from caustic wet APC
Mineral Processing
Waste zinc contaminated with mercury
Mineral Processing
Rhenium
APC Dust/Sludge
Mineral Processing
Spent Barren Scrubber Liquor
Mineral Processing
Spent Rhenium Raffinate
.Mineral Processing
Roaster Dust
Mineral Processing
Spent Ion Exchange/SX Solutions
Mineral Processing
Spent Salt Solutions
Mineral Processing
Slag
Mineral Processing
Scandium
Crud from the bottom of the solvent extraction unit
Mineral Processing
Dusts and spent filters from decomposition
Mineral Processing
-------
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Scandium (continued)
Spent acids
Mineral Processing
Spent ion exchange resins and backwash
Mineral Processing
Spent solvents from solvent extraction
Mineral Processing
Spent wash water
Mineral Processing
Waste chlonne solution
Mineral Processing
Waste solutions/solids from leaching and precipitation
Mineral Processing
Selenium
Spent filter cake
Mineral Processing
Plant process wastewater
Mineral Processing
Slag
^Mineral Processing
Tellurium slime wastes
Mineral Processing
Waste Solids
Mineral Processing
Silicon and Ferrosilicon
APC Dust Sludge
Mineral Processing
Dross discard
Mineral Processing
Slag
Mineral Processing
Sulfur
Spent catalysts (Claus process)
Mineral Processing
Spent vanadium pentoxide catalysts from sulfuric acid production
Mineral Processing
Spilled product (Claus process)
Mineral Processing
Wastewater from wet-scrubbing, spilled product and condensates
Mineral Processing
Synthetic Ruule
APC Dust/Sludges
Mineral Processing
Spent Iron Oxide Slurry
Mineral Processing
Spent Acid Solution
Mineral Processing
Tantalum. Columbium and
Ferrocolumbium
APC Dust Sludge
Mineral Processing
Digester Sludge
Mineral Processing
Spent Potassium Titanium Chloride
Mineral Processing
Process Wastewater
Mineral Processing
Spent Raffinate Solids
Mineral Processing
Scrubber Overflow
Mineral Processing
Slag
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge
Mineral Processing
Tellurium
Slag
Mineral Processing
Solid waste residues
Mineral Processing
Waste Electrolyte and Wastewater
Mineral Processing
Wastewater
Mineral Processing
Tin
Brick Lining and Fabric Filters ,
Mineral Processing
Dross
Mineral Processing
Process Wastewater and Treatment Sludge
Mineral Processing
Slag
Mineral Processing
Slimes
Mineral Processing
Waste Acid and Alkaline baths
Mineral Processing
Titanium and Titanium Dioxide
Spent Brine Treatment Filter Cake
Mineral Processing
-------
845
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Titanium and Titanium Dioxide
FeCl Treatment Sludge
Mineral Processing
(continued)
Waste Feme Chloride
Mineral Processing
Finishing Scrap
Mineral Processing
Leach Liquor and Sponge Wash Water
Mineral Processing
Waste Non-Contact Cooling Water
Mineral Processing
Pickling Liquor and Wash Water
Mineral Processing
Scrap Detergent Wash Water
Mineral Processing
Scrap Milling Scrubber Water
Mineral Processing
Reduction Area Scrubber Water
Mineral Processing
Chlonnation Off gas Scrubber Water
Mineral Processing
Chlonnation Area - Vent Scrubber Water
Mineral Processing
Melt Cell Scrubber Water
Mineral Processing
Chlorine Liquefaction Scrubber Water
Mineral Processing
Chip Crushing Scrubber Water
Mineral Processing
Casting Crucible Contact Cooling Water
Mineral Processing
Smut from Mg Recovery
Mineral Processing
Spent Surface Impoundment Liquids
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
TiC14 Purification Effluent
Mineral Processing
Spent Vanadium Oxychloride
Mineral Processing
Sodium Reduction Container Reconditioning Wash Water
Mineral Processing
Casting Crucible Wash Water
Mineral Processing
Waste Acids (Chloride process)
Mineral Processing
Waste Acids (Sulfate process)
Mineral Processing
Waste Solids (Sulfate process)
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge/Solids
Mineral Processing
Tungsten
Spent Acid and Rinse water
Mineral Processing
Scrubber wastewater
Mineral Processing
Process wastewater treatment plant effluent
Mineral Processing
Water of formation
Mineral Processing
Uranium
Waste Nitric Acid from Production of UOj
Mineral Processing
Vaporizer Condensate
Mineral Processing
Superheater Condensate
Mineral Processing
Slag
Mineral Processing
Uranium Chips from Ingot Production
Mineral Processing
Waste Calcium Fluoride
Mineral Processing
Vanadium
Filtrate and Process Wastewaters
Mineral Processing
Solid Waste
Mineral Processing
Spent Precipitate
Mineral Processing
Slag
Mineral Processing
-------
EXHIBIT 5-2 (Continued)
Commodity
Waste Stream
Nature of Operation
Vanadium (continued)
Wet scrubber wastewater
Mineral Processing
Zinc
Acid Plant Blowdown
Mineral Processing
Spent Cloths. Bags, and Filters
Mineral Processing
Waste Ferrosilicon
Mineral Processing
Spent Goethite and Leach Cake Residues
Mineral Processing
Process Wastewater
Mineral Processing
Discarded Refractory Brick
Mineral Processing
Spent Surface Impoundment Liquid
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
Spent Synthetic Gypsum
Mineral Processing
TCA Tower Blowdown (ZCA Bartlesville. OK - Electrolytic Plant)
Mineral Processing
Wastewater Treatment Plant Liquid Effluent
Mineral Processing
Wastewater Treatment Plant Sludge
Mineral Processing
Zinc-lean Slag
Mineral Processing
Zirconium and Hafnium
Spent Acid leachate from zirconium alloy production
Mineral Processing
Acid leachate from zirconium metal production
Mineral Processing
Ammonium Thiocyanate Bleed Stream
Mineral Processing
Reduction area-vent wet APC wastewater
Mineral Processing
Caustic wet APC wastewater
Mineral Processing
Feed makeup wet APC wastewater
Mineral Processing
Filter cake/sludge
Mineral Processing
Furnace residue
Mineral Processing
Hafnium filtrate wastewater
¦Mineral Processing
Iron extraction stream stripper bottoms
Mineral Processing
Leaching nnse water from zirconium alloy production
Mineral Processing
Leaching nnse water from zirconium metal production
Mineral Processing
Magnesium recovery area vent wet APC wastewater
Mineral Processing
Magnesium recovery off-gas wet APC wastewater
Mineral Processing
Sand Chlonnation Off-Gas Wet APC wastewater
Mineral Processing
Sand Chlonnation Area Vent Wet APC wastewater
Mineral Processing
Silicon Tetrachloride Purification Wet APC wastewater
Mineral Processing
Wet APC wastewater
Mineral Processing
Zirconium chip crushing wet APC wastewater
Mineral Processing
Zirconium filtrate wastewater
Mineral Processing
-------
EX,. ^IT 5-3
Listinc; of Hazardous Mineral Processing Wastes iiy Commodity Sector
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(100(1 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
lllgli
As
Ha
Cd
Cr
Pb
Us
Se
AS
Corr
Igiiil
Kitv
Alumina and Aluminum
Metallurgical grade alumina is extracted from bauxile by the Bayer
process and aluminum is obtained from this purified ore by electrolysis
via the Hall-Heroull process. The Bayer process consists of the
following five steps: (1) ore preparation, (2) bauxile digestion, (3)
clarification, (4) aluminum hydroxide precipitation, and (5) calcination
to anhydrous alumina In the 1 lall-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.
Cast house dust
19
-
Y
Y
N7
N?
N7
Electrolysis
waste
58
-
-
Y?
N7
N?
N7
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 tetrahednte or lead ore Antimony can be produced using either
pyrometallurgical processes or a hydroinctallurgical process For the
pyromelallurgical processes, the method of recovery depends on the
antimony content ol 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
leaching and electrowinmng.
Autoclave
filtrate
-
0 38
32
64
Y?
Y?
Y7
Y?
Y?
N?
N?
Slag and fui mice
residue
32
-
Y7
N?
N?
N?
Stripped anolyte
solids
0 19
-
-
-
Y?
N?
N7
N?
Beryllium
Bertrandite and beryl ores are treated using two separate processes to
produce beryllium sulfate, BeSO,t: 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(Gl l)2 The beryllium
hydroxide is further converted to beryllium fluoride, BcF2, which is
then catalytically reduced to form metallic beryllium
Spent barren
filtrate streams
88
-
-
Y
N?
N7
N?
Bertrandite
thickener slurry
370
-
Y?
N9
N?
Beryl thickener
slurry
3
Y
N?
N?
Chip treatment
wastewater
-
02
100
2000
Y?
N'
N7
•N7
Filtration
discaid
0 2
45
90
Y?
N?
N?
N?
Spent ralfinalc
380
Y
Y
N?
N'
-------
00
00
EXHIBIT 5-3 (Continued)
Commodity and Summaiy Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC MetuLs
Other Hazardous
Characteristics 1/
lx>w
Med.
High
As
R»
Cd
Cr
Pb
"8
Se
Corr
Ignil
Rctv
Bismuth
Bismuth is recoveied mainly during llie smelling of copper and lead
ores. Bismuth-containing dust from copper smelting operations is
transferred to lead smelling operations for recovery. At lead smelting
operations bismuth is recovered either by the llclterton-Kroll process
or the Belts Electrolytic process. In the Betterton-Kroll process,
magnesium and calcium are mixed with molten lead io 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.
Alloy residues
-
0.1
3
6
Y?
N?
N?
N7
.Spent caustic
soda
-
0 1
6 1
12
Y?
N?
N7
N7
Electrolytic
slimes
-
0
0.02
02
Y'l
N?
N?
N?
Lead and zinc
chlorides
-
0.1
3
6
Y?
N?
N?
N7
Metal chloride
residues
3
-
-
Y?
N?
N?
N?
Slag
-
0 1
1
10
y
N?
N7
N?
Spent electrolyte
-
0 1
6.1
12
Y?
N?
N?
N?
Spent soda
solution
-
0.1
6 1
12
Y'
Y?
N?
N7
Waste acid
solutions
0.1
6.1
12
Y7
N?
N7 .
Waste acids
-
0
0.1
0.2
Y7
N?
N7
Boron
Boron (borax) is either lecovered from ores or from natural mineral-
rich lake brines by two companies in the U.S. Recovery from ores
involves the following steps: (1) ore is dissolved in water, (2) llie
resulting insoluble material is separated from the solution; and (3)
crystals of sodium borate are separated from the weak solution and
dried. Boron is lecovered from brines involves solvent extraction,
acidification, and fractional distillation followed by evaporation.
Waste liquor
0.3
150
300
Y?
N'
N7
N7
-------
EXHIBIT 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Ix>w
Med.
High
As
Ua
Cd
Cr
Pb
Hg
Se
Ag
Corr
Ignll
Rclv
Cadmium
Cadmium is obtained as a byproduct of zinc metal production
Cadmium metal is obtained from zinc fumes or precipitates via a
hydrometallurgical or a pyrometallurgical process. 'Hie
hydroniclnllurgical 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 lo 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 convened to water-
or acid-soluble form, (2) leached solution purified, (3) galvanic
precipitation or electrolysis, and (4) metal briquetted or cast.
Caustic
washwater
-
0.19
1 9
19
Y?
Y?
N?
N?
Copper and lead
sulfate filter
cakes
-
0.19
1 9
19
Y?
Y?
N?
N?
N?
Copper removal
filter cake
-
0.19
1 9
19
Y?
N>
N?
N?
Iron containing
impurities
0.19
1.9
19
Y?
N?
N?
N?
Spent leach
solution.
-
(1.1-9
1 9
19
Y'
Y?
Y?
Y?
N?
N?
Lead sulfate
waste
0.19
1.9
19
Y?
Y?
N'
N?
N?
Post-leach filter
cake
-
0 19
1 9
19
Y?
N?
N?
N?
Spent
purification
solution
-
0.19
1 9
19
Y7
Y?
N?
N?
Scrubber
wastewater
-
0.19
1 9
19
Y?
Y?
N?
N?
Spent electrolyte
0 19
1.9
19
Y?
Y?
N?
N?
Zinc precipitates
0.19
1.9
19
y?
N?
N?
N?
Calcium Melal
Calcium metal is produced by the Aluminothermic method. In the
Aluminothermic method, calcium oxide, obtained by quairying and
calcining calcium limestone, is blended with finely divided aluminum
and leduccd under a high temperature vacuum. The process produces
99% pure calcium metal which can be fuithcr purified through
distillation.
Dust with
quicklime
-
0 04
0.04
0 04
Y?
N''
N?
00
IX)
-------
00
Ln
O
•EXHIBIT 5-3 (Continued)
Commodity nnd Summary Description
Waste Stream
Reported
Generation
(1000
int/yr)
Estimated Generation
(1000 m(/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Da
Cd
C'r
Pb
"t!
Se
AS
Corr
Ignff
Kclv
Coal Gas
Coal is crushed and gasified in Ihe presence of steam and oxygen,
producing carbon dioxide and carhon monoxide, which further react to
produce carbon oxides, methane and hydrogen 'l"he product gas is
separated from the flue gas, and is processed and purified to saleable
methane
Multiple effecls
evaporator
concentrate
-
0
0
65
Y
Y
N?
N?
N?
Copper
Copper is recovered from ores using either pyiometallurgical or
hydrometallurgical processes In both cases, the copper-bearing ore is
crushed, ground, and concentrated (except in dump leaching).
Pyrometallurgical processing can lake as many as five steps: roasting,
smelting, converting, fire refining, and electrorefining
Hydrometallurgical processing involves leaching, followed by either
precipitation or solvent extraction and eleclrowinning.
Acid plant
blowdown
4800
-
-
Y
Y
Y
Y
Y
Y
Y
Y
N?
N?
APC
dusts/sludges
-
1
220
450
Y?
N?
N?
N?
Spent bleed
electrolyte
310
-
-
-
Y
Y
Y
Y
Y
Y
Y
N?
N?
Waste contact
cooling water
13
-
-
Y?
N7
N?
N?
Piocess
wastewaters
4900
-
-
Y
Y
Y
Y
Y?
Y
N?
N?
Scrubber
blowdown
-
49
490
4900
Y
Y
Y?
Y
N?
N?
N?
Suiface
impoundment
waste liquids
620
-
-
Y?
Y?
Y7
Y
N?
N?
Tankhouse
slimes '
4
-
Y? ¦
y>
Y''
Y?
N7
N?
N?
WW IT sludge
6
-
y>
Y?
N?
N?
N?
-------
I XIimil 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics ]_/
Low
Med,
IMgl.
As
Bu
Cd
Cr
Pb
"K
Se
Ag
Corr
IHl.lt
Rctv
Elemental
Phosphorus
Phosphate rock or sintered/agglomerated fines are charged into an
electric arc furnace with coke and silica. 'Ihis 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.
Dust
.4.4
-
-
-
Y?
N?
N?
N7
AFM rinsate
2
-
-
-
Y
Y
N7
N?
N7
Furnace offgas
solids
24
-
-
-
Y
N?
N?
N7
Furnace
scrubber
blowdown
-
270
Y
YS
N?
N?
Slag
quenchwaler
0
0
1000
Y?
Y?
N?
N''
N7
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.
Off-spcc
fluosilicic acid
0
15
44
Y?
N7
N7
Germunlum
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. Hie sintering fumes, containing oxidized germanium, arc
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 bv adding
hydrochloric acid or chlorine gas to produce germanium tetrachloride,
winch is hydrolyzed to produce solid germanium dioxide. The final
step involves reducing germanium dioxide with hydrogen to produce
germanium metal
Waste acid wash
and iinsc water
-
04
22
4
Y?
Y7 '
Y7
Y?
Y7
Y?
Y?
N7
N7
Clilorinator wet
air pollution
control sludge
0.01
0.21
0.4
Y?
Y?
Y?
Y?
Y7
Y7
N?
N7
N7
Hydrolysis
filtrate
-
0.01
0.21
0.4
Y?
Y7
Y?
Y7
Y7
Y?
N7
N?
N7
Leach residues
0.01
Y7
Y?
N7
N?
N7
Spent
acul/lenchate
0 4 '
' 22
4
Y?
Y>
Y7
N'
N7
Waste still
liquor
0.01
021
0.4
Y?
Y?
Y?
Y?
Y?
Y?
N?
Y?
N7
00
cn
-------
00
Ln
NJ
EXIUK1T 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metuls
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ita
Cd
Cr
I'b
"g
Se
Corr
ignlt
Rclv
Gold and Silver
Gold and silver may be recovered from either ore or the refining ol
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.
Activatedscarbon 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 by acid leaching or electrolysis, 'l"he Merrill Ciowe process
consists of filtering and dcaerating the leach solution and then
precipitating the piecious melals 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 Irom previous stages of refining is brought
into contact with a zinc bath which absorbs the precious metals. Base
metals are removed and the dorfc is sent to refining
Spent furnace
dust
0.1
360
720
Y?
Y?
N?
. N?
Refining wastes
-
0.1
360
720
Y'
N?
N?
N?
Slag
-
0.1
360
720
Y?
N>
N?
N'
Wastewater
treatment sludge
-
0.1
360
720
Y?
N?
N?
N?
Wastewater
440
870
1700
Y?
Y? -
Y?
Y7
Y?
N?
N?
N?
Lead
Lead ores are crushed, ground, and concentrated. I'cllelizcd
concentrates are then fed to a sinter unit with other materials (e.g.,
smeller 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 dccopperized before being sent to the refining stages. Refining
operations generally consist of several steps, including (in sequence)
softening, desilverizing, dczincing, bismuth removal and final refining.
During final refining, lead bullion is mixed with various fluxes and
reagents to remove remaining impurities
Acid plant
blowdown
560
-
-
-
Y
Y
Y
Y?
Y
Y
N?
N'
Acid plant
sludge
14
-
-
-
Y?
N?
N?
Baghousc dust
46
-
-
Y
Y
N?
N>
N7
Baghousc
incinerator ash
0.7
3
30
Y
Y
N?
N?
N?
Process
wastewater
4000
-
-
-
Y
Y
Y
Y7
Y
N?
N?
N?
Slurried APC
dust
7
-
Y
Y
N>
N?
N'
Solid residues
0 4
-
Y?
N?
N?
N?
Spent luinace
brick
1
-
Y
N?
N''
N'
-------
EXHIBIT 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
(feneration
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Oilier Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
Se
Ag
Corr
Ignil
Rclv
l^ead (continued)
Stockpiled
miscellaneous
plant waste
0.4
80
100
Y
Y
N?
N?
N'
Surface
impoundment
waste liquids
1100
-
-
Y?
Y?
Y?
N?
N?
N7
WWTP liquid
effluent
3500
-
-
Y7
Y
N?
N?
WWTP
sludges/solids
380
-
Y'
Y'
Y
N?
N''
Magnesium and Magnesia
from llrlnes
Magnesium is recover through iwo processes- (1) electrolytic and (2)
thermal In electrolytic production with hydrous Teed, magnesium
hydroxide is precipitated from seawater and settled out. The underflow
is dewatered, washed, reslurried with wash water, and neutralized with
tlcl and I I2S04. 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. Pie
resulting powder is melted, fed into the electrolytic cells, and then
casled. The Iwo thermal pioduction processes for magnesium are the
carbothermic process and the silicothcrmic 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 sihcothermic 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.
Cast house dust
0.076
0 76
7.6
Y?
N?
N?
N7
Smut
26
Y
N?
N?
N?
00
Ln
LO
-------
00
LTI
¦P*
EXHIBIT 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
T<* Metals
Oilier Hazardous
Characteristics 1/
bw
Med.
High
As
Ba
Cd
Cr
Pb
»g
Se
Ag
Corr
Ignll
Rclv
Mercury
Mercury curiently is lecovered only from gold ores. Sulfide-bearing
gold ore is roasted, and tlic mercury is recovered from the exhaust gas.
Oxide-based gold ore is crushed and mixed with water, and senl to a
classifier, followed by a concentrator. The concentrate is sent to an
agitator, where it is leached with cyanide. 'Hie slurry is filtered and the
filtrate is sent to eleclrowinning, where the gold and mercury are
deposited onto stainless steel wool cathodes. The cathodes are sent to
a relort, where the mercury vaporizes with other impurities, 'llie vapor
is condensed to recover the mercury which is then purified.
Dust
0.01
-
Y?
N?
N?
N?
Mercury quench
water
-
81
99
540
Y?
Y?
N?
N?
N?
Furnace residue
0 1
-
-
Y7
N?
N?
N?
Molybdenum,
Ferromolybdenum, and
Ammonium Molybdale
Production of molybdenum and molybdenum products, including
ammonium molybdale, begins with roasting. Technical grade molybdic
oxide is made by roasting concentrated ore. I'ure molybdic oxide is
produced from technical grade molybdic oxide either by sublimation
and condensing, or by leaching Ammonium molybdale is formed by
reacting technical grade oxide with ammonium hydroxide and
crystallizing out the pure molybdale 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
mctallothermic process using silicon and/or aluminum as the reduclant.
Flue dust/gases
-
1 2
270
540
Y?
N?
N?
N?
Liquid residues
1
V
Y?
Y?
Y?
N?
N?
N?
Molybdic oxide
refining wastes
2
-
Y?
N?
N?
N?
Platinum Group Metals
I'latinum-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 tieated by fioth 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
Slag
0 0046
0 046
0 46
Y?
Y?
N?
N?
N'
Spent acids
03
1.7
3
Y?
Y?
Y>
N?
N'
Spent solvents
03
1 7
3
Y?
Y'
N'
Y>
N'
¦
-------
EXHIBIT 5-3 (Continued)
Reported
Generation
(1000
nil/yr)
Estimated Generation
(1000 mly'yr)
TC Metals
Oilier Hazardous
Characteristics 1/
Commodity find Summary Description
Waste Stream
Low
Med.
High
As
Ba
Cd
Cr
Pb
He
Se
Aft
Corr
Ignil
Rctv
Pyrobltumens, Mineral
Waxes, and Natural Asphalt
The production process for pyrobltumens consists of cracking in a still,
recondensation, and grading. Mineral wax processing consists of
Still bottoms
-
0.002
45
90
N?
Y?
N?
solvent extraction from lignite or cannel coal. To produce natural
asphalt, ore is processed through a vibrating bed dryer, and sorted
according to particle size. The material is either loaded directly as
bulk product, fed to a bagging machine, or fed into a pulverizer for
further size reduction.
Waste catalysts
-
0 002
10
20
Y?
Y?
Rare Earths
Rare earth elements are produced from monazitc and bastnasitc 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 eaith metals commonly.
Spent
ammonium
nitrate
processing
solution
14
-
Y
N?
N?
Electrolytic cell
caustic wet APC
waste
0.07
07
7
Y?
N7
N'.'
known as mischmelal
Spent lead filter
cake
-
3.3
4.2
5
Y?
N?
N7
N7
Process
wastewater
7
-
-
Y
Y?
N?
N?
Spent scrubber
liquor
-
0 1
500
1000
YS
N?
N7
Solvent
extraction crtid
-
2
45
90
N?
Y?
N7
Waste solvent ¦
2
1000
2000
N7
Y7
N7
Wastewater
from caustic wet
APC
-
0 1
500
1000
Y7
Y'l
Y?
N?-
N?
Waste zinc
contaminated
with mercury
-
2
45
90
Y?
N7
N7
N7
00
LT1
U1
-------
00
Ln
cr»
EXHIBIT 5-3 (Continued)
Commodity and Summitry Description
Waste Stream
Reported
Generation
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
»8
Se
Ag
Corr
Ignll
Rctv
Rhenium
In general, rhenium is recovered from the off-gases produced when
molybdenite, a byproduct of the piocessing 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. 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 Hcl) and
filtration; (4) oxidation and evaporation; and (S) reduction.
Spent barren
scrubber liquor
0
0.1
02
y
N?
N
N
Spent rhenium
raffinate
88
-
-
Y7
N'.'
N?
N?
Scandium
Scandium is generally produced by small bench-scale batch processes.
The principal domestic scandium resource is fluorile tailings containing
thortveitite and associated scandium-enriched minerals .Scandium can
be recovered from thortveitite using several methods. Hach method
involves a distinct initial step (i e., acid digestion, grinding, or
chloi mation) followed by a set of common recovery steps, including
leaching, precipitation, filtration, washing, and ignition at 900 °C to
form scandium oxide.
Spent acids
-
0 7
3 9
7
Y?
N?
•N?
Spent solvents
from solvent
extraction
-
0.7
3.9
7
N?
Y?
N7
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 from the calcine. To
purify the crude selenium, it is dissolved in sodium sulfite and filleted
to remove unwanted solids. The resulting filtrate is acidified witli
sulfuric acid to precipitate selenium. The selenium precipitate is
distilled to drive off impurities.
Spent filter cake
.0.05
0.5
5
Y?
N'>
N?
N'
Plant process
wastewater
66
-
Y
Y
N7
N7
Slag
-
0 05
05
5
Y?
N?
N?
N7
Tellurium slime
wastes
-
0 05
0.5
5
N7
Y'
N?
N7
Waste solids
0 05
05
5
Y?
N?
N7
N7
-------
EXHIBIT 5-3 (Continued)
1
ff«l» StKJin
fteporkd
GOunUoa
(ICOO
litaemM
(1«66 wVyr)
TC Meml>
Other Eanntous
Chantciutaifcv ¦/.-
CtnMlItt and Snnunsrv DacripifeMi
Low
Mfd.
Rich
As
Ba
Cd
Cr'
Pb
**
Se
*e
Cccr.
Ipll
Itrtv
j Sjnlbcttc KutOc
I Synthetic rutile is manufactured tkrotgji the upgrading of ilmenilc ore
¦ u> remove impurities (msilly iron) and yield a teahtock tor production
] of titanium leiraditoride ihrnujh the cblorvfc process The vancus
R processes developed can be organized in throe categories: (1)
U processes in which the inn in ttie ilmenitc ox te ocmptetely reduced to
metii and separated ehter cfccmally or phjiicafly; (2) pooesae* ia
which iron is [ educed to (he tenons slate ani chemically bached from
the arc, and (3) prooeiws in which idective chlarir-atioo u used
remove tiki iron In addition, i process caQcd (be Benelitc CVctic
pmcm ¦"« hydrochloric acid (o bach iron from reduced ibrienix.
APC
duitysludges
30
-
Y?
Y?
N?
N>
M?
Spent iron oxide
starry
45
-
-
-
Y?
Y?
N?
N?
M?
Spent acid
solution
35
-
-
-
Y?
Y1
-
Y?
Y
N?
N?
M?
N?
Tailtlon, Cohanbtain, uri
Ferrer otambtuia
Tantalum iod cohimbitm ores are processed by physically and
chenically breaking doun (he ore to form cotambium and tantalum
salt* or and separating [he coJumbiuni and tantalnii salts or
oxides from one ano&ei. Theie salts or oxides mar be tdd, or further
proaessed to reduce (he sails la (be respective metab.
Feirocotriobium is made by inciting tbc tat with von, ard can jc
sold as a product or fur-bcr processed to produce tantalum and
cotambiuiB products.
Digester sludge
1
-
-
-
Process
wastewater
150
-
-
Y?
Y7
Y7
Y?
Y?
Y
N?
N?
Spert rafflrate
solkfc
-
-
-
Y
N?
N?
Tellurium
llic process Qow for tbc prodscuoii of tellurium can be separated into
Mc stages The Tint stigc m»tva tk renaal of copper from die
cofper iluia. The second stage inmlwt (be rtaweiy of tellurium
me'al and purification r aeratim in dilate salfuric add, aoidalivc
preuuie-ieadring wilh sulfuric acid, or digestion with straag acid.
TdUirouiacid (n the form of precipitates) is then recovered by
cementing, leaching tbccemcd mud, and ncuualtoqg will sulfuric
add. Tdktrittm is recovered from ths precipitated (elturaus acid by
the following three ractxids: (1) direc« rcducrioo, (2) acic
piccipitatioa, and (3) elect rotate purification.
Slag
0.1
1
4.S
V?
N-
N?
N?
Solid waste
restates
0.1
1
4.S
Y?
NV
NT
Y?
Wane
efcclrojyte
0.1
1
10
rt
Y?
NT
N?
N?
I
Wastewater
0.1
le
20
Y
N?
N?
OP
in
-------
00
U1
00
EXHIBIT 5-3 (Continued)
1
Reported
CtctmynthMi
(WW
mt^rr)
HMhuate*GtMrattra
(1000 mVyr)
TC Metals
Odtcr UnaurtkHB
dancktbtfcsy
9 OtUBHMlUMMid Smmjamtf IWHpflan
W«steStn«n
14*
MtA
ib*u
As
Bm
ca
Cr
n>
fit
St
Ag
•CtNflf
IgnU
Rdr
and
Titanium MosMt
Waste ferric
chloride
-
22
29
35
Y
Y
Y
Y
Y?
N7
N?
Titanium ana are utilized in the production of four major titanium-
bated products: lilanimn dkxdde (TiO^ pigment, titanium
Pickle Uqoor and
wash water
-
2.2
2.7
3.2
Y?
Y?
Y?
Y7
N7
N?
tetrachloride (TiO^), illMlum sponge, and titanium IngtX/toctaL The
primary litanium ore* for manufacture of these products arc ilmenitc
and nittts. TlO^ pigment is manufactured through either the sulfate,
chloride, or chloride-ilmeoite proem. The sulfate piuceM employs
digestion of ihnenite ore or TiO^ridi slag with sttfnric acid to produce
a cake, which is purified and calcined to produce TK>2 pigment In the
chloride process, rotife, synthetic rutile, or high-parity ihnenite b
chlorinated to form HCI* which is purified to form TSOt pigment. In
the chlonde-riinemte process, a low-purity ihnenite is converted to
I TSC^in a two-stage cMorinatinn process. Titanium sponge is produced
1 by purifying TiC14 generated by the chloride or cMocidc-ilmcnilc
I process. Tllanroni sponge is cast into ingots for farther processing into
Soap milling
scrubber water
-
4
5
6
Y?
Y?
Y7
Y?
N?
N7
N7
Scrap detergent
wash water
-
360
450
540
Y?
Y?
Y?
Y?
Y
N7
N?
Smot from Mg
recovery
-
0.1
22
45
N7
N7
Y
Leach liquor
and sponge wash
water
-
380
480
580
Y?
Y?
Y
N7
Y?
1 titanium metaL
Spent surface
impoundment
liquids
-
.63
3.4
6.7
YT
Y?
N?
N7
N?
Spent surface
impoundments
solids
36
-
-
-
Y?
Y?
N7
N7
N?
Waste acids
(Chloride
process)
49
-
-
-
YT
Y?
Y7
Y
N
N
Waste adtb
(Sulfate process)
-
02
39
77
Y
Y
Y
Y
Y
N
N |
WWTF sludge/
solids
420
¦
'
Y
N
N
N 1
-------
EXHIBIT 5-3 (Continued)
Commodity and Summaiy Description
Waste Stream
Reported
Generation
(1000
mt/yr)
Estimated Generation
(1000 mt/yr)
'I'C Metals
Oilier Hazardous
Characteristics 1/
lyOW
Med.
High
As
Ba
Cd
Cr
l*b
He
Se
Corr
Ignit
Kcfv
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 solubili/.e
Ihc tungsten as ammonia tungstate. Further purification and
processing yields APT. AP T 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.
Spent acid and
rinse water
-
0
0
21
Y?
N'
N''
Process
wastewater
-
1.8
37
7 3
Y7
N?
N7
Uranium
Uranium ore is recovered using either conventional milling or solution
mining (in situ leaching). Bencficiation 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 leacli 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 nitric acid
from UOz
production
1 7
2.5
34
Y?
N?
N?
Vaporizer
condensate
-
1.7
9.3
17
Y?
N?
N''
Superheater
condensate
-
1 7
93
.17
Y?
N?
N?
Slag
0
85
17
N?
Y?
N?
Uranium chips
from ingot
production
-
1.7
25
34
N?
Y?
N?
00
Lfl
ID
-------
00
o
EXHIBIT 5-3 (Continued)
Reported
(jenerntlon
(1000
ml/yr)
Estimated Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Commodity and Summary Description
Waste Stream
Low
Med.
High
As
Ba
Cd
Cr
Pb
"K
Se
Corr
Ignil
Kctv
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 pyromelallurgical.
Acid plant
blowdown
130
-
-
-
Y
Y
Y
Y?
Y7
Y
Y
Y
N
N
Waste
ferrosilicon
17
-
-
Y?
N?
N?
N>
Electrolytic processing involves digestion with sulfuric acid and
electrolytic refining. In pyromelallurgical processing, calcine is sintered
and smelted in hatch horizontal retorts, externally-heated continuous
veitical retorts, or electrothernuc furnaces. In addition, zinc is smelted
Spent goethite
and leach cake
residues
15
-
-
-
Y
Y
Y
Y?
Y?
Y
Y
N?
N7
N?
in blast furnaces through the Imperial Smelting Furnace process, which
is capable of recovering both zinc and lead fiom mixed zinc-lead
concentrates
Process
wastewater
6600
-
-
Y
Y
Y
Y
Y
Y
Y
N7
N7
Discarded
refractory brick
1
-
-
Y?
Y?
Y?
Y?
N?
N?
N7
Spent cloths,
bags, and filteis
02
-
-
Y?
Y?
Y?
Y7
Y'
N7
N7
N7
Spent surface
impoundment
liquids
2500
-
-
-
Y?
Y
N?
N7
Spent surface
impoundment
solids
1
-
-
Y?
Y?
Y?
Y?
Y?
Y?
N7
N?
N7
Spent synthetic
gypsum
21
-
-
-
Y7
Y
Y?
N7
N7
N7
TCA tower
blowdown (ZCA
Baitlesville,
OK-IIIcctrolytic
plant)
25
-
-
Y ?
Y?
Y7
Y?
Y?
N?
N7
WWTI' liquid
effluent
3500
-
Y7
N'
N7
N'
-Zinc lean slag
17
Y>
N'
N?
N7
-------
EXHIBIT 5-3 (Continued)
Commodity and Summary Description
Waste Stream
Reported
Generation
(1000
mt/yr)
listimaled Generation
(1000 mt/yr)
TC Metals
Other Hazardous
Characteristics 1/
Low
Med.
High
As
Ba
Cd
Cr
Pb
»g
Se
Corr
1k»»
Rctv
Zirconium and
Hafnium
The production processes used al 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.
Spent acid
leachatc from
zirconium alloy
production
0
0
850
Y?
N?
N>
Spent acid
leachate from
zirconium metal
production
-
0
0
1600
Y?
N?
N?
Leaching rinse
water from
zirconium alloy
production
-
34
42
51
Y?
N''
N?
Leaching rinse
water from
zirconium metal
production
0.2
1000
2000
Y?
N?
N'>
If Corr., Ignit., and Rctv. refer to the RCRA hazardous charactenstics of corrosivity, ignitability, and reactivity.
00
-------
EXHIBIT 5-4
Identification of Hazardous Mineral Processing Waste Streams
Likely Subject to the LDRs
Mineral Processing Commodity Sectors
Number of
Waste
i Streams 1/
Estimated Annual Generation Rate (1,000 mf>T)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
Alumina and Aluminum
2
77
77
77
Antimony
" 3
33
64
96
Beryllium
6
740
990
2.900
Bismuth
10
3.7
35
73
Boron
1
030
150
300
Cadmium
11
2.1
21
210
Calcium Metal
.1
0.040
0.040
0 040
Coal Gas
1
0
0
65
Copper
9
10,000
11.000
15.000
Elemental Phosphorus
5
30
30
1.300
Fluorspar and Hydrofluoric Acid ,
1
0
15
44
Germanium
6
084
50
92
Gold and Silver
5
440
2.300
4.600
Lead
12
9.600
9,700
9.800
Magnesium and Magnesia from Brines
->
i.
26
27
34
Mercury
3
81
99
540
Molybdenum, Ferromolybdenum, and
Ammonium Molybdate
3
4.2
270
540
Platinum Group Metals
3
0.60
3.5
6 5
Pvrobitumens, Mineral Waxes,
and Natural Asphalt
2
0.0040
55
110
' Rare Earths
9
39
2.100
4.200
Rhenium
2
88
88
88
Scandium
2
1.4
7.8
14
Selenium
5
66
68
86
Synthetic Rutile
3
100
100
100
Tantalum. Columbium, and Ferrocolumbium
3
150
150
150
Tellurium
4
0.40
13
39
Titanium and Titanium Dioxide
11
1,300
1.500
1,800
Tungsten
2
1.8
3.7
28
Uranium
5
6.8
32
58
-------
863
EXHIBIT 5-4 (Continued)
Mineral Processing Commodity Sectors
Number of
Waste
Streams 1/
Estimated Annual Generation Rate (1,000 mt/yr)
(Rounded to the Nearest 2 Significant Figures)
Low Estimate Medium Estimate High Estimate
Zinc
12
13.000
13,000
13.000
Zirconium and Hafnium
4
34
1,000
4,500
TOTAL;
148
36.000
43.000
60.000
1/ In calculating the total number of waste streams per mineral sector, EPA included both noil-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).
-------
864
-------
pyM-Soool.F
-------
-
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
-------
866
-------
867
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
-------
869
ANTIMONY
Autoclave Filtrate: High: 64,000 mt/yr (32,000 * 2)
Medium: 32,000 mt/yr ((64.000 + 380)/2)
Low: 380 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.
BERYLLIUM
Chip Treatment
Wastewater:
Filtration Discard:
High: 1,000,000 mt/yr
Medium: 50,000 mt/yr
Low: 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.
BISMUTH
Alloy Residues: 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.
-------
870
Spent Caustic Soda: 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.
Waste stream may contain lead since the process uses lead as the starting
material.
Electrolytic Slimes:
High: 200 mt/yr (100 * 2 * 1 facility),
Medium: 20 mt/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).
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.
Lead & Zinc
Chlorides:
High:
Medium:
Low:
6,000 mt/yr (3,000
3,000 mt/yr
100 mt/yr
2*1 facility)
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 streaim contains lead.
-------
Slag:
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.
Spent Electrolyte: 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.
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.
Spent Soda Solution: 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)
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 Acid
Solutions:
Waste stream may be corrosive (engineering judgment). No further
information which may classify the waste stream as hazardous was found.
-------
872
Waste Acids:
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.
Waste stream may be corrosive (engineering judgment). No further
information which may classify the waste stream as hazardous was found.
BORON
Waste Liquor:
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.
CADMIUM
Methodology for estimating waste generation rates for the waste
streams listed below is provided at the end of the sector.
Caustic Wash water:
High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 190 mt/yr
This waste may be toxic for cadmium and/or be corrosive.
Copper and Lead
Sulfate Filter Cakes:
High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 190 mt/yr
This waste may be toxic for cadmium and/or lead.
Copper Removal
Filter Cake:
High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 190 mt/yr
This waste may be toxic for cadmium.
Iron Containing
Impurities:
High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 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
This waste' may be toxic for arsenic, cadmium, and/or lead and/or may be
corrosive.
Lead Sulfate Waste: High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 190 mt/yr
This waste mav be toxic for cadmium and/or lead.
Post-Leach Filter
Cake:
High:
Medium:
Low:
19,000 mt/yr
1,900 mt/yr
190 mt/yr
This waste may be toxic for cadmium.
Spent Purification
Solution:
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.
Scrubber Wastewater: High: 19,000 mt/yr
Medium: 1,900 mt/yr
Low: 190 mt/yr
Spent Electrolyte:
Zinc Precipitates:
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.
According to RTC II (Report to Congress on Solid Wastes from Selected
Metallic Ore Processing Operations; Technical Memorandum for the Zinc
Sector, 1988), saleable 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
-------
874
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: 65,000 mt/yr
Medium: 0 mt/yr
Low: 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
tower 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.
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875
ELEMENTAL PHOSPHORUS
Furnace Scrubber High: 270,000 mt/yr
Blowdown: Medium: 0 mt/yr
Low: 0 mt/yr
The Newly Identified Waste Characterization Data Set Reports that
680,000 mt/yr of Furnace Scrubber Blowdown 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: 1,000,000 mt/yr
Medium: 0 mt/yr
Low: 0 mt/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 High: 44,000 mt/yr
Acid: Medium: 15,000 mt/yr
Low: 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.
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876
GERMANIUM
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.
Waste Acid Wash
& Rinse Water:
High: 4,000 mt/yr (1,000 * 4 facilities)
Medium: 2,200 mt/jr ((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
100 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).
Chlorinator Wet
APC Sludge:
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).
Hydrolysis Filtrate: 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.
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877
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)/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 tons/yr. The low estimate was set at 100 mt/yr.
Waste stream may be corrosive and toxic (arsenic and lead).
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, High: 720,000 mt/yr
Refining Wastes, Medium: 360,000 mt/yr
Slag, and Wastewater Low: 100 mt/yr
Treatment Sludge:
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.
Wastewater: High: 1,700,000 mt/yr
Medium: 870,000 mt/yr
Low: 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,
Spent Acid/Leachate:
Waste Still Liquor:
-------
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
~ Silver chloride reduction spent solution: .4 L/troy ounce silver
reduced
~ Electrolytic cells wet APC: 19 L/troy ounce gold refined
electrolytically
Gold ana 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.
LEAD
Baghouse Incinerator High:
Ash:
Stockpiled
Miscellaneous
Plant Waste:
Medium:
Low:
30,000 mt/yr
3,000 mt/yr
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.
High:
Medium:
Low:
180,000 mt/yr
90,200 mt/yr
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
Casthouse Dust: High: 7,600 mt/yr
Medium: 760 mt/yr
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879
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: 540,000 mt/yr
Medium: 270,000 mt/yr
Low: 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.
PLATINUM GROUP METALS
Slag: High: 460 mt/yr
Medium: 46 mt/yr
Low: 4.6 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 (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.
Spent Acids: 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/vT)
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.
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880
Spent Solvents: High: 3,000 mt/yr (1,000 * 3 facilities)
Medium: 1,700 mt/yr (3,000 + 300/2)
Low: 300 mt/yr (1CX) * 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
Methodology for estimating waste generation rates for the waste
streams listed below is provided at the end of the sector.
Still Bottoms:
Waste Catalysts:
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/yT
Medium: 10,000 mt/yr
Low: 2 mt/yr
2 facilities)
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: 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.
RARE EARTHS
The methodology for estimating waste generation rates for the
waste streams listed below is provided after the estimates.
Electrolytic Cell High: 7,0 00 mt/yr
Caustic Wet APC: Medium: 700 mt/yr
Low: 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
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881
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.
~ 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
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.
Solvent Extraction High: 90,000 mt/yr
Crud: Medium: 45.000 mt/yr
Low: 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.
Spent Lead High: 5,000 mt/yr
Filter Cake: Medium: 4,200 mt/yr
Low: 3,300 mt/yr
This waste may be toxic for lead.
spent acruDDer
Liquor:
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.
Waste Solvent:
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.
Wastewater from
Caustic Wet APC:
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.
Waste Zinc
Contaminated with
Mercury:
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.
-------
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:
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).
Spent Solvents from
Solvent Extraction:
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).
SELENIUM
The methodology for estimating waste generation rates for the
waste streams listed below is provided at the end of the sector.
Spent Filter Cake: .
High: 5,000 mt/yr
Medium: 500 mt/yr
Low: 50 mt/yr
This waste may be toxic for selenium.
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884
Waste Solids:
Slag:
Tellurium Slime
Waste:
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.
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.
TELLURIUM
Slag:
Solid Waste
Residues:
High:
Medium:
Low:
4,500 mt/yr (4,500
1,000 mt/yr
100 mt/yr
1 facility)
No information about production rates or waste stream is available,
therefore, high and low estimates of 4,500 and 100 mt/yr were selected,
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.
A
High:
Medium:
Low:
4,500 mt/yr (4,500
1,000 mt/yr
100 mt/yr
1 facility)
See previous comment.
The waste may contain selenium since selenium is produced in the process.
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885
Waste Electrolyte:
Wastewater:
High: 10,000 mt/yr (10,000
Medium: 1,000 mt/yr
Low: 100 mt/yr
1 facility)
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.
High: 20,000 mt/yr (20,000
Medium: lO,000 mt/yr
Low: 100 mt/yr
1 facility)
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/^r
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.
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Surface
Impoundment
Liquids:
High: 6,700 mt/yr
Medium: 3.400 mt/yr
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.
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. 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.
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.
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
Smut from Mg
Recovery:
High: 45,000 mt/yr (high vol. threshhold)
Medium: 22,000 mt./yr
Low: 100 mt/yr
This waste may be reactive in water.
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887
Ingot Production
Pickle Liquor &
Wash Water:
High:
Medium:
Low:
3,200 mt/yr
2,700 mt/yr
2,200 mt/vr
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-ll, 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-12, p. 4870) for 1 plant
(unidentified). Use scrap 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.
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888
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
High: 2,100 mt/yr
Medium: 0 mt/yr
Low: 0 mt/yr
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 rates 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.
Process Wastewater: High: 7,300 mt/yr
Medium: 3,700 mt/yr
Low: 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.
Spent Acid and
Rinse Water:
This waste may be corrosive.
URANIUM
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 High: 7,650,000 mt/yr (450,000 * 17 facilities)
Seepage: Medium: 3,833,500 mt^r ((7,650,000 + 17,000)/2)
Low: 17,000 mt/yr (1,000 * 17 facilities)
Seepage from one facility is estimated at 1,855 m3/day (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.
-------
889
Since this seepage is treated, the low value was estimated to be 1,000 mt/yr.
High Waste Generation Rate = 1.855 nr'/day * 250 days/yr * 1.01 mt/irr''
(using density for water) = Approximately 450,000 mt/yr. per facility-
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.
Barren
Lixiviant:
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.
Waste Solvents:
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).
Waste Acids from
Solvent Extraction:
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 characteristics of toxicity (arsenic,
chromium, lead, and selenium) and corrosivity.
Slimes from
Solvent Extraction:
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).
-------
890
Waste Nitric Acids
from the Production
of U02:
Vaporizer
Condensate:
Superheater
Condensate:
Slag:
Uranium Chips from
Ingot Production:
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 + l,700)/2)
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).
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 + l,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.
-------
891
This waste stream may be ignitable (engineering judgment) since it contains
uranium metal (DOT Emergency Response Guidebook).
ZIRCONIUM AND HAFNIUM
Spent Acid Leachate High: 850,000 mt/yr
Zirconium and Medium: 0 mt/yr
Hafnium Alloy Low: 0 mt/yr
Production:
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.
This waste may be corrosive.
Spent Acid Leachate
Zirconium and
Hafnium 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 N
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.
High: 1,600,000 mt/yr
Medium: 0 mt/yr
Low: 0 mt/yr
This waste may be corrosive.
Leaching Rinsewater High: 51,000 mt/yr
from Zirconium Alloy Medium: 42,000 mt/yr
Production: Low: 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
-------
892
Leaching Rinsewater High: 2,000.000 mt/yr (1,000,000 * 2 facilities)
from Zirconium Medium: 1,000,000 mt/yr
Metal Production: Low: 200 mt/vr
This waste may be corrosive.
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX B
Work Sheet For Waste Stream Assessment
For
Recycling, Recovery, and Reuse Potential
-------
895
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.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
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 us
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
-------
896
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX C
Definitions For Classifying
Mineral Processing Waste Streams
-------
898
-------
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
• chlonnator wet air pollution control sludges
• 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
• scrubber wastewater
• 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."
-------
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX D
Recycling Work Sheets For
Individual Mineral Processing Waste Streams
-------
902
-------
903
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
tdustrial Sector and Process: JJ Lp- / ; U'^IU1 ! '¦
/aste Stream: ^'^'>7 \:~^j rt )JX
Waste Generation Rate: M OOP PhII 'lOQjT |
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C. R iClD
Hazardous Constituents (major): C"'C rn! om n no fo o k ' \) ~ u
sJ
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: COl.'^ i f t ^
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: ; ' \ {\ HO' Jf;€^ rili
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: V Recyclable
4. Material Classification:
(curie one)
Non-Recyclable Partially Recyclable
(^SludgeJ Spent Material By-Product
-------
904
Work Sheet for Waste Stream Assessment for Recycling, recovery, and Reuse Potential
Industrial Sector and Process: O^LinfLLTO / QUi '.m'TJifr:
Waste Stream: PJj? r-rvQi U M r\ \f\in .
Waste Generation Rate: OOP V^i'$rkA
Waste Fonn: Liquid(Aq./Non-Aq*.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all):
Hazardous Constituents (major):_
Hazard Characteristics (all): \ ' Q Qj$^ ^
0
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: US C^vol'-1. /V.') ('.j-ffiC 1 )'¦ L'M )
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?: (^es^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/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recoveiy/Reuse: (Yes^No/Can't Tell
Comment:
,:V
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: fSludge\ Spent Material By-Product
Ccircle one)
-------
905
*vork Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
lodastrial Sector aa
AynV-s^ \rVvj(3vpT*e-^\Wv^CgJ( Rerov-e /V
Ire \ Wa Vp
Ptv^-Vtst- W,
»"«¦ f ¦ I ¦¦¦Hnw an* -7.A/-?. -*>n-QQ°;
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids( Wet/Dty)
Hazard Characteristics (all): I CL R _T .
Hazardous Constituents f mater): , ca , P;?,
1. Process Flow Diagram & Waste Characterization: By looking at both documents, »y 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: Au-Vo C-(LpiV"-€~
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: Uasit s-hvejxv^ kv..
-------
906
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Ptogok yv\qv\^ . S^° C\a^A y^-
Waste Streaa: S\cs ' -re. ^ ®
Waste Generation Rate:
Waste Form: Liquid(Aq7Non-Aq.)/Slurry/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.&, 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 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 Recycling/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Y_ Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge Spent Material
(circle one)
-------
907
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
dustrial Sector and Process: V~r7 we \-gW\j-c5^g£bvevy
Waste Stream: S:Vv^ ~d^d fV^rAWVe ' c,n\ x A % u_
Waste Generation Rate:
Waste Form: Liquid(Aq-/Non-Aq.)/Sluny/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:
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., 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 Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
.Comment:
Conclusion: Recyclable Non-Recydable
4. Material Classification: Sludge
(circle one)
Partially Recyclable
Spent Material
-------
908
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: ; 11 (,
Waste Stream: Spaj-
-------
909
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ustrial Sector and Process: fx- i
..aste Stream: I t7S ;
Waste Generation Rate: 2,000 rv\~t/t/r
Waste Form: Liquid(Aq./Non-Aq.)/§lun^olids(Wet/Dry)
Hazard Characteristics (all): I CfD R T
Hazardous Constituents (major): i
1. Process Flow Diagram & Waste Characterization: Bv 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: Cu.rrt'^ bec
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: ^ pl-l
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 Recycling/Recovery/Reuse: Yes/No/Can'i Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge Spent Material ( By-Product"
(circle one) —'
-------
910
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 3ero //, ^ -o ; .
Waste Stream: Cin.p -frea-K^, w-
Waste Generation Rate: JoQ/vyrVw- c>o cQQ ^Syr- i J.QCG occ^'t/^
Waste Form: ^
Hazard Characteristics (all): ICR (Ty
Hazardous Constituents (major): *--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: P*- "Hi.-- ^ <-
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neiTber
D. Comment: h>\s 1%' 'hur.^'h, ,,m /v->qw r-^c cy^kvj
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, physic
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.g., physical contact during oroduction. 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 JTJpept lwatel
(circle one)
-------
911
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
jstriai Sector and Process: 3cn, I i< u m
.. dSte Stream: _ tfrg-he, "> t^rc^rd1
Waste Generation, Rate: /CO j <93.C\QC ™"tVorj ' nW/y~
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R (j)
Hazardous Constituents (major): fb ;
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: _ P"~/ of7 ^ F ji^
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products7removable 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: f£.v\Ovi*. L«i;i, /n'CVcv; O/V, "r f^cro
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: YesyNo/Can't Tell
Comment:
C On-site Waste Recyding/Recoverv/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)
-------
912
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Oc-Tw II ut aa ,
Waste Stream: Sp^n-f
Waste Generation Rate: -3 %0,QCQ /»7//V'~
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I (C) R (JT
Hazardous Constituents (major): 5£
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-
B. Waste generation is closest to: Raw Material/Maior Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: oasm .-/t.
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 wastejenerated at every facility using the process?: X^/No/Can't Tell
Comment: i
B. What was the basic purpose for generating this waste (e.g., 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 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
4. Material Qassification:
(circle one)
Non-Recyclable Jx. Partially Recyclable
Sludge y^Spent MateriaT\ By-Product
-------
913
^ of 1
Page _J__ of I
WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY AND REUSE POTENTIAL
Industrial Sector and Process: £yra>TT7Aft/ i I hM /ICc At U\M if. ten.
Waste Stream: RtHi.TR A*/T\m. THiCKF*/r- ¦
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have:, recoverable products/removable' 'contaminants/neither
D. Comment: %'clumh SrciPi UkjR£P>ctw Uitk Scl^Lc fk/Q aC fJdro^sczvitrCK i */
2. Reasons for 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: u/ktT ri+MArirfiiztotcri MAv i/ nrf w Asn? . fitf-TUL Lc7\-Ct-bA,i: bPC-Cme*
JJ±is Eni tx-c r-M-rzi\creg.i7 r-r> Dcfaivz P/icc Hi
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/Don't Know
Comment: U-rru to Pn.fnjc-^sT {Z£Si D-b iH. 0-ti iniT^f \d(\ STb -
B. Water Use Reduction: Yes/No/Don't Know
Comment: Mfrv a-ftt/r- to >tLdTt" Vj*-ir£ TP ^fcTH'c:- frt
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Don't Know
Comment: 1?Ky £ t-nnsCPi LuinrMj /a/ /lfa?JRKrr*r
D. Off-site Waste Recycling/Recovery/Reuse: ¥es/No/Don't Know
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
-------
914
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: "W ? \ ~V\-\ Vs-
Waste Stream: P\ \ \ no ft. p ^ \ A w e. S ^
Waste Generation Rate: \6o (^,yeO .
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major): P )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: Q"X \ d gv\' i v^K
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have:, recoverable products/removable contaminants/neither
D. Comment: Q\ yq\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?: Yes/No/Caq't Tell
Comment: r\/\p ^Q/gg \> C e v
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
(
-------
915
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ustrial Sector and Process:
.aste Stream:
ud Process: ^t>\ yc\
cvy\_<& "Zw^c y CJAdy\A-e. <\ ^
Waste Generation Rate: \0Q, ~}oc>o^ bce>D
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Pry)
Hazard Characteristics (all): I CRT
Hazardous Constituents (major): $ 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: 9cW Ve s ^ gvx
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: C ) pv 'JLoo r\ fe yevv^cy-t_vX AS \ y,,-V- 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
Comment: ffvO f!W /lyrO^\Kf^
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
4. Material Qassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge Spent Material By-Product
-------
916
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: ^Sxsvwo"3^ . \\r(XC. ~V\ 6V\
Waste Stream: So-ew^1 rvxusV^C s nCkoV-
Waste Generation Rate: 1 OO , £\0Q , \\ D QQ w\4-/ Vy
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids( Wet/Dry)
Hazard Characteristics (ail)*. I CRT
Hazardous Constituents (major): 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: ~K
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ^ tx -v\^ \ij>. \r r-Li J^\ .
2. Reasons for Waste Generation: Based on the description of the process, ana 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: gy>K n/o /juff v
D 0
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physicaf
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
Material Classification:
(circle one)
Sludge
Spent Material
By-Product
-------
917
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ustrial Sector and Process: ^ ^ S w> . ^>€~V-Vs ^ ^-e sV\ C Q-rcceSS
,»aste Stream: S opa'-V J
Waste Generation Rate: O O OOP v) Y v
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/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: \-e c <— -i~\ ^ "y- .
B. Waste generation is closest t& 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: (c\,—OYor/\;cp/\
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, >ther 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
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)
-------
918
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: T^>\SW\Q~V V\ ^
Waste Stream: ^ ^ r) rx rv-s
Waste Generation Rate: \CQ, A\OD. \~L-OOD "WnV/Vv''
Waste Form: Liquid(Aq./#on-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major): P\2>
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
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: 5-pfw\ soriex W> \^e. cvP-Vev r~>focei"-Sw\
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: r $\a \ a\/s -e nVo n \) C -v
^ 3
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: V Recyclable
4. Material Qassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
By-Product
-------
919
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
¦riustrial Sector and Process: \ S WA \) ~VA^ •>£ Vr fr. C Vv -£viyv\ 1V\S>^v4W w^K/ie
Waste Stream: u^cV€ F\ c \ r) is\a^
Waste Generation Rate: )C Oj 6/PQ, J~L-OQO
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C_ _R 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: \jv v-Cp cAa\dv> (£ ¦£ ^ CxycV^pvx & ?
-------
920
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 'jj^\ S rvy ^ V~Vy£L gv\
Waste Stream: "6 Ve^V^cA v^-Va c ^ to, q
Waste Generation Rate: J
Waste Form: Liquid(Aq7Non-Aq.)/Slurry/Soli
-------
921
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
adustriaJ Sector and Process: ^e-V-Ver-W/N -"KroD £Vo C-gJl
Waste Stream: DaIov Je R-e,s.\/tve-?>
Waste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Diy)
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 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 Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable X Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
-------
922
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potek
Industrial Sector ami Ptxmmk £ *H(Xf "T?
WonStrmm: UasfeT Prc./rfC
Bluff CtBtiyH— P—- & , too, -2-OD ivl-r/ j V~
Warn Font Uquid(AqJNon-AQ. )/Slurry/Solids( Wet/Dry)
Hmd CbincttfUki (all)! I .5 R T
Hawdous CuuiUlimiii (ma|»):
1. Process F]™* ^iagT?IH ^ Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of ibcsame waste generated is the process. Complete a separate form for
each major source.
A. Source: £Y.i\c^CTi
B. Waste generation is closest to: Raw Maierial/Mnior Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither /-
D. Comment: A-r , d / r^h-fj b-e arorstc-zJ a ^/y
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 pnrpoK 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^, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment
3. Waste Management Alternatwm. Review the. potential for reducing the quantities of waste generated ai
any of its sources by considering the foflowinf waste management alternatives.
A. Wtste Segregation: Yes/No/Cart Tefl>
Commeae '
B. Water Use RcdacdoK Yea/No/Cant Tell
PflmwM'
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Cant Ted
Comment .
D. Off-site Waste Recyding/Recovety/Reuae: Yes/No/Cant Tell
Comment:
CondaskMS: RecydaMe Non-Recydable Partially Recyclable
4. Material Classification? <:i™w
-------
923
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Austria! Sector and Process: S ^
Waste Stream: ,
Waste Generation Rale: v
Waste Form: Liquid(AqVNon-Aq.)/SlurTy/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 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:
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
(circle one)
-------
.924
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector aad Proem: ; 'fepvvc P\C\fk (VooxK 5v>
Waste Stream: vJta Ve A -\ v o
Waste OagftfcM Rasa: 0
Waste Form: Liquid(AqjNon-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at boch 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, physk
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/Can't Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
f circle one) ^
-------
925
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
-iustrial Sector and Process: \i\ym
iste Stream: CC\ 1 \ \ \NH PjV~\ .hSCl'XOn
Waste Generation Rate: 'P C /) Dc) ryrr i J.i? 9, i i '
Waste Form: Liquid(Aq./Non"Aq.)/Slurry/Solids( Wet/Dry)
Hazard Characteristics (all): I . R /T^)
Hazardous Constituents (major): -"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.
Source: \j?
A.
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: V) T'\ i rO-
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: ^ZZ
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:
ConclusionX/ Recyclable Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge I Spent Material I By-Product
(circle one) ——-
-------
926
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: (~*CfH ' J AA r-—>
Waste Stream: rPfiS) rA ( ? f\ 4 (V I 0Pfjjrf J\) 9+? J rr\ j/ nry
Waste Generation Rate:~ 1"-^/! po4 j t /
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids( Wet/Dry)
Hazard Characteristics (all): I C R . (l^ ,
Hazardous Constituents (major): ("/~l rj : > ; ; T'd ' C'C\H
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 I 11 ^ 1" i :'?P,
B. Waste generation is closest to: Raw MaterialTMajor 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.
B.
C.
D.
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge spent Material
(circle one)
Waste Segregation: Yes/No/Can't Tell
Comment:
Water Use Reduction: Yes/No/Can't Tell
Comment:
On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Off-site Waste Recycling/Recovety/Reuse: Yes/No/Can't Tell
Comment:
-------
927
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndustrial Sector and Process:
rndrrn^r,
MM
/Vaste Stream: CP)Op£A KYI Ckf^0 r'' ¦ 4 0A
Waste Generation Rate: j\QcY) ' PPrf /' JUI i ^
Waste Form: Liquid(Aq./Non-Aq.)/Sluriy/Solids(Wet/Dry)
Hazard Characteristics (all): I C R (J)
Hazardous Constituents (major): 0-H.v
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: 11 vtIa
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.gM 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/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)
-------
928
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
r.
Industrial Sector and Process:
(:adfriion/
Waste Stream: "X/TTQ f Arrtfl 1 Hi PiC\ \ ^ ^
Waste Generation Rate:OH 4- ; \J). 1y{ / ! ^ '
Waste Form: Liquid(Aq./N6n-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I R /r
Hazardous Constituents (major): i i
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.
r>" ' ;
A. Source: V i '"L? A
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/Recoveiy/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 Qassification: Sludge^ Spent Material By-Product
(circle one)
-------
929
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
idustrial Sector and Process:
Waste Stream: SpP ri f ! 0,0 r p Pnl '¦ ^ \ On ^
Waste Generation Rate: 'NO/ RoO A.A~f i 'J-PflA / M -U
Waste Form: Liquid(Aq./N6n-Aq.)/Sluny/Solj4s(Wet/Dry)
Hazard Characteristics (all): N I . (^Cj R . VJTJ
Hazardous Constituents (major): H h !<' i nHl rhj-Tl/t . - 0'.^
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: ( 00. f'fi I f' 'JfQCOfY)
B. Waste generation is closes^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: V Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge ; Spent Material \ By-Product
-------
930
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: CjQ-idf H 10 [ /I
Waste Stream: 1 Pfld hk \ Q.Mfp I 1 {?rr
Waste Generation Rate:l°Ci j HC'O' ml r 1A \ rQ-fTO
Waste Form: # Liquid(AqjNon-Aq.)/Slurry/Solicls( Wet/Dry)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): lA TP ; > \>rr\ r\ v~r) t
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.
I * >,
A. Source:
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:
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: V Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
Spent Material
By-Product
-------
931
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndustrial Sector and Process:
Aaste Stream: "?cx>T -LD H fh' t 1 .
Waste Generation Rate: 1 ! \^C)D 1TH; A ( i -Q--
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I . C R
Hazardous Constituents (major): CQfjl^U./riH
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: (pf\ "10 I
B. Waste generation is closest -ti: 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:
y pjri-lach- rcttirO)
Conclusion: \/ Recyclable Non-Recyclable Partially Recyclable ' i/iCO Id bff''' r-
4. Material Classification: Sludge Spent Material
(circle one)
By-Product
-------
HI
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: fY~) I O'/Tl
Waste Stream: Sp? PlT p i Y\W Cf\ -j l^Tfi ST) I Of tl?|A
Waste Generation Rate.PQ K^Gc) Vn41 iI^a I';1- ¦
Waste Form: Liquid(Aq./Non-Ai}.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I <
-------
933
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
dustrial Sector and Process: dlPP) i f^
Q F~(D ¦' 'fl \ j i
Waste Form: Liquid(Aq.yNon-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I R (^T)
Hazardous Constituents (major): C^'a'^D- M*~P
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.
HFC
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 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/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: V_ Recyclable Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge ( Spent Material By-Product
(circle one) ^
-------
934
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: V. 0^fipTV,0\' H
Waste Stream: ¦ IT IQ C tvOh
Waste Generation Rate: yTf
Waste Form: ' Liquid(Aqr/Non-Aq.)/Sluny/Soiids£Wet/Dry)
Hazard Characteristics (all): I ,^Cj R CtQ
Hazardous Constituents (major): T'JT/ '
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: Q J A'. ,0
B. Waste generation is closest t6: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither3'"
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 eveiy 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
4. Material Classification:
(circle one)
\/ Non-Recyclable Partially Recyclable
Sludge Spent Material By-Product
-------
935
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndustrial Sector and Process*.
Waste Stream: ^ [ r{ D'f Q( \ OI \
Waste Generation Rate: pQQO rrMi AO a' A i \-}CGXJ
Waste Form: Liquid(Aq./Nori^Aq.)/Sliiny/Solids( Wet/Dry)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): Cf 1 r\ rr,'JiVv,
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: (K\ ^1 11 (. Y'fQjC, 101 1 CO
B. Waste generation is closest to: Raw MateriafMajor 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: V Recyclable Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge Spent Material
(circle one)
-------
936
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Poteybal
Industrial Sector and Prorasr Wg-WV . P\\\)v^yv\ p VU JV ocess
Waste Slim 'D^V *Ln-Vu
Waste Generation But
Waste Form: Liquid(Aq7Non-Aq.)/Slurry/Solids( Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents (major):
1. Process Flow Djagpin^ Sc Waste Characterfeation: 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.&, plant maintenance, chemical reaction, pnysic*.
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 Redaction: Yes/No/Cant Tell
Comment:
C On-site Waste Recyding/Recovciy/Reuse: Yes/No/Can't Tell
Comment: :
D. Off-site Waste Recyding/Recoveiy/Reuse: Yes/No/Cant Tell
Comment:
_ Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable Non-Recydable _
4. Material Classification: ; Sludge
(circle one) —
-------
937
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
iStrial Sector and Process: <"CWiu.xi f~e,rroC~J\.rcr*itu.,'* ,
Waste Stream: Dus't & <• SluJ^t ^,"^ciirc^nLi,vi
Waste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R (T)
Hazardous Constituents (major): &o<.? Cr 9: Pb 7. , Sz,9. 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 m
D. Comment: V -fa,-., A.l*& l% ¦> res
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 frpm 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
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
Spent Material By-Product
-------
938
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: C I £>2*
Waste Stream: efforts. rT~fcy"' orocissi^ C pns^ r°ss '"tn.^ oF '/^opct
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/Recdvery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
YS
Sludge Spent Material f By-Product
-------
939
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
i
strial Sector and Process: d&r I Q i ^
,te Stream: . ;4 fo gj so/t.P^r^c.
Waste Generation Rate: SOcQ mt/. r. i7.QO&r j VCOOn^/yr-
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Sfllids(Wet/Dry) ??
Hazard Characteristics (all): I C (Ky T
Hazardous Constituents (major): (knc+wn, ?
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 -^aA&.pt'
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: 1 ^.(L^
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)? , f
Comment: £ Cae^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/Reuse: Yes/No/Can't Tell
Comment: .
Conclusion: Recyclable _K_ Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent MatemK7 By-Product
(circle one)
-------
940
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Cc r,cn ^
Waste Stream: -5cl/r\sz>rir, /'<=7utc/'c
Waste Generation Rate: 6a, r ;
Waste Form: ^Liquid/Aq./Non-Aq.VSlurry/Solidsi'Wet/Dry')
Hazard Characteristics (all): I (cT) R
Hazardous Constituents (major): cerros>\u* !\s 7. Pb S<* 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: ^ pCJw' ywzd A.,' TP -*
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: ficvrJ-eJ c.^ ^ c ti-nu ^ a ^
m* 1 ^ Cc>f P. rttiy ^ «
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.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, 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) ,
-------
941
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
atrial Sector and Process: Oc-.oo
,te Stream: iVuj~tp ¦
Waste Generation Rate: £ coo
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): ¦ , Pv7 ;
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: sc^sces, -rh'-c^c-'hc^'t /pr^-^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: ^ f ^0%)
, Cet-JcUA +0 CUoo - to S,r.cj-
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: 3. kr1 cq\c_ jx.'^ mv
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
4. Material Classification:
(circle one)
Non-Recyclable _X_ Partially Recyclable
""Ovs t>4 ^ ^5
^Sludge^; Spent Material By-Product
-------
942
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Ccgp^r .
Waste Stream: iUujTP g£P/u?-i-/-
Waste Generation Rate: H Z^Q.cCQMtA.r
Waste Form: Liquid(Ag./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): ICR (JT ^
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: fLHuliScuraa
B. Waste generation is closest to: Raw MateriaiyMajor Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither i
D. Comment: to.3 -L^r ECl-iv ' 3/-.^ ¦ ^ih^
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: '
'TUa- i+«y Jlo-e.s npU1Z. 9 ^ -fUr^ C.J« f<*(/ r
Conclusion: Recyclable Non-Recyclable _j§ Partially Recyclable
4. Material Classification: f Sludge J Spent Material By-Product
(circle one) \.
-------
943
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
dustrial Sector and Process: (Q "P f^OQC^ L'\"
./aste Stream:
Waste Generation Rate: 'A-A^ST) kAi -A
Waste Form: LiquidfAq./Non-Aq.)/Starry/Solids( Wet/Dry)
Hazard Characteristics (all): I C R >
Hazardous Constituents (major): CTlr\0"i '¦'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.
A. Source: - 1 i AlH\ / ., C V
B. Waste generation is closesHo: 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:
ConclusionX/ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material / By-Product
(circle one) ^ ^
Kirta srzceir rsthr than W
-------
944
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 7 1 C JOTi D.V~:"t"3! U Iw^phOi'/ /Y
Waste Stream: __ ftf'iVA IS
Waste Generation Rate: ~?r~i~.O
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I C R 'T x
Hazardous Constituents (major): )Cfl f\ T'O^;
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 Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable \/ Non-Recyclable _
4. Material Classification: Sludge
(circle one)
-------
945
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
'ndustrial Sector and Process: ? x V \j •.>><"'. A ^ ^ ^,/i ^ i r\
aste Stream: - ' '' ,yQ.r 2. O^-Tvi -~v- A->i' j."
Waste Generation Rate: ^ ,^/T) fY^ -t :' )p \ -
Waste Form: Liqutd(Aq./Non-Aq.)ii$lurTy/Solids( Wet/Dry)
Hazard Characteristics (all): I C _ R
Hazardous Constituents (major): ? ^ 'i '
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 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)
-------
946
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: T J. C-lfT C v H0 ¦.1 ? /Y
Waste Stream: -f? I ^Pi 0 ( Q . SCH 1A tir9 / DIP; KYi'n/.r,
Waste Generation Rate: iyQ / 9 42D(Y^ rrrf j ¦ if (k/\
Waste Form: ^
Hazard Characteristics (ail): I (~c) R ^Tj
Hazardous Constituents (major): Cj^\ 1 ^fV~i
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions foi 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: .
_ Partially Recyclabte
Spent Material By-Product
\z
Conclusion: Recyclable \/ Non-Recyclable _
4. Material Classification: Sludge
(circle one)
-------
947
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
idustrial Sector and Process: '(l\>UTpJ/TTCX ^ V'-C\ Cj)p1^1 (; I i 1 /Y ,
«Vaste Stream: ) 1 ?ry .KKfTh) A ~
¦ Waste Generation RateOfcfi , VTrH ,[?{J A
Waste Form: Liquid(Aq./Non-A /. ^I PoT j
1. Process Flow Diajgram & 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 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 Recycling/Recovery/Reuse: yes/No/Caril Tell
Comment: . rr)iJcL CiTill DO
J
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)
-------
948
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: l~ /'-(p-scc..- f-ivC^&Hcionc,
Waste Stream: -S-Bgwl,, Que*;, 1, 1.^ Ag.ci
Waste Generation Rate: ' o. v- V^r
Waste Form: Liquid(Aq./Non-Aq.)/Slurrv/SoiidsfWet/Dry)
Hazard Characteristics (all): I (S^ ^ 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: y/vWtaj-
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither /
D. Comment: g
-------
949
AVou Shut for Waste Strcam AasamoNT for Rzcycung, Rscovexy, and Reuse Potential
aad Pracaac ^, P/iy^aVy' $ Sg^cw^AKi/ Pyc>^- tf'oOr.
,0-tArx [Ja / A o v^/i \sJo> ~he Y~
Waste Cmmfinn - l^v Z-~Lc> O . <-r >^^/g, A-pu
Process Flow Diagram & Waste Chara^ri7i>^9n' 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: (Sfi/yw?V) )v\.Q,D'7~~ <5 i h ' ^
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable produca/removabte contaminants/neither , a
D. Comment: Uaihr ^^ C*r£> C£^\
-------
950
Work Sheet to* Waste Stuam Assessment tor recycling, Recovery, and Reuse Potent
Indoffrial Smetar ami Procw: (3^ r <2 ^ m fftw\Ay~y $ jCW^\d!a.ry £*e 1/11 i/ vvn
fro^c.7, „
WimSmk /pyi/x~l-£>y A~flCs utJtjte "" /yd c!?j j
Wastt CtmnrtWI Rw ~2- ! £? ¦> CrOC?
Wim Form: Uqaid(AqVNoe.Aq.)/Sluny/Sgj^WeVDiy)
Hazard Characteristics (afl): I C _R_ T__
H.nniott« rmwrttnuta (mate): fH. Trf. c, r-6j <><-,< ^hr
1. Process Flnw Diagram A Waste Cha^tf
-------
951
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector aad Proems: ikwv Pviy^aYi/ i rviAVMi/r^ C- ^ <5V\
Wast* Strew: bh//7/nl^sif f/l fra -he.
Waste Generation Rate ;
Waste Form: Liquid(Aq./Non-Aq.)/SlurTy/Solids( Wet/Dry)
Hazard Characteristics (all): I C R T
Hazardous Constituents fauito):
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 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/Cant TeU
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C On-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Reeowry/Rense: Yes/No/Can't TeU
Comment:
Conclusion: Recyclable Y Non-Recyclable Partially Recyclable
4. Material Classification: Sludge (^SpeM^ateriaT^ By-product
(circle one)
-------
952
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Proem: vv-, ff ?w\c f/<. jS>n-
Wast* Stream: Lekp j-)J[/CS 7 ' ^ ^
Waste Generation Rate:
Waste Form: Liquid(AqTNon-Ajq.)/Slurry/Soiids( Wet/Dry)
Hanrd 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.£, 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 AlteraReview the potential for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yea/No/Cant Ten
Comment: ¦
B. Water Use Reduction: Yes/No/Can't Tell
Comment: _
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Cant Tell
Comment*
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable X* Non-Recyciable
4. Material Classification: Sludge
(circle one)
Partially Recyclable
Spent Material
-------
953
Wou Shbt fob W*m Simam Amsmokt rot Ricycukc, Ricovory, ^ Reuse Potential
niiiiiihis^«rfl*>«wc ro/r-iwn^ r (ectv,tUvs CratesS
mmsurnm *=>P*.*+ //.? *cA*'1
WMtCuwtiMtow: g/?g>g
Warn Fom: Q^(Aq^ ~
Hazard Characteristics (afl): I Q_ R_ T
Hazardous CuiuUlmuU (mlor): 9 „ P b
1. Process Ffow 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. Compute a separate form for
each major source.
A. Source: /_ PaoW I ~>
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Produa
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 wade (eg, plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)? ~
Comment:
C Why did this waste become hazardous (ex. physical contact darina production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management AKCTMliwCT' Rwiear the potrniial for reducing the quantities of waste generated at
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/Nc^Cant Tefl
Comment:
B. Water Use Reduction: Yea/No/Cant Tefl
Comment;
C On-site Waste Reqctiag/Recwery/Reaee: Yes/No/Cant TeU
Comment: ¦
D. Off-site Waste Recycling/Recovery/Renae: Yes/No/Cant Tefl
Comment:
Conclusion: Recyclable Non-Rocydabte ^ Partially Recyclable
Mattrial Cl?^ificatkxb Sludge (^Sp^MatataP) By-Product
(arde one)
-------
954
Work Sheet for Waste Stream assessment for Recycling, Recovery, and Reuse Potential
Industrial Sectorand Process: ^>pv7^Aymi/vw , Ps-fifotJoc
Waste Strew: *" S-h 7/ L/^u&v^ 1
Waste Generation Rite
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/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, 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 AltCTpatjwy- 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/NoAIant 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. OS-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: .
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge I Spent Material' By-Product
(circle one)
-------
955
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector and Process:
Waste Stream:
QolfirirJ \i\Jit
\)GiA)nr«o iMftfttP/y
Waste feneration Rate: f -J ^ mW'-JJtnsI /?$¦ -
Waste Form: Liquid(Aq7Non-Aq.)/Slurry/St!»lids(Wet/Dry)
Hazard Characteristics (ail): I v R
Hazardous Constituents (major): SiVjQA
¦' 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:
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?: YesyNo/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: C\C \ A
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 Recycling/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell.
Comment: ~fOQ IflfQP 'JoluTfliL
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: ( Sludge J Spent Material By-Product
(circle one) \ /
-------
956
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream: 9>
Waste feneration Rate: ^ ?_Q) (XX) ml lUQCLA f CCD
Waste Form: Liquid(Aq./Non-Aq.)/SferTy/So'iids(Wet/Dry)
Hazard Characteristics (all): I C R (^Ty
Hazardous Constituents (mator): ^ i \\l ?X~
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 Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: IHQ \/d\jfYY^
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material (By-Product
(circle one)
-------
957
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
y,\\n \j \. irk
n
\A \\i?,r
ndustrial Sector and Process:
Waste Stream:
Waste Generation Rate:
Waste Form: Liquid(Aq./Non-A4)/Slurry/Solids( Wet/Dry)
Hazard Characteristics (all): I • C R
Hazardous Constituents (major): SAV K _
rY^i'APQA
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/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell ^ i ,
Comment: |(jC) 1 (i ifofj? 'JOOPPiiL
Conclusion: Recyclable
4. Material Classification:
(circle one)
V
Non-Recyclable V_ Partially Recyclable
Spent Material
By-Product
-------
958
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream
Waste Generation
Id an.-i ^Ym
i: ' _ _
ition RaterPHf 1UPfl A f {^'CGOL'
Waste Form: Liquid(Aq./Non-Axj.)7SluiTy/Solids( Wet/Dry)
Hazard Characteristics (all): I. C R QT) .
Hazardous Constituents (major): S I Vxt ^ Cf- ^ '' y ^ UfD> i_l2i
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/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
tV
Conclusion ¦\L Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: v Sludge J spent Material By-Product
(circle one)
-------
959
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector and Process; &~>IA nhdVilvwr
Waste Stream: fZllOjniv^ VJ fl/riPA
Waste Generation Rate v }
an-Aii.ySlunv/SolidsfWet/Drv) 0
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): I
Hazardous Constituents (major): SJJ
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/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 , > By-Product
(circle one)
-------
.960
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Poten-^vl
Industrial Sector andProem:
Waste Stream: !feiDvj dr>z^ n
Waste Generation Rate
Waste Form: Liquid(Aq.yNon-Aq.)/Sluny/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.&, 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 Alterp3^^- 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 Redaction: Yes/No/Cant 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
4. Material Classification:
(circle one)
Non-Recydable Partially Recyclable
Sludge ( Spent Material^) By-Product
-------
961
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
fcdustrial Sector and Process: \ v\ iy\ c-\
fVaste Stream: P\C\ (\ ^\g3v\~V A -Vn RTI Wvev,
3~ 0 ^
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. wateT 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-Recydable Partially Recyclable
4. Material Classification: f Sludge) Spent Material By-Product
(circle one)
-------
962
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Procos:
Waste Stream:
Waste fi+nrarinn R«l>: V
Waste Form: Liquid(Aq./Noh-Aq.)/Sluny/Solids(Wet/Dty)
Hazard Characteristics (all): I C R T
Hazardous Constituents f ma tor):
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.£, plant maintenance, chemical reaction, physi
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/Cant 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 Recyding/Recc^ery/Rense: Yes/No/Cant Tell
Comment: __
Conclusion: Recyclable Non-Recydable Partially Recyclable
4. Material Classification: Q Sludge; Spent Material By-Product
(circle one)
-------
963
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
us trial Sector and Process: L^< \ wxa V ^ Svna 6 \ V v vn c\-y\ (V >re( \V\ ^vxV
aste Stream: ^So^VouSTf Ur'wg^^ov w ^
Waste Generation Rate: e c.. oa^s f va "Ve^C cxV~
OVM? * J
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 X Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material By-Product
(circle one)
-------
964
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: L^A. A , £VvW\/-aV-^ Sw\e IflvvvJi ^^
Waste Stream: 9nror&^ V ^ ,j
Waste Generation Rate: CPDo^ nOo
Waste Form: Liquid(Ag./Non-Aq.)/Slurry/Solids(Wet/Diy)
Hazard Characteristics (all): ICR T
Hazardous Constituents (major): A 5 .
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: vlftYious S><9\ayC€ S U/xi Vgw/xVe v
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product ^ V
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)? 1
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^ 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
4. Material Qassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
Spent Material J By-Product
-------
965
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
odnstrial Sector aad Proem: LPfrJl.
Waste Stream: A PC. t>USt~
Waste G«acradoo Ran:
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/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 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
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyciing/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: V Recyclable Non-Recydable Partially Recyclable
4. Material Classification: ( Sludge ) Spent Material By-Product
(circle one)
-------
966
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:' r\ c. CwJ' v\ \ v-sa
Waste Stream: ScA \ A ;> \ HI \j e. ^ ^
Waste Generation Rate: urO O Iwv
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): ICR T
Hazardous Constituents (major): f )o
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: "P\gw\V
B. Waste generation is closest tcr Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: iOaS,-Ve \s /ecy.4-e f fiTx SL,'We
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
(circle one)
-------
967
Work Sheet for Waste Stream assessment for Recycling, Recovery, and Reuse Potential
P*du8triel Sector and Proem: a $
Warn Straw
Waste Generation Rain,
Waste Fonn: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): I C R T
Hazardous Constituents fmajor):
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 Redaction: 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: X- Recyclable
4. Material Qassification:
(circle one)
Non-Recydable Partially Recyclable
Sludge
Spent Material / By-Product
-------
968
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 'Lp g ^ ^-wyeA^-Nyy g-. Ve_-['A>AA
Waste Stream: w\^ ^rp \Aa.VN-ei7>\;_T S~V-g '
Waste Generation Rate: <^Oo, rlO.pQo o&n
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
Hazardous Constituents (major): d~c) , P~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: \)cK~fiOO S f Je -Y ) cK , , $ we 3 , tv~A
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 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 it Material/ By-Product
(circle one)
-------
969
Work Sheet fob Waste Stream Assessment fob Recycling, Recovery, and Reuse Potential
Wuta Fow Liqaid(AqJNon-Aq.)/Sluny/Solid»( Wet/Pry)
Haard Characttrtetki (all): -- . I C R T
Haarrioas Coturtfmnts (matart: n S , CJ , P&
s 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: I $DUYCeS
B. Waste generation is closest to: Raw Matenai/Mator 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 wane (eg* plant maintenance, chemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C Why did this waste become haiaidous (e.g^ physical contact daring production, minni with other waste
streams, results from imparity removal)? "
Comment
3. Waste Management Altep^jwg* Review the potential for nadnring the quantities of waste generated at
any of its sources by comideriaf the following waste managnnwut alternatives.
A. Waste Segregates; Ycs/No/Caat Tefl
Comment: ¦
B. Water Uaa Radnctk* Yo/NoiCant TeU
Comment: •
C On-site Waste Reqcting/Racovery/Reuse: Yes/No/Can't Tefl
Comment:
D. Off-site Waste RecycUog/Racovery/Reoac: Yes/No/Cant Tett
Comment:
Conclusion: RecydaMe Non-Recyclable Partially Recyclable
4. M?tgrill Cl?«ifwationt ^SludgT^) Spent Material By-product
(arck owl — ——
-------
970
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector aad Ptocmk sdl
Wast*Stnut \J\sJTf1* L\c)\j\d '
Waste flffrahnn Ratr V
Waste Form: Liqu>d(AqJNon-Aq.)/Sluny/Solids(Wet/Diy)
Hazard Characteristics (all): I C R T
Hazardous Constituents (mqfor):
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 Matenal/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.&, 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 TeU
Comment:
B. Water Use Redaction: Yes/No/Can't Tell
Comment: .
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant TeU
Comment: __
D. Off-site Waste Recyding/Recoveiy/Reuse: Yes/No/Cant TeU
Comment:
Conclusion
ion: Recyclable Non-Recydable Partially Recyclable
4. Material Classification:
(carle one)
Spent Material
By-Product
-------
971
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
mnstrial Sactor tad Ptocmk !.e
Want Straw \JvJTP~ c; . i/ia e ! I,
Waste flwiiiirtM gmr y
a/ntf pom: Liquid(Aq./Non-Aq.)ySluny/Solids(Wet/Diy)
Hazard Characteristics (all): I CRT
Hazardous Coasttajeati (n^Jar):
1. Process Flow Diagram 8l 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 eveiy 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 (e.g, physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment:
3. Waste Management Altersfjy^- 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 Redaction: Yes/No/Can't Tell
Comment:
C On-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't TeU
Comment:
D. Off-site Waste Recyding/Recovoy/Rense: Yes/No/Cant TeO
Comment:
Partially Recyclable
Spent Material By-Product
Conclusion: y Recyclable Non-Recyclable _
4. Material Classification: ( sludge
(circle one)
-------
972
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: M I Lz
.01 n Xtonc/miM
Waste Stream: Cf\ --vth/Ti of r ) )/j
Waste Generation Rate: ^(c/ ~>loQ m4IU?ftyi
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids( Wet/Dry)
Hazard Characteristics (all): I C R C£)
Hazardous Constituents (major): 'S&AiAihn
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: Pflphm - noUr: 6)7r.rfaD
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, physics'
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
Comment:
C. On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment'
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion = V Recyclable
4. Material Qassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge) Spent Material By-Product
-------
973
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndustrial Sector and Process: lUnawflta I Ummnim ,
Waste Stream: SPPfll lf f Ai ] i.ij} ft'rfi OfiP)J
Waste Generation Rate: 7LU i (72) n-y) I \\$CX A
Waste Form: Uquid(Aq-/Non-Aq^/5lurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R (if)
Hazardous Constituents (major): fin P>J i I VP
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: ("~Q/)T IP) Q
B. Waste generation is ctesest 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 Redaction: Yes/No/Can't Tell
Comment
C. On-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
Spent Material By-Product
-------
974
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream: l~Us r noo, GCO ."n'f/L-r ^OS', 0 cC /m1
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Soiids£Wet/Dry)
Hazard Characteristics (all): I . C R (TJ
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: c^~ sc,/u~bic^
B. Waste generation is closest to: Raw Material/Maior Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: Aw coa^-" Cv-=./1(cJU_ t h C, ^"¦g.c 1^1
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/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable _2L Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
-------
975
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
/V\,
Ndustrial Sector and Process: W
iste Stream: fes.rl,.ha
Waste Generation Rate: 1OO /vi~r/\aC
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): ICR (£}
Hazardous Constituents (major): tiey
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: '-Fl/l vl
-------
976
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Afercwv
Waste Stream: Cjj i.'.i ji Leu f.u" (jjo-J fetuiHlir
Waste Generation Rate: -&= iD—a |(Q ^/\
Waste Form: Liquid(Aq./Non-Aq.)/Slurry(S6L^( Wet/Dry)
Hazard Characteristics (all): I C R (P)
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: sV^*- A'^ /Dei- i
-------
977
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Vaste Stream: Oxic^
Waste Generation Rate: Dcqjn>^~/\,r
Waste Form: Liquid(Aq./Non-Aq.)/SlurTy{SoIi
-------
978
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: /^lyifld^oCv'CSic, procjv V/ r • 0 IP. CO0 *d/yr
Waste Form: Liquid(Aq./Non-Aq.)/Slurrv/SQlids(Wet/Dry)
Hazard Characteristics (all): I C R (T)
Hazardous Constituents (major): bz&di
1. Process Flow Diagram & Waste Characterization: Bv 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: iPKl-hu^ /c r
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!i Tell
Comment: C^~ /vm, i.s ^ a/c oCi
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 -n .o;. r, ~i < c a n or 4
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)
-------
979
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
,_4ustrial Sector and Process:
nij/v\
,e Stream: L-LC^ U td &s>idh-es
Vvaste Generation Rate: As~j~T- f 'Tp.^ss/jpc^.^r \
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product fc-w ,^-r J
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: Caoi-.T^,
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: .g c^"
B. Water Use Reduction: Yes/No/Can't Tell
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: C^vH, w
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable _V_ Non-Recyclable Partially Recyclable
4. Material Classification: Sludge By-Product^
(circle one) ~~~~~ "
-------
980
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: P\g-V\\A vW\ C-^Vo\j-0 PApXxQs) . Q-.€_-£-w\\^G)/
Waste Stream: ^opa/a-V <^WewV~S 1 0
Waste Generatton*Ratfc 'h O O , \ 1 0 O, *\Q O O
Waste Form: Uquid(Aq7N^n-Aq.)/Slurry/SoLids(Wet/Dry)
Hazard Characteristics (all): J_ CRT
Hazardous Constituents (major): ; Aiv
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: 'P Yg C iX^gOn ffVv
-------
981
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Dd Process: <9\(xAa YXVYvn
^9-pvnV P\r .i/ivi ^ ^ O0, )1 C O ^ ^nPD wvV /'/v
Waste Form: Liquid(AqVNon-Aq .)/Sluny/Solids( Wet/Dry)
Hazard Characteristics (all): I C_ R T
Hazardous Constituents (major): Pk> , ,'CV^
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: Qe n vn-n/Os€-gI "Vo OYodvcQ. claIdy^^U ot- v'flV/euJ' rv\i
B. Waste generation is closed toi^Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
Comment: ^QsVe ll-er^s //$w s ot pr-M
£v\(?V EV\£\^'V\ \ v\ vvm-.'Vv tv--£^c.U1ji)i "^c>3
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:
D.
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 A 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: ^ \aA W\vj wy !VVeAtTvV - ^wxeA-V^vN'-^-
Waste Stream:
1b\c\_g)r * ^ "
Waste Generation Rate: T . ®
Waste Form: Liquid(Aq7Non-Aq.)/Sluny/Solids(Wet/Dry) ^
Hazard Characteristics (ail): I CRT
Hazardous Constituents (major): £ by :
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: Vo~p Wlfww ^v>ueV~V^-V f ~\~^3s
B. Waste generation is closest to: Raw Material/Major Intennediates/FinarProduct
C. Waste appears to have: recoverable products/removable^contaminants/iieiThfr
D. Comment: S-VUXu^ccVe v Cjt, %(&r,)-) v
-------
983
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
idustrial Sector and Process:
?Wob'rtuTOyy
.<•«< Smm: <=^1 11
Waste Generation Rate: 2, /F>)££D a A^TTi^ Q A /QC '/9T)
Waste Form: Liquid(Aq-/Non-Aq.))^lurry/Solids( Wet/Dry)
Hazard Characteristics (all): (^T) CRT
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: C!\C\f\(\^ fvfill
B. Waste generation is closest to:J 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/Recovery/Reuse: Yes/No/Can't Tell r ,
Comment lUil fcptftirg •
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
_ Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable V Non-Recyclable _
4. Material Classification: Sludge
(circle one)
-------
984
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream- \MlPcfo rrrfayftf
Waste Generation Rate
a/irt;gf)r^hi/^/^o,axi
Liquid(Aq^on-Aq.)/Slurry/S
Waste Form: Liquid(AqjNon-Aq.)/Slurry/SoIids(Wet/Dry)
Hazard Characteristics (all): ICR (T)
Hazardous Constituents (major): mrimi\UA npA
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for eacb major source of the same waste generated in the process. Complete a separate form for
each major source.
A- Source: f/V)f i aaS'hi) 11
B. Waste generation is closest jp: 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/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Oassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge ^SpentMateriaT^ By-Product
-------
985
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
idustrial Sector and Process: ''Eons PlU-Hn/r
^p>nt nmnn/Truir*>. nrtaaig r^lMh^
ate: )4i(TO m-Ul^A {
Liquid(Aq./Non-Aq.)/Sluny/Solids( Wet/Dry)
Waste Stream:
Waste Generation Rate:'
Waste Form: Liquid(Aq./NoiP-Aq.)/Sluny/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: _ ¦Htvft (4 iVta
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:
(circle one)
Sludge
Spent Material By-Product
-------
986
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: V fb\J A~j~k/T
Waste Stream: ^ Hf I OnA 4-1 Ijpj\ CC\ 1
-------
987
^mtostrtal
Warn Si
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
-* Eoai oax-H>w
Jlir&iiAu rot I CTIII /-.4i! Uk>4 AH" Un/W
Waits Gqwrtoo RMk ~~2-cD/ ,c*fD& m-Wugft-A
Waste Form: Uquid(Aq./Non^.)/Sluny/SoUds(WePDry)
Hazard Characteristics (all): I (^Cj) 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 tne 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 (e.g^ physical contact during production, mixing with other waste
streams, results from impurity removal)?
Comment: .
3. Waste Management AltenMltFff' 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 Redaction: Yea/No/Cant Ten
Coimwr
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment:
D. Off-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
I Sludge j Spent Material By-Product
-------
988
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 1q\m (?fulW
Waste Stream: nOTP/r> 1 Oft to A'
nrmUM.4
Waste Generation Rate:
Waste Form: Liquid(Aq7Non^
Hazard Characteristics (all): I (c"
Hazardous Constituents (major): I Q d
!.)/Slurry/Solids( Wet/Dry)
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: _ Yvl(u?lnvjccfoi /rirhinft v^oAp/r
B. Waste generation is closest to: Raw Material/faajor 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
4. Material Qassification:
(circle one)
>le\/.
Non-Recyclable \/. Partially Recyclable
" N
Sludge ( Spent Material j By-Product
-------
989
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
'ndustrial Sector and Process: iflfn Pfw.flvir
^ \/\l 1 v i i / \ l r " ~
aste Stream: ^>p?nt Sen u 1 f iftr
Waste Generation Rate:
Spnt ScnixkTHA Ifnufrr
Liquid(Aq./Non-Aq.)/Sluny/Solid
Waste Form: Liquid(AqVNon-Aq.)/Sluriy/Solids(Wet/Dry)
Hazard Characteristics (all): " \ . <^~C) R, T ..
Hazardous Constituents (major) ifjaxi / ln£>gg
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( A AaIqV^
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.
Waste Segregation: Yes/No/Can't Tell
Comment:
Water Use Reduction: Yes/No/Can't Tell
Comment:
On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: ~
Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
A.
B.
C.
D.
V
Non-Recyclable _V_ Partially Recyclable
Sludge ^^Spent Materially By-Product
-------
990
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
pfixlh/y
Waste Stream: SDhPM PXhfl/fain mud ~
Waste Generation Rate: 2£\J ; -^c,q) flT) ml|) li (\A / 9£E lU)
Waste Form: Liquid(Aq'./Non-Aq.)/Sl^ny/Soiicls(Wet/Dry)
Hazard Characteristics (all): (^T) . C R. T j \
Hazardous Constituents (major): 2 45CBD j HXX) YWT IUJlV>
l. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source pf the same waste generated in the process. Complete a separate form for
each major source.
SoWei4 fHWlim
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, physic?1
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 Recycling/Recovery/Reuse: Yes/No/Can't Tell , , ,
Comment:
.V
Conclusion: Recyclable Non-Recyclable y_ Partially Recyclable
4. Material Qassification: Sludge ( Spent Material :) By-Product
(circle one)
-------
991
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
•iustriai Sector and Process:
HeSmu \MflMi nnlvP/y
Waste Generadon Rate: K^> / 1 fffi) £&) \A~" \ki (k^1 j H/35^ <3X
-A#)/Slur '
Waste Form: Liquid(Aq.yNon-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): /TS C j ^ 11
Hazardous Constituents (major): j \ ClD / fhTlbLflQyi
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:
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 Redaction: Yes/No/Can't Tell
Comment:
C. On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell , / ,
Comment: OP)OliMUlO^
Off-site Waste Recycling/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
vA/ifim Iny.
Conclusion: V Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge / Spent Material j By-Product
(circle one)
-------
992
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream: \^ClO±$ HOTtu MriTTif fl 1 JLOfi f VM
Waste Generation Rate: . ) fT) f - 'T<~^fxS~
Waste Form: Liquid(Aq./Non-A
-------
993
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
idustrial Sector and Process: _
Wute Stream:
'MOrtntt ?in( rffpmnninMwi
Waste rtM*~»tkmUate:',^/ nTthyfl^ / cyfH _—
Waste Form: Liquid(Aq7Non-AqJ/SlurTy/Solids( Wei/Dry)
Hazard Characteristics (all): I C R ^T^
Hazardous'Constituents fmalor): A^LACIa/l^-
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.
i
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 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 Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: MTifl flTflrfa flfA/P/uj
Conclusion: Recyclable Non-Recyclable \/ Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
-------
994
Work Sheet for Waste Stream Assessment por Recycling, Recovery, and Reuse Potent1".
Industrial Sector and Piur— $h\Pv\\ uY^t & Q U&'h Sc-Yu j? h )
Wast* Strew: <>f)e/v\¥mt RiKYSr^ss <, <£ v u \a~be v Lu\?vov
Waste Generation Rata:
Waste Form: Liquid
-------
995
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
'ustrial Sector and Process: RVnpvwm vw c^~ V^\qpy\w^ y Vicle wrVe £<5v\c
jte Stream: S ipev\\ RV\^vw\jv^ "R rx-P-£\ VNrtv'V-g
Waste Generation Rate: SS.OPo w\^|vv
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
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>q\\ (3 - V)€ \ gN/\ €. xC
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: \ gv\ - f >-p»VNAr>w'e S of- V/"\ *> 'i } l/~\
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:
Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable /( Non-Recyclable _
4. Material Classification: Sludge
(circle one)
-------
996
Wo** Shut ro» Wa*t* St*eam Assessment ro« Recycling, RECovarr, .jxd R£USe Pottn-
y*'-1!'"*; Cvc^,+-
WkMSaw SOev\+- V/tvn ^Ju-ryy L
Wim rimnHnn llttr ^^OOQ *v\+J <
-------
997
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
WUuitilal Sactor and Procaaa: , /^eV^gi/fg C\SC)iL- fifpceSS
Warn Straw *"
w—** r^>nth» «HK ^
Waste Form: Uquid(AqJNon-Aq.)/Sluny/Solids(WetyDry)
Hazard Characteristics (all): I C R T
Hazardous Cooatttucots (mater):
l. Process Flow Diagram 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.
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.£, 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/Cant TeU
Comment:
B. Water Use Reduction: Yo/No/Cant TeU
Comment:
C On-site Waste Recyding/Recovery/Reme: Yes/No/Cant TeU
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't TeO
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4- Material Classification: ( Sludge J Spent Material By-Product
(circle one)
-------
998
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sactor aai Itmw * ^pe y\i~ A(L/ J 5v\
Waste Stream: SqoxkV* hted. Wt^-bJVx
Waste C*Mnri«i Rfctt:
Waste Form: Liquid(AqJNon-Aq.ySluny/Solids(Wet/Dty)
Hazard Characteristics (all): I C R T
Hazardous Constituents (nutfor):
1. Process Flow Diagram
-------
999
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: ~Ma py-V \] e \ V
-------
1000
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: \L?vy> \ \JWn ~Cv(Sw ~~TV\o>r^rVe \V\^
Waste Stream: \/e^f 7/V
Waste Generation Rate:" 1 OO i 3^7 QO , ~7q£>D
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): J_ 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: SoWev^V ^ x c. ~V~i 5^
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither *
D. Comment: SoNvewVi k>g.
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: X Recyclable
4. Material Qassification:
(circle one)
Non-Recyclable Partially Recyclable
Sludge
3y-Product
-------
1001
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndustrial Sector and Process:
Waste Stream: QpfryA ^
Waste Generation Rate: ^ no /^XT;
Waste Form: Uquid(Aq.7Non-Aq0/^'urTy/Solids( Wet/Dry)
Hazard Characteristics (all): I C R (^)
Hazardous Constituents (major): ^ iP-Tlll) KJ\
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: _ -Pi \kf\~M
B. Waste generation is closest to: R^w 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 Redaction: Yes/No/Can't Tell
Comment:
C. On-site Waste Recyding/Recovety/Reuse: Yes/No/Can't Tell v . .
Comment: rrHw prQGfl A NAtTX!n
D. Off-site Waste Recyding/Recovety/Reuse: Yes/No/Can't Tell
Comment: ,o4i0a pflfViM
ConclusionNy Recyclable Non-Recyclable Partially Recyclable
4. Material Qassification: Sludge Spent Material
(circle one)
-------
1002
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream: "pldftl pC/0/Ti
feneration Rate (ft( o ¦ /TO m4 \ Uf>CjlA
Waste Form:
Hazard Characteristics (all): I (C) R (T
Hazardous Constituents (major. ; PTfi
(oio.^F) mWwrAA
Liquid(AqJNon-Aq.)/Sluny/Solids(Wet/Dry)
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: ^\An/hll1)
B. Waste generation is closest to: Raw Material/Mijor Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neitheT
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.£, 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/Caa'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-Recvclable\ / Partially Recyclable
4. Material Classification: Sludge it Material j By-Product
(circle one)
-------
1003
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ndnstrial Sector and Process: .-3d mUUA
Waste Stream:
Waste Generation Rate: So
^ m4 luo a ,4 / 4 ClO
Waste Form: Liquid(Aq7Non-A(^)/Sluny/SoUds(WetyDry)
Hazard Characteristics (all): _ J C R (p
Hazardous Constituents (ma tori: jtXSX) \Vi lU
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.
2.
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 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:
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 Rccydjng/Recovcry/Rcuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable V_ Partially Recyclable
Sludge
Spent Material
-------
1004
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial S«ctor and Process: rH\;w\A
Waste Stream:
/
UYUVAA Olirr\Q
*5Qdry\4lupf)^
, /SQC3D
Waste Generation Rate
Waste Form: Liquid(AqJNon-Axj^/Sluny/Solids( Wet/Dry)
Hazard Characteristics (all): I C . R <^Tj
Hazardous Constituents (major): Slg\o p\V)fV\
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: VUUXt ;\P\(/A f f\flCY\ .
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, 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)?
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.
A. Waste Segregation: Yes/No/Can't Tell
Comment:
B. Water Use Redaction: Yes/No/Cant Tell
Comment:
C. On-site Waste Recyding/Recovery/Rcuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recvding/Recoverv/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
V
Non-Recyclable Y— Partially Recyclable
Sludge Spent Material
-------
1005
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector and Proceas: _
Waste Stream: fl/vtS CD\\y..
n«aw ju. r r ''r '
Waste Generation .Rate: Scy <^00 yvi\ ll\UlA
Waste Form: Uquid(AqJt
-------
1006
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Ic-rfkLfyy 'wn < ^"rcco1'^.*! (jim-M
Waste Stream: ppgrc.s^ UJb s-fe f, a. t^r ;
Waste Generation Rate: 1 ^^;OCX^ Q, /5 & COO^//y
Waste Form: ^Ligjui^ i-10%, £¦)
Hazard Characteristics (all): I (^7- R (j-'l?
Hazardous Constituents (major): As7 . £<-$7 C " ? - ^
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: ("hpk-
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: -fc> lajuSTP
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, physir
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: Trt-JjuJ-i (joUJT^
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Qassification:
(
-------
1007
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
jstrial Sector and Process: "~7Z.A*L>\ t* •.¦nce^.i !s--o
.. aste Stream: P), a zr 1^^ a,
Waste Generation Rate: /cXX^^r/p --
Waste Form: Uquid(Aq7Non-AqQ/Sluriy/SQU
-------
1008
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: *¦ fra-froob><-y
Waste Stream: l1
-------
1009
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
udostrial Swtar aad Ptochk 7k ) . PjV a ~h Aa crf~ 7e ) I a v c\JS>
Wast* Strew: Ua.tfe~Zjn-hpv' __
Waste Geoentfcm Ratr
Waste Form: Liquid(Aq«/Non-Aq.)/Sluny/Solids( Wet/Dry)
Hazard Characteristics (all): I CRT
Hazardous Coostttocots (—lor):
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.&, physical contact aunng 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 TeU
Comment: .
B. Water Use Redaction: Yes/No/Cant Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment- _____
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment:
Conclusion: ^ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification:
(circle one)
Sludge /Spent Material
By-Product
-------
1010
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: "Tp A\u V^ \ ^ v ca.Vi Sw q-C- Tp V\ w Sq\) J, Acu
Waste Stream: vO Ck ^L\g_c_-Vvo^-Y-e
Waste Generation Rate: \CO. \ ooo ^ )QOC>o W~
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids( Wet/Dry)
Hazard Characteristics (all): I CRT
Hazardous Constituents (major): Pb j —
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: £>€.c-Vvq^ S I 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:
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, 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 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: "
Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable \/ Non-Recyclable _
4. Material Classification-. Sludge
{circle one)
-------
1011
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
kd us trial Sector and Process: Tp.WvJ V\V Grv? jflgv -S ) J e. S
Waste Stream: SrAtH 'R-e^rtJeJ
Waste Generation Rate: / oo / C <9 Z7 , ^ \v D yr^rj Vv-
Waste Form: /Liquid(Aq7NoD-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I C R_ T
Hazardous Constituents (major): S €1
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 e C i <0 vW~h gv\
B. Waste generation is* closest to: Raw Material/Major Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: (Jg sf£- t\fe. io h J •™pvr,4ie.s c\>re
d'S c £A.-ctj e_y ~s w^yFeL
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 Redaction: Yes/No/Can't Tell
Comment:
C On-site Waste Recycling/Recoveiy/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)
-------
1012
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Te\lovM;v\/> ¦ yv^ej
Waste Stream: S\
-------
1013
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
'ustrial Sector and Process: ///m Pit**, cte
>te Stream: t*Jgt,-he /Wv/'c-
Waste Generation Rate: 13oe>Q — <7*>cX> MT/y/Z,
Waste Form: (^lqu^^^^^^/Sluny/Solij^Wet/Dry)
Hazard Characteristics (all): I C*~J R 00
Hazardous Constituents (major): C.A . C«-; Tb, A>c»,
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: c-f a^*3' T~,'Cjy g^S <>rUs
B. Was re generation is closest rn- Raw Materiaffitajor ihtermediates/tjnal Product
C. Waste appears to have: (fecoverable products/reffiovable contaminant^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?: (YM/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)?
Dmment:
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/Cto't Tell)
Comment:
B. Water Use Reduction: Yes/No/C^n't Tell)
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/i
Comment:
D. Off-site Waste Recycling/^ecover>fReuse:YY«/No/Can't Tell
Comment:
Conclusion: _^/Recyclable
Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
-------
1014
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 1 <->>**¦ /e
Waste Stream: fickle L, VVJa-^U
Waste Generation Rate: 1'too — "b^-cp v^t
Waste Form: (1Iiqui^l^/Non-Aq.)/Sluny/SolidsQVet/Dry)
Hazard Characteristics (all): I C R (T) .
Hazardous Constituents (major): y b fe> cctyv^ 5 ,
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: £g/^.rJb.2 OJ* A~c (/~ul "4? r-r> k-:i
B. Waste generation is closest to^Raw Material^Ma'ior Intermediates/Final Product
C. Waste appears to have: recoverable pTOdUCts^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?: (Y^/No/Can't Tell
Comment:
B. What was the basic purpr*" frr jhic^cto (e.g., plant maintenance, chemical reaction, physical
separation,(^ater rinsing|rother purification stepS}?
Comment: — ^
C. Why did thish;parrimic (e.g., physical contact during production, mixing with other waste
streams ^resultsfrom 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 Wastefeecyclmg/Recovery/^euse:^?es/No/Can't Tell
Comment: ^
D.
Off-site Waste Recycling/Recovery/ReusdT(Yes/No/Can't Tell 9 , , 11 ,
Comment: [
-------
1015
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
' ' atrial Sector and Process:
///aa ' k ->* M, ows Dt o*f
Stream:
r. ,p> \Kx k ^ U\>>c. G feev
- o-cv-C' ^ sr/vr
Waste Generation Rate: tooc -tsonO -) ^T/yr-
Waste Form: (Liquid(Aq^on-Aq.)/Sluny/Soli^(Wet/Dry)
Hazard Characteristics (all): T C R (jF) ~ _
Hazardous Constituents (major): Cd , £rt * c> , ,
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. rCfubW v ^
A. Source: . ^f ^ fb /iusf~ ^ ft. f 3
B. Waste generation is closest to: <3%aw MatenatyMajor Intermediates/Final Product ~
C. Waste appears to have: recoverable products^emOvable contaminant^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 eveiy facility using the process?/Ye^/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: 5«-
C. Why rlid Tjiji wmtr hrrnmr lurnnloin (e.g., physical contaa during production, mixing with other waste
streams,Results from impurity rentaval)?
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/^jo)can't Tell
Comment:
B. Water Use Reduction: Yes/No/Can't Tell
Comment: ^
C. On-site Waste R&ycliag/RecoverwReusa: /Yes/No/Can't Tell
Comment: \ J v—'
D. Off-site Waste Recycling/Recoveiy/Reuse: Yes/No/dan't Tely
Comment: ^
Conciiision: Recyclable Non-Recydable _j/^artially Recyclable
4. Material Classification: Sludge ( ^riai By-Product
(circle one)
-------
1016
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: Di~*,
Waste Stream: 52.^*0 l/vaJ&r
Waste Generation Rate: ^ Dtv fAr/te /&_ ~
Waste Form: fLiquid(AqyNon-Aq.)/Slurry/Soiids(Wet/Dry) '
Hazard Characteristics (all): I (c) R (Tj . .
Hazardous Constituents (major): _T - CA , Cr, V |> , ^
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/rsIm^is fry
B. Waste generation is closest (oC^Raw Matenaflfrlijor Intermediates/Etna! Product J
C. Waste appears to have: recoverable productsjremovabie contaminanTsyneither
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)fNo/Can't Tell
Comment:
B. What was the basic purpose foj^easmiag^his waste (e.g., plant maintenance, chemical reaction, physical
separation, ^ater rinsing^ther purification stefe^?
Comment: '
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streamsrtfeSuItsfrom 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.
Waste Segregation: Yes/No/C^n't Tell;
Comment:
B. Water Use Reduction: Yes/No//Can't Tell ;
Comment:
C.
On-site Waste^^cling/Recovery/^use^/Y^No/Can't Tell
Comment: —
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/pan't TeLL
Comment:
Conclusion: Recyclable Non-Recyclable impartially Recyclable
4.
Material Classification:
(circle one)
Sludge sj Spent Materia}. By-Product
-------
1017
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector and Process: 7/>x/i •"«-*> *, <^e
Pste Stream:
Waste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/ .
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: t/Recyclable
4. Material Classification:
(circle one)
Non-Recyclable Partially Recyclable
-------
1018
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: J/t*.A •« &>*>•*,
Waste Stream: lrt&h
Waste Generation Rate: 3&c,oco 5"8^< dpg ' v^t/^{Z
Waste Form: Qljquid(^./Non-Aq.)/SluiTy/So[id^Wet/Dry)
Hazard Characteristics (all): I (^cT) R ^ p
Hazardous Constituents (major): ^ '*", ' b
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: #-t'd ^ 1TJ 77' SPo^aQ g/irj **7 Uz-dds
Waste generation is closest to/ Rav6 Materia'l/M^jor IntermediatesflFukll Pfoduc)
A.
B .
C. Waste appears to have: -o-o (&<.£%* ¦'>a
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
stream^Jjesults 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/dan't Tell/
Comment: ^
B. Water Use Reduction: m^/No/Can't Tell
Comment:
C. On-site Waste Recycling/tflroveiy^Reuserj^ra/No/Can't Tell
Comment: V— sj -*c
D. Off-site Waste Recycling/Recoveiy/Reuse: Yes/No/Can't Tell -^c A/
-------
1019
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
1 "-'strial Sector and Process:
; Stream: irwpiv.-d-vY~&-—( /
V>aste Generation Rate: %c —
-------
1020
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 7/^t/i77-fa.*., a** D>»¦<,'<^e
Waste Stream: Jc/rcU
Waste Generation Rate: *Ti.oJo i^T/v^1
Waste Form: Liquid(Aq./Non-Aq.)/Sluny$oljesults from impurity removal)?
amment:
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: OYa/No/Can't Tell
Comment: ^
B.
Water Use Reduction: Yes/No/Ca^t Te}^
Comment: V—
C.
On-site Waste Recycling/Recovery/Reuse: Yes#S
fa!anVTe5
Comment:
V—
D.
Off-site Waste Recycling/Recovery/Reuse: Ye»Mg
JeJanVTfeU)
Comment:
Conclusion: Recyclable i^^on-Recyclable Panially Recyclable
4. Material Qassification: f SludgeSpent Material By-Product
(circle one)
-------
1021
Work Sheet for Waste Stream Assessment for Recycling, recovery, and Reuse Potential
' 4«istrial Sector and Process: 7/^t* ¦ iu^ ^lo*,'^e
e Stream: IsJztk? s.c<&s. (^Chfo^'dg Pr&
waste Generation Rate: . C°Q v^T/Yr
Waste Form: ^Liquid(Aq./fton-Aq^/Sluriy/Solids£Wet/Dry)
Hazard Characteristics (all): ^ \< (c/ R (Ty
Hazardous Constituents (major): _ cr, ?b,s
-------
1022
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: D\«>•<,
Waste Stream: U/ctfk AoJs (Sidcfett A .
Waste Generation Rate: 9 cp 7>.000
Waste Form: ^C?quid(i^>/Non-Ag.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I R (T~} . ^
Hazardous Constituents (major): ^ 5, (Sr Sc
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 MateriaK^laj6r IntenngliatdyFinal Product
C. Waste appears to have: recoverable products^movable conuminantS/peither
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/^o/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing, otfi^purificationlKps)? - «. y\ „ 1
Comment: V~' It*" 0/
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams^fSuTts 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^to/Can't Tell
Comment:
B. Water Use Reduction: Yes/NcyCan'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 fSpent Material) By-Product
(circle one)
-------
1023
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 7//c/t«mcwv <^e
pie Stream: W IVTP ¦
Waste Generation Rate: boy, poo >^-T /yv<.
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/^n^^e)/Dry)
Hazard Characteristics (all): I C R (ij
Hazardous Constituents (major): C— IT
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: CAhJ&9 57 ^ cL(cr. <1^ pYlc^^
B. Waste generation is closest to: Raw Material/Maior Intemediatesffinal ProSucgP I
C. Waste appears to have: recoverable products^feSovable 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?:/YeVNo/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant maintenance, chefnical reaction, physical
separation, water rinsing, other purification steps)?
Comment: ¦
C. Why did thiswasieJiecoiogJiazardous (e.g., physical contact during production, mixing with other waste
streams,
-------
1024
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: //^i/i'««v T7¥g.n,u^
Waste Stream:
Waste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
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~bt 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)
-------
1025
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
J-«strial Sector and Process: TitkA • * *->* Dm•<> g/e
; Stream:
Vvaste Generation Rate:
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
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 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/Recoveiy/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 Qassification: Sludge Spent Material By-Product
(circle one)
-------
1026
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.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): I CRT
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 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)
-------
1027
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
industrial Sector and Process: lUPA^i^
Waste Stream: ri mA Y 1T\ tf.V'fttPr
Waste Generation Rate: ' 7 \
Waste Form: Ljquid(Aq.yNon-Aq.)/SrurTy/So lids( Wet/Dry)
Hazard Characteristics (all): 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: 7 Q A 1 \ HhfiTTb
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.&, 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 Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable V_ Partially Recyclable
Sludge ( Spent Material ) By-Product
-------
1028
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: _
Waste Strew
Waste t^ncrarinaRate: I jy, I (A A ; > c%X
Waste Form: Uquid(AqJNon-Aq.)/Slu6^/Solids(Wet/Dry)
Hazard Characteristics (all): I f^- \ 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:
yl\)in»Wi (Aohrtc
is closest to: Raw Material/Major Intermediates/
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 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)?
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/Rccoveiy/Reusc: Yes/No/Can't Tell
Comment: ^
D. Off-site Waste Recycling/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: V_ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge sent Material) By-Product
(circle one)
-------
1029
Wore Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Sector aad PracHK O %fo^y\ \ \J w~\ i Pfo0uc/T?fv\ Q-f- U & ?_
Warn SMK LJdsl-pmr Mrhi'ic. VV'7V>> (7^-7- PKo 'rfl/'C?7 £V\
Wasta Generation Rmk - / loo, ~L-\To & > t-r o ZJ w-fV /
Wute Form: Uquid(AqJNon-Aq.)/SluTTy/Solids(Wct/Dty)
Haaard Gwracttristki (all): .. I ,C_ R T
Hazardous CoastttMsts (—tor):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for each major source of tbe same waste generated in the process. Complete a separate form for
each major source.
A. Source: DV $> 0/wh
B. Waste generation is closest to: Raw Material/Major Intennediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: LJasJ-e A-r^cJ /OP A VP-u
1 Reasons for Waste Generation: Based on tbe description of tbe process, and waste generation and its
management practices given lor a sector, make the following assessment.
A. Is tbe same waste generated at every facility using tbe process?: Yes/No/Cant Tell
Comment:
B. What was tbe 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 firom impurity removal)?
Comment:
3. Waste Management p«»vi—/ th» pn»—ti»i h» wxinrmy m »»««» 3,
any of its sources by considering the following waste management alternatives.
A. Waste Segregation: Yes/No/Cant Tefl
Connnmr -
B. Water Uaa RBtecdOK Yes/No/Cant Tell
Comment: .
C On-site Waste Recycling/Recovery/Reuse: Yes/No/Cant TeU
Comment: __ ____
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Cant TeO
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recydabie ^ Partially Recyclable
Sludge
By-Product
-------
1030
Work Sheet fob Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
TiiiImiiIbI Tirtirr -7* wi O w? ,
West* Strmm V/Jo, v> u) ^ \ 0S '-A-strv^ )r\-h Pro ^uc -h /5\^\
Warn 11 ifrtnw RaSK /~7£?C?. K~oO, ^^770 ;v^/W~
Warn Form: Ljquid( Aq7Non-Aq.)/Slu^/Solijfa( Wei/Dry)
Hazard Charnetartdea (aB): _L CRT
Hazardous CoostteMOia (m^or):
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&Y b y' Chpi*9T
B. Waste generation is closest to: Raw Material/Major Intermediates/Final Product
C Waste appears to have: recoverable products/removable contaminants/neither
D. Comment: j&L 1 r> ? w\ay ^ e cm c /7>s^ ^
w'
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?: Yea/No/Cant Tell
Comment:
B. What was the basic purpose for generating this waste (e.g^ ptant maintenance, chemical reaction, pbysica.
separation, water rinsing, other purification steps)?
Comment: pro/Jvc^*
C Why did this waste become hazardous (e.g, physical contact daring production, mixing with other waste
streams, results from imparity removal)? —
Comment:
3. Waste Management Alternative}- 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: YesAWCaat Tell
Comment:
B. Water Use Redaction: Yes/No/Cant Tell
Comment
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tefl
Comment: '
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tefl
Comment: :
Conclusion: V_ Recyclable
/ '
4. Material Classification:
(circle anel
Non-Recydable Partially Recyclable
Sludge Spent Material
-------
1031
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
mdastrial Sector and Proeasa: 1)\T(\y\\uY^ , Ovo/Jor 7^7 Avn n-f' U F~ <-t
Wasta Strew \/a /? 0s 7n.p v
Waste flwrartnn gafc u
Waste Forw Liquid(AqJNoa-Aq.)/SlunyySolids
-------
1032
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Poten^
Industrial Sector and Proem: I )^ (\ I U . Pf o /7\^ D'f V-
Warn Straw /y&v>sa. f-p
Waste Generation Ratr ;
Waste Fona: Liquid(AqVNoo-Aq.)^luny/Soiids(Wet/D(y)
Hazard Characteristics (all): I CRT
Hazardous Constituents (a^or):
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.gn 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/Cant Tell
Comment:
B. Water Use Redaction: Yes/No/Cant Tell
Comment
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment:
D. Off-site Waste Recyding/Recovciy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
/ ;
4. Material Classification: Sludge Spent Material ^ By-Product
(circle OH* l
-------
1033
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
-Wtrlal Sector aad PracHK [ h~(Kv\) t J Wi: Avy^-eS
WarnStrcuL* ^ /CK*y
Waste Generation Rate ¦
Waste Form: Liquid(AqJNon-Aq.)/SlurTy/Solids(Wet/Dty)
Haard Characteristics (all): I CRT
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.&, 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 Altem^ti1^' 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 Tefl
Comment:
B. Water Use Redaction: Yes/No/Canl Tell
Comment:
C On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Cant Tell
Comment:
rion: Y
Conclusion: Y Recyclable Non-Recyclable Partially Recyclable
4. Material Classification:
(circle one)
Sludge
Spent Material
By-Product
-------
1034
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: "tL.'-oc-
Waste Stream: Ac., J Pio~^ &£*—-
Waste Generation Rate: 2Z6, c:: r^T/y&
Waste Form: Q[.iquid(AqI/Non-Aq.)/Slurry/Solid&fWet/Dry)
Hazard Characteristics (all): I (C) R (ij A r \ r 01 u r J
Hat^s Cowttmeots (oujor): V'Cc' Cr' 'M?.5*' ^
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.
i
:: eJbc.4rervbfic /V"^iA nj4 o,
generation is closest to:vRaw MateriagMajor Intermediates/Final Product ~
A. Source: dUchtn/Mic h'ZutJ• a/ dicXtd? ah/- -f^rrr- ^cLfhrc, o ^ $ .
B. Waste
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 this waste (e.g., plant maintenance, chemical reaction! physical
separation/ water rinsing, other purification steps)? '
Comment!
C. Why did this waste ^ayarriniK fp a physical contact during production, mixing with other waste
streams,j results from impurity removal)\
Comments —
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/^nVTeU
Comment'
B. Water Use Reduction: Yes/No/Can't T^ll
Comment: V—^
On-site Waste Recycling/Recoveiy/Reuse: No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No(Can't Tel]
Comment:
Conclusion: _v_ Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge (Spent Material^\ By-Product
(circle one)
-------
1035
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
'ustrial Sector and Process:
,ste Stream: l/hfe .
Waste Generation Rate: s mr/rrz
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/3&lid£4Wet?
Hazard Characteristics (all): I C R (JTJ n i
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 saine waste generated in the process. Complete a separate form for
each major source.
A. Source: chucks ¦
B. Waste generation is closest to: Raw Material/Major Int&rmediatestf-inal yroaucr—„
C. Waste appears to have^fecoverable products/removable contaminants/neither
D. Comment:
7
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?:/rffl/No/Can't Tell
Comment: —
B. What was the basic purpose forgeneratinp this waste (e.g., plant maintenance, chemical reaction, physical
separation, water rinsing^ttlSfpurification steps)?>
Comment:
C. Whv did this waste become haTartnns fe ft 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/Recoveiy/Reuse: (Yes/No/Can't Tell
Comment:
Conclusion: '-'^Recyclable Non-Recyclable Partially Recyclable
toVj I Vor\
4. Material Classification: Sludge Spent Material By-Product)
(circle one)
-------
1036
Work Sheet for Waste Stream Assessment for Recycling, recovery, and Reuse Potential
Industrial Sector and Process:
Waste Stream:
Waste Generation Rate: /s>«-o r^T/ytC.
Waste Form: Liquid(Aq./Non-Aq.)/SlunffSoEd|#ffeT£>ry)
Hazard Characteristics (all): I C R (X? ^ ~ p , . ^
Hazardous Constituents (major): ^T5, Cey Cr, ' P, Hq
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: ^ tT/7 /^r^~ A^k^cn 6^-5.
B. Waste generation is closest to: Raw Material^lajor Intermedia teSTFinal Product ~
C. Waste appears to have: recoverable products/removable contaminants/neither u Jc
D. Comment: 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?: (Y<^/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)? V, /
Comment:
C. Why did this waste become hazardous (e.g., physical contact during production, mixing with other waste
streams^jeSuIts from impurity~rSmeva])?
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/C^tn't Tell
Comment:
B. Water Use Reduction: Yes/No/Qm't Telt-
Comment:
C. On-site Waste Recycling/Recovery/Reuse: Yes/No/CanVTpH
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Cap't T$
Comment:
Conclusion: Recyclable f Non-Recyclable Partially Recyclable
4. Material Classification: Sludge Spent Material
(circle one)
-------
1037
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
Austria! Sector and Process:
VTSste Stream: fix**-* s ¦?
Waste Geoeratioo Rate: 7""/
Waste Form: (pquid(A97Non-A^)/SlurTy/SoUds(Wet/Dfy)
Hazard Characteristics (all): I R (fD A ffl s* /}/
-------
1038
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
( Q.xi /W
/)¦ :sc^J2?-ren£o^ry b*ck~~ ^ '
/ca^ r^r/y/Z.
Industrial Sector and Process:
Waste Stream:
Waste Generation Rate: /c&f ^ ^
Waste Form: Liquid(Aq./Non-Aq.)/Slurry/SoU^W^7/K"~
Hazard Characteristics (all): I C R C~T j a r \ C 9 /
Hazardous Constituents (major): ^ ^CV ^ ^ T cp
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
each major source.
A. Source: IeSu^eSl S-
B. Waste generation is closest tcr^Ri^04ate#ral/Maior^temediates/PtnalViaduct
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
Is the same waste generated at every facility using the process?: [Yes/^o/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.gyphysical 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.
Waste Segregation: Yes/Nd/Can't Tell
Comment: ^
B. Water Use Reduction: Ye&^p'/Can't Tell
Comment:
C. On-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can Tell t
Comment: v
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/pan't Tell ^
Comment:
Conclusion: Recyclable t/Non-Recvdable Partially Recyclable
4. Material Qassification: Sludge /Spent Material) By-Produa
(circle one) K
-------
1039
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
ustrial Sector and Process:
TTvste Stream: r Co-fi s ^
Waste Generation Rate: '
Waste Form: Liquid(Aq!/Non-Aq3/siurry^
Hazard Characteristics (all): I C R (T) ,
Hazardous Constituents (major): rVf ; je ,
! 7 ~ ^
u
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 toCRaw Material/Major .Intermediates/Final Product
C. Waste appears to have: recoverable proaucts/rewuvable ujnuminams/fteither
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?: /^/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.gf plant maintenance,xhemical reaction, physical
separation, water rinsing, other purification steps)?
Comment:
C. Why did this waste become hazardous (e.gj(jjhysical 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^^/Can't Tell
Comment
B. Water Use Reduction: Yes^j/Can't Tell
Comment:
C. On-site Waste Recycling/Recovery/Reuse:/Yes/No/Can't
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: fYesfSo/^f't
Comment: \_y
1: /.
Conclusion: _J*_ Recyclable Non-Recyclable _£} Partially Recyclable
4. Material Classification: Sludge t Material ; By-Product.
(circle one)
-------
1040
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: n
Waste Stream: • , ^3 kv~s*>CF hf,. * cf 5>
Waste Generation Rate: ^.sZ>o,c>o^ -^T/ -
Waste Form: Liquid(Aq^Non-Aq.)/S]uny/Soli^s(Wet/Dry)
Hazard Characteristics (all): I <-^cTy R (_J/ ^ ;
Hazardous Constituents (major): C
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/g/J^S ciL*y°^7jAJz pyicy it>
B. Waste generation is closest to:fRiw Material/Ma)or mtennediatesyFinal Produc?
C. Waste appears to have: recoverable product^removaftle cpntaminantsMeither
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
i
A. Is the same waste generated at every facility using the process?: /Y«yNo/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.
Waste Segregation: Yes/No^CaflTTeD^
Comment: ^ ^
B. Water Use Reduction/Ytt/No/Can'tTell
Comment: —
C. On-site Waste Recycling/Recovery/Reuser^i^/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reme: Yes/No/daa!t-Tell
Comment:
Conclusion: Recyclable Non-Recyclable impartially Recyclable
4. Material Classification: Sludge ; By-Product
(circle one)
-------
1041
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
fclustrial Sector and Process:
Waste Stream:
"iLific, ,
S/i+uT <5" 6'^^/^-L- ¦
B. Waste generation is closest to^rSSw-Nfaieii«ri)Kiajor intermediates/Final Pro
-------
1042
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.)/SlurTySolic
Hazard Characteristics (all): ICR
Hazardous Constituents (major)
~h£l_£-£r
fUT/%
a
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:
-------
1043
WORK SHEET FOR WASTE STREAM ASSESSMENT FOR RECYCLING, RECOVERY, AND REUSE POTENTIAL
us trial Sector and Process:
-------
1044
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: 1—mc-
Waste Stream: AA.;T7° v:ci ^
Waste Generation Rate: — *3/52>Q,Qrcj .
Waste Form: Liquid(^/Non-Aq.)/SlurTy/SoLids(Wet/DTy)
Hazard Characteristics (all): I C R
Hazardous Constituents (major): (—<3-
~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: e-<^4^ £*>-Srk kstjTf* o^s¥e —2J
B. Waste generation is closesMaterial/Major Intermediates/Final Product^
C. Waste appears to have: recoverable products/removable contaminaniS/neitheiN
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?:/Ya/No/Can't Tell
Comment:
B. What was the basic purpose for generating this waste (e.g., plant mainter^atice. 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
streanjs^g&ults from impurity removal)?
SmHient:
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.
Waste Segregation: Yes/No/Can't
Comment:
B. Water Use Reduction:/^^tt/No/Can't Tell
Comment:
C. On-site Waste Recycling/Recovery/Reuse: (Ye^/No/Can't Tell
Comment:
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/^an'TTeU^)
Comment:
Conclusion: Recyclable Non-Recyclable Partially Recyclable
4. Material Classification: Sludge /'Spent Material) By-Product
(circle one)
-------
1045
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
-2. ¦
feitistrial Sector and Process: —"1C-
CVaste Stream: ^ °
Waste Generation Rate: */G~,ooc>
Waste Form: Liquid(Aq./Non-AqQ/SlurTy^dird^Wei/Dry)
Hazard Characteristics (all): I C R S r ! PL / C fl
Hazardous Constituents fmaior): /o. Ca, lb, H-a ,
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: J/7 /Jf£{&£ <; rr^ <>v--J ¦
B. Waste gene&tion is closest to: Ravf frtatenfll/Mator Intermediates/Final Product
C. Waste appears to have: recoverable products/removable contaminants^fiefther^
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?: '^^/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 rhis^wastehrarime hazardous (e.g., physical contact during production, mixing with other waste
streamfTraurtrffomimpurity remove9
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.
Waste Segregation: Yes/N -fe TSS-.
Conclusion: iy^tecyclaBl)g Non-Recyclable Partially Recyclable ^
vr cr
4. Material Classification: '(jSludgeN Spent Material By-Product
(circle one)
-------
1046
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
"7- •
Industrial Sector and Process: u->v)C-
Waste Stream: (e*.r\
4. Material Qassification: Sludge Spent Material (/By^ProducPN
(circle one)
-------
1047
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
p_|/onvnv),A\ //-fdr^iw
ndustriai Sector and Process:
Waste Stream:
• nrir\[OftrinrsAi, )yj u Aio-hJ)
Waste Generation Rate: /O rwt )\t a a (-Vf^fckd PT lorh (Uar-htuig WO / il -
Waste Form: Liquid(Aq7Non-Aq.)/Slurry/Solids(Wet/Dry)
Hazard Characteristics (all): I p T
Hazardous Constituents (major):
1. Process Flow Diagram & Waste Characterization: By looking at both documents, try to answer the
following questions for eacb major source of tbe same waste generated in tbe 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: 1
C. On-site Waste Recyding/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
D. Off-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell
Comment: -
Partially Recyclable
Spent Material By-Product
Conclusion: Recyclable V_ Non-Recyclable _
4. Material Classification: Sludge
(circle one)
-------
1048
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process; / M/XflD)\)M
Waste Stream: n f \ A n I imjfYVYlU^CW
Waste Generation Rate: 7) m-Hwn a I h^nr\*i prn» 1^r\ I/rm k)i ) O/^rx <3R>
Waste Fom: LiquidAq./Non-Aq.)/Sluny/Solids(Wet/Dry)
Hazard Characteristics (all): 1 D 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, 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 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/Recoveiy/Reuse: Yes/No/Can't Tell
Comment: -
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment: '
Conclusion: Recvctable^X/ Non-Recyclable Partially Recyclable
4. Material Classification:
(circle one)
Sludge Spent Material By-Product
-------
1049
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Jdustrial Sector and Process; _ 2\NC6niviA I Hk-fmxuA
Waste Stream: Ipftfhirn ia > a H7i 0 /"tlGV\
Waste Generation RmIk^T' f I n -tTi a" \A I iff f~2
Waste Form: Liquid(Aq./Non-Aq.)#luriy/Solids(Wet/Dry)
Hazard Characteristics (all): I <^CJ ^ 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 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
Comment;
C. On-site Waste Recyding/Recovery/Reuse: Yes/No/Can't Tell ,
Comment: Cfi iM n C- U/il l\ i TUJ. wider
D. Off-site Waste Recycling/Recovery/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable _V_ Partially Recyclable
Sludge
By-Product
-------
1050
Work Sheet for Waste Stream Assessment for Recycling, Recovery, and Reuse Potential
Industrial Sector and Process: ^\rCT)Yll\) k\
Waste Stream: ^ I OQr.hln^Y\Ylrf w>/xW -Zwr/rtniifxA OAty
Waste Generation Rate: ^4-XC' /-A Z < V7ZD a a-I Ujl ^
Waste Form: Liquid(Aq./Non-Aq.)/Sluny/Solids( Wet/Dry)
Hazard Characteristics (all): I R T
Hazardous Constituents (major):.
1. Process Flow Diagram & Waste Characteriration: 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, 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 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/Rcuse: Yes/No/Can't Tell r -¦>
Comment: C0S\ i ^!l/^ f)0ThJ a \j
D. Off-site Waste Recyciing/Recoveiy/Reuse: Yes/No/Can't Tell
Comment:
Conclusion: Recyclable
4. Material Classification:
(circle one)
Non-Recyclable \ / Partially Recyclable
Sludge ( Spent Material ) By-Product
-------
'1051
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX E
Listing of Waste Streams Generated By
Mineral Production Activities By Commodity
-------
1052
-------
1053
EXHIBIT E-l
Listing of Waste Streams Generated by Mineral Production Activities by Commodity
Commodity
Waste Stream
Nature of Operation
Alumina and Aluminum
Water softener sludge
Extraction/Beneficiation
Anode prep waste
Mineral Processing
APC dust/sludge
Mineral Processing
Baghouse bags and spent plant filters
Mineral Processing
Bauxite residue
Mineral Processing
Cast house dust
Mineral Processing
Cryolite recovery residue
Mineral Processing
Wastewater
Mineral Processing
Discarded Dross
Mineral Processing
Flue Dust
Mineral Processing
Electrolysis waste
Mineral Processing
Evaporator salt wastes
Mineral Processing
Miscellaneous wastewater
Mineral Processing
Pisolites
Mineral Processing
Scrap furnace brick
Mineral Processing
Skims
Mineral Processing
Sludge
Mineral Processing
Spent cleaning residue
Mineral Processing
Sweepings
Mineral Processing
Treatment Plant Effluent
Mineral Processing
Waste alumina
Mineral Processing
Antimony
Gangue
Mineral Processing
Wastewater
Mineral Processing
APC Dust/Sludge
Mineral Processing
Autoclave Filtrate
Mineral Processing
Spent Barren Solution
Mineral Processing
Gangue (Filter Cake)
Mineral Processing
Leach Residue
Mineral Processing
Refining Dross
Mineral Processing
Slag and Furnace Residue
Mineral Processing
Sludge from Treating Process Waste Water
Mineral Processing
Stripped Anolyte Solids
Mineral Processing
Beryllium'
Gangue
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Acid Conversion Stream
Mineral Processing
-------
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Beryllium (continued)
Spent Barren filtrate streams
Mineral Processing
Bertrandite thickener slurry
Mineral Processing
Beryl thickener slurry
Mineral Processing
Beryllium hydroxide supernatant
Mineral Processing
Chip Treatment Wastewater
Mineral Processing
Dross discard
Mineral Processing
Filtration discard
Mineral Processing
Leaching discard
Mineral Processing
Neutralization discard
Mineral Processing
Pebble Plant Area Vent Scrubber Water
Mineral Processing
Precipitation discard
Mineral Processing
Process wastewater
Mineral Processing
Spent RafGnate
Mineral Processing
Scrubber Liquor
Mineral Processing
Separation slurry
Mineral Processing
Sump Water
Mineral Processing
Waste Solids
Mineral Processing
Bismuth
Alloy residues
Mineral Processing
Spent Caustic Soda
Mineral Processing
Electrolytic Slimes
Mineral Processing
Excess chlorine
Mineral Processing
Lead and Zinc chlorides
Mineral Processing
Metal Chloride Residues
Mineral Processing
Slag
Mineral Processing
Spent Electrolyte
Mineral Processing
Spent Material
Mineral Processing
Spent soda solution
Mineral Processing
Waste acid solutions
Mineral Processing
Waste Acids
Mineral Processing
Wastewater
Mineral Processing
Boron
Crud
Extraction/Beneficiation
Gangue
Ext raction/Benefi ciation
Spent Solvents
Extraction/Beneficiation
Waste Bnne
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Spent Sodium Sulfate
Mineral Processing
Waste liquor
Mineral Processing
Underflow Mild
Mineral Processing
-------
1055
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Bromine
Slimes
Extracnon/Beneficiation
Waste Brine
Extraction/Beneficiation
Water Vapor
Extraction/Beneficiation
Cadmium
Caustic washwater
Mineral Processing
Copper and Lead Sulfate Filter Cakes
Mineral Processing
Copper Removal Filter Cake
Mineral Processing
Iron containing impurities
Mineral Processing
Spent Leach solution
Mineral Processing
Lead Sulfate waste
Mineral Processing
Post-leach Filter Cakes
Mineral Processing
Spent Purification solution
Mineral Processing
Scrubber wastewater
Mineral Processing
Spent electrolyte
Mineral Processing
Zinc Precipitates
Mineral Processing
Calcium Metal
Off-gases
Extraction/Beneficiation
Overburden
Extraction/Beneficiation
Calcium Aluminate wastes
Mineral Processing
Dust with Quicklime
Mineral Processing
Cesium/Rubidium
Alkali Alums
Extraction/Beneficiation
Calctner Residues
Extraction/Beneficiation
Cesium Chlorosonnate
Extraction/Beneficiation
Non-Pollucite Mineral Waste
Extraction/Beneficiation
Precipitated Aluminum
Extraction/Beneficiation
Precipitated Barium Sulfate
Extraction/Beneficiation
Spent Chlorine solution
Extraction/Beneficiation
Spent Ion-exchange solution
Extraction/Beneficiation
Spent Metal
Extraction/Beneficiation
Spent Ore
Extraction/Beneficiation
Spent Solvent
Extraction/Beneficiation
Waste Gangue
Extraction/Beneficiation
Chemical Residues
Mineral Processing
Digester waste
Mineral Processing
Electrolytic Slimes
Mineral Processing
Pyrolvtic Residue
Mineral Processing
Slag
Mineral Processing
Chromium. Ferrochrome, and
Ferrochromium-Silicon
Gangue and tailings
Extraction/Beneficiation
Dust or Sludge from ferrochromium production
Mineral Processing
Dust or Sludge from ferrochromium-silicon production
Mineral Processing
Slag and Residues
Mineral Processing
-------
1056
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Coal Gas
Baghouse Coal Dust
Extraction/Beneficiation
Coal Pile Runoff
Extraction/Beneficiation
Fines
Extraction/Beneficiation
Gangue
Exiraction/Beneficiation
API Oil/Water Separator Sludge
Mineral Processing
API Water
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Dissolved Air Flotation (DAF) Sludge
Mineral Processing
Flue Dust Residues
Mineral Processing
Liquid Waste Incinerator Blowdown
Mineral Processing
Liquid Waste Incinerator Pond Sludge
Mineral Processing
Multiple Effects Evaporator Concentrate
Mineral Processing
Multiple Effects Evaporator Pond Sludge
Mineral Processing
Sludge and Filter Cake
Mineral Processing
Spent Methanol Catalyst
Mineral Processing
Stretford Solution Purge Stream
Mineral Processing
Surface Impoundment Solids
Mineral Processing
Vacuum Filter Sludge
Mineral Processing
Zeolite Softening PWW
Mineral Processing
Copper
Crud
Extraction/Beneficiation
Spent Kerosene
Extraction/Beneficiation
Raffinate
Extraction/Beneficiation
Slime
Extraction/Beneficiation
Slimes or "Muds"
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste Rock
Extraction/Beneficiation
Acid plant blowdown
Mineral Processing
Acid plant thickener sludge
Mineral Processing
APC dusts/sludges
Mineral Processing
Spent bleed electrolyte
Mineral Processing
Chamber solids/scrubber sludge
Mineral Processing
Waste contact cooling water
Mineral Processing
Discarded furnace brick
Mineral Processing
Non-recyclable APC dusts
Mineral Processing
Process wastewaters
Mineral Processing
Scrubber blowdown
Mineral Processing
Spent black sulfuric acid sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
Tankhouse slimes
Mineral Processing
-------
1057
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Copper (continued)
WWTP liquid effluent
Mineral Processing
WWTP sludge
Mineral Processing
Elemental Phosphorous
Waste rock from mining
Extraction/Beneficiation
Condenser phossv water discard
Mineral Processing
Cooling water
Mineral Processing
AFM nnsate
Mineral Processing
Dust
Mineral Processing
Waste ferrophosphorus
Mineral Processing
Furnace offgas solids
Mineral Processing
Furnace scrubber blowdown
Mineral Processing
Precipitator slurry scrubber water
Mineral Processing
Slag quenchwater
Mineral Processing
Sludge
Mineral Processing
Spent furnace brick
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
Surface impoundment waste solids
Mineral Processing
Waste filter media
Mineral Processing
WWTP liquid effluent
Mineral Processing
WWTP Sludge/Solids
Mineral Processing
Fluorspar and Hydrofluoric Acid
Gangue
Extraction/Beneficiation
Lead and Zinc sulfides-
Extraction/Beneficiation
Spent flotation reagents
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
APC Dusts
Mineral Processing
Off-spec fluosilicic acid
Mineral Processing
Sludges
Mineral Processing
Gem Stones
Overburden
Extraction/Beneficiation
Spent chemical agents
Extraction/Beneficiation
Spent polishing media
Extraction/Beneficiation
Waste minerals
Extraction/Beneficiation
Germanium
Waste Acid Wash and Rinse Water
Mineral Processing
Chlonnator Wet Air Pollution Control Sludge
Mineral Processing
Hydrolysis Filtrate
Mineral Processing
Leach Residues
Mineral Processing
Spent Acid/Leachate
Mineral Processing
Waste Still Liquor
Mineral Processing
Wastewater
Mineral Processing
-------
1058
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Gold and Silver
Black sand
Extraction/Beneficiation
Filter cake
Extraction/Beneficiation
Mercury bearing solution
Extraction/Beneficiation
Mine water
Extraction/Beneficiation
Spent carbon
Extraction/Beneficiation
Spent leaching solution
Extraction/Beneficiation
Spent ore
Extraciion/Beneficiauon
Spent stripping solution
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste rock, clay and sand
Extraction/Beneficiation
Zinc cyanide solution
Extraction/Beneficiation
Spent Furnace Dust
Mineral Processing
Refining wastes
Mineral Processing
Slag
Mineral Processing
Wastewater treatment sludge
Mineral Processing
Wastewater
Mineral Processing
Iodine
Filtrate waste
Extraction/Beneficiation
Sludge
Extra ctiorvBeneficiation
Sulfur compounds
Extraction/Beneficiation
Waste acid
Extraction/Beneficiation
Waste bleed liquor
Extraction/Beneficiation
Waste bleed liquor and filtrate wastes
Extraction/Beneficiation
Waste bnne
Extraction/Beneficiation
Iron and Steel
Tailings
Extraction/Beneficiation
Wastewater and Waste Solids
Extraction/Beneficiation
Wastewater
Mineral Processing
Lead
Concentration Wastes
Extraction/Beneficiation
Mine water
Extraction/Beneficiation
Waste Rock
Extraction/Beneficiation
Acid Plant Blowdown
Mineral Processing
Acid Plant Sludge
Mineral Processing
Baghouse Dust
Mineral Processing
Baghouse Incinerator Ash
Mineral Processing
Cooling Tower Blowdown
Mineral Processing
Waste Nickel Matte
Mineral Processing
Process Wastewater
Mineral Processing
Slurried APC Dust
Mineral Processing
Solid Residues
Mineral Processing
Solids in Plant Washdown
Mineral Processing
-------
1059
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Lead (continued)
Spent Furnace Brick
Mineral Processing
Stockpiled Miscellaneous Plant Waste
Mineral Processing
Surface Impoundment Waste Liquids
Mineral Processing
Surface Impoundment Waste Solids
Mineral Processing
SVG Backwash
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludges/Solids
Mineral Processing
Lightweight
Overburden
Extraction/Beneficiation
Aggregate
Screenings
Extraction/Beneficiation
APC control scrubber water and solids
Mineral Processing
APC Dust/Sludge
Mineral Processing
Surface impoundment waste liquids
Mineral Processing
WWTP liquid effluent
Mineral Processing
Lithium and
Acid roaster gases
Extraction/Beneficiation
Lithium Carbonate
Flotation Tailings
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Magnesium/Calcium Sludge
Extraction/Beneficiation
Roaster Off-gases
Extraction/Beneficiation
Salt solutions
Extraction/Beneficiation
Wastewater from Wet Scrubber
Extraction/Beneficiation
Magnesium and Magnesia
Calcium sludge
Extraction/Beneficiation
from Brines
Offgases
Extraction/Beneficiation
Spent seawater
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
Calcuier offgases
Mineral Processing
Calcium sludge
Mineral Processing
Casthouse Dust
Mineral Processing
Casting plant slag
Mineral Processing
Cathode Scrubber Liquor
Mineral Processing
Slag
Mineral Processing
Smut
Mineral Processing
Spent Brines
Mineral Processing
Manganese, Manganese
Dioxide, Ferromanganese
and Silicomanganese
Flotation tailings
Extraction/Beneficiation
Gangue
Extraction/Beneficiation
Spent Flotation Reagents
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
APC Water
Mineral Processing
-------
1060
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Manganese. Manganese
Dioxide, Ferromanganese
and Silicomanganese (continued)
Electrolyte Purification Waste
Mineral Processing
Iron Sulfide Sludge
Mineral Processing
Ore Residues
Mineral Processing
Slag
Mineral Processing
Spent Graphite Anode
Mineral Processing
Spent Process Liquor
Mineral Processing
Waste Electrolyte \
Mineral Processing
Wastewater (CMD)
Mineral Processing
Wastewater (EMD)
Mineral Processing
Wastewater Treatment Solids
Mineral Processing
Mercury
Concentrator Wastewater
Mineral Processing
Dust
Mineral Processing
Mercury Quench Water
Mineral Processing
Filter Cake Waste
Mineral Processing
Furnace Residue
Mineral Processing
Molybdenum.
Ferromolybdenum, and
Ammonium Molybdate
Flotation tailings
Extraction/Beneficiation
Gangue'
Extraction/Beneficiation
Spent Flotation Reagents
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
APC Dust/Sludge
Mineral Processing
Flue Dust/Gases
Mineral Processing
Liquid Residues
Mineral Processing
H2 Reduction Furnace Scrubber Water
Mineral Processing
Molybdic Oxide Refining Wastes
Mineral Processing
Refining Wastes
Mineral Processing
Roaster Gas Blowdown Solids
Mineral Processing
Slag
Mineral Processing
Solid Residues
Mineral Processing
Treatment Solids
Mineral Processing
Phosphonc Acid
Waste Scale
Mineral Processing
Platinum Group
Metals
Filtrate
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Slag
Mineral Processing
Spent Acids
Mineral Processing
Spent Solvents
Mineral Processing
Pyrobitumens.
Mineral Waxes,
and Naturel Asphalts
Spent coal
Extraction/Beneficiation
Spent solvents
Extraction/Beneficiation
Still bottoms
Mineral Processing
Waste catalysts
Mineral Processing |
-------
1061
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Rare Earths
Magnetic fractions
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
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 hydroxide cake
Mineral Processing
Spent iron/lead filter cake
Mineral Processing
Lead backwash sludge
Mineral Processing
Monazite solids
Mineral Processing
Process wastewater
Mineral Processing
Spent scrubber liquor
Mineral Processing
Spent sodium fluoride
Mineral Processing
Spent sodium hypochlorite filter backwash
Mineral Processing
Solvent extraction crud
Mineral Processing
Spent surface impoundment solids
Mineral Processing
Spent surface impoundment liquids
Mineral Processing
Waste filtrate
Mineral Processing
Waste solvent
Mineral Processing
Wastewater from caustic wet APC
Mineral Processing
Waste zinc contaminated with mercury
Mineral Processing
Rhenium
APC Dust/Sludge
Mineral Processing
Spent Barren Scrubber Liquor
Mineral Processing
Spent Rhenium Raffinate
Mineral Processing
Roaster Dust
Mineral Processing
Spent Ion Exchange/SX Solutions
Mineral Processing
Spent Salt Solutions
Mineral Processing
Slag
Mineral Processing
Scandium
Crud from the bottom of the solvent extraction unit
Mineral Processing
Dusts and spent filters from decomposition
Mineral Processing
Spent acids
Mineral Processing
Spent ion exchange resins and backwash
Mineral Processing
Spent solvents from solvent extraction
Mineral Processing
Spent wash water
Mineral Processing
Waste chlorine solution
Mineral Processing
Waste solutions/solids from leaching and precipitation
Mineral Processing
-------
1062
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Selenium
Spent filter cake
Mineral Processing
Plant process wastewater
Mineral Processing
Slag
Mineral Processing
Tellurium slime wastes
Mineral Processing
Waste Solids
Mineral Processing
Silicon and
Ferrosilicon
Gangue
Extraction/Beneficiation
Spent Wash Water
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
AP.C Dust Sludge
Mineral Processing
Dross discard
Mineral Processing
Slag
Mineral Processing
Soda Ash
Airborne emissions
Extraction/Beneficiation
Calciner offgases
Extraction/Beneficiation
Filter aid and carbon absorbent
Extraction/Beneficiation
Mother liquor
Extraction/Beneficiation
Ore msolubles
Extraction/Beneficiation
Ore residues
Extraction/Beneficiation
Overburden
Extraction/Beneficiation
Particulate emissions from dners
Extraction/Beneficiation
Particulates
Extraction/Beneficiation
Purge liquor
Extraction/Beneficiation
Scrubber water
Extraction/Beneficiation
Spent brine
Extraction/Beneficiation
Spent carbon and filter wastes
Extraction/Beneficiation
Spent dissolution wastes
Extraction/Beneficiation
Suspended particulate matter
Extraction/Beneficiation
Taibngs
Extraction/Beneficiation
Trona ore particulates
Extraction/Beneficiation
Trona ore processing waste
Extraction/Beneficiation
Waste mother liquor
Extraction/Beneficiation
Sodium Sulfate
Waste Brine
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Strontium
Calciner offgas
Extraction/Beneficiation
Dilute sodium sulfide solution
Extraction/Beneficiation
Filter muds
Extraction/Beneficiation
Spent Ore
Extraction/Beneficiation
Vacuum drum filtrate
Extraction/Beneficiation
Waste solution
Extraction/Beneficiation
-------
1063
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Sulfur
Air emissions
Extraction/Beneficiation
Filter cake
Extraction/Beneficiation
Frasch process residues
Extraction/Beneficiation
Sludge
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Spent catalysts (Claus process)
Mineral Processing
Spent vanadium pentoxide catalysts from sulfunc acid production
Mineral Processing
Spilled product (Claus process)
Mineral Processing
Wastewater from wet-scrubbing, spilled product and condensates
Mineral Processing
Synthetic Rutile
APC Dust/Sludges
Mineral Processing
Spent Iron Oxide Slurry
Mineral Processing
Spent Acid Solution
Mineral Processing
Tantalum. Columbium
APC Dust Sludge
Mineral Processing
and Ferrocolumbium
Digester Sludge
Mineral Processing
Spent Potassium Titanium Chloride
Mineral Processing
Process Wastewater
Mineral Processing
Spent Raffinate Solids
Mineral Processing
Scrubber Overflow
Mineral Processing
Slag
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge
Mineral Processing
Tellurium
Slag
Mineral Processing
Solid waste residues
Mineral Processing
Waste Electrolyte and Wastewater
Mineral Processing
Wastewater
Mineral Processing
Tin
Process Wastewater
Extraction/Beneficiation
Tailings Sluny
Extraction/Beneficiation
Brick Lining and Fabric Filters
Mineral Processing
Dross
Mineral Processing
Process Wastewater and Treatment Sludge
Mineral Processing
Reactor slurry -- acid and sludges
Extraction/Beneficiation
Slag
Mineral Processing
Slimes
Mineral Processing
Waste acids
Extraction/Beneficiation
Waste Acid and Alkaline baths
Mineral Processing
Waste liquids
Extraction/Beneficiation
-------
1064
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Titanium and
Titanium Oxide
Flotation Cells
Extraction/Beneficiation
Tailings
Extraction/Beneficianon
Spent Brine Treatment Filter Cake
Mineral Processing
FeCI Treatment Sludge
Mineral Processing
Waste Feme Chloride
Mineral Processing
Finishing Scrap
Mineral Processing
Leac£ Liquor and Sponge Wash Water
Mineral Processing
Waste Non-Contact Cooling Water
Mineral Processing
Pickling Liquor and Wash Water
Mineral Processing
Scrap Detergent Wash Water
Mineral Processing
Scrap Milling Scrubber Water
Mineral Processing
Reduction Area Scrubber Water
Mineral Processing
Chlorination Off gas Scrubber Water
Mineral Processing
Chlonnation Area - Vent Scrubber Water
Mineral Processing
Melt Cell Scrubber Water
Mineral}Processing
Chlorine Liquefaction Scrubber Water
Mineral Processing
Chip Crushing Scrubber Water
Mineral Processing
Casting Crucible Contact Cooling Water
Mineral Processing
Smut from Mg Recovery
Mineral Processing
Spent Surface Impoundment Liquids
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
TiCI4 Purification Effluent
Mineral Processing
Spent Vanadium Oxychlonde
Mineral Processing
Sodium Reduction Container Reconditioning Wash Water
Mineral Processing
Casting Crucible Wash Water
Mineral Processing
Waste Acids (Chloride process)
Mineral Processing
Waste Acids (Sulfate process)
Mineral Processing
Waste Solids (Sulfate process)
Mineral Processing
WWTP Liquid Effluent
Mineral Processing
WWTP Sludge/Solids
Mineral Processing
Tungsten
•Alkali leach wash
Extr^tion/Beneficiation
Calcium tungstate precipitate wash
Extraction/Beneficiation
Ion exchange raffinate
Extraction/Beneficiation
Ion exchange resins
Extraction/Beneficiation
Leach filter cake residues and impurities
Extraction/Beneficiation
Molybdenum sulfide precipitation wet air pollution control
Extraction/Beneficiation
Scrubber wastewater
Extraction/Beneficiation
Spent mother liquor
Extraction/Beneficiation
Tungstic acid rinse water
Extraction/Beneficiation
-------
1065
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Tungsten (continued)
Waste fines
Extraction/Beneficiation
Waste rock and tailings
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Wet scrubber wastewater
Extraction/Beneficiation
Spent Acid and Rinse water
Mineral Processing
Scrubber wastewater
Mineral Processing
Process wastewater treatment plant effluent
Mineral Processing
Water of formation
Mineral Processing
Uranium
Waste Rock
Extraction/Beneficiation
Tailings
Extraction/Beneficiation
Spent Extraction/Leaching Solutions
• Extraction/Beneficiation
Particulate Emissions
Extraction/Beneficiation
Miscellaneous Siudges
Extraction/Beneficiation
Spent Ion Exchange Resins
Extraction/Beneficiation
Tailing Pond Seepage
Extraction/Beneficiation
Waste Acids from Solvent Extraction
Extraction/Beneficiation
Barren Lixiviant
Extraction/Beneficiation
Slimes from Solvent Extraction
Extraction/Beneficiation
Waste Solvents
Extraction/Beneficiation
Waste Nunc Acid from Production of UO,
Mineral Processing
Vaporizer Condensate
Mineral Processing
Superheater Condensate
Mineral Processing
Slag
Mineral Processing
Uranium Chips from Ingot Production
Mineral Processing
Waste Calcium Fluoride
Mineral Processing
Vanadium
Roaster Off-gases
Extraction/Beneficiation
Solid residues
Extraction/Beneficiation
Spent Filtrate
Extraction/Beneficiation
Spent Solvent
Extraction/Beneficiation
Filtrate and Process Wastewaters
Mineral Processing
Solid Waste
Mineral Processing
Spent Precipitate
Mineral Processing
Slag
Mineral Processing
Wet scrubber wastewater
Mineral Processing
Zinc
Refuse
Exiraction/Beneficiation
Tailings
Extraction/Beneficiation
Waste rock
Extraction/Beneficiation
Acid Plant Blowdown
Mineral Processing
Spent Cloths, Bags, and Filters
Mineral Processing
-------
EXHIBIT E-l (Continued)
Commodity
Waste Stream
Nature of Operation
Zinc (continued)
Waste Ferrosilicon
Mineral Processing
Spent Goethite and Leach Cake Residues
Mineral Processing
Process Wastewater
Mineral Processing
Discarded Refractory Brick
Mineral Processing
Spent Surface Impoundment Liquid
Mineral Processing
Spent Surface Impoundment Solids
Mineral Processing
Spent Synthetic Gypsum
Mineral Processing
TCA Tower Blowdown (ZGA Bartlesville. OK - Electrolytic Plant)
Mineral Processing
Wastewater Treatment Plant Liquid Effluent
Mineral Processing
Wastewater Treatment Plant Sludge
Mineral Processing
Zinc-lean Slag
Mineral Processing
Zirconium and
Hafnium
Monazite
Extraction/Beneficiation
Wastewater
Extraction/Beneficiation
Spent Acid leachate from zirconium alloy production
Mineral Processing
Acid leachate from zirconium metal production
Mineral Processing
Ammonium Thiocyanate Bleed Stream
Mineral Processing
Reduction area-vent wet APC wastewater
Mineral Processing
Caustic wet APC wastewater
Mineral Processing
Feed makeup wet APC wastewater
Mineral Processing
Filter cake/sludge
Mineral Processing
Furnace residue
Mineral Processing
Hafnium filtrate wastewater
Mineral Processing
Iron extraction stream stripper bottoms
Mineral Processing
Leaching rinse water from zirconium alloy production
Mineral Processing
Leaching rinse water from zirconium metal production
Mineral Processing
Magnesium recovery area vent wet APC wastewater
Mineral Processing
Magnesium recovery off-gas wet APC wastewater
Mineral Processing
Sand Chlonnation Off-Gas Wet APC wastewater
Mineral Processing
Sand Chlorination Area Vent Wet APC wastewater
Mineral Processing
Silicon Tetrachloride Purification Wet APC wastewater
Mineral Processing
Wet APC wastewater
Mineral Processing
Zirconium chip crushing wet APC wastewater
Mineral Processing
Zirconium filtrate wastewater
Mineral Processing
-------
1067
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX F
Mineral Processing Facilities
Generating Hazardous Wastes
(Including Facilities Generating "Special 20" Bevill-Exempt
Wastes and/or Colocated Facilities)
-------
1068
-------
EXHIBIT F-l
Summary of Mineral Processing Facilities by Mineral Sector - Hazardous Waste Streams
(Includes Identification of Collocated Facilities and Generators of "Special 20" Wastes)
. •' Mineral CwtunwKtfea
•.. .• v:% •:
< < :
% I
: xfadlltV NfflnSg::
MP,
-------
EXHIBIT F-l (Continued)
• £" :;?f '
- FadBt* Hattkfes
rucHft*
Mining twd 5®?
of Itws
S«edat JK> Waste* •
Antimony (Continued)
M & T Chemcial
(inactive)
Baltimore, MD
no
Processing
no
McGean Chemical
Cleveland, OH
no
Processing
no
Sunshine Mining
Company
Kellogg, ID
no
Processing
no
US Antimony Corp.
Thompson Falls, MT
no
Processing
no
Beryllium
Brush Wellman
Delta, UT
yes
mining, produces Be(OH)2
no
Brush Wellman
Elmore, OH
no
Secondary ore processing or Be
Melal and Alloys
no
NGK Metals
Revere, PA
110
Secondary ore processing of Be
Metal
no
Bismuth
ASARCO
Omaha, NR
no
Processing
no
Boron
U.S. Borax
Boron, CA
Kern County
yes
Mining and production of
Sodium Borate and Boric Acid
no
North American
Chemical Co.
(Westend, Argus &
Tyrona Plants)
Searles Lake, CA
yes
Borate recovered via brines
mined from Searles Lake
no
Cadmium
ASARCO
Denver, CO
no
Processing
no
Big River Zinc
Corp.
Sauget, IL
no
Processing
no
Jersey Minierc
Zinc. Corp
Clarksvillc, TN
no
Processing
no
ZCA
Bartlesville, OK
no
Processing
110
Calcium Mefnl
Pfizei Clicni
(Qnigley Company)
Canaan, CP
no
Processing
110
-------
EXIIHllT I I (Continiied)
Mittfcttd.CottHaedhtes
FadttoiNdmeS;,:-
H'P S«*ctei 10
Chromium, Ferrochromc,
and Ferroclironilum-Sillcon
American Chrome
& Chemicals Inc.
Corpus Christi, TX
no
Processing
yes
Tiealed residue from
roasting/lcnching of cluome oie
Elkem, AS, EJkem
Melals Co
Marietta, OH
no
Processing
no
Elkem, AS, Elkem
Metals Co.
Alloy, WV
no
Processing
no
General
Refracloi ies Co
Lelii, UT
no
Processing
no
1 larbison-Wnlker
Refractories
Hammond, IN
no
Processing
no
Macalloy Corp
Charleston, SC
w>
Processing
no
National
Refractories anil
Mining Corp,
Moss Landing, CA
no
Processing
no
National
Refiactories and
Mining Corp.
Columbiana, OH
HO
Processing
no
North Amei ican
Refractories Co.
Ltd.
Womelsdorf, PA
no
Processing
no
Occidental
Chemicals Cot p.
Castle Hayne, NC
no
Processing
yes
Tieated residue from
masling/Ieaching of chrome ore
Chromium, Ferrochrome,
and Ferrocliromlum-Slllcon
(Continued)
Satra Concentrates
Inc.
Steubenville, OH
no
Processing
no
-------
i:\IIIIUT 1-1 (Continued)
> *
¦¦ •>
Fadlit* Nam**
lottos* :
MlniDf mi MP
Comment*
one of flre
aa#
Coal gas
Great Plains Coal
Gasification Plant,
Dakota Gasification
Co.
Bculah, ND
yes
Synthetic Gas produced
yes
Gasifer Ash, Process Wastewater
Copper
ASARCO
El Paso, TX
rio
Smelling
yes
Slag, slag tailings and/or calcium
sulfate sludge
ASARCO
Amarillo, TX
no
Electrolytic Refining
yes
Slag, slag tailings and/or calcium
sulfate sludge
ASARCO
Ray, AZ
no
Mining and Electrowinning
no
ASARCO
I layden, AZ
yes
Mining, Smelling and
Electrowinning
yes
Siag, slag tailings and/oi calcium
sulfate sludge
Burro Chief Copper
Mine
'lVrone, NM
no
Mining and Electrowinning
no
Copper Range
While Pine, Ml
yes
Mining, Smelting & Refining
yes
Slag, slag failings and/or calcium
sulfate sludge
Cyprus Pinos Altos
Mine
Silver City, NM
no
Mining only
no
Cyprus
Claypool, AT,
yes
Milling, Smelting, Relintng, &
Electrowinning
yes
Slag, slag tailings and/or calcium
sulfate sludge
Cyprus Casa
Grande Mine
Casa Grande, AZ
no
Mining and Roasting
no
Copper (Continued)
Cyprus Miami
Mining Corp.
Claypool, AZ
no
Mining and 1 leap Leaching
no
Cyprus Mineral
Park Corp
Kingman, AZ
yes
Mining and Dump l.eaching
no
Cyprus Sierrila/
l\vin Unties
Green Valley, AZ
no
Milling and 1 leap 1 caching
no
-------
EXHIBIT I I (Continued)
,•. Mining: fllut MP
Comments;.:
Cyprus Mining
Bagdad, AZ
no
Mining and Electrowinning
no
Cyprus Bagdad
Copper Mine
Bagdad, AZ
yes
Mining, Heap Leaching and
Milling
no
Flambeau Copper
Mine
Salt Lake City, UT
no
Mining only
no
Gibson Mine
Mesa, AZ
no
Mining and Leaching
no
Johnson Camp
Mine
Tucson, AZ
no
Mining and 1 leap Leaching
no
Kennecotl
Garfield, UT
no
Smelting and Refining
yes
Slug, slag tailings and/or calcium
sulfate sludge
Magma Mine
Superior, AZ
no
Mining
no
Magma
San Manuel, AZ
yes
Mining, Smelting, Rclimng, and
Electrowinning
yes
Slag, slag failings and/or calcium
sulfate sludge
Mineral Park Mine
Kingman, AZ
no
Mining only
no
Mission Unit
Sahuarita, AZ
no
Mining only
no
Monlanoie Mine
Ubby, MT
no
Mining only
no
Morenci Mine
Morenci, AZ
no
Heap Leaching (owned by
Phelps Dodge)
no
Noranda
Casa Grande, AZ
no
Electrowinning (owned by
Cyprus AMAX Minerals)
no
Oracle Ridge Mine
San Manuel, AZ
no
Mining only
no
Copper (Continued)
Phelps Dodge
Morenci, AZ
no
Mining and Electrowinning
no
Phelps Dodge
Playas, NM
no
Smelting only
yes
Slag, slag tailings and/or calcium
sulfate sludge
Phelps Dodge
HI Paso, TX
no
Refining only
yes
Slag, slag tailings and/or calcium
sulfate sludge
-------
EXIIIIHT F-l (Continued)
ftlfcntfog and MP 1
ffcc&fcv
Cwameats
one of rhs
Phelps Dodge
1 lurley, NM
yes
Mining, Smelting and
lilcctrowinning (same as Chino
Mines)
yes
Slag, slag tailings and/or calcium
sulfate sludge
Pinos Alios Mine
Silver City, NM
no
Mining only
no
Pinto Valley
Operations
Miami, AZ
no
Mining and lilectrowinning
(mining owned by Magma
Copper Co.)
no
Pinto Valley
Pinto Valley, AZ
no
lilectrowinning (possibly owned
by Magma Copper Co )
no
Ray Complex
Hayden, AZ
no
Mining only
no
San Manuel Div.
Mine
San Manuel, AZ
no
Mining only
no
San Pedro Mine
Truth or
Consequences, NM
no
Mining only
no
Silver Butte Mine
Riddle, OR
no
Mining only
no
Silver Bell Unit
Marana, AZ
no
Mining only
no
St. Cloud Mining
Co.
Truth or
Consequences, NM
no
Mining only
no
Sunshine Mine
Kellog, ID
no
Mining only
no
-------
i:\IHIWT 1-1 (Continued)
• ¦>: • •: • -? v.--. : ::::•::« x.v^.+\:;:jx
i i i.i.Mijjj 'J.VM.ft.WflW.*11
mw.-.*.-.' -t
hi-c-K+M i :ii:: i: 111 ii • ;+s^KH+m;
liirPBailW'eSttitrtaBr!!!!
....... j.\>\ '.***!' V' '¦
11111nimhh+^w'^j:x-\y ^
:! ?: i!" 2 ^=
««i» of the "»>'»»<
Copper (Continued)
Tennessee Chemical
Copperhill, TN
no
Facility closed
no
'l^rone Branch
Mine
'iyrone, NM
no
Dump Leaching and
Flectrowinning (owned by
Phelps Dodge)
no
Western World
Copper Mine
Marysville, CA
no
Mining only
no
Ycringlon Mine
Tucson, AZ
no
Mining only
no
Elemental Phosporous
FMC
Pocatello, ID
no
(located near
phosphate rock
reserves)
Processing
yes
Slag
Monsanlo
Soda Springs, ID
no
(located near
phosphate rock
reserves)
Processing
yes
Slag
Occidental
Chemical
Columbia, TN
no
(located near
phosphate rock
reserves)
Processing
yes
Slag
Stauffer
Mount Pleasant, TN
no
(located near
phosphate rock
reserves)
Processing
yes
Slag
Stauffer
Silver Row, MT
no
(located near
phosphate rock
ieserves)
Processing
yes
Slag
-------
EXHIBIT I I (Continued)
CottMnodlttee
tfadlfcv Locattottit"
gOOMtttBte
.. , Of
Germanium
Atomergic Chem
Plainview, NY
no
Processing
no
Cabot
Revere, PA
no
Processing
no
Eagle-Picher
Quapaw, OK
no
Processing
no
Jersey Miniere
Clarksville, TN
no
Mining
no
Musto Exploration
St George, UT
yes
Mining and Refining
no -
Gold and Silver
ASARCO, Inc.
Amarillo, TX
no
Smelter/Refinery
no
ASARCO, Inc.
Omaha, NE
no
Smelter/Refinery
no
AURlC-CHLORj
Inc.
Rapid City, SD
no
Smcltcr/Refincry
no
David Fell &
Company, Inc.
City of Commerce,
CA
no
Smelter/Refinery
no
Drew Resources
Corp.
Berkeley, CA
no
Smelter/Refinery
no
Eastern Smelting &
Refining Corp
Lynn, MA
no
Smellcr/Rcfinery
no
Hngleliard
Industries West,
Inc.
Anaheim, CA
no
Smelt er/Reftncry
110
GD Resources, Inc.
Sparks, NV
no
Smelter/Refinery
no
Handy & llarman
Attleboro, MA
no
Smelter/Refinery
110
I Iandy & I Iarman
South Windsor, CI'
no
Smelter/Refmery
no
Johnson Matlliey
Salt Lake City, UT
yes
no
Metalor USA
Refining Corp
North Atllcboio, MA
no
Smellcr/Refineiy
no
-------
EXHIBIT 1-1 (Continued)
¦ fticHitv IjOtaHoiiS::..
Contmtnta
V ::: j
borates of ttos j
Gold and Silver
Muliimetco, Inc
Anniston, AL
no
Smeller/Refinery
no
(Continued)
Nevada Gold
Refining Group
Reno, NV
no
Smeller/Refinery
no
Sunshine Mining
Co.
Kellogg, ID
no
Smelter/Refinery
no
Williams Advanced
Materials
Buffalo, NY
no
Smelter/Refmeiy
no
Lead
ASARCO
East Helena, M P
no
Smelter
yes
Slag
ASARCO
Glover, MO
no
Snieltei/Refinery
yes
Slag
ASARCO
Omalia, NE
no
Refinery
yes
Slag
ASARCO Lcadvillc
Unit
Leadville, CO
no
Mining
no
Doe Run Co
Boss, MO
no
Smelter/Refinery
yes
Slag
Doe Run Co.
Herculaneum, MO
no
Smclter/Refincry
yes
Slag
Pourlh of July Mine
Yellow Pine, ID
no
Extraction
no
Galena Mine
Mullan, ID
no
Extraction
no
Glass Mine
Pend Oreille County,
WA
no
Extraction
no
Greens Creek Mine
Admiralty Island, AK.
no
Extraction
no
Lucky Friday Mine
Mullan, ID
no
Exl i act ion
no
-------
EXIIIltIT F-l (Continued)
: ^clMtv:C6llo«at«a
: ifcf. ^
I^ead (Continued)
Magmonl Mine
Bixby, MO
no
F.xlraction
no
Montana Tunnels
Mine
Jefferson City, MT
no
Extraction
no
Red Dog Mine
Kotzebue, AK
no
Extraction
no
Sunnyside Mine
Silverton, CO
no
Extraction
no
Sweetwater Mine
Bunker, MO
no
Extraction
no
Viburnum Mines
(6 mines)
Brushy Creek
Ciistecl
Fletcher
Viburnum 28
Viburnum 29
Buick
Iron, Reynolds, and
Washington Counties,
MO
no
Extraction and Bcneficiation
no
West Fork Mine
Bunker, MO
no
F.xlraction
no
Lightweight Aggregates
Norlite
Colioes, NY
no
Processing, burns hazardous
waste fuels
no
Solite
Arvonia, VA
no
Processing, burns hazardous
waste fuels
no
Carolina Solite
Norwood, NC
no
Processing, burns hazardous
waste fuels
no
Kentucky Solite
Brooks, KY
no
Processing, burns hazaidous
waste fuels
no
Florida Solite
Green Cove, FL
no
Processing, burns hazardous
waste fuels
no
-------
EXHIBIT 1-1 (Continued)
• • iPaellltv •:•
• •• ii'.
Mlnio£nnd MP/:
ttommeate
1: MdSli Ift
Magnesium
Barcroft Co
I.ewes, DE
yes
MgO from seawater
no
Basic Inc.
Gabbs, NV
no
Magnesin processing
no
Dow Chemical Co.
I'rceport, l'X
yes
MgCl from seawater, Mg metal
processing, magnesia processing
no
Greal Sail Lake
Odgen, UT
yes
MgCl from lake brine
no
Magnesia
Operations
San Francisco, CA
no
Magnesia processing
no
Magnesium Corp.
of Ameiica
Rowley, UT
no
Mg metal processing
yes
Process wastewater
Marine Magnesium
Co.
South San Francisco,
CA
yes
MgO from seawater
no
Martin Marietta
Chemicals
Manistee, Ml
yes
MgCl fiom brine
no
Morion Chemical
Co.
Manistee, Ml
yes
MgCl from biine
no
National
Refractories &
Minerals Corp.
Moss Landing, CA
yes
MgO from seawater
no
Northwest Alloys
Inc.
Addy, WA
no
Mg metal piocessmg
no
Premier Services
Inc
Tort St. Joe, Fl.
yes
MgO from seawatei
no
Premier Services
Inc.
Gabbs, NV
yes
Mine magnesium cuibonaic and
calcine to MgO
no
Reilly Ind
Wendover, UT
yes
Urine Extraction
no
-------
EXHIBIT 1-1 (Continued)
Mtoaal Commodltfe*
fctdlftv tocatfotM'
texamtMht,
of
Mercury
Barrick Mccur Gold
Mines, Inc.
Toole, UT
yes
Milling and Retorting
no
FMC Gold Co.
1 Iumboldt, NV
no
Mining
no
FMC Gold Co.
Nye, NV
no
Mining, operation closed
no
llomestake Mining
Co.
Napa, CA
no
Mining
no
Independence
Mining Co. Inc.
F.lko, NV
no
Mining
no
Newmont Gold Co.
liureka, NV
no
Mining
no
Pinson Mining Co.
Humboldt, NV
no
Mining
no
Placer Dome U.S.
White Pine~ NV
no
Mining
no
Western Hog
Ranch Co
Washoe, NV
no
Mining
no
Molybdenum, Ferro-
molylidenum and
Cyprus-Climax-
Mendcrson
Empire, CO
yes
Mining and Processing
no
Ammonium Molybdnle
Cyprus-Climax
Fort Madison, IA
no
Processing
no
Cyprus-Climax
Clear Water, MI
no
Processing, possibly phased out
no
Cyprus-Climax-
Green Valley
Tucson, AZ
no
Processing
no
Cyprus-Climax
Bagdad, AZ
no
Mining
no
Kennecott
Salt Lake City, LI T
no
Processing
no
Montana Resources
¦ Inc.
Butte, MT
no
Processing
no
-------
liXHIMT K-l (Continued)
FatllltvNames ;
. Mining: MP
.: Facttto Coltocated s
Comments ...l:,::;;:
Generate* of Hw
Molybdenum, Ferro-
molybdenum nnd
Ammonium Molyhdale
(Continued)
Phelps Dodge
Chino, NM
no
Processing
no
San Manuel
San Manuel, AZ
no
Processing
no
San Manuel
Morenci, AZ
no
Processing
no
Thompson Creek
Chalis, ID
no
1'iocessing
no
Thompson Creek
Langeloth, I'A
no
Processing
no
Plullnum Group Melals
Stillwater Mine
Nye, MT
yes
Mining and Smelling
no
Pyrobllumens, Mineral
Waxes, and Natural
Asphalts
American Gilsonilc
Bonaza, UT
Uintah County
no
Production of gilsonite (naluial
asphalt)
no
Ziegler Chemical
anil Mineral Corp.
Vernal, UT
Uinlah County,
no
Production of gilsonite (naluial
asphalt)
no
Rare ftarths
Crucible Materials
Elizabethtown, KY
no
Processing of Rare Eaith
Materials
no
Delco Kemy
Division of Geneial
Motors
Anderson, IN
110
Processing ol Rare Earth
Materials
no
I litachi Magnetics
Edmore, Ml
110
Piocessing of Rare Earth
Materials
no
IG Technologies
Valparaiso, IN
no
Processing of Rare Earth
Materials
no
Molycorp
York, PA
no
Processing of Rare Eaith
Materials
no
Molycoip
l.ouviers, CO
no
Facility closed,
Previously Processed Rare
Earth Materials
no
-------
1X1 llltll l -l (Continued)
Facility Names
3MEhb*£ mi MP
.• aw. vav.a. : v> ••••
Cw»a»»ts
{fcmerates om of flw
M ,v-:
Rare Earths (Continued)
Molycorp
Washington, PA
no
Facility closed,
Previously Processed Rare
Earth Materials
no
Molycorp
Mountain Pass, CA
yes
Mining of Bastnasite
no
Molycorp
Canton, OH
no
Processing of Rare Faith
Materials
no
Neomel
West Pittsburgh, PA
no
Processing of Rare Earth
Materials
no
Nord Resources
Jackson, NJ
no
Processing of Rare Earth
Materials
no
Reactive Metals &
Alloys Corp.
West Pittsburgh, PA
no
Processing of Rare Earth
Materials
no
Research
Phoenix, AZ
110
Processing of Raie Earth
Materials
110
RGC (USA)
Mineral Inc.
(formerly
Associated Minerals
(USA) Ltd. Inc.)
Green Cove Springs,
FL
no
Previously mined Monazite, still
mining other materials
no
Rhone-Poulenc
Chemicals Co.
Phoenix, AZ
no
Processing of Rare Garth
Materials
no
Rhonc-Poulenc
Chemicals Co.
Mineville, NY
no
Processing of Rare Earth
Materials
no
Rhone-Poulenc
Chemicals Co.
Freeporl, TX
no
Processing of Rare Earth
Matei ials
no
W.R. Grace
Chattanooga, IN
no
Processing of Rare Earth
Matennls
no
-------
EXHIBIT F-l (Continued)
llMteerai eattMaoilKtftfl. ..
fibril ttx itocatfoiii.. ¦:
ftiinin? WOP .
ffcellitv Cheated
•
-------
EXHIBIT l -l (Continued)
<
. V
vm of flws
Tilanlum and Titanium
Dioxide
E.I. duPonl de
Nemours & Co. Inc.
Antioch, CA
no
Ti02 Production
yes
Chloride process waste solids
I?, 1. duPont
Edgemoor, DE
no
Ti02 Production
yes
Chloride process waste solids
13.1. duPont
New Johnsonville, I N
no
TiU2 Production
yes
Chloride process waste solids
E.I. duPont
Pass Chnstian, MS
no
TiOz Production
yes
Chloride process waste solids
Kcmira, Inc.
Savannah, GA
no
TiO, Production
yes
Chloride process waste solids
Kcrr-McGec
Chemical Corp.
Hamilton, MS
no
TiG2 Production
yes
Chloride process waste solids
Kronos, Inc.
Lake Charles, LA
no
Ti02 Pioduction
yes
Chloride process waste solids
SCM Chemicals,
Inc.
Ashtabula, OH
no
Ti02 Production
yes
Clilonde process waste solids
SCM Chemicals,
Inc
Baltimore, MD
no
Ti02 Production
yes
Chloride pioccss waste solids
l lowmel Corp
Titanium Ingot Div.
Whitehall, Ml
no
Ingot Production
no
A Johnson Metals
Corp.
Lionville, PA
no
Ingot Production
no
Lawrence Aviation
Industries, Inc.
Port Jefferson, NY
no
Ingot Production
no
Oregon
Metallurgical Corp.
(Ormct)
Albany, OR
no
Sponge & Ingot Pioduction
no
-------
EXHIBIT F-l (Continued)
:• :.MJnefeiia ...
: Fadfttv NAittfcs ,*
IxwmHobs
RiP.-}
; farfMt* Coltocafctf
C6»iySiisL
Titanium and Tilnniuni
RMI Co.
Niles, Ol 1
no
Ingot Production
no
Dioxide (Conlinued)
Tclcdyne Ailvac
Monroe, NC
no
Ingot Production
no
Teledyne Wah
Chang Albany
Albany, OK
no
Ingot Production
no
Titanium Hearth
Technologies of
America
Lionvillc, I'A
no
Ingot Production
no
Titanium Metals
Corp. of America
(TIMET)
Henderson, NV
no
Sponge & Ingot Production
yes
Chloride process waste solids
Viking Metallurgical
Corp.
Verdi, NV
no
Ingot Production
no
Wyman-Gordon Co.
Worchester, MA
no
Ingot Production
no
Uranium
no facilities listed
Zinc
Big River Zinc
Corp.
Saugct, 11.
no
Smelter (electro-
lytic)
no
Jersey Miniere Zinc
Co.
Clarksville, TN
no
Smelter (electro-
lytic)
no
Zinc Coi p of
America
Bartlesville, OK
no
Smelter (electro-
lytic), facility closed
no
Zinc Coi p of
America
Monaco, l'A
no
Smelter (pyrometal-
luigical)
yes
Slag
-------
EXHIBIT l -l (Continued)
Kadtttv N«*a»s
vi-fj7:-fx"*':'
Locations
: Mining iMflP
oneoftW
Zirconium and Hafnium
American Mine
Camden, NJ
no
Processing
no
RGC (USA)
Mineral Inc.
(formerly
Associated Minerals
(USA) Lid. Inc.)
Green Cove Spiings,
l-L
no
Production of I Ieavy Mineral
Mined Sand
no
CIBA-GEIGY
Corp.
Washington, PA
no
Processing
no
Conlinenlal
Sharonvillc, OI1
no
Processing
no
Corhart Refractory
Corning, NY
no
Processing
no
Corharl Refractory
Buckhannon, WV
no
Processing
no
Corharl Refractory
Louisville, ICY
no
Piocessing
no
Didier-Taylor
Refractories Corp
South Shore, KY
no
Processing
no
Didier-'I'aylor
Refractories Corp.
Cincinnati, Oil
no
Processing
no
Du Pont
Starke/Trail Ridge,
l-L
no
Production of Heavy Mineral
Mined Sand
no
lilken Metals Corp
Alloy, WV
no
Processing
no
FcrioCorp
Penn Yan, NY
no
Processing
no
I larshaw
Rlyria, Ol 1
no
Processing
no
Heritage
Lakehurst, NJ
no
Piocessing
no
Leco Corp
St. Joseph, Ml
no
Processing
no
Lincoln Rlec
Cleveland, OH
no
Processing
no
-------
EXHIBIT I -l (Continued)
t ; ^ : i : di: ^0. -
Zirconium and llnfniuni
M & T Chem
Andrews, SC
no
Processing
no
(Continued)
Magnesium
Elcktron Inc.
Remington, N.I
no
Processing
no
Norton Co
Huntsville, AL
no
Processing
no
Shieldalloy
Newfield, NJ
no
Piocessing
no
Shieldalloy
Oimhridgc, Oi l
no
Processing
no
Sola Basic
Gilberts, IL
no
Processing
no
Standard Oil
Falconer, NY
no
Processing
no
TAM Ceramics
Niagara Falls, NY
no
Piocessing
no
Tclcclync
Albany, OR
no
Processing
noo
Thiokol Corp.
Beverly, MA
no
Processing
no
Western Zirconium
Ogden, IJT
no
Processing
no
Z-Tecli
Bow, NH
no
Processing
no
Zed mark
Dover, OH
no
Processing
no
Zicar Products, Inc
Florida, NY
no
Processing
no
Z1RCOA Pioducts
Solon, OH
no
Processing
no
-------
EXHIBIT 11 (Continued)
SECTORS PRODUCING HAZARDOUS WASTES:
TOTAL NUMBER OF COLLOCATED
FACILITES
29
TOTAL NUMBER OF FACILITIES
GENERATING SPECIAL 20 WASTES
42
TOTAL NUMBER OF MINERAL
PROCESSING FACILITIES
191
o
00
00
-------
1089
IDENTIFICATION AND DESCRIPTION OF
MINERAL PROCESSING SECTORS
AND WASTE STREAMS
APPENDIX G
Mineral Processing Facilities
Generating Non-Hazardous Wastes
(Including Facilities Generating "Special 20" Bevill-Exempt
Wastes and Colocated Facilities)
-------
1090
-------
EXHIBIT G-l
SECTORS PRODUCING NON-HAZARDOUS WASTES:
Arsenic Acid
(arsenic is no longer
produced domestically)
Hiekson Corp.
Conley, OA
Processing
CSI
Harrisburg, NC
Processing
Osmose Corp.
Memphis, TN
Processing
Bromine
Dow Chemical Company
Ludington, Ml
Bnne extraction
Ethyl Corp.
Magnolia, AR
Urine Infraction
Great l^akes Chemical Corp.
El Dorado, All
Brine Extraction
Cesium and Rubidium
(not recovered from ores
mined domestically)
Cabot Corp.
Revere, PA
Recovery of Cesium
and Rubidium
Calley Chem
Pittsburgh, PA
Uncertain
Carus Corp.
I .a Salle, IL
Acid Digestion
Coming Glass
Coming, NY
Uncertain
Fluorospar and
Hydrofluoric Acid
Allied Signal
Geismar, LA
Processing
yes
Ruorogypsuni and process
wastewater
-------
EXHIBIT G-l (Continued)
^ *¦
'• '¦ WfH1 ¦ Ij %
'.:y. :U
m
UK
E.I. duPont
La Port, TX
no
Processing
yes
Fluorogypsum and process
wastewater
Altochemical, N.A.
Calvert City, KY
no
Processing
yes
Fluorogypsum and process
wastewater
Gemstones
(NOTE: no mineral
processing occurs in this
sector)
Iodine
Asahi Glass Company or
Japan
Woodward, OK
no
Brine extraction
no
Iochem Corp. of Japan
Vici, OK
no
Brine extraction
no
North American Brine
Resources (miniplant)
Dover, OK
no
Brine extraction
no
North American Brine
Resources (major plant)
Woodward, OK
no
Brine extraction
no
Iron and Steel
Acme
Riverdale, IL
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dust,
sludge, and/or slag
Alleghany Ludlum
Brackenridge
no
Processing
i yes
Iron blast (urnace dust, sludge,
and/ oi slag, BOF and Ol IF dust,
sludge, and/or slag
-------
EXHIBIT G-l (Continued)
; '¦ ;. > ¦ -%' i
|:1| V y'f $, < %;'% ?¦%?.
;:?|| :4'£f'¦ -'' ^ Jags
«#$> (.t r ;M
Armco Steel Co., L.P.
•WW WW
Mtddletown, OH
> << v n ' >;,N s
no
^ «.v. .v.*..
. Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dust,
sludge, and/or slag
Armco Steel Co., L.P.
Ashland, KY
no
Processing
yes
Iron hlasl furnace dust, sludge,
and/ or slag, BOF and OllF dust,
sludge - rn|/or slag
Bethlehem Steel
Sparrows Point, MD
no
Processing
yes
Iron Lijm lurnace Uust, sludge,
and/ or slag, BOF and OllF dust,
sludge, and/or slag
Bethlehem Steel
Bethlehem, PA
no
Processing
yes
Iron bias) furnace dust, sludge,
and/ or slag, BOF and OHF dust,
sludge, and/or slag
Bethlehem Steel
Chestertown, IN
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dusl,
sludge, and/or slag
Geneva Steel
Orem, UT
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dust,
sludge, and/or slag
Gulf Stales Steel
Gasden, AL
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and Ol IF dust,
sludge, and/or slag
-------
EXHIBIT G-l (Continued)
m—
J> s;
.r-M
Inland Steel
B. Chicago, IN
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OIIT dust,
sludge, and/or slag
LTV
E. Cleveland, OH
no
Processing
yes
Iron blast furnace dusl, sludge,
and/ or slag, BOF and O! II-' dust,
sludge, and/or slag
LTV
W. Cleveland, Oil
no
Processing
yes
Iron blast furnace dusl, sludge,
and/ or slag, BOI-' and OIIF dust,
sludge, and/or slag
LTV
Indiana Harbor, IN
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OIIF dust,
sludge, and/or slag
McLouth Steel
Trenton, Ml
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OIIF dust,
sludge, and/or slag
National Steel
Granite City, IL
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dusl,
sludge, and/or slag
National Steel
Escore, MI
no
Processing
yes
Iron blast furnace dust, sludge,
and/.or slag, BOF and OI IF dust,
sludge, and/or slag
-------
EXHIBIT (M (Continued)
* , i - " > £
^ '<5 , ii <" 4-' i &
-' -%"
' '¦¦ i w ¦¦
IbWI^M^w^
Dearborn, Ml
-i >
< K vwmmmmmi
''^ShSSh
no
M j •••,'"" t •,.••
«\vav>:v -a :•:¦:••.¦ ¦ vftvC'V-'AW' • <•:•<•:< :•:• •:
<¦ ' "
fc"fcr -\;
"jti •. .v •/.¦
-------
EXHIBIT G-l (Continued)
WSiiWgsmmsmmemm
¦—
wmmSSmm
'¦ US Steel/Kobe
Mlllifiipil
Lorain, OH
j
no
. v.-.-.'.-.-.-.-,-.-:-.-.-:-;v-;-.v;-:-:-: :¦•; V! !¦
Processing
- k-;- ¦¦ -M-mmlmm
fi§
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OIIP dust,
sludge, and/or slag
Warren Sleel
Warren, OH
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OMF dust,
sludge, and/or slag
Weirton Steel
Weirton, WV
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OI1F dust,
sludge, and/or slag
Wheeling-Pittsburgh Sleel
Steubenville, OH
no
Processing
yes
Iron blast fumacc dust, sludge,
and/ or slag, BOF and OlIF dust,
sludge, and/or slag
Wheeling-Piltsburgh Steel
Mingo-Junction, OH
no
Processing
yes
Iron blast furnace dust, sludge,
and/ or slag, BOF and OHF dust,
sludge, and/or slag
l.iehlweieht Aggregates
Arkansas Lightweight
Aggregate
West Memphis, AR
yes
Processing
no
Big River
Livingstone, AL
no
Processing
no
Big River
Erwinville, LA
no
Processing
no
Buildex
Dearborn, MO
no
Processing
no
Buildex
Ottawa, KS
yes
Mining and processing
no
-------
EXHIBIT G-l (Continued)
" 'i < T
4k 'rtty -f ¦',
< v"$ vs s
, y&£fflZ#iX/
la&mtr-''- ' fill
fflMMHmMMljW
SM^WiWf Bill
> s % >" } p
¦\> <" % \ J- % SN'^*
f-i. ;
XV-XfiSJXv --&.V.•>». . sS
' V^A' /.V'AVAWA' uvX'.v/'Xv.
TCTv; 1
%
CftlfifUMrf
J ' J", V % s %v%'' ? Ky "j% /
Buildex
Marquette, KS
no
Processing
no
Chandler Materials Co.
Tulsa, OK
yes
Mining and processing
no
Chandler Materials Co.
Choctaw, OK
yes
Mining and processing
no
Dakota Block Co.
Rapid City, SD
no
Processing
no
Edward C. I^evy Co.
Detroit, MI
no
Byproduct of iron and
steel slag
no
Teatherlite
Slrawn (Ranger), TX
no
Processing
no
HP Brick Co.
Brooklyn, IN'
no
Processing
no
HP Bnck Co.
Independence, OH
no
Processing
no
Jackson Concrete
Jackson, MS
yes
Mining and processing
no
Kanta
Three Forks, MT
no
Processing
no
Koch Minerals
Gary, IN
no
Byproduct of iron and
steel slag
no
Lehigh'Portland Cement Co.
Woodsboro, MD
no
Processing
no
Lorusso Corp.
Plainvilte, MA
no
Processing
no
Parkwood Lightweight Plant
Bessemer, AL
no
Processing
no
Porta Costa
Porta Costa, CA
yes
Mining and processing
no
Ridgelite
Frazier Park, CA
yes
Mining and processing
no
Solile
Cascade, VA
no
Processing
no
Northeast Solite
Mount Marion, NY
no
Processing
no
-------
EXHIBIT G-l (Continued)
ftflgfelHi
Standard LaFarge Corp.
Cleveland, OH
S4iil*lll
no
¦illiiili; f :
BBMBIN'*
Byproduct of iron and
steel slag
no
Strawn
Strawn, TX
no
Processing
no
Texas Industries
Streetman, TX
no
Processing
no
Utelite
Coalville, UT
no
Processing
no
Waylight
Bethlehem, PA
no
Byproduct of iron and
steel slag
no
Weblite
Blue Ridge, VA
yes
Mining and processing
110
Lithium and Lithium
Carbonate
Cyprus-Foote
New Johnsonville, '174
no
Processing
no
Cyprus-Foote
Sunbright, VA
no
Processing
no
Cyprus-Foote
Kings Mountain, VA
no
Mining
no
FMC Corp.
Bessemer City, NC
yes
Mining with Processing
facility nearby
no
Maneanese. MnO,.
Ferromansanese, and
Silicomanganese
Chemetals Inc.
Baltimore, MD
no
Processing
no
Chemetals Inc.
New Johnsonville, TN
no
Processing
no
Elkera Metals
Marietta, OH
no
Processing
no
Kerr McGee Chemical Corp.
Hamilton, MS
no
Processing
no
Kerr McGee Chemical Corp.
Henderson, NV
no
Processing
no
-------
EXHIBIT G-l (Continued)
• 5 i s" ,
........ ..o> ..v> y.'.'.' v. vav.'.v
' */"
, "ti
• * V.V.' ¦rtAW/.V.W.VAW.V.1 •(/. . . .'. . * .'l i. .\V'X
,
% ' ' ' '
^ ¦¦ ;;>
¦illlHK'i? %>;*:
S^^^^^wBHWwlMliiKS^BWyvt ¦>>.' wa'/ -.'.
s- , ^
¦ ¦¦ .¦ ¦¦-¦ :¦,!- ¦¦ '¦
s
"vp- ¦ -i
\
Everready Battery Co.
Marietta, OH
no
Processing
no
Phosporic Acid
Agrico Chem
Pierce, FL
(Mulberry)
no
Processing
yes
Phosphogysum, process
wastewater
Agrico Chem
Uncle Sam, I^A
no
Processing
yes
Phosphogypsum, process
wastewater
Agrico Chem
Donaldsonville, LA
no
Processing
yes
Phosphogypsum, process
wastewater
Albright & Wilson
Fernald, OH
no
Processing
no
Albright & Wilson
Charleston, SC
no
Processing
no
Arcadian
Geismar, LA
no
Processing
yes
Phosphogypsum, process
wastewater
Cargill
Riverview (Tampa), l7L
no
Processing
yes
Phosphogysum, pioccss
wastewater .
(no listed in special waste
manual)
Central Phosphates
Plant City, FL
no
Processing
yes
Phosphogysum, process
wastewater
CF Ind.
Raitow, FL
(Bonnie)
no
Processing
yes
Phosphogypsum, process
wastewater
-------
EXHIBIT G-l (Continued)
> 'KSL \y&mm
|-;
WL* u±-:"
£#$£&&' '>> <' <^< «
SkfcMMSw-^s V \S%t '
aSw^^ *^1
|P|i^ v^V <* ^b"
y ^ "¦> ^
"- ...,fl|ii
Chevron
Rock Springs, WY
no
Processing
yes
Phosphogypsum, process
wastewater
Conscrv
Nichols, FL
no
Processing
yes
Phosphogypsum, process
wastewater
Farmland
Pierce (Bartow), FL
no
Processing
yes
Phosphogypsum, process
wastewater
FMC
Carteret, NJ
no
Processing
no
FMC
Lawrence, ICS
no
Processing
no
FMC
Newark, CA
no
Processing
no
Gardinier, inc.
Riverview, FL
(Tampa)
no
Processing-
yes
Phosphogypsum, process
wastewater
I iydrate
Milwaukee, Wl
no
Processing
no
IMC Fertilizer
Mulberry, FL
(New Wales)
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
JR Simplol
Pocatello, ID
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
Mobil
Pasadena, TX
no
Processing
yes
Phosphogypsum, process
wastewater
-------
EXHIBIT (.-I (Continued)
_ _ _
HIE
fel —
Monsanto
Trenton, NJ
no
Processing
no
Monsanto
Augusta, GA
no
Processing
no
Monsanto
Carondelet, MO
no
Processing
no
Monsanto
Long Beach, CA
no
Processing
no
Nu West
Soda Springs (Conda), II)
no
Processing
yes
Phosphogypsum, process
wastewater
Nu South
Pascagoula, MS
no
Processing
yes
Phosphogypsum, process
wastewater
Occidental Chem
Jeffcrsonville, IN
no
Processing
no
Occidental Chem
Columbia, TN
no
Processing
no
Occidental Chem
While Springs, FL
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
Occidental Chem
Dallas, TX
no
Processing
no
Royster
Palmetto (Piney Pi.), PL
no
Processing
yes
Phosphogypsum, process
wastewater
Royster
Mulberry, 1-1.
no
Processing
yes
Phosphogypsum, process
wastewater
-------
EXHIBIT G-l (Continued)
iimmmmmmmmmm wmmmmmmmm
fk, -- h; *'-; "JPmmIH
:; 1; :;¦'.(*" ^ ^
jXyy.;;;X*:,XiX,:,x,x,x,w,::X-xi::.:X^:X<;X,X:XjR;>!:C:^:X£Wx.v!:5 .AWxXwiw:?Si«?w^w«i«8E»»S*S»i%«?-w
|gg||rew $ rp 11 >'<<5:»' j,:
Iiiiyiii:fiMi wmmmsm
Seminole
Bartow, FL
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
Slaurrer
Morrisville, PA
no
Processing
no
Slauffer
Nashville, TN
no
Processing
no
Slauffer
Richmond, CA
no
Processing
no
Slauffer
Chicago Heights, IL
no
Processing
no
Slauffer
Chicago, IL
no
Processing
no
1'exasgulf
Aurora, NC
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
US Agri-Chemicals Corp
(USAC)
(Fort Meade Chem)
Ft. Meade, FL
yes
Mining and Processing
yes
Phosphogypsum, process
wastewater
Scandium
Baldwin Metals Processing Co.
Phoenix, AZ
no
Processing
no
Boulder Scientific Co.
Mead, CO
no
Refining
no
Interpro (subsidiary of
Concord Trading Corp.)
Golden, CO
no
Refining
no
Materials Preparation Center
Ames, 1A
no
Processing
no
Rhone-Poulenc, Inc.
Phoeniz, AZ
no
Processing
no
-------
EXHIBIT G-l (Continued)
i:^9H|Pi^s
mmmmmmmmmmmmm
'
_|§§
Kennecott
Garfield, UT
no
Refining (as a
byproduct generated
during uranium
processing at a copper
mine)
no
Climax Mine
Climax, CO
no
Refining (as a
byproduct generated
during molyb-
denum operations)
no
APL Engineered Materials
Urbana, IL
no
Refining
no
Sausville Chemical Co.
Garfield, NJ
no
Refining
no
Silicon and Ferrosilcon
American Alloys Inc.
New Haven, WA
no
Processing
no
Applied Industrial Minerals
Corp.
Bridgeport, AL
no
Processing
no
Dow Coming Corp.
Springfield, OR
no
Processing
no
Elkem Metals Co.
Alloy, WV
no
Processing
no
Elkem Metals Co
Ashtabula, Ol 1
no
Processing
no
Globe Metallurgical Inc.
Beverly, OH
no
Processing
no
Globe Metallurgical Inc.
Selma, AL
no
Processing
no
Keokuk Ferro-Sil Inc.
Keokuk, IA
no
Processing
no
Silicon Metaltech
Wenalchee, WA
no
Processing
no
Simetco Inc.
Montgomery, AL
no
Processing
no
-------
EXHIBIT G-l (Continued)
^MwilillllIIMIP
SKW Alloys Inc.
Calvert City, KY
no
Processing
no
SKW Alloys Inc.
Niagara Falls, NY
no
Processing
no
Soda Ash
FMC Corp.
Green River, WY
yes
•Mining and Processing
no
General Chemical Partners
Green River, WY
yes
Mining and Processing
no
North American Chemical
Company
Argus, CA
yes
Mining and Processing
no
North American Chemical
Company
Westend, CA
yes
Mining and Processing
no
Rhone-Poulenc Mine
Green River, WY
yes
Mining and Processing
no
Tenneco
Green River, WY
yes
Mining and Processing
no
TG Soda Ash Mine
Green River, WY
yes
Mining and Processing
no
Sodium Sulfate
Great Salt Lake Minerals and
Chemicals Corp.
Great Salt Lake, UT
no
Mining
no
North American Chemical,
Inc.
Searles Lake, CA
no
Mining
no
Ozark-Mahoning Co.
Western Texas
no
Mining
no
Strontium
Chemical Products Corp.
(CPC)
Cartersville, GA
no
Processing
no
Tunesten
AVOSET Ventures (Pine
Creek Mine)
Bishop, CA
yes
Production temporarily
idle
no
-------
EXHIBIT G-l (Cbatlued)
Bufbk> I'tmptm
ilepew. NY
HO
KlKYtthf
nu
Ontii Tkmgptca, Inc.
Upland, ( A
r*
Pioductioa temporarily
KlIC
IK>
Utanl Bitdric
Eadid, Oil
AO
PiiM-nsini
(1(1
OSKAM Sytvaaia, Inc.
TVwwurti. P A
DO
Processing
no
KnumHil
FUtoa.NV
Pl(KOSlfl|
-
Kcuioku)
LaTrufcc. FA
ao
Proccsuqg
no
....
Tetedync Hrth States
la Vtrpte, TN
DO
Procctsui|
no
Tctodyua Advance Materials
HaUvlBe, AL.
no
ProoeMNf
no
U.S. TUogtten
Bwhop. CA
Production temporarily
kite
no
Vaaadmi
Akxo Ckaicil Company
Walot, Ml
DO
Piuccuiof
mi
AMAX Mciib Rccoscry
Cofp.
BnilhmHc, LA
ao
Prooaah^
no
Bear Metallurgical Corp.
Butler, PA
DO
ProcoMB|
DO
CMia Oip.
Cauua Chj, CO
mu
PllXOMIf
no
OktCkanal A McuIIh|N
Corp\
Frecpurt, IX
DO
P(OCOSlfl(
DO
Kot k\*« t ftcmtril Corp.
Soda Spnap, ID
QO
PlOCCUiqg
UU
Reading /Hup
Rntomti, PA
IMi
PrOTA«lfl|
ou
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KXllIUi r C I (Coatiiwd)
'v\ -
U-1
~©
=£>
aQ —\
0"\ J?
SMddaOof Minllunii ¦! Corp.
Canbridge. Oil
DO
Proce&iiJig
no
Sumtooc
Niagara halls, NY
np
Procrninf
IMl
Wcdyic Wab Quag
Albany, OK
no
hucoiui|
DO
Undoo Mtncnts
Blinding, IT
w>
Proccaamg
no
Statoor
Kim Sfriogx. AR
no
Piuccssioi
00 |
sexmNts producing noniiazardous wastks:
TOTAL HIJMBBH OF C0UOCA1VD
rAqomn
"
TOTAL NUMBBR OF FAC1U1UB
CBNOUT1NC STBCUL H WASTES
¦
TOTAL NUMBER OF MINERAL
rj^mNorMji'inw
163
_£>
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|